Chem Factsheet

September 2000 Number 01

Atomic Structure
The particles within a nucleus are drawn together by extremely powerful
To succeed in this topic you need to:
forces capable of overcoming the repulsion of the protons (+ve to +ve)
• be able to use the periodic table to find atomic and mass numbers.
However, these forces act over a short distance as they do not pull the
electrons in.
After working through this Factsheet you will be able to:
• describe and understand the accepted model of an atom
• interpret simple mass spectra The electrons are in constant motion, orbiting the nucleus.
• understand the importance of ionisation energies of different elements,
and use them as evidence in describing atomic structure Atomic number, atomic mass number and isotopes
• assign electronic configurations to atoms
• understand the impact of electronic configuration on chemical Atomic number (Z): the number of protons in an atom
properties Mass number (A): the number of protons + neutrons in an atom.
• define electron affinity

Exam Hint: A thorough understanding of atomic structure is

essential for success throughout AS Chemistry. Questions often
require candidates to
Remember also that the number of protons (+ve charges) will be equal to
• work out the electronic configuration of an atom the number of electrons (-ve charges) in a neutral atom.
• deduce chemical properties from electronic configuration
• describe and explain trends in ionisation energy Given the information on the periodic table, it is possible to calculate the
• interpret mass spectra number of protons, neutrons and electrons present in an atom of any given
element. Fig 2.
Fundamental particles
An atom is the smallest particle of a chemical element. Atoms themselves Fig 2.
consist of protons, neutrons (in the nucleus) and electrons (see Fig 1). The
mass number
mass of an atom is concentrated in the nucleus. The nucleus is very small 9
and massive, so therefore has an incredibly high density.

Fig 1. Fundamental particles of an atom

4
Be
atomic number

Atomic number = 4 ∴ number of protons = 4

No. protons = no. electrons ∴ number of electrons = 4
electrons Mass number = no. p + no. n ∴ number of neutrons = 9 – 4 = 5

All atoms of the same element have the same atomic number - e.g atomic
number of magnesium = 12, therefore all magnesium atoms contain 12
protons.

nucleus Mass numbers of atoms of the same element may, however, vary – due to
(contains protons different atoms containing different numbers of neutrons. These atoms are
and neutrons called isotopes.

Remember - Isotopes of one particular element are atoms which

have the same atomic number and so the same number of protons
(therefore are atoms of the same element) but different mass numbers,
Table 1 Shows the relative charge, relative mass and position of atomic
because they have different numbers of neutrons.
particles. (For most purposes, the mass of the electron is taken as 0).

Table 1. Atomic particles data One example is hydrogen - there are three isotopes, all with atomic number
Particle Relative mass Relative charge Position within 1, but with mass numbers 1, 2 and 3.
atom
Proton 1 +1 Elements with isotopes do pose a problem when wanting to assign a mass
nucleus number on for the element. An average atomic mass is calculated - called
Neutron 1 0 nucleus the relative atomic mass, Ar. The calculation of this average mass needs
to take account of the relative abundance of each isotope; the method for
Electron 1 -1 shells doing this is illustrated in the following example:
1850

1
Atomic Structure Chem Factsheet

For example, naturally occuring chlorine consists of 2 isotopes. Ionisation Energies

75% of the atoms have a mass of 35 (Cl-35) If an atom is supplied with enough energy, it will lose an electron, and
25% of the atoms have a mass of 37 (Cl-37) additional supplies of energy may cause the loss of a second electron, then
75 25
a third and so on. If a neutral atom loses an electron, it becomes a positively
To work out Ar, we do × 35 + × 37 = 35.5 charged ion (cation).
100 100

The actual definition of relative atomic mass involves carbon - 12 - this

must be learnt. First Ionisation Energy - the energy required to remove 1 mole of
electrons from 1 mole of gaseous atoms.
mass of one atom of an element e.g. Na(g) → Na+(g) + e- ∆HIE = +494 KJ mol-1
Relative Atomic Mass (Ar) =
1/12 mass of one atom of carbon–12
Second Ionisation Energy - the energy required to remove 1 mole of
electrons from 1 mole of gaseous 1+ charged cations
e.g. Na+(g) → Na2+(g) + e- ∆HIE2 = +4564 KJ mol-1
Carbon – 12 is used to because carbon is a common element and as a solid
is easy to store and transport.
Examining successive ionisation energies for an element can give us further insight
into atomic structure – specifically the arrangement of electrons (Fig 6 overleaf)).

The mass spectrometer

The mass spectometer is a machine which provides chemists with a way
Fig 4. Mass spectrometer traces
to measure and compare masses of atoms and molecules (Fig 3.)
Sodium
(100 %)
Fig 3. Mass Spectrometer 100 sodium (Na)
80
% abundace

+
60
1. 1234567890123456
1234567890123456
3.
1234567890123456
1234567890123456
40
1234567890123456
1234567890123456
20
○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○
4.
1234567890123456
12345678
1234567890123456
12345678
0
1234567890123456
12345678
1234567890123456 0 10 20 30 40 70 80
2. 12345678
1234567890123456
12345678
1234567890123456
12345678
Mass / Charge Ratio
1234567890123456
12345678
1234567890123456
1. vaporisation To 12345678
1234567890123456 Iron
2. ionisation vacuum pump 100
○

3. accleration
(91.68%)
○

(by electric field)

○

4. deflection
○

Relative Abundance / %

5.
5
(by magnetic field)
○

5. detection

50
The way in which the mass spectrometer works can be broken down into
5 stages.
1. Vaporisation - The sample being tested has to be turned into a gas,
so individual atoms/molecules are separated. (2.17%)

2. Ionisation - A heated filament gives out electrons into the ionisation (5.84%) (0.31%)
0
chamber. As the sample enters the ionisation chamber, its atoms/ 20 30 40 50 60 70 80
molecules are bombarded by these electrons. The collisions cause Mass / Charge Ratio
electrons to be removed from the atoms/molecules of the sample, so
positive ions are formed. (This is where fragmentation can occur –
molecules may break into pieces.) From the mass spectra shown, it is clear that the sodium sample tested
consisted solely of sodium –23.
3. Acceleration - An electric field is applied, which will accelerate the
positive ions (as they are charges particles). The sample of iron was a mixture of 4 isotopes, iron –54, iron –56,
iron –57 and iron –58. The percentage abundancies are given (i.e. 91.68%
4. Deflections - A magnetic field deflects the beam of ions. Ions with iron –56, showing it to be the most common isotope) so now the relative
a high mass/charge ratio (eg. Heavy, 1+ charge) will be deflected less atomic mass of iron can be calculated.
than ions with a low mass/charge (e.g. light 13+ charge)
Ar = avge mass = 5.84 × 54 + 91.68 × 56 + 2.17 × 57 + 0.31 × 58= 55.91
100 100 100 100
5. Detection - Those ions which have the correct mass/charge ratio will
be detected. If the magnetic field is kept constant whilst the electric
field causing acceleration is continuously varied, one species after Note:many ions have a charge of +1, so the mass/charge (m/e) ratio is
another will be detected, so a complete spectrum, or trace, is obtained. equal to the mass (m) of the ion.

2
Atomic Structure Chem Factsheet

Fig 5. Successive ionisation energies for sodium Notice that within a period, sets of elements with similar first ionisation
energies exist, consisting o f 2, 3, 3, members - within period 2, this is (Li, Be)
1000000 these 2 electrons are in the n=1 shell, (B,C,N) and (O, F, Ne). These are explained by the existence of subshells
closest to the nucleus. These - see later.
experience very strong attractive
100000 forces from the nucleus.
There is also a trend in first IEs down any group – there is a general
decrease due to the increased distance and shielding of the outer electrons
ionisation energy / kJ mol-1

10000 from the nucleus.

these 8 electrons are in the n=2 shell,
1000 between the n=1 and n=3 shells. Electronic Configurations
These electrons experience strong
attractive forces from the nucleus
You are aware that electrons exist in different energy levels (or quantum
100
shells).
this electron is in the n=3 shell,
furthest from the nucleus. This Electrons can also be split within a quantum shell, into subshells.
10 electron experiences comparatively
weak attractive forces from the
nucleus. e.g. in the second shell (referred to as" n = 2") there are 8 electrons in a full
0 shell. This can be split into 2 subshells:
0 1 2 3 4 5 6 7 8 9 10 11 • 2s - containing 2 electrons slightly harder to remove
ionisation number • 2p -containing 6 electrons slightly easier to remove.

The pattern shows us that sodium has 11 electrons arranged in 3 shells, or Each sub-shell is a collection of orbitals:
energy levels. The first electron is relatively easy to remove as:
(a) it exists further from the nucleus Sub-shell orbitals max e-
(b) the electrons orbiting closer to the nucleus ‘shield’ it from the positive s 1 2
centre so the attractive forces are comparatively weak. p 3 6
The next 8 electrons have similar ionisation energies (as they are all a d 5 10
similar distance from the nucleus) but do get successively slightly harder to f 7 14
remove, as the relative positive charge in the ion is increasing. The last 2
electrons are very difficult to remove as they exist very close to an Fig 7 shows the orbitals for the s and p sub-shells
unshielded nucleus.
Fig 7. s and p orbitals
Ionisation Energy and the Periodic Table
• alkali metals are the easiest to ionize three p-orbitals
• noble gases are the hardest to ionize s-orbital p-orbital
• As we move across a period, the first IE tends to increase, as
♦ nuclear charge increases
♦ electrons are added to the same shell, the same distance from the
nucleus with the same degree of shielding
Fig 6. First ionisation energies for the first 20 elements

Each orbital can hold up to 2 electrons, but electrons in a pair must have
opposing spin. We represent each orbital by a box, and the electrons by
Each 'peak' marks a noble gas (He, half-arrows. One half arrow points up and one down, to represent the
Ne, Ar) at the end of each period different spins of the two electrons

He
Ne
first ionistaion energy

F Ar When electron sub shells are filling up, one electron is placed in each
N available orbital first; the electrons only pair up when no more orbitals are
Cl
H C O P
Be available in that sub-shell.
Mg S
B Si Ca
Li Na Al
K

0 10 20
atomic number
Each 'trough' marks an alkali Exam Hint:
metal (Li,Na, K) at the start • You need to be able to draw the shapes of the s and p orbitals,
of each period but not of d or f orbitals.
• You need to know the number of orbitals - and hence number of
electrons - in each sub-
shell.

3
Atomic Structure Chem Factsheet

Order of filling of sub-shells Table 2. Electronic arrangement of the elements from hydrogen
We already know that the electrons in an atom fill up the first shell before to krypton
going into the second, and fill that before going into the third shell. We now Element Atomic 1s 2s 2p 3s 3p 3d 4s 4p
need to look at the order in which the sub-shells fill up. This is described number
by Fig 9.
Hydrogen 1 1
Fig 9. Order of filling of sub-shells Helium 2 2
!s level full

1s Lithium 3 2 1
Beryllium 4 2 2
2s 2p 2s level full
3s 3p 3d
Boron 5 2 2 1
4s 4p 4d 4f Carbon 6 2 2 2
Nitrogen 7 2 2 3
5s 5p 5d 5f Oxygen 8 2 2 4
Fluorine 9 2 2 5
6s 6p 6d
Neon 10 2 2 6
2p level full

Using the diagram, the order in which the subshells fill is: Sodium 11 2 2 6 1
Magnesium 12 2 2 6 2
3s level full
1s 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p .... etc
Aluminium 13 2 2 6 2 1
Silicon 14 2 2 6 2 2
We are now able to write out electronic configurations in more detail, using Phosphorus 15 2 2 6 2 3
the following notation: Sulphur 16 2 2 6 2 4
number of electrons Chlorine 17 2 2 6 2 5
5
shell
2p in subshell Argon 18 2 2 6
3p level full
2 6

number subshell Potassium 19 2 2 6 2 6 1

Calcium 20 2 2 6 2 6 2
or using arrows in boxes 4s level full
2p
Scandium 21 2 2 6 2 6 1 2
Titanium 22 2 2 6 2 6 2 2
Vanadium 23 2 2 6 2 6 3 2
Using the principles covered so far, we can now find the electronic Chromium 24 2 2 6 2 6 5 1 **
configurations of the first 36 elements (Table2) Manganese 25 2 2 6 2 6 5 2
Iron 26 2 2 6 2 6 6 2
Evidence for sub-shells from ionisation energies Cobalt 27 2 2 6 2 6 7 2
Whilst there is a general increase in IE across the period, this is not a Nickel 28 2 2 6 2 6 8 2
smooth trend, which can be explained by the existence of sub-shells. Copper 29 2 2 6 2 6 10 1 **
Zinc 30 2 2 6 2 6 10 2
3d level full
Fig 10. First ionisation energies across period 2
Gallium 31 2 2 6 2 6 10 2 1
Germanium 32 2 2 6 2 6 10 2 2
Arsenic 33 2 2 6 2 6 10 2 3
Ne Selenium 34 2 2 6 2 6 10 2 4
filling of 2p Bromine 35 2 2 6 2 6 10 2 5
sub-shell Krypton 36 2 2 6 2 6 10 2 6
F
first ionisation energy

4p level full
N pairing of
2p electrons Note: a) how the 4s level fills up before the 3d level,
filling of 2s C
Be O b) for chromium and copper (labelled **) the sequence is out of
sub-shell step; you will meet this point again when studying the
2p sub-shell half-fills transition elements.
B You will be required to write the electronic arrangement (or configuration)
Li for elements and there are two accepted ways for doing this. For example,
the electronic arrangement for iron could be written: 1s2, 2s2, 2p6, 3s2, 3p6,
atomic number 3d6, 4s2 or [Ar] 3d6, 4s2 where [Ar] represents the electronic arrangement
of the noble gas argon.

4
Atomic Structure Chem Factsheet

You will notice from Fig 10 that the first ionisation energy decreases from Both F and Cl need to gain 1 electron to acquire a stable noble gas electronic
Be to B and from N to O. A similar phenomenon occurs between groups 2 configuration. An electron would be more strongly attracted to F rather
to 3 and 5 to 6 in the other periods. This can be explained by examining the than the larger Cl, as it could join a lower energy level closer to the nucleus
electron configurations of the elements: with less shielding from it. Therefore, the smaller the halogen atom, the
more reactive it is. So reactivity decreases down the group.
Comparing Be and B
Electron Affinities
1s 2s 2p 1s 2s 2p
As shown with the halogens, it is possible to add electrons to an atom,
Be B
forming a negative ion (anion). The energy required to do this is the electron
affinity.
Beryllium has full-subshell stability, as the highest occupied subshell is
complete. Boron has one electron in a higher (2p) sub-shell, which is easier
to remove, hence its 1st IE is lower than that of Be
First Electron Affinity - the energy required to add1 mole of electrons
Comparing N and O to 1 mole of gaseous atoms.
e.g. O (g) + e- → O− (g) ∆HEA1 = -141 kJ mol-
1s 2s 2p 1s 2s 2p
N O Second Electron Affinity - the energy required to add 1 mole of electrons
to 1 mole of gaseous 1- charged anions
Nitrogen has half-shell stability. e.g. O− (g) + e- → O2− (g) ∆HEA2 = +798 kJ mol-1

Oxygen has one 2p orbital which has a pair of electrons and paired electrons
repel, so one of these electrons is easier to remove, hence it has a lower 1st The 1st EA is always exothermic (energy is released) because the electron
IE than that of nitrogen. goes into a vacancy in the outer energy level. This is ‘bond-making’ so
energy is released.
Electronic Structure and Chemical Properties
Chemical reactions involve the making and/or breaking of bonds. Bond However, this creates a 1- ion so to put the second electron into the vacant
involve the movement of electrons. site needs energy to be put in to overcome the repulsion (–ve to –ve)
between the ion and the electron - so the 2nd EA is always endothermic
e.g. Covalent bond - sharing of electrons (energy is absorbed).
Ionic bond - transfer of electrons
Questions
It makes sense therefore that the electronic configuration of an atom has an 1. a) Define the terms first ionisation energy.
impact on its chemical properties.
b) The graph shows a plot of lg (ionisation energy) vs number of the
Any group on the periodic table can be considered a ‘family of elements’ as electron removed for aluminium.
the elements in that group will exhibit similar chemical properties. This is
due to each member of the group having the same number of electrons
in its outer shell.

Even within groups, trends in reactivity can be explained by electronic

configuration:
lg(ionisation energy)

e.g.1 For Group 1 – the alkali metals – reactivity increases down

the group.

If we consider lithium and sodium, their electron configurations are as

follows:
Li: 1s2 2s1
Na: 1s2 2s2 2p6 3s1

Both Li and Na require to lose 1 electron to gain a stable noble gas electronic 0 1 2 3 4 5 6 7 8 9 10 11 12 13
configuration. It is difficult to remove the outer electron from lithium as it number of electrons removed
is close to the nucleus and experiencing little shielding. These factors mean Explain the form of this graph in terms of the electron structure of
lithium: aluminium.
• has a higher 1st IE than sodium
• is less reactive than sodium 2. a) Define the terms
This trend continues down the group. (i) atomic number (ii) mass number
(iii) relative atomic mass (iv) isotope
e.g.2 For Group 7 – the halogens – reactivity decreases down the
group. b) Describe in detail the five stages in the operation of a mass
spectrometer.
If we consider fluorine and chlorine, their electron configurations are as
follows: c) The mass spectrometer analysis of neon shows it exists of two
F: 1s2 2s2 2p5 isotopes of different relative abundances ie. 20 (90%) and 22 (10%).
Cl: 1s2 2s2 2p6 3s2 3p5 Calculate the relative atomic mass of neon.

5
Atomic Structure Chem Factsheet

3. Sketch a graph on the axes below to show the successive ionisation 3.

energies of sodium.

lg (ionisation energy)
lg(ionisation energy)

0 1 2 3 4 5 6 7 8 9
0 1 2 3 4 5 6 7 8 9 10 11
number of electrons removed
number of electrons

Na is 2, 8 1. There is one electron in the outer orbit, 8 electrons in the

Give reasons for the shape of the line you draw. next orbit and 2 in the innermost orbit.

4. For each of the following elements give the electronic configuration 4. a) P = 15 1s2 2s2 2p6 3s2 3p3
in terms of s, p and d orbitals’: b) C = 6 1s2 2s2 2p2
a) phosphorus
b) carbon 5. a) 1st I.E’s decrease down a Group.
The outer electron is further from the nucleus and the inner electron
5. Explain the trend in first ionisation energies and the reasons for it: orbitals shield the pull of the nucleus on the outer electrons. The
a) down a group outer electrons are easier to remove.
b) across a period
b) 1st I.E’s increase across a Period.
The outer electrons go into the same outer orbital so the shielding
6. a) Why is the first ionisation energy of nitrogen higher than that of
effect is the same across the Period. At the same time one extra
oxygen?
proton is added, increased the nuclear charge. This makes the outer
electrons increasingly more difficult to remove.
b) Write equations which represent for oxygen:
6. a) N is 1s2 2s2 2p3 O is 1s2 2s2 2p4
(i) the first electron affinity Half-shell stability of p3, compared to O where the p electron
(ii) the second electron affinity is more easily removed.

7. Give reasons for each of the following: b) (i) O (g) + e- Ô O- (g)

a) sodium is more reactive than magnesium (ii) O- (g) + e- Ô O2- (g)
b) potassium is more reactive than sodium
c) chlorine is less reactive than fluorine 7. a) Na only has to lose one electron to gain the Noble Gas configuration,
and its 1st I.E. is lower than for magnesium. The Na single electron
Answers is lost more easily, so sodium is more reactive.
1. a) The energy needed to remove one mole of electrons from 1 mole of
b) K has a bigger atomic number so more electron orbits. Increased
gaseous atoms.
shielding on an electron further from the nucleus means the outer
b) Al has a 2, 8, 3 configuration ie. 3 outer electrons, 8 electrons in the
electron is easier to remove than the one for Na..
next orbialt and 2 electrons in the inner orbital.
c) F has a smaller atomic number so less electron orbits so less shielding
2. a) (i) number of protons in the nucleus
of the pull of the nucleus for the electron needed to complete is
(ii) number of protons and neutrons in the nucleus
outer orbital. The F atom therefore has more pull on electrons so is
(iii) the mass of an atom compared to 1/12 mass of an atom of
more reactive than Cl.
carbon 12
(iv) atoms with the same atomic number but different mass numbers/
atoms with the same number of protons but different numbers
of neutrons

b) Vaporisation – heating the sample to turn it into a gas

Ionisation – bombarding the gaseous sample with an electron beam
to remove electrons and produce positive ions.
Acceleration – attraction of the positive ions to an electrical field.
Acknowledgements:
Deflection – passing the ions through a magnetic field to deflect This Factsheet was researched and written by Sam Goodman
them according to mass/charge ratio. Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham,
Detection – ions being measured according to mass/charge ratio B18 6NF
and their relative abundance being calculated.
ChemistryFactsheets may be copied free of charge by teaching staff or students,
c) 20.20 provided that their school is a registered subscriber.
No part of these Factsheets may be reproduced, stored in a retrieval system, or
transmitted, in any other form or by any other means, without the prior
permission of the publisher. ISSN 1351-5136

6
 Chem Factsheet
September 2000 Number 02

Moles and Formulae

To succeed with this topic you need to: Example: What is the percentage by mass of each of the elements present
• be able to find Ar (atomic mass number) values from the Periodic Table in C2H5Br?
• use a calculator to do basic arithmetic
Mr (C2H5Br) = (12 × 2) + (1 × 5) + (80 × 1)
After working through this Factsheet you will be able to: = 109
• calculate Mr (molecular mass number) from Ar values 12 × 2
• calculate percentage composition by mass for a compound %C = × 100 = 22.02 %
109
• calculate moles from grams and grams from moles of a substance
1×5
• calculate empirical formulae using a variety of different methods %H = × 100 = 4.59 %
• convert empirical formulae into molecular formulae 109
80 × 1
% Br = × 100 = 73.39 %
Examination guide 109
The calculations covered by this Factsheet can appear in nearly every Check! these should add up to 100%
module of the AS and A2 specification. The concepts and methods
introduced are the basis of all quantitative chemistry and it is vital you can 3. Moles
handle them. What is a mole?
A mole of something is just 6.023 × 1023 of it. A mole of hydrogen atoms
1. Finding Mr(relative molecular mass or formula mass) is 6.023 × 1023 hydrogen atoms, a mole of water molecules is 6.023 × 1023
The Mr of a compound is found by adding up the relative atomic masses water molecules - you could even imagine a mole of people or a mole of
(Ar) of the elements in the compound's formula.
cars! The number 6.023 × 1023 is called the Avagadro Number - you do
Remember: The Ar value is found from the Periodic Table. NOT have to learn it!
Ar value
Exam Hint: - Be careful what it's a mole of! A mole of hydrogen
23 atoms (H) is not the same as a mole of hydrogen molecules (H2).
11 Na A mole of hydrogen molecules contains 2 moles of hydrogen atoms!
If a question refers to a mole of an element, it means a mole of
Atomic molecules of that element.
number
Hint: Ar is always the larger of the two number in the boxes Why that particular number?
Avagadro's number is chosen to "fiddle" it so that one mole of a substance
Example 1: What is the Mr of C2H6? has mass (in grams) equal to the Aror Mr of that substance. So as hydrogen
atoms have Ar = 1, one mole of hydrogen atoms will have mass one gram.
C2H6 includes 2 C atoms and 6 H atoms. Similarly, as C2H6 has Mr = 30, one mole of C2H6 will have mass 30 grams.
So Mr(C2H6)= 2 × Ar(C) + 6 × Ar(H) This makes moles easier to work with!
(Ar = 12 for C and 1 for H)
∴ Mr = (2 × 12) + (6 × 1) = 30 Definition of a mole
The definition of a mole given below probably seems a bit odd, but it is the
one that must be given in an exam!
Example 2: What is the Mr of Ca(NO3)2 ?

NB: The small 2 outside the brackets multiplies everything Definition: One mole is the amount of substance which contains
inside the bracket - just like in maths. the same number of particles (atoms, molecules or ions) as there are
atoms in 12.00g of 12C
So Ca(NO3)2 includes 1 Ca atom, 2 N atoms and 6 O atoms.
So Mr(Ca(NO3)2)= Ar(Ca) + 2 × Ar(N) + 6 × Ar(O)
(Ar = 40 for Ca, 14 for N and 16 for O) Calculating with Moles
∴ Mr = 40 + (2 × 14) + (6 × 16) = 164 The important thing is to be able to use the mole in calculations.
The basic equation is:
2. The percentage composition of a compound
You may be asked to find (for example) the percentage of sodium nitrate
Number of mass (g)
that is nitrogen. N.B this is a commonly asked examination question! =
moles Ar or Mr
Method
Step 1:- find Mr (by totalling Ar values) or rearranged

Step 2:- find % of an element using:

no. of atoms of element × A r

× 100% Mass (g) = moles × Ar or Mr Ar or Mr =
mass (g)
Mr moles

1
Moles and Formulae Chem Factsheet

Finding Empirical Formulae

Some students find the 'triangle method' useful in remembering and
There are several ways to calculate empirical formulae, and these are
rearranging equations.
shown below in order of increasing difficulty:-

Mass 1. Calculating EF from Moles

What is the EF of the compound formed when 6 moles of potassium
atoms react with 3 moles of oxygen atoms?
Moles × Mr
K:O
Moles 6 :3
You cover up the thing in the triangle you want to find. Then, what you Simplest ratio 2 :1 (divided by 3)
can see tells you the calculation to do. For example, if you want to find EF = K 2 O
moles, cover it up and you are left with mass/Mr
2. Calculating EF from Mass
This method can be used for ANY equation that has a fraction on one What is the EF of the compound formed when 6g of carbon reacts with
side and just one thing on the other side. Whatever is on the top of the 32g of sulphur?
fraction goes in the top of the triangle.
First find moles:
Here are some examples:
Example 1: How many moles are there in 6g of C? 6 32
moles C = = 0.5 Moles S = = 1
mass(g) 12 32
moles = (Ar = 12 for C)
Ar C :S
moles 0.5 : 1 (now divide by 0.5 - the smaller number)
∴ moles = 6 = 0.5 moles Simplest ratio 1 : 2
12
EF =CS2
Example 2: How many moles are there in 36g of H2O?
3. Calculating EF from Percentage Composition
Since Mr is in the formula, we must calculate this first NB. This is the most commonly examined method of finding EF. The
approach is exactly the same as calculating from mass; you treat the
Mr(H2O) = (1 × 2) + (16 × 1) = 18 percentages as if they are masses. One method of approaching these is
using a table, as shown below - but you must use whichever style of
mass(g) 36 presentation you are most comfortable with.
moles = = = 2 moles
Mr 18
What is the empirical formula for the compound which contains the
following elements by percentage composition of mass?
Example 3: What is the mass of 0.5 moles of H2S?
C = 66.67%, H = 11.11%, O = 22.22%
Mr(H2S) = (1 × 2) + (32 × 1) = 34
Element % Ar % ÷Ar Ratio *
mass(g) = moles × Mr = 0.5 × 34 = 17 g C 66.67 12 5.56 5.56 ÷1.39 = 4
H 11.11 1 11.11 11.11 ÷1.39 = 8
Example 4: 0.2 moles of a metal have a mass of 4.6g. O 22.22 16 1.39 1.39 ÷1.39 = 1
i) Calculate the element's atomic mass
EF = C4H8O
ii) Suggest an identity for the metal.
*To find the ratio column, take the smallest of the %÷Ar values (which
is 1.39 here) and divide all the %÷Ar values by it.
mass(g)
i) Ar =
moles
4. Calculating EF from Combustion Data
4.6 This method is one step up in difficulty from the last example because you
= = 23
0.2 have to calculate the masses of the elements first. The combustion products
are always oxides. CO2 and H2O are the commonest and the following
ii) Looking at the Periodic Table, we see that sodium
example uses these, although the method can be adapted for others.
has an atomic mass of 23, and it is a metal.

Method
Challenge Question: Does the metal HAVE to be sodium?
Step1:- find mass of the carbon and hydrogen using
metals could have atomic mass 23.
Answer: No. It is the most likely answer, but isotopes of other no. of atoms of element × Ar
mass of oxide ×
Mr for oxide
Find the mass of any other element in the
4. Empirical and Molecular Formulas compound by subtraction.
For calculation purposes there are 2 types of formulae you need to know:
Step 2:- convert mass to moles for each element by
dividing by Ar
• The empirical formula (ef) shows the ratio of the atoms present in
their lowest terms i.e. cancelled down to smallest whole numbers.
Step 3:- find the simplest ratio by dividing all the values
from step 2 by the smallest of them.
• The molecular formula (mf) shows the actual number of each type
of atom present in one molecule.
2
Moles and Formulae Chem Factsheet

Example: 1g of a compound undergoes complete combustion and Practice Questions

produces 2.38g of CO2 and 1.215g of H2O. The compound contains Mole calculations (except for volumetric analysis) make up parts of 'A'
only C, H and O. What is its empirical formula? level questions. The 13 questions below are designed to give you practice
in the different types covered by this Factsheet.
Step 1: Mr for CO2 = 44
12 1. Calculating moles of elements (using Ar values)
So mass of C = 2.38 × = 0.65g
44 How many moles are there in each of the following?

Mr for H2O = 18 (a) 46g Na (b) 12g Mg

2 ×1 (c) 44g Sr (d) 21g Li
So mass of H = 1.215× = 0.135g (e) 64g S (f) 127g I2
18
(g) 64g O2 (h) 7g Si
(i) 7g N2 (j) 142g Cl2
Mass of O = 1 - 0.65 - 0.135 = 0.215g (k) 12.5g of bromine gas (l) 0.787g of neon
(m) 37.9g of fluorine gas (n) 1.89g of potassium
(o) 7.14g of oxygen gas
Step 2: Moles of C = 0.65 ÷ 12 = 0.054167
Moles of H= 0.135 ÷ 1 = 0.135 2. Calculating the mass of element (using Ar values)
Moles of O = 0.215 ÷ 16 = 0.0134375 What is the mass (in g) of each of the following?

(a) 4 moles Ar (b) 0.5 moles Ca

(c) 0.75 moles Mg (d) 1.5 moles Li
Step 3: Ratio is: (e) 2 moles Fe (f) 0.5 moles Br2
C : 0.054167 ÷ 0.0134375 = 4 (g) 7 moles I2 (h) 2.5 moles O2
H: 0.135 ÷ 0.0134375 = 10 (i) 3 moles Cu (j) 0.25 moles C
O :0.0134375 ÷ 0.0134375 = 1 (k) 0.18 moles of fluorine gas (l) 1.75 moles of argon
So the empirical formula is C 4H10O (m) 0.102 moles of silver (n) 12.5 moles of lead
(n) 3.9 moles of sodium
Finding Molecular Formulae
To do this, you need to know (or be able to find) the empirical formula and 3. Calculating Ar values from mass and moles
Mr for the compound. What is the Ar value of the following elements?

(a) 0.27 moles of Pl has a mass of 55.89g

Method (b) 18g of O2 contains 0.563 moles
Step 1:- divide Mr by EF formula mass to get scale factor (c) 0.40 moles of S has a mass of 12.8g
Step 2:- multiply EF by scale factor to give MF (d) 240g of Ca contains 6 moles
(e) 14.80g of Mg contains 0.617 moles

Example 1: If the EF = CH2 and Mr = 42, what is the MF? 4. Finding relative molecular mass (Mr) from relative atomic masses (Ar)
What is the relative molecular mass of the following?
EF = CH2 Mr (CH2) = (12) + (1 × 2) = 14
(a) CO2 (b) H 2 O (c) H2 SO4
42 (d) SO3 (e) CH 4 (f) (CH 3)2 CO
= 3
14 (g) C2H5OH (h) MgCO3 (i) Cu(NO3) 2
(j) SiCl4 (k) Na2CO3.10 H2O
∴ MF = (CH2) × 3 = C3H6 (l) CuSO4.5H2 O (m) CH3 (CH2)5 Br
(n) Na2S2O3.5H2O (o) Cl2 O7

Example 2: 0.24 moles of a compound, containing carbon and hydrogen 5. Calculating moles of compounds (using Mr values)
only, have mass 18.72 grams. On complete combustion, this amount of How many moles are there in each of the following?
the compound yields 63.36g of carbon dioxide and 12.96g of water. Find (a) 32g SO2 (b) 90g C2H6 (c) 160g SO3
the molecular formula of this compound. (d) 22g CO2 (e) 8g CH4 (f) 8g MgO
(g) 100g Ca CO3 (h) 2g CO (i) 14g SiO2
First find the EF. We use the combustion data for this: (j) 80g NO2 (k) 30.5g LiNO3 (l) 0.87g C2H5OH
12 (m) 6.9g HNO3 (n) 18g Na2CO3.10H2O
Mass of C = 63.36 × = 17.28g (o) 21.55g CaCl2
44
2 ×1 6. Calculating the mass of compounds (using Mr values)
Mass of H = 12.96 × = 1.44g
18 What is the mass (in g) of each of the following?
Moles of C = 17.28 ÷ 12 = 1.44 (a) 2 moles C4H8 (b) 0.33 moles CO
Moles of H= 1.44 ÷ 1 = 1.44 (c) 5 moles CaO (d) 1.5 moles NO
So ratio is 1:1 and EF is CH (e) 0.1 moles C3H7OH (f) 0.2 moles Na2O
(g) 0.5 moles CaCO3 (h) 2.7 moles H Cl
Now we need Mr in order to find the molecular formula. (i) 0.7 moles Na Cl (j) 8 moles C 4H9Br
We must use the other information in the question: (k) 4.6 moles H2SO4 (l) 0.012 moles C2H6
Mr = mass ÷ moles = 18.72 ÷ 0.24 = 78 (m) 4 moles ClO4 (n) 0.25 moles (CH3)2 I
Mr (CH) = 13. (o) 0.56 moles MgCl2
78 ÷ 13 = 6
So MF = (CH) × 6 = C6H6

3
Moles and Formulae Chem Factsheet

7. Calculating Mr values from mass and moles Answers

What is the Mr value for each of the following compounds? 1. (a) 2 (b) 0.5 (c) 0.5
(a) 1.0g of compound A contains 0.0208 moles (d) 3 (e) 2 (f) 0.5
(b) 1.5 moles of compound B has a mass of 105g (g) 2 (h) 0.25 (i) 0.25
(c) 14.8g of compound C contains 0.117 moles (j) 2 (k) 0.078 (l) 0.0385
(d) 7.0g of compound D contains 0.219 moles (m) 2.11 (n) 0.048 (o) 0.223
(e) 0.24 moles of compound E has a mass of 13.92g
2. (a) 160g (b) 20g (c) 18g
8. Find the percentage composition by mass of elements in a compound (d) 10.5g (e) 112g (f) 80g
What is the percentage composition by mass of each element in the (g) 1778g (h) 80 (i) 193.5g
following compounds? (j) 3g (k) 3.24g (l) 70g
(a) SiCl4 (b) C2H6 (c) Na2CO3 (m) 11.02g (n) 2587.5g (o) 89.7g
(d) CaBr2 (e) CuSO4.5H2O
3. (a) 207 (b) 32 (c) 32
9. Calculating empirical formula from moles (d) 40 (e) 24
What is the empirical formula of compounds with the following
composition? 4. (a) 44 (b) 18 (c) 98
(a) 2 moles Na with 2 moles I (d) 80 (e) 16 (f) 58
(b) 0.1 moles K with 0.05 moles O (g) 46 (h) 84 (i) 188.5
(c) 0.5 moles N with 1.5 moles H (j) 170 (k) 286 (l) 249.5
(d) 0.2 moles Mg with 0.4 moles Cl (m) 123 (n) 248 (o) 183
(e) 1.2 moles of a carbon oxide contains 0.4 moles of carbon
5. (a) 0.5 (b) 3 (c) 2
10. Calculating empirical formula from mass (d) 0.5 (e) 0.5 (f) 0.2
What is the empirical formula of compounds with the following (g) 1 (h) 0.071 (i) 0.23
composition by mass? (j) 1.74 (k) 0.44 (l) 0.019
(a) 12g C with 16g O (m) 0.11 (n) 0.063 (o) 0.194
(b) 6g Mg with 4g O
6. (a) 112g (b) 9.24g (c) 280g
(c) 46g Na with 80g Br
(d) 42g (e) 6g (f) 12.4g
(d) 14g N reacting with H to form 17g of compound
(g) 50g (h) 98.55g (i) 40.95g
(e) 22g Sr reacting with O to form 26g of compound
(j) 1096g (k) 450.8g (l) 0.36g
11. Calculating empirical formula from percentage composition (m) 398g (n) 42.75g (o) 53.2g
What is the empirical formula of each of the following compounds?
7. (a) 48 (b) 70 (c) 126.5
(a) 80% C, 20%H
(d) 32 (e) 58
(b) 52.2% C, 13.1% H, 34.7% O
(c) 40.4% C, 7.9% H, 15.7% N, 36.0% O 8. (a) 16.57% Si, 83.43% Cl
(d) 38.7% C, 9.7% H, 51.6% S (b) 80 % C, 20 % H
(e) 40.2% K, 26.9% Cr, 32.9% O (c) 43.40%Na, 11.32%C, 45.28% O
(f) 85.25% BaCl2, 14.75% water of crystallisation (d) 20 % Ca, 80 % Br
(e) 25.45% Cu, 12.83% S, 4.00 % H, 57.72% O
12. Calculating empirical formula from combustion data
What is the empirical formula of each of the following compounds? 9. (a) Na I (b) K 2 O (c) NH3
(a) Complete combustion of 1.0g of a compound produced 2.99g CO2 (d) MgCl2 (e) CO 2
and 1.64g H2O
(b) 1.0g of a compound underwent complete combustion and produced 10. (a) CO (b) MgO (c) Na2 Br
3.035g CO2 and 1.55g H2O (d) NH 3 (e) Sr O
(c) 2.0g of a compound produced 5.86g CO2 and 3.6g H2O on complete
11. (a) CH 2 (b) C2 H6O (c) C3 H7 NO2
combustion
(d) K2 CrO4 (e) BaCl2 . 2H2O
(d) A compound made of carbon, hydrogen and oxygen produced 2.2g
CO2 and 1.2g H2O when 1.0g of it underwent complete combustion 12. (a) C 3H 8 (b) C 2 H 5 (c) CH3
(d) C 3 H 8O
13. Finding molecular formula from empirical formula and Mr
What is the molecular formula of the following? 13. (a) C 6H 6 (b) C 2 H 2O (c) C4H6 Br2
(a) E.F. = CH Mr = 72 (d) C 4 H 8O 4 (e) Na2 O2
(b) E.F. = C2H2O Mr = 42
(c) E.F. = C2H3Br Mr = 214
(d) E.F. = CH2O Mr = 120
(e) E.F. = NaO Mr = 78

Acknowledgements:
This Factsheet was researched and written by Sam Goodman.
Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham,
B18 6NF
ChemistryFactsheets may be copied free of charge by teaching staff or students,
provided that their school is a registered subscriber.
No part of these Factsheets may be reproduced, stored in a retrieval system, or
transmitted, in any other form or by any other means, without the prior
permission of the publisher. ISSN 1351-5136

4
 Chem Factsheet
September 2000 Number 03

Moles and Equations

To succeed with this topic, you need to: c) Formulae that can be worked out from the charge on their ions:
• ensure you understand the work on ‘moles’ from Factsheet No. 2
- Moles and Formulae These compounds usually contain metals (the cations) and non-metals
• learn thoroughly the valencies of the commonest cations and anions (the anions). You are expected to know these cations and anions; some
• learn thoroughly those common formulae you are expected to know have to be learnt, but you can use the Periodic Table to help you for the
• practice writing formulae and balancing equations because unless ions of elemental atoms - the box below reminds you how to do this.
these are correct your calculations will always give the wrong
answers!
Using the Periodic Table to help you find the charges on ions
After working through this Factsheet, you will understand: • Group 1 form ions with charge +1
• how to write chemical formulae • Group 2 form ions with charge + 2 (but beryllium compounds
• putting formulae together in an equation to describe a chemical may not be ionic)
reaction
• Group 6 form ions with charge -2
• balancing chemical equations
• calculating quantities from balanced equations • Group 7 form ions with charge -1
• using molar volumes of gas in equations
• writing ionic equations
The table below contains the commonest ions at AS level, but more are
used as you progress through the course. You must learn these - and you
Exam Hint: Writing formulae and balanced chemical equations is will find later work much easier if you do it now, rather than waiting until
central to all questions at AS level. The time spent working on
the exam.
these will repay you in terms of marks and grades.

Table 1. Cations and Anions for AS-level

CATIONS ANIONS
Writing chemical formulae
Chemical formulae fall into three main categories: Ions that can be worked out Ions that can be worked out
from Periodic Table rules above from Periodic Table rules above
a) Formulae which must be learnt: Name Formula Name Formula
lithium Li+ chloride Cl –
Water H 2O Sulphuric acid H2SO4 sodium Na+ bromide Br –
Oxygen O2 Hydrochloric acid HCl potassium K+ iodide I–
Nitrogen N2 Nitric acid HNO 3 magnesium Mg2+ oxide O 2-
Ammonia NH 3 Phosphoric acid H 3 PO 4 calcium Ca2+ sulphide S 2-
Ozone O3 Chlorine Cl2 strontium Sr2+
barium Ba2+ Other Anions
Argon Ar Bromine Br2
Name Formula
Neon Ne Iodine I2 Other Cations hydroxide OH –
Hydrogen H2 Name Formula nitrate (V) NO3 –
hydrogen H+ nitrate (III) NO2 –
N.B. Use the Periodic Table whenever you can for elements eg. Mg, Fe, zinc Zn2+ cyanide CN –
Na, etc., but notice those elements in the list above are diatomic (two aluminium Al3+ hydrogencarbonate HCO3 –
atoms in a molecule) - O2, H2, and the Halogens (Cl2, Br2, I2). silver Ag+ hydrogensulphate HSO4 –
Noble gases (Ne, Ar, etc.) are monatomic. cobalt Co2+ carbonate CO3 2 –
* copper Cu+/Cu2+ sulphate (IV) SO3 2 –
* iron Fe2+/Fe3+ sulphate (VI) SO4 2 –
b) Formulae that can be worked out from their names alone: * lead Pb2+/Pb4+ phosphate PO4 3 –
* manganese Mn2+/Mn4+ manganate (VII) MnO4 –
The list of terms used is shown below
ammonium NH4+
mono=1 penta=5 octa=8
di=2 hexa=6 nona=9 * = elements with more than one valency
For these, Roman Numerals are used to show which valency is being used -
tri=3 septa=7 deca=10
eg copper (II) hydroxide contains Cu2+, whilst copper (I) oxide contains Cu+
tetra=4 For non-metals, this refers to the oxidation state (see Factsheet 11) of the
non-metal involved - eg sulphate (VI) contains sulphur in the +6 oxidation
Carbon dioxide CO2 Carbon monoxide CO
state
Sulphur trioxide SO3 Phosphorus pentachloride PCl5
Dinitrogen trichloride N2Cl 3 Sulphur dioxide SO2

NB: Hydrocarbons have a different system of naming Exam Hint: If a question uses compound names with roman numerals
- eg sodium sulphate (IV) - make sure you take note of them! Many
eg methane,CH4 ethane, C2H6
students lose marks through assuming sodium sulphate (IV) is Na2SO4,
This is covered in the Factsheet No. 13. rather than Na2SO3

1
Moles and Equations Chem Factsheet

Using Ions to Find Formulae eg 1. Mg + O2 Ô MgO

The method used is the "cross-over rule" as shown below: 1× Mg 2× O Ô 1× Mg 1× O
We have different numbers of oxygens on each side. We balance them by
eg 1: Magnesium chloride
having 2 lots of MgO:
Mg2+ Cl-
⇒ MgCl2
1 2 Mg + O2 Ô 2 MgO
1× Mg 2× O Ô 2× Mg 2× O
eg 2: Sodium oxide Now the magnesiums are unbalanced! So we balance them by having two
Na+ O2- lots of Mg
⇒ Na2O
2 1 2Mg + O2 Ô 2MgO
2× Mg 2× O Ô 2× Mg 2× O
eg 3: Magnesium nitrate (V) Now the equation is balanced, because we have the same number of each
type of atom on each side
Mg2+ NO3-
⇒ Mg (NO3)2 eg 2. Fe + O2 Ô Fe 2O 3
1 2 1× Fe 2× O Ô 2× Fe 3× O
We notice with the oxygens that we have 2 on one side and 3 on the other.
Tip: If the formula involves a poly-atomic ion (i.e. an ion containing We won't manage to balance them by multiplying just one side by something
more than one atom), you will need to put brackets round it in any - there's no whole number we can multiply 2 by to get 3. So we have 3 lots
formula that involves more than one of that ion.
of O2 and 2 lots of Fe2O3 - so we end with 6 oxygens on each side (this is
In the above example, you could not write MgNO32 - since this would not
a bit like the cross-over rule)
show that we had two lots of nitrogen.
Fe + 3 O2 Ô 2 Fe2O3
It is also incorrect to "multiply out the brackets" and write MgN2O6, since 1× Fe 6× O Ô 4× Fe 6 × O
we need to show that we have two lots of the nitrate (V) ion NO3– , not just
that we have 2 nitrogen atoms and 6 oxygen atoms.
The irons still are not balanced:
4Fe + 3 O2 Ô 2 Fe2O3
In some cases, you can "cancel down": 4× Fe 6× O Ô 4× Fe 6 × O
eg 4: Zinc Sulphate
Question 3 at the end provides further practise with balancing equations.
Zn 2+ O2-
⇒ ZnO
(b) Writing balanced chemical equations from word equations
2 2
The method is to replace the names with their formulae and then balance
i.e. 2:2 ‘cancels down’ to 1:1,
them.
Some compounds do have formulae that do not cancel down - for example
hydrogen peroxide (H2O2) and ethane (C2H6), but these are either covalent
eg 1. Calcium + hydrochloric Ô calcium + water + carbon
carbonate acid chloride dioxide
(like ethane) or contain special ions (like the peroxide ion O22- )
Formulae:
You need to be happy with working out formulae before going onto the rest
of this Factsheet. Questions 1 and 2 at the end will give you practice at CaCO3 + HCl Ô CaCl2 + H2O + CO2
this.
Balance:
Writing and Balancing Chemical Equations CaCO3 + 2HCl Ô CaCl2 + H2O + CO2

(a) Balancing chemical equations

A ‘balanced’ chemical equation is one which has the same number of atoms
of each element on both sides of the arrow, Ô. eg 2. methane + oxygen Ô carbon + water
dioxide
The rule for balancing is very simple:
Formulae:

You can change the numbers in front of formulae but you never
CH 4 + O2 Ô CO2 + H 2O

change the formulae themselves

Balance:
CH 4 + 2 O2 Ô CO2 + 2 H2O
When you are balancing, you should not expect to get it all balanced in one
step! You may need to change numbers as you go along. The examples
below show how to go from one side to the other to balance the equation.

2
Moles and Equations Chem Factsheet

(c) Using the description to find the word equation In all mass calculations based on equations, you must always follow these
steps:
The process is: 1 Write a balanced equation
2 Work out the mass ratio
description word balanced chemical 3 Use the mass ratio, together with the information given in the question,
of reaction equation equation to find the unknown masses.

Sometimes the description gives you all the reactants and products, and in The following examples illustrate how to do this:
other cases you have to apply your knowledge of chemical reactions to
find the products. Both types are shown in the following examples: eg 1. How much magnesium oxide will be made by burning 12g of magnesium?

eg 1. Calcium hydroxide is the only product when calcium oxide dissolves

2Mg + O2 Ô 2MgO
in water. Mass ratio 48 32 80
Actual mass 12 ?
Calcium oxide + water Ô calcium hydroxide To work out the required mass of magnesium oxide, we use the fact that
CaO + H 2O Ô Ca(OH)2 48:80 and 12:? are in the same ratio. One easy way of dealing with ratios is
using the "cross method", shown in the box below
eg 2. Sulphuric acid reacts with potassium hydroxide
Working with ratios using the "cross method"
Acid + Alkali Ô salt + water This method involves 3 easy steps:
1 Write down the two ratios underneath each other, putting in a ? for
Sulphuric + potassium Ô potassium + water
the number you don't know.
2 Draw a cross
acid hydroxide sulphate
3 Multiply the two joined numbers and divide by the other one.

H2SO4 + KOH Ô K2SO 4 + H 2O Using the example above, our two ratios are:
H2SO4 + 2KOH Ô K2SO 4 + 2H 2 O
48 : 80
Question 4 at the end provides further practise with writing equations. 12 : ?
So we do 12 × 80 ÷ 48 = 20
Calculation work based on equations If you are not happy working with ratios, see Factsheet 14: Maths
All calculation work must be based on balanced chemical equations - for Chemists 1
ones that have the same number of atoms of each type on each side of the
arrow. Any calculation based on an unbalanced equation will automatically
So mass of MgO = 20g
be wrong!
eg 2. What mass of calcium carbonate is needed to make 0.12g of calcium
Calculation work also requires you to use moles. You need to ensure you
oxide? (Mr values: Ca = 40, C = 12, O = 16)
are happy converting between masses and moles (see Factsheet 2 - Moles
and Formulae) before you go any further.
CaCO3 Ô CaO + CO2
e.g. 2Mg + O2 Ô 2 MgO 1 mole Ô 1 mole + 1 mole
Mass ratios 100 Ô 56 + 44
The numbers in front of the formulae tell us the mole ratio in the reaction Actual mass ? 0.12
- for every 2 moles of magnesium, we need 1 mole of oxygen, and we will
produce 2 moles of magnesium oxide. So our ratios are 100 : 56 and ? : 0.12
So ? = 100 × 0.12 ÷ 48 = 0.25g
So if you wanted to react 4 moles of magnesium, you'd need 2 moles of
oxygen and you would get 4 moles of magnesium oxide. Similarly, if you Gas Molar Volumes
reacted 1 mole of magnesium, you'd need 0.5 moles of oxygen and you'd get Up to this point state symbols have not been used in any of the equations:
1 mole of magnesium oxide. (s) = solid
(l) = liquid
Tip: The equation can never tell you how much of a substance is
actually reacting - that depends on how much of the chemicals you
(g) = gas
decide to use! It only tells you the ratios (aq) = solution (i.e. dissolved in water ≡ ‘aqueous’)
They are important and in effect complete any balanced chemical equation.
They are used in examination questions, and are useful because you may
We can use these mole ratios to find out mass ratios - which are what we
need to specify that something is precipitated (so it will have an (s) not an
need to work with to find masses. To find these, we need to use the
(aq)), and, most importantly in this section, because some formulae - and
equation mass = moles × Mr . So for the equation above, we have:
hence some methods - only work for gases! The key fact is:

2Mg + O2 Ô 2 MgO
1 mole of any gas has a volume of 24 dm3 (24000cm3) at room
Mole ratio 2 1 2
Multiply by Mr: 2 × 24 1 × 32 2 × 40 temperature and pressure (rtp) - which is 1 atmosphere and 25oC
Mass ratio 48 32 80 At standard temperature and pressure (stp) - which is 1 atmosphere
and 0oC - the volume of 1 mole of any gas is 22.4dm3 (22400cm3)
Note that the masses balance - the total is 80 on both sides of the equation.

3
Moles and Equations Chem Factsheet

There are two types of questions that use this fact: So we have 0.2 moles of CO2.
1. Equations involving only gas volumes Now we must find the volume of CO2.
The method here relies on the fact that mole ratio = gas volume ratio
So the steps are: Volume CO2 = moles × 24000cm3 = 4800cm3

1 Write a balanced equation eg 2. Iron reacts with oxygen to make iron (III) oxide. Calculate the mass of
2 Write down the mole ratio iron and the volume of oxygen required to produce 3 grammes of iron (III)
3 Use the mole ratio, together with the gas volume information given in oxide. (Ar values are Fe: 56 O:16)
the question, to find the unknown volume.
4Fe + 3O2 Ô 2Fe2O3
eg 1. What volume of SO3 would be made from 200cm3 O2 reacting with SO2?
Mole ratio 4 3 2
2SO2 (g) + O2 (g) Ô 2SO3 (g)
We're told about iron (III) oxide, so find moles of it:
mole ratio 2 1 2
Mr(Fe2O3) = 112 + 48 = 160
volumes 200 ?
moles of Fe2O3 = 3 ÷ 160 = 0.01875
NB: We do not round at this stage - it leads to loss of accuracy.
So 1: 2 and 200 : ? are in the same ratio.
So ? = 200 × 2 ÷ 1 = 400cm3
We need to find the moles of iron and the moles of oxygen:
Moles of iron = 0.01875 × 4 ÷ 2 = 0.0375
2. Equations involving gas volumes and masses.
Here, we cannot rely on simple ratio methods. We need to convert between Moles of oxygen = 0.01875 × 3 ÷ 2 = 0.028125
masses/volumes and moles, then work with moles and the mole ratio. Now we need to find the mass of iron and volume of oxygen:
NB: This approach will also work with all the previous types of calculation, Mass Fe = moles × 56 = 2.1g
so if you'd rather remember just one method, use this one! Volume O2 = moles × 24000cm3 = 675cm3
The procedure is:

1 Write a balanced equation Tip: If you are at all unsure what to multiply by and what to divide
2 Write down the mole ratio by when you are using ratios:
3 For the substance you have information about, work out how many • Use the "cross method"
moles of it there are
4 Use the mole ratio to find out how many moles there are of the substance • Double check that the substances with the larger number in the
you're asked about mole ratio has the higher the number of moles.
5 Find out the mass or volume you're asked for using the correct moles
equation
Writing ionic equations for precipitation reactions
You may find the "triangles" below helpful: In precipitation reactions, the reactants are solutions, but one of the products
is a solid. So state symbols are very important when writing equations for
these reactions.
eg 1. What volume of CO2 would be made by heating 20g of CaCO3?
Triangles for moles formulae The key idea used here is that when an ionic substance is in solution, the
ions seperate - so we can consider sodium chloride solution, for example,
to consist of Na+ (aq) and Cl− (aq).
Mass
The worked example below shows how it works:
Volume (cm 3)

Moles × Mr eg. Write the following equation in its ionic form.

Moles × 24000
FeSO4 (aq) + 2NaOH(aq) Ô Fe (OH)2 (s) + Na2SO4 (aq)
Cover up the thing in the triangle you want to find. Then, what you can
see tells you the calculation to do. For example, if you want to find
moles, cover it up and you are left with mass/Mr Three of the substances are in solution (we know this from the (aq)), so we
split them into ions:
NB: Convert litres (= dm3) to cm3 by multiplying by 1000.
Fe2+(aq) + SO42-(aq) + 2Na+(aq) +2OH-(aq)Ô Fe(OH)2(s) + 2Na+ (aq) + SO42- (aq)
Convert cm3 to litres by dividing by 1000
Note that some ions appear on both sides of the equation - they started off
in solution and they stay in solution. These are called spectator ions. We
must "cancel them out" to give the final ionic equation:
CaCO3(s) Ô CaO(s) + CO2(g)
Fe2+(aq) + SO42-(aq) + 2Na+(aq) +2OH-(aq)Ô Fe(OH)2(s) + 2Na+ (aq) + SO42- (aq)
Mole ratio 1 Ô 1 + 1

We know we have 20g of CaCO3. So we work out how many moles this is:
Fe2 (aq) + 2 OH- (aq) Ô Fe (OH)2 (s)
Mr(CaCO3) = 40 + 12 + 48 = 100
moles of CaCO3 = mass÷Mr
= 20÷ 100 = 0.2 moles
We're asked about CO2. The mole ratio CaCO3: CO2 is 1:1.

4
Moles and Equations Chem Factsheet

Practice Questions 8. a) The equation below shows the fermentation process:

1. Write the formulae for the following compounds: C6H12O6 (aq) Ô 2 C2H5OH(l) + 2 CO2 (g)
a) Sodium iodide b) Iron (III) nitrate (V) c) Lithium sulphide What volume of CO2 would be made from 5g of C6H12O6?
d) Copper (II) nitrate(V) e) Magnesium carbonate f)Dihydrogen monoxide b) 2 NaNO3 (s) Ô 2 NaNO2 (s) + O2 (g)
g) Silver (I) oxide h) Calcium chloride i) Barium sulphide What volume of hydrogen would be made by adding 5.8g magnesium to
j)Potassium sulphate(VI) k) Carbon disulphide l) Zinc carbonate excess hydrochloric acid?
m) Magnesium oxide n) Sulphur dioxide o) Sulphur dichloride
p) Aluminium hydroxide q) Hydrochloric acid r) Lead (IV) oxide 9.Write the ionic equation for each of the following:
s) Hydrogen chloride t) Hydrofluoric acid u)Trioxygen (Ozone) a) NaOH (aq) + HCl (aq) Ô NaCl (aq) + H2O (l)
v) Hydrogen gas w)Ammonium chloride x) Argon gas b) Mg (s) + H2SO4 (aq) Ô MgSO4 (aq) + H2 (g)
y) Dinitrogen monoxide z)Aluminium fluoride aa) Magnesium iodide
c) Al2 (SO4) (aq) + 6 NaOH (aq)Ô 2Al (OH)3 (s) + 3 Na2 SO4 (aq)
ab)Disulphur dichloride ac) Copper (I) carbonate ad)Carbon tetrafluoride
d) Na2CO3 (aq) + 2 HNO3 (aq) Ô 2 NaNO3 (aq) + H2O (l) + CO2 (g)
2. Write the names of the following compounds, as fully as possible: e) 2 AgNO3 (aq) + CuCl2 (aq) Ô Cu(NO3)2 (aq) + 2 AgCl (s)
a) SO3 b) Ca(OH)2 c) FeCl2 d) ZnS e) FeS
f) ZnCO3 g) I2 h) Sr(HSO4)2 i) Li2S j) H2O2 Answers
k) NO l) Fe(OH)3 m) (NH4)2SO4 n) CuF o) NaHSO4 1 .a) NaI b) Fe(NO3)2 c)Li2S d) Cu(NO3)2 e) MgCO3 f) H2O
p) NaOH q) P2O3 r) BeO s) Mg(CO3)2 t) CuSO4 g) Ag2O h) CaCl2 i) BaS j)K2SO4 k) CS2 l) ZnCO3
m)MgO n) SO2 o) SCl2 p) Al(OH)3 q) HCl r) PbO2
3. Balance each of the following equations: s) HCl t) HF u) O3 v) H2 w) NH4 Cl x) Ar
a) ___Na + O2 Ô ___Na2 O y) N2O z)AlF3 aa)MgI2 ab) S2Cl2 ac) Cu2CO3 ad) CF4
b) K2CO3 + ___HCl Ô ___KCl + CO2 + H2O
2.a)sulphur trioxide b) calcium hydroxide c) iron (II) chloride
c) Ba + ___H2O Ô Ba(OH)2 + H2
d) zinc sulphide e) iron (II) sulphide f) zinc carbonate
d) C4H8 + ___O2 Ô ___CO2 + ___H2O g)iodine h) strontium hydrogen sulphate (VI)
e) Al2 (SO4)3 + ___NaOH Ô ___Al (OH)3 + ___ Na2SO4 i) lithium sulphide j) dihydrogen dioxide k) nitrogen monoxide
f) SrCO3 + ___ HNO3 Ô Sr (NO3)2 + H2O + CO2 l) iron(III) hydroxide m)ammonium sulphate (VI)
n) copper (I) fluoride o) sodium hydrogen sulphate (VI)
g) ___ Fe + ___ O2 Ô Fe3 O4
p) sodium hydroxide q) diphosphorus trioxide
h) ___HNO3 + ___Cu Ô ___Cu(NO3)2 + ___NO + ___H2O r) beryllium oxide s) magnesium carbonate t)copper (II) sulphate
i) ___NaOH + H3PO4 Ô Na3PO4 + ___H2O
j) Na2CO3 + CuCl2 Ô CuCO3 + ___NaCl 3. a).4, 2 b) 2, 2 c) 2 d) 6, 4, 4 e) 6, 2, 3
f) 2 g) 3, 2 h) 8, 3, 3, 2, 4 i) 3, 3 j) 2
k) ___NaNO 3 Ô ___NaNO2 + O2
k) 2, 2 l) 3, 4, 4 m) 2, 2 n) 3, 2
l) ___Fe + ___H2O Ô Fe3O4 + ___H2
m) ___SO2 + O2 Ô ___SO3 4.a) 2 C2H6 + 7 O2 Ô 4 CO2 + 6 H2 O
n) N2 + ___H2 Ô ___NH 3 b) SiCl4 + 2 H2O Ô SiO2 + 4 HCl
c) SrCO3 Ô SrO + CO2
4. Write the balanced chemical equation for each of the following: d) 2 H2 + O2 Ô 2 H2 O
e) 2 Mg + O2 Ô 2 MgO
a) Ethane (C2H6) burns in oxygen to produce carbon dioxide and water vapour.
b) Silicon tetrachloride reacts in water to make silicon dioxide and hydrogen
5.a) 2 HNO3 + CuCO3 Ô Cu (NO3)2 + H2O + CO2
chloride. b) 4K + O2 Ô 2 K2 O
c) Heating strontium carbonate to produce the metal oxide and carbon dioxide. c) 2 NaOH + ZnCl2 Ô Zn(OH)2 + 2 NaCl
d) Hydrogen reacting with oxygen to produce water. d) K2O + H2SO4 Ô K2SO4 + H2O
e) 2 C8H18 + 25 O2 Ô 16 CO2 + 18 H2O
e) Magnesium burning in are to make the oxide.
6. a) 71.52g b)2.496g c)1.12g, 0.88g d) 0.5g e) 0.73g
5. Write the balanced chemical equation for each of the following reactions:
a) Nitric acid with copper carbonate. 7. a) i) 150cm3 ii)100cm 3 b)25cm 3 , 12.5cm 3 c) 200cm 3
b) Burning potassium in air
c) Adding sodium hydroxide solution to zinc chloride solution 8. a) 1344cm 3 b) 5760cm3
d) Potassium oxide with sulphuric acid
9. a) H+ + OH- Ô H 2O
e) Burning octane (C8H18) in air b) Mg + 2H+ Ô Mg2+ + H2
c) Al3+ + 3 OH- Ô Al (OH)3
6. a) What mass of iron (III) oxide would be made by reacting 50g of iron d) CO32- + 2 H+ Ô H2O + CO2
with oxygen? e) Ag+ + Cl- Ô AgCl
b) What mass of sulphur needs to be burnt in oxygen to produce 5g of
sulphur dioxide?
c) What mass of calcium oxide and carbon dioxide would be made by heating
2g of calcium carbonate?
d) What mass of hydrogen would be produced by adding 10g of calcium to
water?
e) What mass of oxygen would need to be added to 0.5g of carbon to turn
it all into carbon dioxide?
Acknowledgements:
7. a) In the reaction N2 (g) + 3 H2 (g) Ô 2 NH3 (g)
This Factsheet was researched and written by Sam Goodman & Kieron Heath
i) What volume of hydrogen would react with 50cm3 of nitrogen
Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham, B18 6NF
ii) What volume of ammonia would be made?
ChemistryFactsheets may be copied free of charge by teaching staff or students,
b) 2 SO2 (g) + O2 (g) Ô 2 SO3 (g)
provided that their school is a registered subscriber.
What volumes of SO2 and O2 would be needed to produce 25 cm3 of SO3?
No part of these Factsheets may be reproduced, stored in a retrieval system, or
c) CO2 (g) + C(s) Ô 2 CO (g)
transmitted, in any other form or by any other means, without the prior
What volume of carbon monoxide would be made from 100cm3 of carbon
permission of the publisher. ISSN 1351-5136
dioxide?
5
 Chem Factsheet
September 2000 Number 04

Shapes of Molecules and Ions

To succeed with this topic you need to:
• be able to find an atom/element in the Periodic Table and decide which group it is in
• know that the number of the group an element is in tells you how many electrons it has in its outer shell
• understand how to draw dot-and-cross diagrams to show covalent bonding
• understand that positive ions have lost electrons, and negative ions have gained them, and that the size of the charge on the ion tells
you how many electrons are involved

After working through this Factsheet you will:

• have met the commonest examples of the shapes used in ‘AS’ level examination questions
• be able to work out the shape of any molecule from its dot-and-cross diagram
Examination guide Bond pairs, lone pairs and electron clouds
Success in this topic relies on you understanding how shapes of molecules The electrons in a bond pair are shared between two atoms. The positive
are determined and learning the names of, and diagrams for, the basic shapes. nuclei of both atoms are attracting the negative electrons, so the electron
It is very important to name the shapes correctly and present the shapes cloud for a bond pair is pulled between the nuclei.
clearly as 3D structures.
In a lone pair, only one nucleus is attracting the electrons, so the electron
What determines the shape of a molecule? cloud is close to that nucleus. This means that the electron cloud for a lone
In a molecule there are covalent bonds that hold the group of atoms together. pair looks "short and fat", and for a bond pair "long and thin" (Fig 1.)
A single covalent bond is a shared pair of electrons (called a bond pair)
between two nuclei (the central parts of the two atoms involved). It is Fig 1. Lone pair and bond pair electron clouds
negative in charge because the electrons have a negative charge themselves.
lone pair bond pair
Not all electrons around an atom are in a bond. We can see this by looking
at a dot and cross diagram, like the one below for water (H2O). A pair of
electrons not in a bond is called a lone pair.
nucleus
nuclei
H O lone pairs

bond pairs
H Repulsion, bond pairs and lone pairs
The shape of the electron cloud for bond pairs and lone pairs matters
because it affects the amount of repulsion between them. Both types of
If you have several electron pairs (bond pairs or lone pairs) around an atom electron cloud have the same total charge (-2 from the two electrons), but
then they will repel one another (two negatives repel -electrostatic repulsion) with the lone pair, the charge is concentrated close to the nucleus. This
and because of this the electron pairs become as far apart as possible. means the lone pair has a higher charge density - so it repels more strongly
This is the basic principle on which this topic is based. This theory is than a bond pair does. (You can imagine this with balloons as well - each
called 'valence shell electron pair repulsion (vsepr)' and you may be lone pair is a short fat balloon, and each bond pair a long thin balloon. To
asked to explain it. model the water molecule shown in the first column, (which has two LP
and two BP around the oxygen atom) we'd tie two short fat balloons and
VSEPR theory states that each electron pair tries to separate
two long thin balloons to one point. The short fat balloons will push the
itself as much as possible from other electron pairs (due to electrostatic
other balloons away more effectively!) Fig 2 shows how repulsion varies
repulsion.)
for lone pairs and bond pairs.
The shapes of molecules and ions are thus determined by the number of
Fig 2. Differences in repulsion with lone pairs and bond pairs
electron pairs not by the atoms.
Two bond Lone pair and Two lone
pairs bond pair pairs
Electron clouds and orbitals
Although at GCSE we always thought of electrons as simple particles, and
Increasing Repulsion
we show them like that in dot and cross diagrams, it's not really as simple
as that! We never know exactly where an electron is in an atom - just that N.B. The difference between lone and bond pairs does not alter the basic
it's somewhere in a region of space called an orbital (see Factsheet 1 - shape of a molecule BUT it does distort it and so alter bond angles (i.e. the
Atomic Structure). Each pair of electrons has its own orbital. Because we angle between two adjacent bond pairs).
can't know where in the orbital the electrons are, the most helpful way of
thinking about an electron pair is as a kind of cloud of negative charge - the
shape of the orbital tells you the shape of the cloud. Electron clouds are
three dimensional - it can help to think of them as like balloons!
1
Shapes of molecules and ions Chem Factsheet

Finding the shape Drawing 3D shapes

To find the shape of any molecule, go through the following procedure: No one finds drawing 3D shapes very easy!
1. Draw a dot and cross diagram One way of showing things more clearly is to
Bond going
2. Count the number of electron pairs (both types) around the central use different sorts of line to show bonds
into the page
atom. coming out of the page towards you and
3 Decide the shape adopted by the electron pairs (see table below) bonds going into the page away from you.
4 Look at the number of lone pairs, and decide the shape adopted by the Other bonds - shown with a normal line - are
atoms (see table on page 3) in the plane of the page, going along it. You Bond coming
5. Draw the shape, including bond angles can also add dotted lines to diagrams to make out of the page
the shape clearer.
Exam Hint: - Although you have to work out the shape adopted by the
Exam Hint: - Learn the names, examples and diagrams (with angles!)
electron pairs first, your answer must always be the shape adopted in tables 1 and 2 - they cover all the common cases you can be asked
by the atoms in the exam.

Table 1. Shapes of molecules and ions

electron pairs around Example dot - cross diagram Name of shape Bond angles
central atom molecule

2 180o
BeCl2 Cl Be Cl linear
Cl Be Cl

3 F
F
Note that in these first
two, the central atom
B trigonal planar 120o
does not have 8 electrons BF 3 B
- they are electron F F
deficient . You'll learn F F
more about this later!

H
H
109.5o
4 CH 4 H C H tetrahedral C
H H
H
H

Cl

Cl Cl
90o
5 PCl5 Cl
Cl trigonal 120 o P Cl
P bipyramidal

Cl
Cl Cl
Cl

F F

F F F F
6 SF6
S octahedral S
Note in these last two,
the central atom has F F
F F
more than 8 electrons. F
That's because it's using F
its d-orbitals, so there's all angles 90o
extra space.

2
Shapes of molecules and ions Chem Factsheet

Effect of lone pairs on shape The best examples to look at are CH4, NH3 and H2O. Each of these have
Although the overall shape is determined by the total number of electron four pairs of electrons.
pairs, lone pairs are important because they affect the shape in two ways: • CH4 is a perfect tetrahedral (4 bond pairs).
• The bond angles are reduced
Because lone pairs have a greater repulsive effect, they push • NH3 is based on a tetrahedral shape as it has 4 electron pairs, but because
the bond pairs closer together. Learn the angles in table 2. it has 3 bond pairs and 1 lone pair, the bond angle is less due to the
• The name of the shape is different increased repulsion from the lone pair. The shape is trigonal pyramidal.
Because we can't actually "see" lone pairs, the name of the shape • H2O, similarly, is based on a tetrahedral, but as it has 2 bond pairs and
depends on the bond pairs. Learn the shape names in table 2. 2 lone pairs, the bond angle is even less due to the repulsion from the
two lone pairs.The shape is bent.
Table 2. Distortion of the basic shapes due to lone pairs
molecule electron pairs around dot - cross diagram Name of shape Bond angles
orbital atom

NH 3 4 H N H trigonal N
3 BP + 1 LP pyramidal H H
H 1070 H

H O
O bent
H 2O 4 H
2 BP. + 2 LP 104.50 H
H

Cl
F F

6 F Xe F square planar Xe
XeF 4
4 BP + 2 LP
F
F

F the lone pairs get as far as

possible from each other

Multiple bonds and shapes

Some molecules - most commonly ethene (C2H4), ethyne (C2H2), CO, CO2 Exam Hint:- Some molecules and ions (like CO on this page) contain
and SO2 - contain double or even triple bonds. This is the rule: dative bonds (shown as à), where both electrons come from one
When working out the shape of a molecule a double or triple bond atom. These behave just like normal single bonds - once the bond is
counts as 1 bond pair. But it has greater repulsive power! formed, it doesn't matter where the electrons came from in the first
place!
Fig 3. Shapes of molecules with multiple bonds

C 2H 4 CO
H H H 121 o H C O
C O
C C 118 o
C C linear
o
H 121 H
H H
trigonal planar CO 2 180o

O C O O C O
linear
C 2H 2 180o

H C C H H C C H
SO2
S
linear 1200
O S O O O
bent

3
Shapes of molecules and ions Chem Factsheet

Shapes of ions
Exam Hint:- Learn the dot and cross diagrams for the ions - they
Working out shapes of ions is very similar to molecules. You draw a dot may not be that easy to work out in an exam!
and cross diagram as before, but you must remember:
• If it's a positive ion (cation), remove the same number of electrons
as the charge on the ion. Useful Websites
• If it's a negative ion (anion), add the same number of electrons as There are many useful resources on the internet for this topic,
the charge on the ion including animated diagrams and free software for drawing and
This will give the central atom a full outer shell. viewing molecules. Here are three!

1. Cations http://wunmv.wustl.edu/EduDev/Vsepr
You only need to know two of these - NH4+ and H3O+ http://www.spusd.k12.ca.us/chemmybear/shapes.html
Fig 4. Shapes of cations http://www.chem.ufl.edu/~myers/chm2045/shapes.htm
NH4 + + H
H +
Practice Questions
109.5o
H N H Examination questions on this topic usually form one part of a complete
N question and ask for the dot and cross diagram of a molecule/ion along with
H its shape and bond angles. The molecules below have all been asked in AS
H H
and A2 specimen questions.
H tetrahedral
(4 bond pairs, so the same shape as CH4) 1. For each of the molecules/ions below
(i) draw its dot-cross diagram
H3O + (ii) sketch its shape
H (iii) show its bond angles
O + (iv) give the name of the shape
O H H H
1070 (a) H 2S
H (b) CHCl3
H (c) F 2O
trigonal pyramidal
(d) PF 5
(3 bond pairs + 1 lone pair, so the same shape as NH3) (e) PCl6-
(f) SiCl4
2. Anions (g) HCN
You need to know NO3-, SO42- and CO32- (h) POCl3
(i) BeF2
All of these ions, from the dot and cross diagrams, appear to contain a (j) PCl3
mixture of normal single bonds, dative single bonds and double bonds. (3 marks each)
Although the dative bonds wouldn't affect the shape, the double bonds
normally would. But they don't in these anions! All the bond angles are 2. Explain, using a dot-cross diagram, why XeF4 has a square planar
the same! structure.
(4 marks)
This is because of something called delocalisation, which you will study
properly in organic chemistry. What it basically means is that in, for example, 3. What factors affect the shape of a molecule?
the nitrate ion, instead of having one normal single bond, one dative bond (3 marks)
and one double bond, the "spare" electrons in the double bond are "shared"
between all three bonds, so that all the bonds are the same. You don't have
to worry about the details of this yet!
Fig 4. Shapes of anions - Remember all the bond angles are equal!

NO 3 − e CO3 2− SO4 2−
O O O O e O
O e
N C
S
e
O O
e O O

-
O O - O
O O
N
120o C 109.5o
120o
S
O -
O
O - O
NB: the "extra" electrons in these ions are shown as "e" O-

4
Shapes of molecules and ions Chem Factsheet

Answers (h) Cl
marks:- (1) dot-cross (1) shape (1) bond angles Cl
109.5o
1. (a) H H O P Cl
S P
S H H Cl Cl
105o Cl
bent (3) (3)
Cl

tetrahedral
(b)
H
H (i)
180o
109.5o
Cl C Cl
C F Be F F Be F
Cl Cl linear
Cl
(3)
Cl (3)
tetrahedral (j)
P
(c) Cl Cl
O P Cl Cl
O
1070
F F F Cl
F 105o Cl
(3)
(3)
bent

F F
(d) 2.
F F F
90o
F P
P trigonal
F Xe
F 120o bipyramidal F F (1)

Cl (3) F
F
F

Around the central Xe atom there are 6 electron pairs - 2 lone pairs and 4
bond pairs (1)
- Cl
(e) Cl 6 pairs give an octahedral shape.(1) Lone-pairs repel more than bond-
pairs, so the lone-pairs position themselves away form each other on
Cl Cl Cl opposite sides
Cl
P P 90 o

e F F
Cl Cl
Cl Cl Xe (1)
Cl Cl
(3) F F
octahedral

(f) Cl 3. The factors are

Cl (a) the number of electron pairs in total (1)
109.5o (b) how many are bond-pairs and how many are lone-pairs (1)
Cl Si Cl (c) lone-pairs repel more than bond-pairs. (1)
Si
Cl Cl
Cl
Cl
(3)
tetrahedral Acknowledgements:
This Factsheet was researched and written by Kieron Heath
Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham,
(g) 180o B18 6NF
ChemistryFactsheets may be copied free of charge by teaching staff or students,
H C N H C N provided that their school is a registered subscriber.
(3) No part of these Factsheets may be reproduced, stored in a retrieval system, or
linear transmitted, in any other form or by any other means, without the prior
permission of the publisher. ISSN 1351-5136

5
 Chem Factsheet
September 2000 Number 05

Bonding
To succeed with this topic you need to The classic example is NaCl (Fig 1)
• be able to recall the basics of Atomic Structure (Factsheet 1)
• understand the concepts of Fig 1. NaCl
- Ionization Energy
- Electron Affinity
Na Cl
- Electronegativity
• recall the idea of electron shells and orbitals

After working through this Factsheet you will

• know the different kinds of intramolecular bonding
• know the different kinds of intermolecular bonding +
_

• be able to represent the different bonding types diagrammatically and Na Cl

give a written explanation for each type

Exam Hint: - Exam questions on bonding will require you to know

the specific examples covered here and to be able to apply the Na Cl Na+ Cl-
same thinking to similar atoms forming other compounds. Questions (2.8.1) (2.8.7) (2.8) (2.8.8)
involving bonding will usually lead to other questions about structure
and physical/chemical properties of the compound. (See Factsheet
1s22s22p63s1 1s22s22p63s23p2 1s 22s 22p 6 1s22s22p63s23p6
6 - Structure of Elements & Compounds).
(electronic (electronic
configuration configuration
Types of bonding of neon) of argon)
There are two main types of bonding:
1. Intramolecular - this is the bonding that takes place when atoms join The more electrons that are transferred between the atoms, the larger the
to other atoms. The bonding within (‘intra’) a molecule or crystal. changes on the cations and anions. Example
2. Intermolecular - the bonding between(inter) molecules.
Mg + O Mg2+ + O2-
Bonding is important because it determines the structure and properties of 22
1s 2s 2p 6
1s 2s22p43s2
2
1s 2s22p6
2
1s 2s22p6
2

compounds.

Remember: Remember - Ionic bonding is when there is complete transfer of an

Atoms ⇒ Bonding ⇒ Structure ⇒ Physical/Chemical Properties electron (or electrons) from one atom to another, and the subsequent
formation of oppositely charged ions. These ions are held together by
Intramolecular bonding non-directional forces of electrostatic attraction.

Why do atoms bond together? 2. Covalent bonding - takes place between non-metallic atoms, both of
All atoms "want" to achieve the stability of a complete outer orbital of which are electron deficient in their outer orbitals. The only way they can
electrons i.e. the electronic configuration of the Noble Gases. They do this achieve the electronic configurations of noble gas is by the sharing of
by losing or gaining outer electrons to form ions, or by sharing outer electrons. The bond pair of electrons is formed when each atom donates 1
electrons with other atoms. electron. This type of bonding is always shown using dot/cross diagrams.
The following represent some examples of covalent molecules (Fig 2).
Remember : All types of bonding involve just the outer electrons of the
atoms concerned
Fig 2. Covalent bonding
H H H
Atoms to atoms – the main bonding types H
O O C
1. Ionic bonding - takes place between an atom that wants to lose one or
more electrons and an atom that wants to gain one or more electrons. O
H H
• The atoms that lose electrons are classified as being metallic.
They form positive ions (called cations) because they are losing
electrons, which are negatively charged. H

• The atoms that gain electrons are classified as being non-metallic. H H C

O H O O H
They form negative ions (called anions) because they are gaining
negatively charged electrons.
H
H 2O O2 CH4
1
Bonding Chem Factsheet

Stick diagrams are another way of showing the bond pairs and their positions. What decides the type of bonding between two atoms?
The examples given so far are the classic examples, showing ideal ionic,
Fig 3. Stick diagrams covalent and metallic bonding.

However, this does not explain everything! For example, we would expect,
H H
A molecule of water O from what we have seen so far, that aluminium chloride (AlCl3) would be
ionic ( as it involves a metal and a non-metal). However, is actually covalent!

At AS-level we need to use the concept of electronegativity to explain

H why different atoms bond in the way that they do.
can be redrawn as O H

Definition : The electronegativity of an atom is the ability of

its nucleus to attract electrons in a bond pair.
A molecule of oxygen O O

The incomplete picture of the periodic table shows the trends in

electronegativity in periods and groups - it increases across each period
can be redrawn as O O and up each group, so fluorine is the most electronegative element, with
electronegativity 4.0 (fig 6). Textbooks and databooks give tables of
electronegativity values.

Fig 6. Electronegativity trends

3. Dative covalent bonding/ coordinate bonding - This is a special case
of covalent bond where 1 atom donates both electrons that form the shared H
bond pair (see fig 4) Li Be B C N O F
Na S Cl Trends in
Fig 4. Dative covalent bond electronegativity in
K Br
the periodic table
Both electrons H H Rb I
donated from the
nitrogen
H N B H To explain types of bonding think ‘differences in EN values’ !!
• If the EN difference is 0 (the same atoms, e.g. Cl – Cl) there will be a
H H pure covalent bond.
• If the EN difference is very large there will be a complete transfer of
H3N→ BH3 electrons causing an ionic bond.
The diagram shows the effect of EN differences on bond – types (Fig 7).
Notice that instead of a stick (____) an arrow (→) is used to signify the
dative covalent bond. Fig 7. EN difference and bonding
Remember: Once the bond is formed, it does not make any difference electron distribution
EN Difference
whether it is dative covalent or normal covalent - it behaves in exactly
the same way.
pure
covalent 0

4. Metallic bonding - The bonding in metals is caused by metal atoms

losing their outer electron(s) to gain the stability of a noble gas electronic
configuration. The metal atoms therefore become positive ions (cations)
and the electrons move around this structure of cations, holding it together
polar bond-
through electrostatic attraction (Fig 5).
some ionic δ+ S+ S- δ-
small
character
Fig 5. Metallic bonding
_ _ _ _
+ _ + _ +_ _ + _ +
_ __ _ _ _
electron sea ionic, but polar-
+ _ +
_
_ +
_
_ +
_
_ +
_
_ + ised, so some
+ _ large
+ _ + + + _ + covalent character
_ _
_ _ _ _ _
+ _ + _ + _ + _ + _ +
this is called the ‘sea of electrons’ model. The electrons are said pure ionic - _
to be delocalised (meaning they are not fixed in one place but are spherical ions + very
free to move around). large

2
Bonding Chem Factsheet

The diagram shows the change from pure covalent through intermediate Fig 10. Molecules with polarised covalent bonding, but no dipole
bond-types to pure ionic. It is vital that you understand that whilst you δ-
have seen a few examples of pure covalent and pure ionic (to illustrate Cl
these bond types) in reality most bonds lie somewhere in between the two.
δ- δ+ δ-
We can now explain why AlCl3 is covalent - the EN difference between Al
O C O δ+
C
and Cl is not large enough to cause the transfer of electrons from Al to Cl, δ -

Cl δ-
therefore bonding is covalent not ionic. However, it will be a polar covalent Cl
bond, since there is an EN difference.
Cl δ-
Intermediate bonds
We need to look in more detail at the 2 intermediate bond types shown in
Fig 7. Fig 11. Molecules with permanent dipoles

δ- δ-
1. Polarization of anions H O
Pure ionic compounds have ions which are perfectly spherical. However, δ+
δ+
if there is a large difference in charge density between the cation and the H H
anion, then the anion (because it has the extra electron cloud) becomes distorted δ +
C δ+ δ-
by the pull of the cation. (Fig 8). δ-
H δ- H Cl
H
Fig 8. Electron cloud distortion
H δ-

The existence of permanent dipoles of molecules means that the positive

+
_
+ _ and negative ends of these molecules will be attracted to these on other
molecules, leading to inter-molecular forces.

Inter-molecular forces
There are 3 types of intermolecular forces (bonds between molecules).
This is called polarization of the anion and Fajan's Rules explain the
effect of ion size and ion charge in this situation: 1. Permanent dipole – Permanent dipole attraction - the negative part
of one molecule is attracted to the positive part of another, hence there is
Fajan's Rules: An ionic compound will have appreciable a bond between the molecules.
covalent character if: Fig 12. Dipole - dipole attraction
• either the anion or the cation is highly charged (as this would
δ-
make the cation highly polarising and the anion highly
polarisable) Cl
δ+
• the cation is small (so it will have a high charge density) δ- H
• the anion is large (so the electrons are far from the nucleus and δ+
Cl H
hence less under its control) δ+

H δ-
Cl

2. Polar covalent molecules

In a molecule differences in electronegativity between the bonded atoms
2. Hydrogen Bonding - This is a special case of permanent dipole –
leads to the bond pair of electrons being pulled towards the more
permanent dipole bonding.
electronegative atom (Fig 9).
• The "δ+" is always on a hydrogen atom.
Fig 9. Polarised covalent bond • The "δ −" is on one of the three most electronegative atoms -
nitrogen,oxygen or fluorine
The high EN difference results in the N, O or F atom having a much greater
"share" of the electrons than the H atom. As hydrogen only has electrons
in the lowest energy level, this results in its nucleus being unshielded. The
δ+ S+ S- δ- O, N or F atom has lone pair(s), which are attracted strongly to the hydrogen
nucleus. (See Factsheet 4 Shapes of molecules for more on lone pairs)

Fig 13. Hydrogen bonds

H H H
The atoms gain a small charge because of this electron shift (δ = “delta”, is N: H
H
used to show a small amount). The existence of this δ+ and δ- within a H N
:

bond is called a dipole.

• If these δ+ and δ- charges are spread symmetrically in a molecule there
is no overall polarity (Fig 10). H
• Unsymmetrical molecules containing polar bonds will be polar δ+ δ- δ+ δ- δ+ δ- H
N
molecules and are described as having a permanent dipole. (Fig 11) H F: H F: H F:
H

3
Bonding Chem Factsheet

3.Temporary Dipoles/ Van der Waals (VdW) Forces - If you consider an 5. (a) Which chloride of the Group 2 elements would you expect to have
atom to be a central positive nucleus surrounded by electrons which are the greatest degree of covalency?
constantly in motion , there will at any one time be at least one atom whose (b) Explain the reasons for your choice of chloride in part (a).
electrons are on one side or the other. This causes a temporary dipole
within the atom itself. 6. What type of bonding is present in each of the following?
(a) Bromine
Fig 14. Temporary dipoles (b) Caesium fluoride
(c) Ammonia
_
_
_ 7. HCl is very soluble in water, but HF is not. Explain the difference in
_
+ + _ properties.
+ _
_
8. Explain why CH3(CH2)3 CH3 has a higher boiling point than its isomer

δ+ δ- CH3

CH3 – C – CH3
This atom will affect the other atoms around it producing induced dipoles (Fig 15).
CH3
Fig 15. Induced dipoles
9. Hydrogen sulphide, H2S, is a gas while the lighter molecule, water,
δ+- δ-- δ+- δ-- δ+- δ-- δ+- δ--
_ _ _ _ H2O, is a liquid. Explain this difference in physical properties.
_ _ _ _
__ __ __ __
++ _ ++ _ ++ _ ++ _ Answers
+ _ + _ + _ + _
_ _ _ _ 1. Si and Cl have different ENs so bonds are polar
Si Cl4 is tetrahedral - it is symmetrical so no overall polarity
induction along atom
2. (a) The complete transfer of electrons from one atom to another
(b) A shared pair of electrons where each atom donates one electron
Therefore there will be attraction between atoms or molecules that have no (c) A shared pair of electrons where one atom donates both electrons
permanent dipole. This weak force explains many structural and physical
properties e.g. – the properties of graphite, different boiling points of the 3. (a) N (b) Y (c) N (d) Y (e) Y (f) N (g) Y
elements etc.
* All molecules have VdW Forces in them * 4. The difference in ENs between Al and I is small
so leading to electron sharing i.e. covalent bonding
The difference in ENs between Al and F is large
Remember - in terms of strength of intermolecular forces: so leading to a complete transfer of electrons/ionic bonding
H-Bonds → Permanent dipole → Temporary dipole
5. (a) BeCl2
(b) Be is a small atom
Be is more polarising
The strength of the Van der Waals forces increases with the number of EN differences between Be and Cl is small
electrons in the atom or molecule, since the temporary dipoles can be of
a larger size if there are more electrons. For noble gases such as helium or 6. (a) pure covalent
neon, which exist as single atoms and have relatively few electrons, the (b) pure ionic
forces are weak - this explains the very low boiling point of these gases. (c) covalent with partial ionic/ polar character

The strength also depends on the shape of the molecule - long molecules 7. HF has strong H-bonding so hard to break when put into water
can have induced temporary dipoles all along them. In general, larger HCl is polar - bond breaks with water molecules
molecules will have larger Van der Waals forces.
8. The linear molecule has larger Van der Waals forces
Practice Questions because of the induction effect along the chain
1. Silicon tetrachloride, SiCl4, is a colourless liquid. The individual bonds The molecule which has smaller chain lengths has less VdW forces
are polar, but the molecule is not. Explain these facts.
9. H2O has H-bonding which leads to strong intermolecular forces which
2. Explain what is meant by the following require energy to break
(a) Ionic bond (b) Covalent bond (c) Dative covalent bond H2S has no H-bonding so less energy is needed to vaporise it.

3. Indicate whether each of the following molecules has an overall polarity.

(a) Carbon dioxide (b) Ethanoic acid (c) Ethane
Acknowledgements:
(d) Propanone (e) Trichloromethane (f) Tetrachloromethane This Factsheet was researched and written by Sam Goodman & Kieron Heath
Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham, B18 6NF
(g) Ethanol ChemistryFactsheets may be copied free of charge by teaching staff or students,
provided that their school is a registered subscriber.
4. Explain why aluminium iodide is covalent but aluminium fluoride is ionic. No part of these Factsheets may be reproduced, stored in a retrieval system, or
transmitted, in any other form or by any other means, without the prior
permission of the publisher. ISSN 1351-5136

4
 Chem Factsheet
September 2000 Number 06

Structure of Elements and Compounds

To succeed with this topic you need to:
• Understand what is meant by ionic, covalent and metallic bonding (covered in Factsheet 5 - Bonding)
• Understand the different types of intermolecular forces
• Know how to work out the sort of bonding in a compound from the elements in it

After working through this Factsheet you will:

• understand how bonding determines the structure and properties of compounds
• be able to deduce bonding from structure, or structure and properties from bonding, for unfamiliar substances
• know the structures and properties of elements and compounds specifically mentioned at AS level
In covalent compounds, sometimes one atom (the more electronegative
Exam hint:- Questions will often use "unfamilar" compounds. element) exerts a greater "pull" on the electrons; if this happens, the electron
However, they will fit into the general pattern outlined in this sheet, so
will be effectively the same as the specific examples you have learnt.
cloud is pulled out of shape towards this atom. Such a bond is known as
For example, potassium bromide (KBr) is similar to sodium chloride covalent with ionic character, or polar covalent.
(NaCl) because sodium and potassium are in the same group, and
bromine and chlorine are in the same group. Fig 1. Ionic, covalent and intermediate bonding

_ Pure ionic - ions are spherical

Bonding +
There are three main types of bonding between atoms - ionic, covalent and
metallic (Factsheet 5 - Bonding). The key characteristics of these are Ionic, with covalent character - the cation
summarised in Table 1. ++ _ has pulled the electron cloud out of shape on
the anion. This is called polarisation.
However, in most compounds the bonding is not really pure ionic or pure
covalent - it is somewhere in between. Such types of bonding are known as
intermediate. This affects the structure and physical and chemical Covalent, with ionic character - the molecular
orbital is shifted towards the more
properties. δ+ S
+
S δ--
electronegative atom causing dipoles (small
In an ionic compound, if the positive ion (cation) is very small, it has a high charges, δ+ and δ-). These are the cause of polar
charge density - which means it has a lot of charge in a small volume! This molecules ie. molecules with charges on certain
high charge density attracts the electron cloud on the negative ion (anion) atoms.
and tends to pull it out of shape. This is particularly likely if the anion is
big - since then the electron cloud is a long way away from the nucleus, and Pure covalent - equal distribution of the
so it is not so tightly held by the nucleus. Ionic compounds in which this electron cloud (molecular orbital) between the
occurs are said to be polarised, or ionic with covalent character. two nuclei.

Table 1. The three main types of bonding

Type of bonding Involves Occurs in Example

Ionic Electrons being transferred Compounds of Sodium chloride (NaCl)

from one atom to another so metals and non- Na + Cl à Na+ + Cl−
that positive and negative metals 1s2 2s2 2p6 3s1 1s2 2s2 2p6 3s2 3p5 1s 2 2s2 2p6 1s2 2s2 2p6 3s2 3p6
ions are formed. Each atom
then (usually) ends up with a
full outer shell of electrons.

Covalent Atoms sharing electrons, so Compounds of Methane (CH4) H

that each atom (usually) ends two (or more)
up with a full outer shell of non-metals. H C H
electrons Non-metal
H
elements, except
noble gases
- -
Metallic Metal atoms in a lattice losing Metal elements Copper (Cu) - + - + - Copper ions
their outer electrons, which
- + - + - + -
become delocalised - free to
move from place to place. - + - + - electrons
- -
1
The Structure of Elements and Compounds Chem Factsheet

Intermolecular forces
These are the forces attracting molecules to each other. They are important All types of intermolecular force rely on dipoles - this is when one end of
because the stronger they are, the more energy is required to seperate the a molecule is slightly positive and one is slightly negative. The positive end
molecules from each other. Since melting a solid, or boiling a liquid, requires of one molecule is attracted to the negative end of another (unlike charges
seperating the molecules, this means that the stronger the intermolecular attract) Table 2 summarises the three types of intermolecular forces.
forces, the higher the melting/boiling point of the substance.
Table2. Intermolecular forces
Name Relative strength Occurs Explanation Examples
Hydrogen bond Strongest In molecules The highly electronegative N, O or F atom attracts most NH 3, H2O, HF δ+
containing a of the electron cloud away from the hydrogen, leaving the δ+ H δ−
nitrogen, oxygen hydrogen slightly positive and the other atom slightly δ+ H δ− O
H δ− O
or fluorine atom negative. O Hydrogen
bonded to a
bond H+
hydrogen. H+ δ
H+ δ
δ
Dipole-dipole Middle In molecules The more electronegative atom attracts a greater "share" HCl, CHCl3
(or permanent containing atoms of the electrons, giving it a small negative charge, and the
dipole) of differing other atom a small positive charge. If the molecule is
electronegativity asymmetrically arranged, this leads to a negative "end"
δ+ δ− δ+ δ− δ+ δ−
- arranged and a positive "end", giving the molecule itself an overall H Cl H Cl H Cl
asymmetrically dipole. However, in molecules where the electronegative
atoms are symmetrically arranged, like CCl4 and CO2, (see dipole-dipole attraction
Factsheet 4 - Shapes of Molecules and Ions) all "ends" of
the molecule are equally charged.

Van der Waals Weakest In any atoms or The position of electrons around the nucleus in an atom Any molecular substance, but they
forces (or molecules can be instantaneously unbalanced, leading to a negative increase in strength as the number of
temporary region and a positive region in the atom electrons in the atom increases and the
dipoles) number of atoms in the molecule
This creates induced dipoles in neighbouring atoms - the increases
electrons in atoms near the positive region will be attracted, ___
_ +__ temporary
and those in atoms near the negative region wil be repelled, δ+ δ− dipole
so creating an imbalance in neighbouring atoms

δ+ δ− δ+ δ− δ+ δ− induced dipoles

The effect of bonding on structure and properties e.g. H2O is simple molecular with an RMM = 18 (i.e. it is a small light-
Table 3 below shows how structure and bonding are related for "typical" weight molecule) so should be a gas at room temperature. It is, of course,
substances with ionic, covalent and metallic bonding. These general ‘rules’ a liquid and this is due to the presence of strong hydrogen-bonding because
explain the behaviour of the vast majority of elements and compounds. of the presence of the oxygen atom. These ‘special cases’ are quoted in the
However, there are other influences e.g. intermolecular forces and sizes of AS level Chemistry specification and are given in the tables of specific
atoms and molecules that affect the properties of elements and compounds examples that follow.
Table 3. Bonding, structure and properties
Bonding type Structure Key Properties
ionic Millions of ions arranged in a crystal lattice (a regular • Solids with very high mpts/bpts ( a lot of energy needed to break up
structure) so it is a giant ionic structure held together the millions of bonds in the lattice).
by electrostatic attraction (+/-) • Most are soluble in water because of the ions which are attracted to the
polar water molecules.
• Conducts electricity when in solution or molten due to being made of
ions which can move. Solids do not conduct, as ions cannot move.

covalent (a) i) a small group of atoms joined together as ‘simple’ • i) are usually liquids or gases with low mpts/bpts. (easy to separate
molecular. because intermolecular forces between are weak).
ii)simple molecules arranged in a lattice to produce • ii) are solids with low mpts/bpts. (easy to separate because intermolecular
a molecular giant structure forces between are weak).
• Polar molecules may dissolve in water,
• Non-polar molecules do not, but will dissolve in non-aqueous solvents.
• No electrical conductivity.

(b) many atoms joined together to form a • Solids with very high mpts/bpts (a giant structure so a lot of energy
giant covalent structure. needed to separate the millions of covalent bonds) which are insoluble
in water
• No electrical conductivity (except graphite - see page 3)

metallic Millions of cations in a ‘sea of electrons’ making • Solids(except mercury) with high mpts/bpts ( a lot of energy needed to
a giant metallic structure. break up the giant structure).
• Conduct electricity because of the delocalised electrons.

2
The Structure of Elements and Compounds Chem Factsheet

Table 4. Specific examples of giant structures

Name/ Formula Structure Description Physical Properties

Sodium chloride Cl Na Cl
Giant ionic lattice • Solid at room temperature
NaCl(s) Na Cl Na
• High MPt/BPt
• Soluble in water
Cl Na Cl
• Conducts electricity when
molten or in solution
Na Cl Na
• Crystalline
Cl Na Cl
Na Cl Na

Cl Na Cl
Na Cl Na
Cl Na Cl

Diamond Giant covalent molecule. Each • Solid at room temperature

C(s) carbon atom joined to 4 other • High MPt/BPt
carbon atoms in a tetrahedral • Insoluble in water and non-
arrangement – this makes a very aqueous solvents
strong and rigid structure. • Does not conduct electricity
• Crystalline – the hardest known
natural material

Graphite Giant covalent molecule. • Solid at room temperature

C(s) Arranged in layers held together • High MPt/BPt
by weak Van der Waals forces. • Insoluble in water and non-
The carbon atoms in the layers aqueous solvents
are arranged in hexagons (each • Conducts electricity in one
connected to 3 others, the non- direction/plane only
bonded electron from carbon joins • Feels soft when rubbed (used
with others.) These delocalised as a lubricant) because
electrons flow along layers but pressure makes the layers
not between them. move across each other as the
weak bonding is broken

Iron _ _ _ _ Giant structure of cations • Solid at room temperature

Fe(s) + _ + _ +_ _ + _ + surrounded by a ‘sea of • High MPt/BPt
_ __ _ _ _ delocalised electrons’. • Conducts electricity in all
+ _ + _ + _ + _ + _ + directions
_ _ _ _
• Insoluble in water and non-polar
+ _ + _ + _ + _ + solvents
_ _ _ _ _
+ + + + + + electron • High density
_ _ _ _ _
sea

Silicon dioxide Giant covalent structure. • Solid at room temperature

(silica) Every Si atom is linked to 4 O • High MPt/BPt
SiO2 (s) atoms, and in turn every O atom • Poor conductor of electricity
is linked to 2 Si atoms. • Insoluble in water and non-polar
solvents

= silicon atom = oxygen atom

= covalent bond

3
The Structure of Elements and Compounds Chem Factsheet

Table 5. Specific examples of molecular structures

Name/Formula Structure Description Physical Properties

Iodine Giant molecular structure. • Solid at room temperature

I2(s) Weak van der Waals forces hold • Low MPt/BPt
the I2 molecules in a 3- • Soft
dimensional structure. • Does not conduct electricity
• Virtually insoluble in water, very soluble
in non-polar solvents

= I2 molecule

Giant molecular structures, • Solid at room temperature

Polythene where long chains of carbon • Low MPt i.e. softens easily when heated
( C2H4 )n atoms lie alongside each other, • Does not conduct electricity
attracted together by van der • Will stretch
Waals forces. • Insoluble in water

Simple molecular structure, • Gas at room temperature

Carbon dioxide strong covalent bonding within • Low MPt/BPt
CO2(g) molecule, but only weak van
der Waals forces between the
molecules. A small light
molecule. (RMM = 44)

= carbon atom
= oxygen atom
Ice Giant structure of water • Solid at, or below, 0oC
H2O(s) molecules held together by • Less dense than water
strong hydrogen bonding.
This 3-dimensional network of
covalent bonds and hydrogen
bonds keeps the H2O molecules
further apart than in liquid
water (this is why its density is
less than water, so it will float
on water).

= hydrogen atom
= oxygen atom
= hydrogen bond

Water Polar molecules held together • Liquid between 0o-100oC

H2O(l) by hydrogen-bonding. Because
the molecules are moving about
the hydrogen-bonds are
frequently broken and reformed
but still cause the molecules to
be attracted to one another.

= hydrogen atom
= oxygen atom

4
The Structure of Elements and Compounds Chem Factsheet

Fig 2. Physical properties and structure Exam hint:- Questions on this topic may require:
• deduction of the properties of a compound from the elements in it
STATE
GIANT IONIC • diagrams of the structure of named compounds (see Tables 4 and 5)
• deduction of the structure of a compound from its properties, and
GIANT possibly identification of the compound (from a list) (see Fig 2)
VERY HIGH COVALENT
MELTING POINT
Questions
HIGH MELTING
(1) PbCl4 is a liquid at room temperature which does not conduct electricity,
SOLID POINT METALLIC and is insoluble in water. PbCl2 is a solid at room temperature which
dissolves in water to form a solution which conducts electricity.
What can be deducted from these physical properties about the structure
LOW MELTING
and bonding of PbCl4 and PbCl2?
POINT GIANT
MOLECULAR (2) Why is H2O a liquid at room temperature, and not a gas?

(3) Carbon and silicon are both in group 4 of the periodic table. SiO2 is a
solid with a high melting point, whereas CO2 is a gas. Explain this.
LIQUID/GAS SIMPLE
MOLECULAR (4) Graphite conducts electricity only in one plane, whereas metals conduct
in all planes. Why is this?
CONDUCTIVITY (5) Put the following compounds and elements into their correct positions
METALLIC in the table.
KBr, Hg, SO2, Ne, SiCl4, Rb2O, PVC.
WHEN SOLID
GRAPHITE

STRUCTURE ELEMENT/COMPOUND

CONDUCTS WHEN MOLTEN GIANT IONIC Giant ionic lattice

ELECTRICITY OR IN SOLUTION

Metallic
SIMPLE
NEVER MOLECULAR
Simple molecular
GIANT
MOLECULAR
Simple atomic
GIANT
COVALENT
(except graphite)
Giant molecular
SOLUBILITY MOST GIANT
IONIC
Answers
POLAR SIMPLE (1) PbCl4 -covalent, simple molecular. PbCl2 -ionic, giant ionic lattice.
MOLECULAR
IN WATER (2) Presence of H-bonding causes polar molecules to be attracted to one
another, so more energy is required to separate the molecules.
NON-POLAR (3) SiO2- giant covalent structure, with many Si and O atoms inter-linked.
SIMPLE
IN NON- POLAR
CO2 -simple molecular structure. Only weak inter-molecular forces.
MOLECULAR
SOLUBLE (ORGANIC)
(4) Graphite is made of layers of C atoms arranged in hexagonal rings,
SOLVENT SOME GIANT along which electrons can flow. Electrons cannot move in between
MOLECULAR
layers – hence conduction in 1 plane.
(eg iodine)
The de-localised electrons in metals can move in any direction because
the structure is symmetrical.
NOT AT ALL GIANT
COVALENT (5) Giant ionic lattice KBr, Rb2O
Metallic Hg
SOME GIANT Simple molecular SO2, SiCl4
MOLECULAR
Simple atomic Ne
(eg polythene)
Giant molecular PVC
SOME IONIC
NB: We must distinguish between substances reacting (eg calcium Acknowledgements: This Factsheet was researched and written by Kieron
with water and dissolving in water. carbonate) Heath. Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham,
• Metals will either react with water (like sodium) B18 6NF. ChemistryFactsheets may be copied free of charge by teaching staff
or students, provided that their school is a registered subscriber. No part of
or be insoluble (like copper)
these Factsheets may be reproduced, stored in a retrieval system, or transmitted,
• Some covalent compounds (such as phosphorus in any other form or by any other means, without the prior permission of the
pentoxide) will react with water, not dissolve. publisher. ISSN 1351-5136

5
 Chem Factsheet
January 2001 Number 07

Moles and Volumetric Analysis

To succeed with this topic, you need to be able to: This equation can be used to find the moles, volume or molarity (M) as
• Do basic moles and formulae calculations (see Factsheet No. 2 - shown below.
Moles and Formulae)
• Use equations to calculate reacting amounts (see Factsheet No 3 - eg 1. How many moles of NaOH are there in 250cm3 of a 0.1M solution?
Moles and Equations).
First change the volume to dm3: 250cm3 = 0.25dm3
After working through this Factsheet, you will understand: Now use the formula: moles = volume in dm3 × molarity
• How moles are related to the term ‘concentration’ for solutions. = 0.25× 0.1
• The use of equations in calculating reacting volumes of solutions. = 0.025 moles
• The concept of ‘percentage purity’ when used in volumetric
analysis (.i.e. titration) eg 2. What is the concentration in mol dm-3 of 0.5 moles of sodium chloride
dissolved in 2 dm3 ?
Exam Hint: Many candidates find volumetric analysis calculations
The volume is already in dm3.
frightening, and complain of not knowing where to start on the
problems. To avoid being in this situation, you need to: Formula: molarity = moles÷ volume
• ensure you learn the equation linking moles, volume and
= 0.5÷ 2
concentration, and can rearrange it as necessary. = 0.25 mol dm-3
• practise examples frequently, so you do not forget how to do it,
eg 3. What volume of water should 1.5 moles NaCl be dissolved in to
working carefully through each step in the method.
produce a 0.5M solution?

Formula: volume = moles ÷ molarity

Chemicals in solution = 1.5 ÷ 0.5
The amount of a chemical in a certain volume of solvent is called its
= 3 dm3
concentration.
Questions involving Mass
The concentration of a solution is the number of moles of the Questions will often require you to find or use masses in molarity
substance in 1 litre ( = 1 dm3 or 1000 cm3 ). calculations. The rule is simple:
Concentration in mol dm-3 is also called molarity. • If you are given a mass, change it to moles at the start,
It is measured in mol dm-3, which can also be written as M. using moles = mass ÷ Mr
For example, 2 moles in 1000cm3 is a concentration of 2mol dm-3or 2M • If you have to find a mass, find moles first, then change to mass,
using mass = moles × Mr

Calculations on Concentrations eg 1. What mass of NaOH is present in 50cm3 of a 2M solution?

The equation used is:- (Ar values Na: 23 O:16 H:1)

We are asked to find a mass, so we first aim to find moles of NaOH.

moles = volume in dm3 × molarity We change the volume to dm3: 50cm3 = 0.05dm3
Now use moles = volume × molarity
= 0.05 × 2 = 0.1 moles
NB. The volume must be in dm3. If you are given a volume in cm3, divide Now we find mass:
by 1000 to change it to dm3. before you start! Mr = 23 + 16 + 1 = 40.
As with many other equations in Chemistry, a "triangle" may help with mass = moles × Mr
rearranging this equation (see box). = 0.1 × 40 = 4 g.

eg 2. What is the concentration in mol dm-3 of 49 g H2SO4 dissolved in

Triangle for concentration formula 50 cm3? (Ar values S:32 O:16 H:1)

We are given a mass, so we change it into moles first:

moles Mr = 2 + 32 + 64 = 98.
moles = mass ÷ Mr
volume in dm3 × molarity = 49 ÷ 98 = 0.5
Change the volume to dm3: 50cm3 = 0.05dm3
Cover up the thing in the triangle you want to find. Then, what you can Now use molarity = moles ÷ volume
see tells you the calculation to do. For example, if you want to find = 0.5÷ 0.05 = 10M
molarity, cover it up and you are left with moles/ volume

1
Moles and Volumetric Analysis Chem Factsheet

eg 3. What volume of water must 5.85g NaCl be dissolved in to produce a

eg 2. What volume of 0.02M KMnO4 solution is needed to react with
0.2M solution? (Ar values Na:23 Cl:35.5)
50cm3 of 0.2M Fe2+? The equation for the reaction is:
MnO4-(aq) + 5Fe2+(aq) + 8H+(aq) èMn2+(aq) + 5Fe3+(aq) + 4H2O(l)
We are given a mass, so we change it into moles first:
Mr = 23 + 35.5 = 58.5
Step 1. equation given
moles = mass ÷ Mr
= 5.85 ÷ 58.5 = 0.1 Step 2. MnO4- : Fe2+ is 1:5
Now use volume = moles ÷ molarity
= 0.1÷ 0.2 = 0.5 dm3 Step 3. no masses involved.
50cm3 is 0.05 dm3
All the work from now on depends on you being competent at these
Step 4. We're given both volume and molarity for Fe2+
types of calculation! You should stop now and attempt questions 1-6 at
the end of the Factsheet before carrying on - until you can answer them all Step 5. moles of Fe2+ = molarity × volume in dm3
with no errors, there is no point in attempting the harder work. = 0.2 × 0.05 = 0.01 moles

Volumetric Analysis Calculations (Titration Calculations) Step 6. moles of MnO4- = moles of Fe2+ ÷ 5 = 0.002 moles
In this section we will cover the type of volumetric calculations needed for
AS level, and we begin with the method that you need to learn and use. Step 7. We need volume.
However, before you start, make sure you are happy with the work in Use volume = moles ÷ molarity
Factsheet 3 - Moles and Equations. = 0.002 ÷ 0.02 = 0.1 dm3

Step 1. Write the balanced equation for the reaction. (If you are not
given it in the question). Tip: If in step 6 of the above examples you would have been unsure
whether to multiply or divide, remember: the substance with the larger
Step 2. From the equation, find the mole ratio for the substances involved number in front of it in the equation has the higher number of moles.
in the question.

Step 3. Convert any masses you are given into moles, and any volumes eg 3. What is the concentration of a hydrochloric acid solution if 50cm3
into dm3 if it reacts exactly with 10g of calcium carbonate?
(Ar values Ca:40 O:16 C:12)
Step 4. Study the information in the question, and find the substance
for which you are given two pieces of information (eg the Step 1. CaCO3 + 2HCl Ô CaCl2 + H2O + CO2
volume and the concentration)
Step 2. CaCO3: HCl is 1:2
Step 5. For the substance in step 4, find its number of moles.
Step 3. Mr for CaCO3 is 40 + 12 + 48 = 100
moles of CaCO3 = mass ÷ Mr
Step 6. Use the mole ratio (step 2) to work out the moles of the
substance you are asked about. = 10 ÷ 100 = 0.1 moles
50cm3 is 0.05 dm3
Step 7. Go back to the question - what have you got to find? Step 4,5 not applicable
Use the information in step 6, together with the right equation,
to find the mass or molarity or volume. Step 6. moles of HCl = moles of CaCO3 × 2 = 0.2 moles

Worked examples using this method Step 7. We need molarity.

The following three examples show you the method Use molarity = moles ÷ volume in dm3
= 0.2 ÷ 0.05 = 4M
eg 1. 25cm3 of 0.1M NaOH reacts with 25cm3 of H2SO4.
What is the molarity of the acid?
Exam Hint: From these worked examples you will have seen how
Step 1. 2 NaOH + H2SO4. Ô Na2SO4. + 2H2O. crucial the ‘reacting ratio’ is to obtaining the correct final answer.
However - In the examination if you write an incorrect equation, so
Step 2. NaOH:H2SO4 is 2:1 getting an incorrect ratio, you will only lose 1 mark if the rest of your
steps are correct. This is why it is vitally important that you
Step 3. no masses involved. show every step in your calculation!
25cm3 is 0.025 dm3

Step 4. We're given volume and molarity for NaOH

Equations
Step 5. moles of NaOH= molarity × volume in dm3 You are expected to know how to write equations for the following:
= 0.1 × 0.025 = 0.0025 moles acid + alkali Ô a salt + water
Step 6. moles of H2SO4 = moles of NaOH ÷ 2 = 0.00125 acid + base Ô a salt + water
NB: alkalis and bases are metal oxides or hydroxides and ammonia
Step 7. We need molarity.
Use molarity = moles ÷ volume in dm3 acid + carbonate Ô a salt + water + carbon dioxide
= 0.00125 ÷ 0.025 = 0.05M acid + metal Ô a salt + hydrogen

Other reaction equations will probably be given in the question.

2
Moles and Volumetric Analysis Chem Factsheet

Before you go on to the next section, you need to make sure you can use Practice Questions
the basic method confidently and accurately. You should do question 7 at 1. Calculate the number of moles present in each of the following:-
the end of the Factsheet before carrying on! a) 500cm3 of 2M NaOH b) 25cm3 of 1M H2S04
c) 100cm3 of 0.5M KOH d) 2dm3 of 0.25M HCl
e) 30cm3 of 0.3M KOH f) 200cm3 of 0.1M HNO3
Percentage Purity
At AS Level the questions relate to solids which are ‘impure’. This means 2. Calculate the concentration of each of the following:-
the chemical is present and reacts but some of the solid is not the chemical a) 2 moles in 2 dm3 b) 0.2 moles in 1 dm3
so does not react. c) 0.1 mole in 100cm3 d) 1 mole in 10cm3
e) 0.25 moles in 250cm3 f) 5 moles in 2 dm3
The object of the calculation is to find the amount of pure chemical, which
3. What volume of liquid would be needed to produce the required
is put into the equation.
concentration in each case?
a) 2 moles to make 1 mol dm -3 b) 0.1 moles to make 1 mol dm -3

mass of pure chemical (g) c) 5 moles to make 0.5 mol dm -3 d) 0.2 moles to make 2 mol dm -3

percentage purity = mass of starting material × 100

4. Calculate the mass present in each of the following:-
a) 500cm3 of NaOH b) 1.5dm3 of 2M KOH
c) 100cm3 of 1M H2SO4 d) 250cm3 of 0.1M HNO3
The ‘method’ is slightly different and you should refer to the original
method above as you look at each step. 5. What is the concentration of each of the following?
a) 3.65g HCl in 500cm3 b) 4.0g NaOH in 100cm3
Percentage Purity Method c) 63g HNO3 in 250cm3 d) 0.98g H2SO4 in 10cm3
Step 1. Write the balanced equation for the reaction. (If you are not
6. What volume of liquid must each of the following masses be dissolved in
given it in the question).
to produce the required concentration?
Step 2. From the equation, find the mole ratio for the substances involved a) 4g NaOH to make 1M b) 0.56g KOH to make 0.1M
c) 49g H2SO4 to make 0.05M d) 5.85g NaCl to make 0.2M
in the question.

Step 3. Convert any volumes you are given into dm3 7. a) 25cm3 of 0.2M NaOH reacts with 50cm3 of HCl.
What is the molarity of the acid?
Step 4. Find the substance for which you are given volume & molarity b) 50cm3 of 1M H2SO4 reacts with 50cm3 of KOH solution
What is the molarity of the KOH solution?
Step 5. For the substance in step 4, find its number of moles. c) 20cm3 of 2M HNO3 reacts with 10cm3 of NaOH solution
What is the concentration of the NaOH solution?
Step 6. Use the mole ratio to work out the moles of pure chemical d) 100cm3 of 0.1M HCl reacts with 50cm3 of Ca(OH)2 solution.
What is the molarity of the Ca(OH)2 solution?
Step 7. Turn step 6 moles into mass e) 30cm3 of 0.01M AgNO3 solution reacts with 10cm3 of AlCl3 solution.
3AgNO3 + AlCl3 è 3AgCl + Al (NO3)2
Step 8. Use step 7 answer and the impure mass from the question to What is the molarity of the AlCl3 solution?
find percentage purity, using the equation above. f) The reaction between NaOH and H3PO4 is:
NaOH + H3PO4 è NaH2PO4 + H2O
Now let’s see how this works on a question: What volume of 0.4M H3PO4 will react with 100cm3 of 0.1M NaOH
solution?
eg. 2.00g of impure NaOH is titrated with 0.5M HCl, and 50cm3 of the g) Barium chloride reacts with sulphuric acid according to the following
equation: BaCl2 + H2SO4 è BaSO4 + 2HCl
acid is used up in neutralising the sodium hydroxide.
What volume of 0.02M BaCl2 solution will react with 40cm3 of
What is the percentage purity of the original sodium hydroxide sample? 0.05M H2SO4 ?
(Ar values Na: 23 O:16 H:1) h) What volume of 0.02M KMnO4 solution will react with 20cm3 of
0.1M Fe2+(aq)? The reaction is:-
Step 1. HCl + NaOH Ô NaCl + H2O MnO4-(aq) + 5Fe2+(aq) + 8H+(aq) èMn2+(aq) + 5Fe3+(aq) + 4H2O(l)

Step 2. HCl : NaOH is 1:1 8. a) 2.50g of impure NaOH reacts with 25cm3 of 2M HNO3
What is the percentage purity of the NaOH?
Step 3. 50cm3 is 0.05 dm3 b) 2.50g of impure iron reacts with 40cm3 of 1M H2S04 according to the
equation: Fe + H2SO4 è FeSO4 + H2
Step 4. We're given both for HCl What is the percentage purity of the iron?
c) 50cm 3 of 0.1M HCl reacts with 1.00g of impure calcium carbonate,
Step 5. moles of HCl = molarity × volume in dm3 CaCO 3.What is the percentage purity of the calcium carbonate?
= 0.5 × 0.05 = 0.025 moles
Answers
Step 6. moles of pure NaOH = 0.025 1. a) 1 b) 0.025 c) 0.05 d) 0.5 e) 0.009 f) 0.05
2. a) 1 b) 0.2 c) 1 d) 100 e) 1 f) 2.5
Step 7. Mr for NaOH = 23 + 16 + 1 = 40 3. a) 2000cm3 b) 100cm 3 c) 10,000cm 3 d) 100cm 3
So mass of NaOH = moles × Mr 4. a) 20g b) 168g c) 9.8g d) 1.57g
= 0.025 × 40 = 1g 5. a) 0.2M b) 1M c) 4M d) 1M
6. a) 100cm 3 b) 100cm3 c) 10,000cm 3 d) 500cm 3
1
Step 8. % purity = 2 × 100 = 50% 7. a) 0.1M b) 2M c) 4M d) 0.1M e) 0.01M
f) 25cm 3 g) 25cm3 h) 20cm 3
8. a) 80% b) 89% c) 50%
Question 8 will give you some practice at percentage purity calculations.
Acknowledgements;
This Factsheet was researched and written by Sam Goodman and Kieron Heath
Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham, B18 6NF
ChemistryFactsheets may be copied free of charge by teaching staff or students, provided that their school is a
registered subscriber. No part of these Factsheets may be reproduced, stored in a retrieval system, or transmitted,
in any other form or by any other means, without the prior permission of the publisher. ISSN 1351-5136

3
 Chem Factsheet
January 2001 Number 08

Energetics I - Hess's Law

To succeed with this topic, you need to: Exam Hint: Do not assume that a reaction is endothermic just because
• understand how to produce balanced chemical equations heat must be applied to make it happen; many highly exothermic
• be able to do arithmetic involving negative numbers on a calculator reactions (such as the combustion of magnesium) require heat to start
the reaction.
After working through this Factsheet, you will be able to:
• recall and understand the definitions of standard enthalpy changes
needed at AS level Exam Hint: You must always show the + or - signs for ∆H values
• understand and use bond enthalpies
• use Hess's Law to calculate enthalpy changes for reactions

Exam Hint: Enthalpy Level Diagrams

1. In examination questions there are always marks for correctly Enthalpy changes can be represented on an enthalpy level diagram. This
giving the definitions of enthalpy changes and quoting Hess’s Law. measures the energy of the system, not the temperature of the surroundings.
These marks are lost by lack of thorough learning.
Fig1. Enthalpy level diagrams
2. Calculations on Hess’s Law have marks for drawing the correct cycle
and then for using the data to produce a correct answer. If the cycle is Exothermic Endothermic
not correct you cannot get full marks. Do not underestimate the need
to draw full and detailed cycles before doing the mathematical
calculation. reactants products
Enthalpy

Enthalpy
Introduction - Energy ∆H ∆H
Energy may take various forms, such as heat, light or electrical energy, and
these types may be converted from one to the other (a light bulb converts products
reactants
electrical energy into light, for example). However, all energy conversions
are governed by the First Law of Thermodynamics (or the Law of
Conservation of Energy), which states: • Reactants less stable than • Reactants more stable than
products products
Energy can be neither created nor destroyed, but can be • Heat leaves the system during • Heat enters the system during
converted from one form to another the reaction the reaction
• Outside temperature goes • Outside temperature goes
The total energy content of a system is known as the enthalpy or heat
up down
content of the system and has the symbol H. The higher the energy content
of a system, the more unstable it is.
Standard conditions
Enthalpy Changes Since the amount of energy taken in or given out will vary depending on the
It is impossible to measure the total enthalpy of a system; the chemist is pressure and temperature, standard enthalpy changes are defined, which
interested in changes in enthalpy accompanying a physical or chemical process. are measured under standard conditions.
These are:
When chemical reactions take place there are always energy changes taking
place because;
• 1 atmosphere pressure
• energy needs to be put in to break bonds. • temperature 298K (= 25o C)
• energy is given out when bonds are made. • substances present in their standard states at 298K
These two amounts of energy are rarely equal in value and the difference (e.g. H2O(l) not H2O(g) or H2O(s)
between the energy absorbed or given out is the enthalpy change for the • all solutions having a concentration of 1 mol dm –3 (= 1M)
reaction. Enthalpy changes have the symbol ∆H (read as "delta H")
The symbol used to show ‘standard conditions’ is O.
There are two types of enthalpy changes:-
The enthalpy change symbol now becomes ∆H° - read it as "delta H
nought" or "delta H standard".
Exothermic reactions:
• Give out heat to the surroundings (so there is a rise in temperature). The units of ∆H °are kJ mol-1 - that is, kilojoules per mole. The "per mole"
• The internal energy of the system decreases so ∆H is negative. is in there because the actual amount of energy given out or taken in during
a reaction will depend on how much of the chemicals there are - two tons
Endothermic reactions: of magnesium burning will give out more energy than two grammes! So we
• Take in heat from the surroundings (so there is a fall in temperature). consider the energy given out per mole.
• The internal energy of the system increases so ∆H is positive.

1
Energetics I - Hess’s Law Chem Factsheet

Enthalpy change definitions

The following definitions need to be learnt.

Table 1: Standard Enthalpies

Name and Symbol of Enthalpy Change Definition Example Key Points
∆Hf° Standard Enthalpy of Formation The enthalpy change when one mole of a compound in its standard ∆Hf° (C2H6 (g)): • For elements, this is zero by definition
state is formed from its elements in standard state, under standard 2C(s) + 3H2 (g) → C2H6 (g) • It must be one mole of the compound
conditions • For compounds, it may be exothermic (most
commonly) or endothermic.

∆Hc° (CH3OH (l)): • This is always exothermic.

∆Hc° Standard Enthalpy of Combustion The enthalpy change when one mole of an element or compound is
CH3OH(l) + 1½O2(g) → CO2(g) +2H2O(l)
completely burned in excess oxygen under standard conditions.
∆Ha° (Cl2(g)): • This is always endothermic
½Cl2 (g) → Cl(g) • This term may also be used to describe the
∆Ha° Standard Enthalpy of Atomisation The enthalpy change when one mole of gaseous atoms is formed shattering of one mole of a gaseous molecule
from an element under standard conditions into its constituent atoms

∆Hr° : • Values are always quoted for the reaction as

∆Hr° Standard Enthalpy of Reaction The enthalpy change for the reaction as written in the equation NH3(g) + HCl(g) → NH4Cl(s) written - the enthalpy of reaction for
under standard conditions H2(g) + Cl2(g) → 2HCl(g) will be twice that for
½H2(g) + ½Cl2(g) → HCl(g)

∆HD° Standard Bond Enthalpy The enthalpy change when one mole of a particular chemical bond ∆HD° (H_Cl(g)) : • This is always endothermic
is broken in the gaseous state to give gaseous atoms under HCl(g) → H(g) + Cl(g) • The weaker the bond, the easier it is to break,
standard conditions and so the lower the bond enthalpy
• Making bonds is the reverse, and is always
exothermic

The average enthalpy required per bond to break all the bonds of H2O (g) → 2H(g) + O(g) ∆Hr° = +926 kJ mol • In a molecule with several identical bonds (eg
-1

∆Hbe° Average Bond Enthalpy a particular type in one mole of a gaseous molecule to give gaseous So ∆H °
be
(H-O(g)) = 926÷2 = + 463kJ mol -1
water), the different bonds may require different
atoms, under standard conditions energies to break - this is why an average is
needed.
• Calculations using average bond enthalpies can
only give approximate values

You will notice that fractions e.g. ½ have appeared in some of the equations in the table - particularly in those for combustion and formation. This is because we need.to have 1 mole of the substance being burned or
formed (as the definition says), so we have to balance the rest of the equation around this. To do this, you balance the equation as normal, then divide everything by the number in front of the substance being burned/
formed - eg for ∆Hc°(CH3OH (l)): the “normal” equation is 2CH3OH(l) + 3O2(g) → 2CO2(g) + 4H2O(l), but we need 1 mole of CH3OH, so divide by 2 to give CH 3OH(l) + 1½ O2(g) → CO2(g) + 2H2O(l)

2
Energetics I - Hess's Law Chem Factsheet

Hess's Law
Enthalpy of Formation
This law says:-
The general cycle is:
The enthalpy change for a reaction is independent of the route ∆ H reaction
°
Reactants Products
taken to achieve the overall change.

∆Hf° (reactants) ∆Hf ° (products)

This makes it possible to find enthalpy changes that cannot be measured
directly by using data such as bond enthalpies, enthalpies of formation or
Elements
enthalpies of combustion (see Table 1 overleaf).

The diagram shows how Hess’s Law works for changing substance A into e.g. Calculate the standard enthalpy of combustion of methanol, given the
substance X. following enthalpy of formation data:

B route 1 CH3OH(l) ∆Hf° = -201 kJmol-1

CO2(g) ∆Hf° = -394 kJmol-1
A X H2O(l) ∆Hf° = -242 kJmol-1
route 2
First construct the triangle:

The reaction is CH3OH(l) + 1½O2(g) → CO2(s) +2H2O(l)

C D
route 3
We are given enthalpies of formation, so the third "point" is the elements
There are three ways of converting A into X. Hess’s Law says that, in their standard states.
∆H (Route 1) = ∆ ∆H (Route 2) = ∆ ∆H (Route 3)

This is the basis of all calculation work using Hess’s Law. ∆ H reaction
°
CH3OH(l) + 1½O2(g) CO2(s) + 2H2O(l)
Hess's law calculations involve drawing a "cycle". These look like upside-
down triangles. The reaction of interest is written on the top side, with an
arrow from reactants to products, as normal. ∆Hf °(CH3OH)(l) + 1½ × ∆Hf°(O2)(g)
= -201 + 1½ × 0 ∆Hf°(CO2)(s) + 2 × ∆Hf°(H2O)(g)
The third "point" of the triangle depends on what data is given - it will be × -242
= -394 + 2×
one of:
• enthalpies of formation C(s) +2O2(g) + 2H2(g)
• enthalpies of combustion
• bond enthalpies To get from reactants to products we go against the first arrow, so
subtract that enthalpy value. We then go with the second arrow, so add
The direction of the other arrows in the cycle is again determined by the those enthalpy values.
information given; if formation enthalpies are given, for example, these refer
to a reaction starting with the elements, so the arrows start at the elements So ∆Hreaction
° = - (-201) + (-394 + 2× -242) = -677 kJ mol-1
and point away from them. With enthalpies of combustion, on the other
hand, the reaction concerned ends with the combustion products, so the
arrows point towards the combustion products. Exam Hint: Remember:
• The enthalpy of formation is zero for an element
Once the triangle is constructed, the known enthalpies are written on the
appropriate sides. The enthalpy of reaction is found by getting from • If there is more than one molecule involved (eg 2H2O in the
reactants to products "the long way round". If this involves going in the above example), then the enthalpies must be multiplied by
the appropriate number.
direction of an arrow, the appropriate enthalpy values are added; if it
involves going against the direction of an arrow, the enthalpy values are
subtracted.
Now try this question:
The examples following show the three types of cycles required for AS
level. Calculate the standard enthalpy change for the following reaction:

C2H4(g) + H2(g)→ C2H 6(g)

Exam
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C2H4(g) ∆Hf°= +52 kJmol-1
C2H6(g) ∆Hf°= -85 kJmol-1
Exam Hint: You must always check carefully what data you have before
drawing your cycle.
Note in particular that if you are given ∆Hf° [oxide], this is the same as
∆Hc° [element] - in other words, it is combustion data
Answer: -137kJmol-1

3
Energetics I - Hess's Law Chem Factsheet

Enthalpy of Combustion Bond Enthalpies

The general cycle is: The general cycle is:
∆ H reaction
°
∆ H °reaction Products Reactants Products
Reactants

∆Hbe° (reactants) ∆Hbe° (products)

∆Hc° (reactants) ∆Hc° (products)

Gaseous Atoms
Combustion products
e.g. Calculate the enthalpy of reaction for the hydrogenation of ethene under
e.g. Calculate the enthalpy of reaction for the hydrogenation of ethene standard conditions, given the following average bond enthalpy data
under standard conditions,using the following enthalpy of combustion data:
C-C ∆Hbe° = 348 kJmol-1
H2(g) ∆Hc° = -285.8 kJmol-1
C=C ∆Hbe° = 612 kJmol-1
C2H4(g) ∆Hc° = -1409 kJmol-1
C-H ∆Hbe° = 416 kJmol-1
C2H6(g) ∆Hc° = -1560 kJmol-1
H-H ∆Hbe° = 436 kJmol-1
First construct the triangle: The reaction is C2H4(g) + H2(g)→ C2H 6(g)
We are given enthalpies of combustion, so the third "point" is the Since bond enthalpies are given, the triangle will be completed with
combustion products - CO2 and H2O. gaseous atoms. When using bond enthalpies, it is vital to draw out
the structural formulae so all the bonds involved can be seen clearly.
∆ H reaction
°
C2H4(g) + H2(g) C2H6(g)
HH ∆ H reaction
° H H
∆Hc° (C2H4)(g) + ∆Hc° (H2)(g) ∆Hc° (C2H6)(g) C=C + H–H Η–C–C–H
= -285.8 + -1409 = -1560 HH H H

∆Hbe° (C=C) + 4∆Hbe

° (C-H) +∆Hbe° (H-H) 6∆Hbe° (C-H)
2CO2(g) + 3H2O(l) = 612 + 4×416 +436 = 6× 416
To get from reactants to products we go with the first arrow, and against
the second:
2C(g) + 6H(g)
° = (-285.8 + -1409) − (-1560) = -134.8 kJ mol-1
So ∆Hreaction
Following the arrows as before, we obtain:

Now try this question: ° = 612 + 4×416 +436 - (6×416) = -130 kJ mol-1
∆Hreaction

Calculate the standard enthalpy of formation of ethyne (C2H2)(g), Now try this question:
given the following combustion data:
Calculate the standard enthalpy of formation of methane (CH4)(g) given
C(s) ∆Hc° = -394 kJmol-1 the following data:
H2(g) ∆Hc° = -286 kJmol-1 C-H ∆Hbe° = 416 kJmol-1
C2H2(g) ∆Hc° = -1300 kJmol -1
H-H ∆Hbe° = 436 kJmol-1
∆Hat° (C(s)) = +718 kJmol-1
Answer: +226 kJ mol-1 Answer: -74 kJmol-1

The difference between bond dissociation enthalpies and mean bond enthalpies
Bond dissociation enthalpy refers to the energy required to break a specific bond in a specific molecule.

Mean bond enthalpy refers to the average energy required to break a specific bond.

To see the difference, consider methane (CH4). This contains 4 C-H bonds. If we break them one at a time, they will not all require the same energy.
That is because taking a hydrogen away from CH4 is not the same as taking a hydrogen away from CH3. In fact, we will require a different amount
of energy to break each bond, as shown in the diagram below:
H
+425

+480 The mean bond enthalpy for the C-H bond in methane is therefore
H +421 C H
(425 + 421 + 480 + 334)÷ 4 = +415 kJmol-1
+334

4
Energetics I - Hess's Law Chem Factsheet

Practice Questions Answers

1. The following are standard enthalpy of combustion values in kJ mol-1 All answers are in kJ mol-1

C(s): -394 C3H8(g) -2220 1. a) -75

H2(g): -286 CH3OH(l) -715 b) +108
CH4(g) -891 CH3COOC2H5(l) -2246 c) -106
C4H6(g) -2542 d) -251
e) -471
Use these values to calculate the standard enthalpies of formation of:
2. a) -1412
a) CH4(g) b) +178
b) C4H6(g) c) -890
c) C3H8(g) d) -64
d) CH3OH(l) e) -106
e) CH3COOC2H5(l)
3. a) -76
2. The following are standard enthalpy of formation values in kJ mol-1 b) +48
c) -42
CO2(g): -394 CH4(g) -76 d) -200
H2O(l): -286 PbO(s) -219 e) +136
C2H4(g) +52 CO(g) -111
CaO(s) -635 Al2O3(s) -1700
CaCO3(s) -1207 MgO(s) -602
C4H6(g) -2542

Use these values to calculate the following

a) the standard enthalpy of combustion of ethene (C2H4(g))

b) the standard enthalpy change for the reaction:

CaCO3(s) → CaO(s) + CO2(g)

c) the standard enthalpy of combustion of methane (CH4(g))

d) the standard enthalpy change for the reaction:

PbO(s) + CO(g) → Pb(s) + CO2(g)

e) the standard enthalpy change for the reaction:

3Mg(s) +Al2O3(s) → 2Al(s) + 3MgO(s)

3. The following are mean bond enthalpies and standard enthalpies of

atomisation in kJ mol-1:

C−C +348 ∆HAt° (C(s)) +718

C=C +612 ∆HAt° (½H2(g)) +218
C−H +412
C−O +360
O−H +464

Use these values to calculate the standard enthalpy change for the
following reactions:

a) 2C(s) + 3H2(g) → CH3CH3(g)

b) 2C(s) + 2H2(g) → CH2=CH2(g)

Acknowledgements: This Factsheet was researched and written by Sam
Goodman & Kieron Heath.
c) CH2=CH2(g) + H2O (g) → CH3CH2OH Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham,
B18 6NF
Use the data to calculate the standard enthalpy of formation of: ChemistryFactsheets may be copied free of charge by teaching staff or students,
provided that their school is a registered subscriber. No part of these Factsheets
d) CH3OCH3(g) may be reproduced, stored in a retrieval system, or transmitted, in any other
form or by any other means, without the prior permission of the publisher.
e) CH2=CHCH=CH2(g) ISSN 1351-5136

5
 Chem Factsheet
January 2001 Number 09

Equilibrium and Le Châtelier's Principle

To succeed in this topic you need to:- Dynamic Equilibrium
• be able to write balanced chemical equations. Consider a café on a busy afternoon – all 40 seats in the café are occupied
After working through this Factsheet, you will understand:- for the whole afternoon. People are coming and going all the time – some
• the terms ‘reversible’ and ‘irreversible’ reactions. stay for long periods, some only a short while, but the population remains
• the meaning of dynamic equilibrium. constant at 40 people. There is obviously a balance between the number
• the working and effects of dynamic equilibrium. leaving and the number arriving. This state of balance is an equilibrium -
• Le Châtalier's Principle. and it is dynamic because the people are changing. (If the same 40 people
• the effect of change of conditions on position of equilibrium. sat there, it would be static equilibrium).
• the Haber Process (production of ammonia).
• the Contact Process (production of sulphuric acid). We must now look at dynamic equilibrium on the scale of particles. Consider
placing 5cm3 of the volatile liquid bromine into a gas jar. At room
Exam Hint: Questions on the effect of change of conditions on position temperature some of the molecules in the liquid have enough energy to
of equilibrium are common. Knowledge of industrial processes is form vapour, meanwhile some of the molecules in the vapour have too
often tested – so the Chemistry behind them needs to be learnt. little energy so move back into the liquid phase. Hence we have a reversible
candidates must be aware of the need for ‘optimum conditions and reaction.
‘maximum efficiency’ in industry for financial reasons. Br2 (l) ž Br2(g)
On adding liquid bromine to an empty gas jar, there is no equilibrium
initially, as vaporisation is taking place, but no condensation (Fig 1).
Many reactions are irreversible, which means that they move in one
direction only. One common example of this is burning an item - it is easy Fig 1.
to burn something, but you cannot reassemble the original item from the
ashes!

If A and B react completely to form product C, the reaction can be

represented by the equation.
A + B→C (1)

There are also many reactions, which are reversible - that is to say that
they can proceed in both directions. For example, if A and B react to form
C, and C can also decompose to form A and B, this can be represented
bythe equation:

A + B žC (2)

→ means irreversible (or ‘one-way’) reaction After 2 minutes, the brown vapour can be seen clearly, and it is getting
ž means reversible (or ‘two-way’) reaction more dense. The level of the liquid bromine is going down. The rate of
vaporisation is higher than the rate of condensation – so equilibrium has
not been reached (fig 2).
In reaction (1) there is a total conversion of reactants A and B to product C.
In reaction (2) there will always be a mixture of reactants and products as
forward and backward reactions continue constantly. Fig 2.

Reversible reactions naturally reach a point when the rate of the forward
reaction equals the rate of the backward reaction - this is known as equilibrium.

Equilibrium
Equilibrium is a state of balance. There are 2 types of equilibrium:-
1. Dynamic Equilibrium.
2. Static Equilibrium.
In static equilibrium, nothing is happening - no changes are occurring. A
book lying on a table is an example of this! You may have met examples
of this in other subjects. In Chemistry, we always work with dynamic
equilibrium.

1
Equilibrium and Le Châteliers Principle Chem Factsheet

After 30 minutes a thick brown vapour can be seen and liquid is still Examples of equilibria in chemical reactions
present. The vapour is no longer getting denser and the level of the liquid
1. If calcium carbonate is heated in a closed container, at first it
is unchanging (Fig 3).
decomposes to calcium oxide and carbon dioxide faster than the
products can recombine. After a while, the levels of calcium oxide
Fig 3. and carbon dioxide are built up to a level at which the rate of
recombination of these products is equal to the rate of decomposition
of calcium carbonate. The system reaches a state of dynamic
equilibrium:

CaCO3(s) ž CaO(s) + CO2(g)

2. Nitrogen and hydrogen gases combine to form ammonia. Ammonia

decomposes to form nitrogen and hydrogen. In a closed system a
dynamic equilibrium is reached where the rate of combination is
equal to the rate of decomposition:

N2(g) + 3H2(g) ž 2NH3(g)

Effect of Change of Conditions on Position of Equilibrium.

Rate of vaporisation = Rate of condensation Le Châtelier’s Principle

If a system in dynamic equilibrium is subjected to a change, processes
Therefore a dynamic equilibrium has been reached. will occur to counteract this change and to restore equilibrium.

Dynamic equilibrium in reversible reactions

In other words, the equilibrium will "attempt to undo any change" - so if
you increase the pressure, it will "try" to lower it etc. This will alter the
All reversible reactions reach a state of dynamic equilibrium. amount of reactants and products present in the equilibrium mixture, as
explained below. We will consider the effect on the equilibrium position of
changing:-
This means that they reach a state where the amount of products present • concentrations
and the amount of reactants present does not change. • pressure
• temperature
At equilibrium: • catalyst
• Despite there being no apparent change, both forward and Table 1 overleaf summarises the effect of all these changes.
reverse processes continue.
• Rate of forward reaction is equal to rate of reverse reaction.
• Concentrations of reactions and products remain constant. The Effect of Changing Concentrations
Consider the reaction:-
Equilibrium can be attained from either forward or reverse directions. In N2 (g) + 3H2 (g) ž 2NH3 (g)
other words, it does not matter whether you start from the reactants or At equilibrium concentration of reactants and products remain constant.
the products - you will still end up with the same equilibrium position. If more N2 (g) is introduced into the closed system the system tries to
counteract this change and reduce the concentration of N2 (g). It does this
Equilibrium can only be attained in a closed system - this means one in by moving the equilibrium to the right - to "use up" some of the N2 (g) in
which reactants and products are not added or removed. producing more NH3 (g).
If some N2 (g) was removed from the system, then the system would
Position of equilibrium counter this by moving the equilibrium to produce more of it - thus shifting
At equilibrium, we know we will have a mixture of reactants and products the equilibrium to the left.
- but we need to know how much of each there is - this is what is meant by
the position of equilibrium. For example, does the equilibrium mixture The Effect of Changing Pressure
contain more reactant than product, or vice versa? Pressure changes only affect equilibrium when a gas is present.
• Increasing the number of gas molecules present in a closed system will
Remember: The rates of the forward and backward reactions are increase pressure.
equal at equilibrium, but this tells us nothing about the amounts (or • Decreasing the number of gas molecules will decrease pressure.
concentrations) of products and reactants. The concentrations of the If the pressure of a system is increased, then the system counteracts this
reactants and products will be different at equilibrium. by moving the position of equilibrium to reduce it. This means that the
equilibrium moves towards the side with fewer gas molecules. If the
pressure is decreased, then this is counteracted by the equilibrium moving
• If the equilibrium mixture contains more products than reactants, we towards the side with more gas molecules.
say the forward reaction is favoured. eg. Increasing pressure for the reaction
• If it contains more reactants than products, we say the N2 (g) + 3H2 (g) ž 2NH3 (g)
reverse reaction is favoured. will cause equilibrium to move to the right, since there are 2 gas molecules
on that side, but 4 on the left.
The position of the equilibrium is affected by changing conditions such as
temperature, pressure and concentration of reactants/products; the next NB: If the number of gas molecules on each side is the same, then pressure
section explains how this works. changes have no effect.
2
Equilibrium and Le Châteliers Principle Chem Factsheet

The Effects of Changing Temperature Table 1. The effects of various factors on equilibrium position
The energy changes involved in reversible reactions are equal and
Factor Effects on equilibrium postion
opposite. This means that in one direction an exothermic reaction occurs
and in the other an endothermic reaction.
Concentration ↑ conc. of reactants ⇒ moves to right
eg. N2 (g) + 3H2 (g) ž 2NH3 (g) ↓ conc. of reactants ⇒ moves to left
↑ conc. of products ⇒ moves to left
The forward process is exothermic:-
↓ conc. of products ⇒ moves to right
N2 (g) + 3H2 (g) → 2NH3 (g) ∆H° = - 92 kJ mol –1

The reverse process is endothermic:- (remember: move to left means more reactants
2NH3 (g) → N2 (g) + 3H2 (g) ∆H ° = +92 kJ mol-1 move to right means more products)

If the temperature of the system in equilibrium is decreased, the equilibrium ↑ pressure ⇒ moves to side with fewer gas molecules
Pressure
will move to counteract this change by releasing heat energy – hence the
exothermic reaction would be favoured and equilibrium moves to the right. ↓ pressure ⇒ moves to side with more gas molecules

If the temperature was increased, then the system would act to reduce it, § Only affects reactions involving gases
by favouring the endothermic reaction - hence the equilibrium would move § Only has an effect if there are different numbers of
to the left. gas molecules on each side

Temperature ↑ temperature ⇒ moves in the direction of endothermic

The Effects of Catalysts
reaction (∆H positive)
Adding a catalyst will have no effect on the position of equilibrium – but ↓ temperature ⇒ moves in the direction of exothermic
as the rates of both forward and reverse reactions is increased, equilibrium reaction (∆H negative)
may be reached more quickly.
Catalyst No effect on equilibrium position (but equilibrium
attained faster)

Equilibrium in Industry 2. The Contact Process - The Production of Sulphuric Acid (H2SO4)
In many reactions the final yield of a chemical product can vary The raw materials are sulphur dioxide (from sulphur being burned in air,
considerably depending on what conditions are used – as the position of or as a by product of metal extraction from sulphides), oxygen from air
equilibrium can be affected. In industry, reactions and conditions must and water.
be considered carefully to produce the most cost-effective method of
making a chemical. When sulphur dioxide and oxygen react, a dynamic equilibrium is reached:
The following points are important:- 2SO2 (g) + O2 (g) ž 2SO3 (g) ∆H ° = - 197 kJ mol –1
• Availability of chemicals required for process. For this process as high a field of SO3 (g) as possible is required. The
• Equilibrium conditions needed for a good yield. forward reaction will be favoured in the following conditions:-
• A rate of reaction which is fast, yet does not make the reaction • Low temperature (forward reaction is exothermic).
explosive or uncontrollable. • High pressure (forward reaction decreases number of gas molecules).
• Safety of workers and environment.
However a very low temperature makes the reaction rate too low and
1. The Haber Process - The Production of Ammonia (NH3) maintaining high-pressure conditions is both expensive and potentially
N2 (g) + 3H2 (g) ž 2NH3 ∆H ° = - 92 kJ mol-1 dangerous. So the reaction is carried out using:-
Raw materials are cheaply available :– nitrogen from the air, and hydrogen • A temperature of 4500C, where reaction proceeds rapidly and
from natural methane gas (CH4) and water (H2O). production of SO3 is still favoured.
• Presence of vanadium(V) oxide catalysts speeds up reactions – so
For a high field of ammonia, the equilibrium needs to be moved to the equilibrium is reached faster.
right (favouring the forward reaction) as far as possible. This requires:- • 1 atm pressure, low (and so cheap and safe) but yield is still high.
• Low temperature - favouring the exothermic forward reaction. In these conditions, a field of approximately 95% SO3(g) is achieved.
• High pressure - favouring the forward reaction, as equilibrium shifts
to reduce the number of gas molecules present. The SO3(g) must then be converted into sulphuric acid (H2SO4). Direct
combination of SO3(g) with H2O(l) is too dangerous as it is a highly
However, a very low temperature means a low rate of reaction, which exothermic process, and would vaporise any sulphuric acid formed.
would not be cost effective, and maintaining very high-pressure Instead SO3 (g) is reached with existing H2SO4(l) to form oleum , H2S2O7(l),
conditions is both expensive and potentially dangerous. So the process which can be converted into the sulphuric acid product safely.
must use a compromise – the optimum conditions:-
• Temperature is picked so that reaction occurs at a realistic rate but Step 1 SO3(g) + H2SO4(l) → H2S2O7(l)
the final yield of ammonia is not too low. 450oC is used
• An iron catalyst is introduced to increase reaction rates to
equilibrium can be reached quickly. Step 2 H2S2O7(l) + H2O(l) → 2H2SO4(l)
• A high pressure is used, but one which can be maintained safely, and
relatively cheaply. 250 atm is used
This gives a 15% field of ammonia – low but profit making!

3
Equilibrium and Le Châteliers Principle Chem Factsheet

Practice Questions Answers

1. Consider the reaction:- 1. (a) Equilibrium moves to right.
2A (g) + 2B (g) ž C (g) + 2D (g) ∆H ° = + 156 kJ mol –1
In a closed system, what would be the effect on the position of (b) Equilibrium moves to left.
equilibrium if:-
(c) Equilibrium moves to left.
(a) The concentration of A was increased?
(d) Equilibrium moves to right.
(b) The concentration of B was decreased?
(e) Equilibrium moves to right (reducing number of gas molecules)
(c) The concentration of C was increased?
(f) Equilibrium moves to left (exothermic reaction favoured)
(d) The concentration of D was decreased?
(g) No effect on position of equilibrium – but equilibrium may be
(e) The pressure on the system was increased? reached faster as rates of forward and reverse reaction are increased.

(f) The temperature of the system decreased? 2. (a) No effect – there are 2 molar molecules of gas molecules on left
hand side of equation and 2 molar volumes of gas molecules on
(g) A catalyst was introduced? right hand side. In this example an increase or decrease in pressure
cannot be counteracted by a shift in the position of equilibrium.
2. Consider the reaction:- Consequently an increase in pressure has no effect on the position
H2(g) + I2(g) ž 2HI(g) ∆H ° = - 10 kJ mol-1 of equilibrium.
In a closed system, what would be the effect on the position of
equilibrium if:- (b) Equilibrium moves to left (endothermic process favoured)
(a) The pressure on the system was increased?
3. (a) Equilibrium moves to left.
(b) The temperature of the system was increased?
(b) Equilibrium moves to left (reducing the number of gas molecules)
3. Consider the reaction:-
CaCO3(s) ž CaO(s) + CO2(g) 4. Optimum conditions in an industrial process, one the reaction conditions
In a closed system, what would be the effect on the position of which produce the required chemical product most cost-effectively
equilibrium if:- and safely. The following must be considered and a compromise worked out.
(a) An amount of calcium oxide was introduced? • Equilibrium conditions picked to produce high field of product.
• Rate of reaction must be manageable.
(b)The pressure on the system was increased? • Cost of maintaining conditions (pressure, temperature)
• Safety to workers and environment.
4. What is meant by the term ‘optimum condition’ for an industrial
process? 5. (a) A reversible reaction is a chemical reaction that can proceed in both
directions.
5. Explain the following terms:- e.g. A + B ž C

(a) Reversible reaction. (b) Dynamic equilibrium in a reversible reaction is where rate of forward
reaction = rate of reverse reaction.
(b) Dynamic equilibrium. Both forward and reverse reactions continues, but because they
are proceeding at the same rate, the concentrations of reactions and
(c) Le Châteliers Principle. products remains constant - if pressure is increased, position of
equilibrium will move to decrease the number of gas particles (if
possible) to reduce the pressure.

If temperature is increased, position of equilibrium will move so

the endothermic process is favoured and temperature is decreased.

Acknowledgements:
This Factsheet was researched and written by Sam Goodman & Kieron Heath
Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham, B18 6NF
ChemistryFactsheets may be copied free of charge by teaching staff or students,
provided that their school is a registered subscriber.
No part of these Factsheets may be reproduced, stored in a retrieval system, or
transmitted, in any other form or by any other means, without the prior
permission of the publisher. ISSN 1351-5136

4
 Chem Factsheet
January 2001 Number 10

Kinetics I - Rates of Reaction

To succeed in this topic you need to:- Two key facts about rates that must be learnt:
• Understand how particles are arranged in solids, liquids and gases
(kinetic theory)
• Be familiar with energy level diagrams. • Chemical equations (also called the stochiometric equation) tell
• Understand the terms exothermic and endothermic reactions and the us nothing about the rate of a reaction
use of energy level diagrams. • The rate of a reaction has to be discovered by experiment.

After working through this Factsheet you will be able to:-

• Understand what the rate of a reaction is. Collision Theory
• Recall the factors affecting the rate of reaction. Collision theory examines what happens on a molecular scale during
• Explain how reaction rate is affected using collision theory. reactions. We will see how this works by looking at a particular reaction:
• Understand activation energies.
• Draw and understand reaction profiles. Consider the reaction between hydrogen and fluorine gases.
• Understand the role of catalysts.
H2(g) + F2(g) Ô 2HF(g)
Exam Hint: At AS Level, the treatment of reaction rates is qualitative,
in that candidates are required to understand the theory but Before molecules of hydrogen fluoride can be produced:-
calculations are not necessary. Good candidates will use diagrams
and graphs in their answers (similar to those used in this Factsheet). • A collision must occur between a hydrogen molecule and a fluorine
molecule, i.e. they have to meet each other.
• There must be enough energy in that collision to break the H-H bond
Rates of Reaction and the F-F bond, before the H-F bonds can be formed.
The rate of reaction describes the speed at which reactants are converted to
products for a particular reaction. More details on the "enough energy" required - the activation energy of
the reaction - will be found below.
Some reactions are slow and therefore have a low rate e.g. the corrosion of
iron. Other reactions are fast, and therefore have a high rate e.g. the detonation Collision theory criteria for a reaction:
of T.N.T. • A collision takes place
• The collision has sufficient energy to overcome the activation
To measure the progress of a chemical reaction, we find the reaction rate. energy of the reaction.
This is the change in concentration of either the reactants or products with
time.
change in concentration (mol dm-3)
Rate of reaction= Therefore if there are no collisions of reacting particles, or the reacting
change in time (s)
Units of rate are mol dm-3s-1 particles only collide with little energy, no reaction occurs. The energy of
the collision depends on the speed with which the particles were moving -
the higher the speed, the greater the energy.

eg 1. The concentration of product P increases by 1.0 mol dm-3 every To increase the rate of reaction the number of high energy collisions per
second. What it the rate of reaction with respect to P? second must be increased. This tells us how various factors affect rates of
reaction (see Table 1 overleaf).
Rate of reaction = ∆(Concentration)
∆(time) Activation Energy, EA
= 1.0 Consider again the reaction:-
1 H2(g) + F2(g) Ô 2HF(g)
= 1.0 moldm-3s-1
This can also be represented as follows:-
eg 2. Concentration of reactant R decreases by 0.5 moldm-3 every 10 seconds. H F
H F
What is the rate of reaction with respect to R? H H F F
H F H F
bonds broken bonds formed
Rate of reaction = ∆(Concentration) (energy required) (energy released)
∆(time) During a chemical reaction, bonds are first broken, and then others formed.
= 0.5 Consequently, energy is required to break bonds and start this process
10 whether the overall reaction is exothermic (giving out energy) or endothermic
= 0.05 moldm-3s-1 (taking in energy). (See Factsheet 8 - Energetics 1 for more on exothermic
and endothermic reactions). It is therefore reasonable to assume that
particles do not always react when they collide since they may not have
sufficient energy for the necessary bonds to be broken.
1
Kinetics I - Rates of Reaction Chem Factsheet

Table 1. Factors affecting reaction rate

Factor How it affects rate Explanation

Concentration (solutions) Increased concentration/ An increase in the concentration of a solution or the pressure of a gas, results in the
Pressure (gases) pressure increases the rate particles being more crowded, and therefore colliding more times per second.

Surface Area (solids) Increased surface area The smaller the size of the reacting particles, the greater their total surface area. The
increases the rate greater surface area means that a larger area is exposed for reaction, allowing more
collisions per second

Temperature Increased temperature As temperature is increased, the average speed of the reaching particles increases. This
increases the rate results in more collisions per second.

Catalyst Catalysts generally speed up Not only are there more collisions per second, but as particles have a higher energy, or
reactions, but some (called greater percentage of the collisions will involve enough energy for a reaction to occur
inhibitors) slow it down (see activation energy later).

A catalyst alters the rate of reaction without itself being used up or undergoing any
permanent chemical change. It alters the rate by lowering the activation energy by
providing an alternative reaction pathway

Light Increased light intensity Light transfers energy to the particles, so the collisions are more energetic.
increases the rate of some
reactions. Some reactions do
not proceed without UV light.

It is important to relate Activation Energy, EA, to rate of reaction.

A reaction only occurs as the result of a collision between
particles, which possess more than the minimum amount of energy
required, the Activation Energy, EA. • If EA is large, only a small proportion of particles have enough
energy to react on collision , so rate is low.
Activation energies can be used to add more detail to energy level diagrams • If EA is small, a greater fraction of particles possess enough
(see Factsheet 8 – Energetics 1) to produce Reaction Profiles. energy to react on collision, so rate is high.

For an exothermic reaction:-

The Maxwell-Boltzmann Distribution
EA = activation energy
Reactants This shows the distribution of molecular energies (in a gas) at a constant
energy temperature.

∆H =enthalpy of reaction 60% of molecules

in this range
Products
Number of molecules

The reaction profile clearly shows how a minimum amount of energy (EA)
is required before the reaction can proceed, but in this exothermic reaction, Only molecules in
this region can react
we have: Energy released > Energy absorbed.

Energy
For an endothermic reaction:- EA

Points to note about this distribution curve:-

energy

EA • The total number of gas molecules is equal to the area under the curve.
• No molecules have zero energy.
Products • Most of the molecules have energies within a relatively narrow range.
∆H
Reactants Notice that the activation energy is marked on the curve – only the molecules
with energy higher than this can react.
Exam Hint: Questions on this area are popular. You need to learn:

Here the reaction profile shows that a large amount of energy (EA) is
• the shape of the curve
required to start the reaction and only a fraction of this energy is released • how it alters with temperature
as the products are formed. In an endothermic reaction, we have: • how this explains the effect of temperature on rate.
Energy released > Energy absorbed.

2
Kinetics I - Rates of Reaction Chem Factsheet

Now consider the effect on the distribution curve of increasing the Thermodynamic / Kinetic Stability
temperature. The fact that a certain minimum energy (the activation energy, EA) is required
to initiate most reactions is well illustrated by the fact that fuels and
T1 explosives usually require a small input of energy before a very exothermic
reaction takes place.
Number of molecules

Consider the combination of methane:-

Note: T2 > T1
CH4 (g) + 2O2(g) Ô CO2 (g) + 2H2O(g) ∆Hc = -890 kJmol-1
T2
The reaction is very exothermic – therefore the products are for more
thermodynamically stable than the reactants. Despite this, combustion
is not spontaneous – heat is required (i.e. supplying the activation energy)
before the reaction takes place. The reactants are therefore kinetically
stable.
Energy
EA
The reaction profile can be represented by this diagram.

The shape of the distribution curve changes with temperature, as shown

above. As the temperature increases:
EA
• the height of the "peak" decreases energy CH4 (g) + 2O2(g)

• the position of the peak moves to the right ∆H = -890 kJmol -1

• the number of molecules having energy greater than EA increases, whatever
the value of EA. CO2 (g) + 2H2O(g)
The total area under the curve - which gives the total number of molecules
- remains the same.

Temperature increases rate because:

• particles move faster, increasing the number of collisions It is worth noting that the activation energy for this reaction is low, and
once started the temperature at which the reaction occurs is quite high, due
• more particles have energy greater than EA, so more collisions
to the heat energy released. Due to these factors, the rate at which this
produce a reaction reaction proceeds is high.

Exam Hint: Many candidates lose marks by suggesting that all the
particles will be moving at a high speed if the temperature is high -
although the average speed increases, there will still be some particles
with low speeds.

The Role of Catalysts

As mentioned before, catalysts alter the rate of a reaction (usually speeding
it up) without being chemically charged themselves. Catalysts are able to
increase reaction rate because they provide a lower energy route for the
reaction - in effect, catalysts lower the activation energy of a reaction.

EA (uncatalysed)
Reactants
energy

EA (catalysed)

Products

This can be linked with the Maxwell-Boltzmann distribution curve - with

the activation energy lowered, a greater number of molecules passes enough
energy to react on collision, so the rate of reaction is increased.
Number of molecules

Energy
EA (catalysed) E A (uncatalysed)
3
Kinetics I - Rates of Reaction Chem Factsheet

Questions Answers

1. 50cm3 of 4M hydrochloric acid is added to 10g of large marble 1. a) 0.0333 moldm-3s-1

(calcium carbonate) chips. The reactants are at room temperature. b) Reaction rate would increase.
• Molecules moving faster, therefore more collisions per second.
2HCl (aq) + CaCO3 (s) Ô CaCl2(aq) + H2O(l) + CO2(g) • More molecules colliding with energies greater that the activation
energy.
a) If the concentration of the acid halved in the first minute, what was the c) Reaction rate would increase.
average rate of reaction during this minute? • Smaller chips have greater surface area exposed for reaction,
leading to more collisions per second with acid particles.
b) What would happen to the rate of reaction if the temperature of the
acid were increased to 50oC? Use collision theory to explain. d) Stoichiometric equations tell us nothing about the rate of a reaction.

c) What would happen to the rate of reaction if 10g of small marble chips
were used instead of large marble chips? Use collision theory to explain. 2. a) A catalyst is a substance which alters the rate of a reaction, but
remains chemically unchanged at the end of the process.
d) What information about the rate of reaction do we gain from the given
stoichiometric equation? b) Activation energy is the minimum amount of energy required before
colliding reactant particles react.
2. Define the following terms:-
a) Catalyst 3.
b) Activation energy. EA
N2(g) + 3H2 (g)
energy
3. Draw the reaction profile of the reaction.
N2(g) + 3H2 (g)ž 2NH3 (g) ∆H = - 92 kJ mol-1 ∆H = -92 kJ mol-1
Assume the reaction is not spontaneous.
2NH3 (g)

4. The graph below requests the Maxwell-Bolzmann distribution of

molecular energies in a gas at a temperature T1.

4. a) (i)
Number of molecules

T1
Number of molecules

T2
Energy

a) (i) Copy the graph, and on the same axes stretch the curve
which shows the distribution of molecular energies at a lower
temperature T2. Assume T2 is around 30oC higher than T1. Energy

(ii) Use the graphs to explain how the rate of a gas phase reaction
is changed when temperature is decreased. (ii) It should be pointed out that he area under the distribution
curve is equal to the number of molecules present. At a lower
b) For a reaction in the gas phase, explain the effect of a catalyst on:- temperature, the average energy of the molecules is lower, and
(i) The energy distribution of the gas molecules. a smaller fraction of the gas molecules have energy in excess of
the activation energy. The rate of the gas phase reaction will
(ii) The activation energy for the reaction. decrease with decreasing temperature because:-
• Molecules move slower, they collide less frequently.
(iii) The rate of reaction. • Fewer molecules passes the activation energy.
b) (i) A catalyst does not effect the energy distribution of the gas
molecules.
(ii) A catalyst lowers the activation energy for the reaction, as it
provides as lower energy route for the reaction.
(iii) A catalyst will increase the rate of reaction, as a greater fraction
of the molecules will possess the new (lower) activation energy,
so there will be more reactive collisions per second.

Acknowledgements: This Factsheet was researched and written by Sam Goodman and Kieron Heath
Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham, B18 6NF
ChemistryFactsheets may be copied free of charge by teaching staff or students, provided that their school is a registered subscriber.
No part of these Factsheets may be reproduced, stored in a retrieval system, or transmitted, in any other form or by any other means, without the prior permission of the publisher. ISSN 1351-5136

4
 Chem Factsheet
January 2001 Number 11

Oxidation and Reduction 1

To succeed with this topic, you need to:
• understand what is meant by ionic and covalent bonding (covered in Factsheet 5 - Bonding), and recognise which compounds have which type
of bonding
• be able to do simple arithmetic involving negative numbers
• understand how to produce balanced chemical equations

After working through this Factsheet, you will understand:

• the meaning of the term Oxidation Number
• how oxidation numbers are found and used in compounds
• the definitions of oxidation and reduction in terms of electrons and changes in oxidation numbers
• the use of ionic equations to form balanced chemical equations
• the idea of “redox”

Exam Hint: Oxidation numbers and oxidation/reduction are used Worked Examples
throughout all the AS topics. The examination papers assume that 1. What is the ON of lead in PbCl4 ?
you have this knowledge, so when the terms occur in questions you Chlorine is one of the elements with a fixed ON (see Rules) of –1.
are expected to be able to use them. It is common to see questions So Pb + 4 × -1 = 0.
on this topic appear several times (as smaller parts) throughout the paper. So ON of Pb is +4
Success in this topic relies on you learning the rules thoroughly,
and.practising plenty of questions so that you are comfortable with 2. What is the ON of manganese in Mn2O7 ?
the concepts and calculations involved. Oxygen has a constant ON of –2 (see Rules)
2Mn + 7 × -2 = 0
2Mn = 14
Introduction
So ON of Mn is +7
At GCSE level, the term oxidation meant adding oxygen to, or removing
hydrogen from, an element or compound. Reduction was the reverse – i.e.
3. What is the ON of iodine in KIO3 ?
add hydrogen or remove oxygen.
Potassium (+1) and oxygen (-2) have fixed ONs (see Rules).
At AS level oxidation/reduction does not have to involve oxygen or hydrogen So +1 + I + 3 × -2 = 0
- it is much more general. Some candidates are initially confused by this - So ON of I is +5
avoid this confusion by learning the new definitions in this Factsheet.
4. What is the ON of chlorine in Cl2O3 ?
Oxidation Number Cl is not –1 when combined with oxygen (see rules). Oxygen is –2.
2Cl + 3 × -2 = 0
Definition: Oxidation Number (ON) is the number assigned
So ON of Cl is +3
to an atom or ion to describe its relative state of oxidation or reduction.
5. What is the ON of carbon in CO32-?
O has a constant ON of –2, and this is a polyatomic ion with charge –2.
To understand what this means and how it works, we will look at the rules
So C + 3 × -2 = -2
for assigning oxidation numbers, then work through some examples.
So ON of C is +4

Assigning Oxidation Numbers - The Rules

• Elements are zero – eg the ON of H in H2 is 0.
• In ionic compounds, the oxidation number is the same as the charge on the ion. Eg in NaCl, we have the ions Na+ and Cl-.
The oxidation number of Na is therefore +1, and of Cl is –1
• The sum of all the ONs in a compound is zero. Eg in MgCl2, the ON of Mg is +2, and the ON of each Cl is –1.
So overall we have +2 + (2 × -1) = 0
• The sum of all the ONs in a polyatomic ion is the same as the charge on the ion. Eg in CO32-, C has ON +4 and each O has ON –2.
So +4 + (3× -2) = -2
• In covalent compounds, one element must be positive ON and another element must be negative, so overall they equal zero.
• The ONs of the following elements in compounds must be learnt:
o Group 1 (Li, Na, K etc) are +1
o Group 2 (Mg, Ca, Sr etc) are +2
o Al is +3
o O is –2, except in peroxides (such as H2O2) where it is –1
o H is +1 except in metal hydrides (such as NaH) where it is –1
o F is –1
o Cl is –1, except in compounds with O and F

1
Oxidation and Reduction 1 Chem Factsheet

6. What is the ON of iron in Fe(CN)64-? To practise using oxidation numbers to identify oxidation and reduction, go
Since the cyanide ion is CN-, it has an ON of –1 to Question 2 at the end.
So we have Fe + 6 × -1 = -4
So ON of Fe is +2
Disproportionation
Disproportionation occurs when an element is both oxidised and reduced
NB: The use of roman numerals in the names of ionic compounds now also
in the same reaction. You will meet examples of this when you study
gives the oxidation number as well as the charge on the metal ion (cation).
Group VII - the halogens. The reaction below shows one example:
Eg copper (I) oxide is Cu+ with O2- - so giving Cu2O. The copper has a +1
oxidation number.
K I O3 + 5 K I + 6HCl à 3I2 + 3H2O + 6KCl
+1+5 -2 +1-1 +1 -1 0 +1 -2 +1 -1
Being able to calculate oxidation numbers is the basis for all this topic.
Before going on to the rest of this Factsheet, try working through Question
Note that the iodine in KIO3 goes from ON +5 to 0 - so it is reduced.
1 at the back to make sure you are happy with finding oxidation numbers.
The iodine in KI goes from ON -1 to 0 - so it is oxidised.
Oxidation and Reduction
Oxidising and Reducing Agents
Definition:
Oxidation takes place when an element in a reaction Definition:
• Increases its oxidation number An oxidising agent (or oxidant) is the species that causes another
• Loses electrons element to increase in oxidation number (oxidise). It is itself reduced in
Reduction takes place when an element in a reaction the reaction.
• Decreases its oxidation number A reducing agent (or reductant) is the species that causes another
• Gains electrons element to decrease in oxidation number (reduce). It is itself oxidised in
the reaction.
To help you remember this, you can use “REG” – Reduction Electron
Gain. If you remember oxidation is the reverse of reduction, then you'll be Note that the oxidising or reducing agent is the compound involved in the
able to work out that oxidation involves electron loss. reaction - not one of the elements in it.
In fact, oxidation never takes place on its own - nor does reduction. When
one substance is oxidised in a reaction, another one is reduced. A Redox Worked Examples
reaction is one in which both reduction and oxidation take place. For each of the following, identify which species are being oxidised and
reduced as well as the oxidising and reducing agents.
To work out which element is oxidised and which is reduced in a reaction,
we go through these steps: 1. CuO + H2 à H 2O + Cu
1 Write down the chemical equation for the reaction. +2 –2 0 +1 –2 0
2 Go through and work out the oxidation numbers for every element
in the equation. Cu: +2 à 0 is reduced
3 Look for an element that has increased its oxidation number from H: 0 à +1 is oxidised
one side of the equation to the other - it has been oxidised. CuO is the oxidising agent
4 Look for an element that has decreased its oxidation number from H2 is the reducing agent
one side of the equation to the other - it has been reduced.
2. 2Fe + 3Cl2 à 2FeCl3
Worked examples 0 0 +3 –1
For each reaction, work out which element is being oxidised and which
element is being reduced:
Fe: 0 à +3 is oxidised
1. 2Na + Cl2 à 2NaCl Cl: 0 à -1 is reduced
Fe is the reducing agent
2Na + Cl2 à 2NaCl Cl2 is the oxidising agent
0 0 +1 –1
For further practise on identifying oxidising and reducing agents, go to
Notice that we ignore the numbers in front of formulae/symbols in this Question 3 at the end.
exercise.

Na: 0 à +1 is oxidation. Oxidising agents are species that "like" to accept electrons - common
examples are halogen or oxygen atoms (so oxygen is an oxidising agent...).
Cl: 0 à -1 is reduction
Reducing agents are species that "like" to give away electrons - common
2. Mg + CuO à Cu + MgO examples are metal atoms and hydrogen.
0 +2 -2 0 +2 –2
Exam Hint: To help you avoid getting confused about oxidising and
Mg: 0 à +2 is oxidation reducing agents, you should remember that an oxidising agent
Cu: +2 à 0 is reduction oxidises something else - so it is reduced itself.

3. 2FeCl2 + Cl2 à 2FeCl3

+2 –1 0 +3 –1

Fe: +2 à +3 is oxidation
Cl: 0 à -1 is reduction
2
Oxidation and Reduction 1 Chem Factsheet

Ionic and Half Equations

As you have worked through this Factsheet and answered questions 1, 2 Questions
and 3, you have been using the concept of ionic equations 1. a) What is the oxidation number of Cl in the following?
i)HCl ii) HClO3 iii) ClO- iv) Cl2O72- v) ClO4-
b) What is the oxidation number of S in the following?
Eg: 2Na + Cl2 à 2NaCl
i) SO2 ii) Na2S2O3 iii) SO42- iv) SO32- v) SO3
Is: 2Na + Cl2 à 2Na+ + 2Cl- c) What is the oxidation number of N in the following?
0 0 +1 -1 i) N2H4 ii) HNO3 iii) NaNO2 iv) HCN v)N 2O
d) Find the oxidation number of the identified elements in the following:
Writing ionic equations was covered in Factsheet No 3, but we will revisit i) Ba in BaCl2 ii) Li in Li2O iii) P in P2O5
the concept as we write half equations which involve electrons. iv) P in P2O3 v) C in CO vi) I in I2
vii) C in CCl4 viii) I in I- ix) Cr in CrO42-
x) Br in BrO3- xi) H in LiH xii) N in N2O4
If we look at the sodium and chlorine reaction, then the two half-equations xiii) Fe in Fe(CN)63- xiv) Cr in Cr2O72- xv) P in PO43-
are: Na à Na+ + e- xvi) O in H2O2 xvii) Mn in MnO2 xviii) Xe in XeF4
Cl2 à 2Cl- − 2e- xix) N in NH3 xx) N in NaNO3

The rules for including the electrons are: 2. Identify which species is being oxidised and which species is being reduced in
each of the following reactions.

a) Zn + Ag2O à ZnO + 2Ag b) 2K + Br2 à 2KBr

• If you have a + ion, you need to + electron(s) c) PbO2 + 4H+ + Sn2+ à Pb2+ + Sn4+ + 2H2O d) N2 + 3H2 à 2NH3
• If you have a − ion, you need to − electron(s) e) 2K + H2 à 2KH f) Mg + 2HCl àMgCl2 + H2
• the amount of charge tells you how many electrons – g) Sn2+ + 2Fe3+ à Sn4+ + 2Fe2+ h) 2Cu + O2 à 2CuO
eg 2+ gives 2e-, 3− gives 3e- i) KIO3 + 2Na2S2O3 à KIO + 2Na2SO4 j) Cu2+ + Cu à 2Cu+
k) 2S2O32- + I2 à 2I- + S4O62- l) 2FeI2 + I2 à 2FeI3
m) IO3- + 5I- + 6H+ à 3I2 + 3H2O n) I2 + I- à I3-
o) Zn + 2HNO3 à Zn(NO3)2 + H2
We can use two half-equations to produce the normal balanced chemical
equation by balancing the electrons. Multiply each equation by the number 3. Go back to question 2 and identify the oxidising agents and reducing agents
of electrons in the other equation (ignoring signs), then add together. The
4. For each of the following equations
electrons must cancel out.
i) write the two half equations
Na à Na+ + e- ii) identify the half-equations as oxidation or reduction
Cl2 à 2Cl- − 2e-
Multiply the Na equation by the number of electrons in the Cl equation - a) Zn + 2AgCl à ZnCl2 + 2Ag
that's 2. Multiply the Cl equation by the number of electrons in the Na b) PbO2 + 4HCl à PbCl2 + Cl2 + 2H2O
equation - that's 1: c) 2K + H2 à 2KH
d) Mg + 2HCl à MgCl2 + H2
2Na à 2Na+ + 2e- e) PH3 + 2O2 à H3PO4
Cl2 à 2Cl- − 2e-
Add up: Answers
2Na + Cl2 à 2NaCl 1 a) i) –1 ii) +5 iii) +1 iv) +6 v) +7
b) i) +4 ii) +2 iii) +6 iv) +4 v) +6
Half-equations are important in redox work because of the definition of c) i) –2 ii) +5 iii) +3 iv) –5 v) +1
d) i) +2 ii) +1 iii) +5 iv) +3 v) +2
oxidation and reduction in terms of oxidation numbers and electrons
vi) 0 vii) +4 viii) –1 ix) +6 x) +5
(remember REG!) xi) –1 xii) +4 xiii) +3 xiv) +6 xv) +5
xvi) –1 xvii) +4 xviii) +4 xix) –3 xx) +5
Na à Na+ + e- is oxidation because electrons are being lost by Na
0 +1 2. The species first given is oxidised, the second is reduced
a) Zn Ag+ b) K Br2 c) Sn2+ Pb4+
d) H2 N2 e) K H2 f) Mg H+
Cl2 à 2Cl- − 2e- is reduction because electrons are being gained by Cl
g) Sn2+ Fe3+ h) Cu O2 i) I S
0 -1 j) Cu Cu2+ k) S I2 l) Fe2+ I2
m) I- I n) I- I o) Zn H+
Worked example
For Mg + 2AgNO3 à Mg(NO3)2 + 2Ag, write 3. The oxidisingagent is given first, the reducing agent second.
a) the ionic equation a) Ag2O Z n b) Br2 K c) PbO 2 Sn2+
b) the two half-equations, identifying which is oxidation and reduction d) N2 H2 e) H2 K f) HCl Mg
g) Fe3+ Sn2+ h) O2 Cu i) KIO3 Na2SO3
j) IO3- I- k) I2 S2O32- l) I2 FeI2
a) Mg + 2Ag+ + 2NO3- à Mg2+ + 2NO3- + 2Ag m ) Cu 2+
Cu n) I2 I- o) HNO3 Zn

Removing the NO3- which is a spectator ion (does not take part in the 4. a) Zn à Zn2+ + 2e- oxidation Ag+ + e- à Ag reduction
reaction) and so "cancels out" leaves: b) 2Cl- à Cl2 + 2e- oxidation Pb4+ + 2e- à Pb2+ reduction
c) Kà K+ + e- oxidation H2 à 2H- - 2e- reduction
Mg + 2Ag+ à Mg2+ + 2Ag d) Mg à Mg2+ + 2e- oxidation 2H+ + 2e- àH2 reduction
e) P3- à P (+5) + 2e- oxidation O2 + 2e- à 2O2- reduction
b)Mg à Mg2+ + 2e- oxidation, as Mg loses electrons
2Ag+ + 2e- à 2Ag reduction, because Ag+ gains electrons Acknowledgements: This Factsheet was researched and written by Sam Goodman & Kieron Heath. Curriculum
Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham, B18 6NF ChemistryFactsheets may be copied
free of charge by teaching staff or students, provided that their school is a registered subscriber. No part of these
Question 4 provides more practice on half-equations. Factsheets may be reproduced, stored in a retrieval system, or transmitted, in any other form or by any other
means, without the prior permission of the publisher. ISSN 1351-5136
3
 Chem Factsheet
January 2001 Number 12

Periodicity - Trends in Period 3

To succeed in this topic you need to:- The Periodic Table
• understand the work in Factsheet 1 on Atomic Structure In the periodic table, elements are placed in order of increasing atomic
• understand the work in Factsheet 6 on structure of elements and number (fig 1.)
compounds, including how bonding relates to physical properties.
• be able to use the periodic table to locate the positions of elements.
The horizontal rows of elements are called periods
After working through this Factsheet you will:- The vertical columns of elements are called groups
• understand the format of the PeriodicTtable.
• understand the term periodicity.
• understand trends in melting point, boiling, electrical conductivity, Modern periodic law states the properties of elements are a periodic function
ionisation energy, atomic radius and electronegativity across the of their atomic numbers. This means that their properties repeat regularly,
third period. so that elements in the same group tend to show similar chemical and
physical properties.

Exam Hint: Examination questions across the syllabus will You need to know the names of the following groups:
require you to understand the format of the periodic table. Specific
questions are often set on describing and explaining the trends in Group Number Group Name
physical and chemical properties down groups and across the third I Alkali Metals
period. Understanding these trends, and the reasons behind them,
II Alkaline Earth Metals
will also make much of the rest of Chemistry easier to remember.
VII Halogens
0 Noble Gases

Fig 1. The Periodic Table

1 2 3 4 5 6 7 0
Key
1 2
Atomic
1 H Number
He
1 4
3 4
Symbol 5 6 7 8 9 10
Relative
2 Li Be Atomic Mass B C N O F Ne
7 9 11 12 14 16 19 20
11 12 13 14 15 16 17 18
3 Na Mg Al Si P S Cl Ar
23 24 27 28 31 32 35.5 40
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39 40 45 48 51 52 55 56 59 59 63.5 65.4 70 73 75 79 80 84
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85 88 89 91 93 96 (99) 101 103 106 108 112 115 119 122 128 127 131
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
6 Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
133 137 139 178 181 184 186 190 192 195 197 201 204 207 209 (210) (210) (222)
87 88 89 104 105 106
7 Fr Ra Ac Unq Unp Unh
(223) (226) (227) (261) (262) (263)

58 59 60 61 62 63 64 65 66 67 68 69 70 71

Lanthanides Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
140 141 144 (147) 150 152 157 159 163 165 167 169 173 175
90 91 92 93 94 95 96 97 98 99 100 101 102 103
Actinides Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
232 (231) 238 (237) (242) (243) (247) (245) (251) (254) (253) (256) (254) (257)

1
Periodicity - Trends in Period 3 Chem Factsheet

The periodic table is divided into four blocks -s, p, d and f, which tell you Periodic Properties
the electron sub-shell being filled in that block (see Factsheet 1 - Atomic Elements in the third period (Na, Mg, Al, Si, P, S, Cl, Ar) illustrate important
Structure). trends in properties across the periodic table. Table 1 overleaf summarises
Fig 2. s, p, d and f blocks these. When looking at trends in these properties, it is important to be able
to explain them using your knowledge of structures.

Melting and Boiling Points

Rise from Na to Si, then fall to low values.
s p
Strong metallic bonding in Na, Mg and Al cause high melting and boiling
d
points. The strength of the metallic bonding depends on the number of
outer electrons - the greater the number, the stronger the bond. So the
strength of the metallic bond increases from Na to Al, as do the melting
points and boiling points.
f
Si has a giant covalent structure, leading to very high melting and boiling
points.
s-block elements: - the metals in group 1 and 2, so called because their
outer shell contains s electrons. P, S and Cl have simple molecular structures, held together by Van der
e.g. Sodium (Na): Atomic no. 11. Elec. config. 1s22s2 2p63s1 Waals forces only, so melting and boiling points are low.

p-block elements: -the elements from groups 3 to 7, as they have outer Ar exists as atoms, not molecules. This means that the Van der Waals
electrons which are p-electrons. forces are very weak, giving it a very low melting and boiling point.
e.g. Carbon (C): Atomic no. 6. Elec. config. 1s2 2s22p2
Electrical Conductivity
d-block elements: -the metals in the block between groups 2 and 3, Relatively high for metals - Na, Mg and Al (due to the de-localised electrons
known as the transition metals. d-block elements have incomplete d- in metallic structures). Lower in metalloids (Si) and almost negligable for
sub shells. non –metals (P, S, Cl and Ar).
e.g. Titanium (Ti): Atomic no. 22. Elec. config. 1s22s2 2p63s23p64s23d2
First Ionisation Energy
f-block elements: - a block of elements within the transition metals, so The general trend is for an increase across a period, due to the increasing
called because electrons are being added into the f-subshell in these nuclear change making it more difficult to remove an electron.
elements. e.g. Cerium (Ce) Atomic no. 58.
Elec. config. 1s22s2 2p63s23p64s23d104s65s24d105p66s24f2 Some anomalies occur; these are due to:
• full sub-shell stability - it is comparatively harder to remove an electron
Metals, Non-metals and Metalloids.
from a full sub-shell
The majority of elements are metals; these are on the left hand side of the
periodic table. All of the s, d and f block are metals. • half-shell stability - it is comparatively harder to remove an electron
from a half-empty p sub-shell
The non-metals are found in the top-right corner of the periodic table; they
• p-electrons being easier to remove than s-electrons, due to being at a
are all in the p-block.
higher energy level.
Along the border between the metals and non-metals there are several This produces the pattern shown below (fig 4) (see Factsheet 1 - Atomic
elements which are difficult to place, so the name metalloid or semi- Structure for more details):
metal is used. Fig 3 shows these elements. Fig 4. Trends in first ionisation energy across period 3
Fig 3. Metals, metalloids and non-metals First p electron
non-metals added Ar
metalloids
123456
3 4 5 6 7
123456 0 Cl
energy

123456
123456
B 123
C N O F Ne
P S
metals
123
Al1234567
123
S i P S Cl Ar Mg
Si
Al Half-shell
1234567
Ge As 1234
Ga1234567 Se Br Kr Na stability
s 1234
In Sn Sb 1234
Te I Xe
d T l Pb Bi P o A t Rn Atomic Radius
Decreases across the period

f If we move from one element to the next across the third period, electrons
are being added to the same third shell at about the same distance from the
nucleus, whilst protons are being added to the nucleus. The increased
To categorise elements, the following criteria are used:- nuclear change pulls the electrons in the third shell closer to it, hence
Metals • Good conductors of electricity. atomic radii decrease.
• Form basic oxides.
Metalloids • Poor conductors of electricity Electronegativity
• Form amphoteric oxides This is the ability to attract electrons within a bond (see Factsheet 5 -
Non-Metals • Virtually non-conductors of electricity (insulators) Bonding). As we move across the period, electronegativity increases to Cl.
• Form acidic oxides. Ar has little or no electronegativity since as a noble gas, it has only completed
shells of electrons and so does not form bonds at all readily.
2
Periodicity - Trends in Period 3 Chem Factsheet

Table 1. Physical properties across Period 3

Group 1 2 3 4 5 6 7 0

Element Sodium Magnesium Aluminium Silicon Phosphorus Sulphur Chlorine Argon

Symbol Na Mg Al Si P S Cl Ar

Character metallic metallic metallic metalloid non-metallic non-metallic non-metallic non-metal

Structure giant metallic giant metallic giant metallic giant covalent molecular molecular molecular atomic

Melting Point (K) 371 922 933 1683 37 392 172 84

Boiling Point (K) 1156 1380 2740 2628 553 718 238 87

Conductance × 1000 10 16 38 4 10-16 10-22 - -

(ohm-1cm-4)
1st Ionisation Energy 496 738 578 789 1012 1000 1215 1521
(kJmol-1)
Atomic covalent 0.156 0.136 0.125 0.117 0.110 0.104 0.099 0.095
radius (nm)

Practice Questions Answers

1. The Periodic Table arranges the different elements in a pattern according 1. a) (i) Increasing atomic number / number of protons
to the structure of their atoms and the way in which they behave. (ii) Groups (iii) Periods
b) (i) Alkali metals (ii) Alkaline earth metals (iii) Halogens
a) (i) In what order are the elements arranged in the Periodic Table? (iv) Noble gases / inert gases
(ii) What name is given to the vertical columns? c) Transition metals / d-block elements
(iii) What name is given to the horizontal rows? d) (i) Group number indicates the number of electrons found in an
atom’s outer shell (1)
b) What names are given to the following groups in the Periodic Table? (ii) In a period, atoms of all elements have the same electron core
(i) Group 1 (ii) Group 2 (iii) Group 7 (iv) Group 0 e) (i) Trend Decreases along the period (1)
Cause Increasing nuclear charge / number of protons in
c) What name is given to the block of elements found between Groups the nucleus
2 and 3? (ii) Trends Increase Na → Si (1)
Decrease P → Ar (1)
d) What is the connection between the electronic configuration of an
element and: Causes Na → Si stronger bonding (1)
(i) the group in which the element is found? P → Ar weaker van der Waals’ forces (1)
(ii) the period in which the element is found? (iii) Trend Increases along the period (1)
Cause Increasing nuclear charge (1)
e) Periodicity is the study of the patterns of properties of the elements
found in the Periodic Table. State the general trends in the variation 2. a) (i) A measure of the power of an atom of that element, within a
of the following properties of the elements Na → Ar across Period 3. molecule (1) to attract towards itself (1) the electrons of a
In each case state the major factor which influences this change. covalent bond (1)
(i) Atomic radius (ii) Melting point (iii) First ionisation energy (ii) Electronegativities increase (1)because the tendency of atoms to
gain electrons increases (1) (Or electron affinities increase (1))
due to an increase in nuclear charge (1) and decreased atomic
2. a) (i) Define the electronegativity of an element.
radius (½) with no increase in shielding (½) Simultaneously, the
(ii) State and explain how the electronegativities of elements vary
tendency of atoms to lose electrons decreases (1)
across a period of the Periodic Table.
(Or ionisation energies increase (1))
b) State how the elements of Period 3 (Na – Ar) vary with regard to 3. a) (i) Type of bonding Metallic bonding (1)
their tendency to undergo ionic bonding and covalent bonding. Description Lattice of cations (1)
3. Electrical conductivity is measured in units called siemens per metre, Sm-1. with delocalised valency electrons / flux
Values for the elements in Period 3 are given in the table below. (or ‘sea’) of electrons (1)
(ii) Electrons (1) can move under an applied p.d. (1)throughout
Element Na Mg Al Si P S Cl Ar the entire metal (1)
(iii) Number of outer shell electrons increases from 1 to 2 to 3 (1)
Electrical 0.218 0.224 0.382 10-10 10-17 10-23 - - Hence there are more free / delocalised / mobile electrons (1)
conductivity
/ 108 S m-1
Acknowledgements;
a) (i) State and describe the type of bonding present in Na, Mg and Al. This Factsheet was researched and written by Sam Goodman and Kieron Heath.
Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham, B18 6NF
(ii) Explain why the electrical conductivity of these elements is ChemistryFactsheets may be copied free of charge by teaching staff or students, provided that their school is
relatively high. a registered subscriber.
(iii) Why does electrical conductivity increase from Na to Mg to Al? No part of these Factsheets may be reproduced, stored in a retrieval system, or transmitted, in any other form
or by any other means, without the prior permission of the publisher. ISSN 1351-5136

3
 Chem Factsheet
April 2001 Number 13

To succeed with this topic you need to:

Groups 1 & 2
§ Understand terms describing physical properties of chemicals (e.g. melting point, density etc)
§ Understand the use of chemical formulae in balanced equations (Factsheet 03 Moles and Equations)
§ Understand atomic structure, electronic configuration and the concept of atomic and ionic radii (Factsheet 01 Atomic Structure)

After working through this Factsheet you will be able to:

§ Recall characteristic physical properties of group 1 and 2 elements Exam Hint - Candidates will need to understand
§ Understand trends in ionisation energies and reactivity within the groups trends in the elements and compounds of groups 1
§ Recall relevant chemical reactions of the elements and 2. Importantly, you must be able to explain these
§ Recall characteristic flame colours trends concisely. Any explanation must be backed
up with evidence, so equations for chemical reactions
§ Recall trends in solubilities of sulphates and hydroxides of groups 1 and 2 must be learnt.
§ Recall trends in thermal stabilities of nitrates and carbonates of groups 1 and 2.

Characteristic physical properties

Group 1

Element Symbol Melting Point oC Boiling Point oC Density gcm-3 Atomic radius nm Ionic radius nm

Lithium Li 181 1330 0.53 0.15 0.06

Sodium Na 98 890 0.97 0.19 0.10

Potassium K 63 774 0.86 0.23 0.13

Rubidium Rb 39 688 1.53 0.24 0.15

Caesium Cs 29 690 1.88 0.26 0.17

Group 2

Element Symbol Melting Point oC Boiling Point oC Density gcm-3 Atomic radius nm Ionic radius nm

Beryllium Be 1278 2477 1.85 0.11 0.03

Magnesium Mg 649 1110 1.74 0.16 0.07

Calcium Ca 839 1487 1.54 0.20 0.10

Strontium Sr 769 1380 2.60 0.21 0.11

Barium Ba 725 1640 3.57 0.22 0.13

Members of groups 1 and 2 are all metals. They are silver in colour and Melting Points & Boiling Points
tarnish in air. Many of the characteristic trends in their physical properties • As group 1 or 2 is descended, melting and boiling points decrease, as
can be explained by the fact that they show weak metallic bonding (See the strength of metallic bonding in the elements decreases.
Factsheet 5). • As atoms/ions get larger, the distance between the delocalized electrons
and nucleii increases, so metallic bonding becomes weaker.
Group 1 metals have only 1 outer valence shell electron per atom – so only • Notice melting and boiling points are higher in group 2, due to stronger
1 electron per atom is donated into the delocalised electron system. metallic bonding as 2 electrons per atom are donated into the delocalised
system.
Group 2 metals have 2 outer valence shell electrons and so have slightly
stronger metallic bonding – this is represented in their physical properties. Density
• In general the density rises as group 1 or 2 is descended, due to the fact
Exam Hint - Examiners may require you to know the trends in the that the mass of the atoms increases more rapidly than their size with
physical properties and the explanation behind them. increasing atomic number.
• Notice Group 2 metals are denser than group 1 – due to closer packing
of ions, due to stronger bonding.
1
Groups 1 & 2 Chem Factsheet

Atomic/ionic radii Chemical properties and reactions of groups 1 and 2

• Increase down groups as number of shells of electrons increase
Li Be
Na Mg
Comparison with other metals Reactivity Reactivity
K Ca
The physical properties of the group 1 and 2 elements differ from those of increases increases
Rb Sr
most metals in several ways
Cs Ba
• They are soft and can be cut with a knife
• Their melting and boiling temperatures are low The lower the ionisation energies, the easier to remove electrons are, and
• They have low densities (Li, Na and K are less dense than water, and hence the more reactive the metals are. Hence reactivity increases down
so float on it) both groups, and group 1 is more reactive than group 2.

Flame Colours Group 1 and 2 metals form ionic compounds (with the exception of
The electrons within the atoms/ions of group 1 or 2 metals can be excited beryllium) and the only oxidation states shown are:
to higher energy levels (Factsheet 01 – Atomic Structure) by heat energy. Group 1: +1
When these excited electrons return to their lower, ground state, energy Group 2: +2
levels, they emit energy – often with a wavelength in the visible light region
- hence each group 1 or 2 metal burns with a characteristic flame colour. Group 1 metals with oxygen
These characteristic flame colours are also shown by the compounds of Group 1 metals react with oxygen vigorously. All except Li form a variety
of oxides:
Flame Colours _
Simple oxides containing the O2 ion (this is the only oxide formed by Li)
Group 1 Group 2
Li – carmine red Mg – white e.g. 4Na(s) + O2(g) → Na2O(s)
Na – yellow Ca – brick red
_
K – lilac Sr – crimson red Peroxides containing the O22 ion (formed in excess oxygen by all of
Ba – apple green group 1 except Li)

e.g. 2Na(s) + O2(g) → Na2O2(s)

these elements – hence they can be used in chemical analysis (i.e. _
identification of salts) Superoxides containg the radical anion O2 (formed by K, Rb, Cs in
excess oxygen). NB: these are coloured compounds
Ionisation Energies e.g. K(s) + O2(g) → KO2(s)
In a large atom (e.g. Cs) there is:
Group 1
Exam Hint - You will be expected to know the equations for the formation
Li of oxides for Group1
Na As group 1 is descended, ionisation energies decrease
K
Rb Group 2 metals with oxygen
_
Cs Vigorous reactions forming simple metal oxides M2+ O2
§ Increased distance between nucleus and outer shell electron e.g. 2Mg(s) + O2(g) → 2MgO(s)
§ Increased “shielding effect” as more electrons exist between nucleus
and outer electron Reactions of Groups 1 and 2 metals with water
Hence, the larger the atom, the easier it is to remove electrons. Group 1 and most Group 2 metals react with water to produce metal
hydroxides and hydrogen gas.
Note: Second ionisation energy will be much greater than first, as electrons
from a different, lower energy level would be removed. e.g. Group 1: 2Na(s) + 2H2O(l) → 2NaOH(aq) + H2(g)
Again, increasing atomic size leads to decreasing ionisation energies.
Group 2: Ca(s) + 2H2O(l) → Ca(OH)2(aq) + H2(g)
Group 2
Reactivity increases as each group is descended, and group 1 metals react
Be
more vigorously than group 2
Mg
Ca As group 2 is descended, ionisation energies decrease
Note: Group 1 metals are stored in oil to stop them reacting with water
Sr
vapour in the air.
Ba

The ionisation energies of group 2 are higher than for group 1, as nuclear Note: Beryllium does not react with water. Magnesium only reacts very
charge is greater. Compare sodium and magnesium – sodium has a nuclear slowly with cold water, but reacts rapidly with steam to form the oxide
charge of +11, whereas magnesium has a nuclear charge of +12. Magnesium and hydrogen
is a slightly smaller atom than sodium, hence the attraction for the outer
e.g. Mg(s) + H2O(g) → MgO(s) + H2(g)
electrons in magnesium is larger, so they are more difficult to remove.

Note: In group 2 there is only a slight increase in ionisation energies from

first IE to second IE, but there is a large jump to the third IE as this would
involve removing electrons from a lower energy level.

2
Groups 1 & 2 Chem Factsheet

Reactions of Groups 1 and 2 with chlorine gas Solubilities of Group 2 sulphates

Groups 1 and 2 react when heated in chlorine gas to give the chloride:
MgSO4 soluble
e.g. Group 1 2K(s) + Cl2(g) → 2KCl(s)
CaSO4 As the group is descended,
Group 2 Mg(s) + Cl2(g) →MgCl2(s) solubility decreases
SrSO4
All group 1 and 2 chlorides are ionic, except for BeCl2 which is covalent –
it forms a polymer, using dative bonds to link the linear BeCl2 molecules BaSO4 insoluble

Cl Cl Cl Cl Cl
Exam Hint - You need to learn the above solubility trends, but do
Be Be Be Be Be Be not need to be able to explain them at AS level

Cl Cl Cl Cl Cl

Now we shall look at some of the reactions of the oxides of the Group 1 Trends in thermal stabilities of nitrates and carbonates
and 2 metals Thermal decomposition is more likely in those compounds if the metal
_ _
cation polarises the anion (CO32 or NO3 ).
Reactions of Group 1 and 2 oxides with water Consequently:
All of the simple metal oxides (containing the O2- anion) react with water • Group 2 compounds (+2 charge on cation) are more likely to decompose
to form the metal hydroxide than group 1 compounds (+1 charge on cation)
• The smaller the cation (near the top of the group) the more likely they
_ _
Ionic equation: O2 (s) + H2O(l) → 2OH (aq) are to decompose.

e.g. Group 1 Na2O(s) + H2O(l) → 2NaOH(aq) Nitrates

Group 1 nitrates (except lithium nitrate) decompose to give the metal
Group 2 CaO(s) + H2O(l) → Ca(OH)2(aq)
nitrite and oxygen gas
Note: MgO is insoluble in water, so will not react in this fashion e.g. 2KNO3(s) → 2KNO2(s) + O2(g)
_
Peroxides (containing the O22 anion) react with water to form the metal Group 2 nitrates (and lithium nitrate) decompose to give the metal oxide,
hydroxide and hydrogen peroxide: the brown gas nitrogen dioxide and oxygen:

2Ca(NO3)2(s) → 2CaO(s) + 4NO2(g) + O2(g)

_ _
Ionic equation: O22 + 2H2O(l) → 2OH (aq) + H2O2(aq) e.g.

e.g. Na2O2(s) + 2H2O(l) → 2NaOH(aq) + H2O2(aq) 4LiNO3(s) → 2Li2O(s) + 4NO2(g) + O2(g)

_
Superoxides (containing the O2 anion) react with water to form the metal Thermal stability increases down both groups
hydroxide, hydrogen peroxide and oxygen gas.
_ _ Carbonates
Ionic equation: 2O2 (s) + 2H2O(l) → 2OH + H2O2(aq) + O2(g) Group 1 carbonates will not decompose on heating, except lithium
carbonate:
e.g. KO2(s) + 2H2O(l) → 2KOH(aq) + H2O2(aq) + O2(g)
Li2CO3 (s) → Li2O(s) + CO2(g)
_
Note: all solutions formed will be alkaline, as the OH ion is produced in Group 2 carbonates all decompose (except for barium carbonate, which
each case. is stable) to form the metal oxide and carbon dioxide gas

The reactions are of the anion, so the metal cation is irrelevant (unless e.g. CaCO3(s) → CaO(s) + CO2(g)
Mg2+, as MgO is insoluble)
Thermal stability increases down both groups
Reactions of Group 1 and 2 oxides with acids
The metal oxides are basic compounds, so they will all react will acids to
form a salt and water

e.g. Group 1 Na2O(s) + H2SO4(aq) → Na2SO4(aq) + H2O(l)

Group 2 MgO(s) + 2HCl(aq) →MgCl2(aq) + H2O(l)

Solubilities of Group 2 hydroxides

Mg(OH)2 insoluble

Ca(OH)2 As the group is descended,

solubility increases
Sr(OH)2

Ba(OH)2 soluble

3
Groups 1 & 2 Chem Factsheet

Practice Questions Answers

1. Explain why both group 1 and 2 elements have low melting points for 1. Group 1 and 2 metals both have relatively weak metallic bonding.
metals, and why group 1 melting points are lower than those of group 2. Metallic bonding in group 1 is weaker than that in group 2, as group 1
metals only donate 1 electron per atom into the delocalised sea of
2. Describe a test which would distinguish sodium chloride from potassium electrons, whereas group 2 metals donate 2 outer valence shell electrons
chloride. per atom.

3. Explain the trend in first ionisation energies as group 1 is descended. 2. Flame test: sodium chloride gives a golden yellow flame, and potassium
chloride gives a lilac flame.
4. Write balanced equations for the following reactions:
(a) strontium with oxygen 3. As group 1 is descended, first ionisation energies decrease, due to
increased distance between the nucleus and outer electron and increased
(b) potassium with water shielding.

(c) magnesium with steam 4. (a) 2Sr(s) + O2(g) →2SrO(s)

(d) sodium with chlorine (b) 2K(s) + 2H2O(l) →2KOH(aq) + H2(g)

5. Which is the only group 2 metal not to form ionic compounds? (c) Mg(s) + H2O(g) → MgO(s) + H2(g)

6. State which of each pair of compounds is more soluble: (d) 2Na(s) + Cl2(g) → 2NaCl(s)
(a) magnesium hydroxide or barium hydroxide
5. Beryllium
(b) calcium sulphate or strontium sulphate
6. (a) barium hydroxide
7. Give two reasons as to why rubidium nitrate is more thermally stable
than magnesium nitrate (b) calcium sulphate

8. Write balanced equations for the following thermal decompositions: 7. larger cation, so less polarising power
(a) sodium nitrate lower cation charge, so less polarising power

(b) magnesium nitrate 8. (a) 2NaNO3(s) → 2NaNO2(s) + O2(g)

(c) magnesium carbonate (b) 2Mg(NO3)2 → 2MgO(s) + 4NO2 (g)+ O2(g)

(c) MgCO3(s) →MgO(s) + CO2(g)

Acknowledgements:
This Factsheet was researched and written by Sam Goodman & Kieron Heath
Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham, B18 6NF
ChemistryFactsheets may be copied free of charge by teaching staff or students,
provided that their school is a registered subscriber.
No part of these Factsheets may be reproduced, stored in a retrieval system, or
transmitted, in any other form or by any other means, without the prior
permission of the publisher. ISSN 1351-5136

4
 Chem Factsheet
April 2001 Number 14

Group 7
To succeed with this topic, you need to: Reactivity of the Halogens
• understand terms describing physical properties of chemicals The halogens do not exist naturally in their elemental form because they
• understand the use of chemical formulae in balanced equations are so reactive – very strong oxidising agents.
(see Factsheet 03 Moles and equations)
• understand practical terms such as precipitate, solution and the F
Cl reactivity decreases as
use of universal indicator
group is descended
• understand atomic structure (see Factsheet 01 Atomic structure) Br
I
After working through this Factsheet, you will be able to: Fluorine is the most reactive as it is the smallest atom. It attracts electrons
• recall physical properties of group 7 into a low energy shell which is close to the nucleus with little shielding.
• recall simple chemical tests for the elements
• recall identification tests for halide ions
• have some understanding of reactions of different halogen Tests for the halogens
compounds Chlorine – a pungent, yellow/green gas, toxic.
• give examples of disproportionation a) Turns damp litmus paper red, then bleaches it white.
• recall the relative oxidising strengths of the elements Cl2(g) + H2O(l) → HCl(aq) + HClO(aq)
• have some understanding of the chlor-alkali industry and the hypochlorous acid (bleach)
extraction of bromine from sea water
b) Bubble chlorine gas through colourless potassium bromide solution
The halogens are the most reactive group of non-metals. They are strong and bromine (orange/brown) is liberated.
oxidising agents, as they require only 1 electron to complete their octet of
electrons. Cl2(g) + 2KBr(aq) → 2KCl(aq) + Br2(aq)
orange/brown
Trends within the group Bromine
• melting /boiling points increase as group is descended A pungent, red/brown volatile liquid, gives off orange/brown toxic fumes in air.
• atomic radii increase as group is descended a) Bromine will bleach damp litmus paper, but much slower than chlorine
• ionic radii increase as group is descended b) Add bromine to water, then add a little dilute sodium hydroxide solution.
The orange/brown aqueous solution of bromine becomes colourless on
Note that ionic radii are larger than atomic radii, as in each case an electron addition of the alkali
is added to the atom to form the –1 halide ion, and repulsions increase as an
extra electron is added. Iodine
A shiny dark grey solid which sublimes on heating, forming pungent,
. violet toxic fumes.
Exam Hint - Questions on the reactions of the halogens and their heat
I2(s) I2(g)
compounds are popular, as they cover redox reactions, practical
tests and industrial chemistry, Do not just learn the equations, but dark grey, dagger like crystals violet fumes
also the context of each chemical reaction. Iodine turns starch solution from colourless to blue/black

Solubility of the halogens

Exam Hint - You do not need to know the actual values of boiling All halogens except fluorine dissolve slightly in water and discolour it.
points and atomic/ionic radi, but you must learn the trends they show. Fluorine is such a powerful oxidising agent that it converts water to oxygen.
Solubility decreases down the group.

Table 1. The Halogens

Element State at RTP Boiling point (oC) Atomic radius (pm) Ionic radius (pm)
Symbol Name Formula

F Fluorine F2 pale yellow gas -188.0 72 136

Cl Chlorine Cl2 yellow/green gas -34.7 99 181

Br Bromine Br2 brown volatile liquid 58.8 114 195

I Iodine I2 dark grey shiny solid 184.0 133 216

1
Group 7 Chem Factsheet

The range of halogen compounds The Halides - Oxidation Number –1

The halogens have oxidation numbers (see Factsheet 11) which range from All metal halides are soluble in water, except for silver and lead halides.
–1 in simple halides to +7 in compounds such as potassium iodate (VII) Precipitates of these halides are produced when aqueous solutions of halides
(KIO4), though some oxidation states are more common than others. are treated with Ag+(aq) or Pb2+(aq)
_
The halogens are able to have such a wide range of oxidation numbers e.g. Ag+(aq) + Cl (aq) → AgCl(s)
because they have the ability to “de-pair” some of their electrons, making
them available for bonding. The action of silver nitrate solution followed by ammonia solution (or
sunlight) can be used as a test for halide ions (Table 2):
e.g. Iodine
5p 5d Table 2. Tests for Halide ions
5s
F- Cl- Br- I

Addition of No White Cream Yellow

With only one unpaired electron, it can form only one covalent bond (e.g. ICl) AgNO3(aq) reaction precipitate precipitate precipitate
But if one electron is promoted to the 5d orbital:
Addition of Soluble Soluble nsoluble Insoluble
5s 5p 5d dilute NH3(aq)

Addition of Soluble Soluble Soluble Insoluble

conc NH3(aq)
Now with three unpaired electrons, we can form three covalent bonds (e.g.
Effect of No effect White → Cream → Remains
ICl3), and so on. Note that fluorine canot do this, as there is no 2d orbital.
sunlight on purple grey green/yellow yellow
silver halide
Hydrogen Halides
These are formed by reacting the halogen with hydrogen:
Reactions of halide salts with concentrated sulphuric acid
H2(g) + X2(g) → 2HX(g) The reaction of each halide salt with concentrated H 2SO4 varies depending
on how easily the halide ion is oxidised.
All are colourless gases at room temperature, and give cloudy white fumes
_ _
in moist air. Due to the size of the anions, I is the easiest halide ion to oxidise, and F the
most difficult, as it is the most stable.
As expected from the order of reactivity, the order of bond strengths is:
H – F > H – Cl > H – Br > H – I If concentrated sulphuric acid is added to solid halide salts, the first product
is the hydrogen halide:
This is also the order of thermal stability.
_ _
Hal (s) + H2SO4(l) → Hhal(g) + HSO4 (s)
The hydrogen halides are covalent substances, but are all highly soluble in
water. They are soluble because they are polar, and so dissociate easily in But concentrated sulphuric acid is also an oxidising agent, and is powerful
water, acting as proton donors (i.e. acids): enough to oxidise HBr and HI to Br2 and I2 (but does not affect HCl and HF)
_
HX(aq) + H2O(l) ž H3O+ (aq) + X (aq) 2HBr(g) + H2SO4(l) → Br2(l) + 2H2O(l) + SO2(g)
_
HI has the weakest bond, due to I being the largest anion. Therefore HI 2HI(g) + H2SO4(l) → I2(s) + 2H2O(l) + SO2(g)
dissociates the most easily, so HI is the strongest acid.
Solid halide
Acidic strength: HF << HCl < HBr < HI
Fluoride Chloride Bromide Iodide
Hydrogen fluoride is a much weaker acid than the rest due to the HF bond Addition HF(g) HCl(g) HBr(g) + Br2(g) HI(g) + I2(g)
being so strong and the presence of hydrogen bonding which discourages of conc H2SO4 produced produced produced produced
dissociation further.

Despite being a weak acid (i.e. donating few H+ ions into solution) HF is a
Oxidation Number +1 eg sodium chlorate (I), NaClO
very corrosive chemical which attacks glass, so solutions of HF are stored
The reactions of sodium chlorate (I) are those of an oxidising agent, for
in polythene bottles.
example it will oxidise pale green Fe2+(aq) ions to yellow brown Fe3+(aq)
_
ions, or I (aq) to I2(aq)
Generally the boiling points of hydrogen halides increased down the group,
as the increase in size of the molecules leads to increased Van der Waals
Sodium chlorate (I) is common household bleach, and is formed from the
forces. However, HF is an exception - it has a much higher boiling point
reaction between chlorine and sodium hydroxide at 15oC
than the other hydrogen halides. This is due to hydrogen bonding (see
Factsheet 05). 15 oC
2NaOH(aq) + Cl2(aq) NaOCl(aq) + NaCl(aq) + H2O(l)
0 +1 -1
Hydrogen halide HF HCl HBr HI
Boiling point +20 -85 -67 -35 The oxidation state of chlorine has been indicated on the above equation –
notice how the element chlorine is simultaneously oxidised and reduced –
so has undergone disproportionation (Factsheet 11)

2
Group 7 Chem Factsheet

If the reaction is carried out at a higher temperature (70o – 80o C) further Practice Questions
disproportionation occurs, of the chlorate (I) ion. 1. Describe the trends in a) reactivity b) boiling point and c) ionic radius
o
as group 7 is descended.
_ 70 C _
3ClO (aq) 2Cl-(aq) + ClO3 (aq)
+1 -1 +5 2. Explain why the ionic radius of fluorine is larger that its atomic radius.

Oxidation number +5 e.g. potassium chlorate(V), KClO3 3. Describe the standard test for chlorine gas.
Decompose on heating, releasing O2(g)
4. What is observed when iodine crystals are heated?
2KClO3(s) → 2KCl(s) + 3O2(g)
5. Explain why the hydrogen halides, as covalent compounds, dissolve in
These substances act as oxidising agents (they oxidise Fe 2+ (aq) ions and water to give solutions of low pH values.
_
I (aq) ions)
6. An unknown halide salt is dissolved in water, and the addition of silver
Oxidising abilities of the halogens nitrate to this solution produces a cream precipitate which dissolves in
The more reactive the halogen, the stronger an oxidising agent it is concentrated ammonia solution, but not dilute ammonia solution. Which
i.e. oxidising strength F > Cl > Br > I halide ion is present?

If a halogen acts as an oxidising agent, it is reduced to the halide ion 7. When chlorine reacts with the alkali sodium hydroxide,a
_ _
X2 + 2e → 2X disproportionation reaction occurs. What is meant by this?

8. Will
Any halogen will oxidise the ions of those halogens below it in group 7 a) chlorine oxidise potassium iodide solution?
e.g. Cl2(g) + 2KBr(aq) → 2KCl(aq) + Br2(aq) b) iodine oxidise sodium bromide solution?
But obviously bromine will not oxidise the chloride ion.
Answers
1. (a) decreases
Manufacture of bromine (b) increases
The world’s supply of bromine is obtained from sea water, which contains (c) increases
a relatively low concentration of bromides such as those of sodium,
potassium and magnesium. 2. The formation of the fluoride ion F- involves the addition of an electron
to the fluorine atom, causing repulsions to increase, increasing the size
Although the process is slightly more complex, the reaction is essentially of the particle.
a simple redox process, using chlorine to oxidise the bromide ions to bromine:
3. In a fume cupboard, test the gas with moist litmus paper. Chlorine
_ _
2Br (aq) + Cl2(g) → Br2(aq) + 2Cl (aq) turns moist litmus (or universal indicator) paper red, then bleaches it
white.
Uses of chlorine
Chlorine is extracted electrolytically from rock salt (which is discussed 4. The dark shiny greay dagger like crystals sublime, producing violet
further in Factsheet 18) and a commonly used chemical in industry. Chlorine fumes
is used in, for example:
• water treatment 5. The hydrogen halides react in water and dissociate, so acting as proton
• bromine manufacture donors (i.e. acids)
• organochlorine compound manufacture (eg CFCs) HX(aq) + H2O(l) ž H3O+(aq) + X-(aq)
• PVC manufacture
• Hydrochloric acid manufacture 6. Bromide Br-(aq)
• Sodium chlorate (I), (NaClO), manufacture, used in bleach and 15o C
disinfectant 7. 2NaOH(aq) + Cl2(aq) NaOCl(aq) + NaCl(aq) + H2O(l)
0 +1 -1
The chlorine is simultaneously oxidesed and reduced

8. (a) yes
(b) no

Acknowledgements:
This Factsheet was researched and written by Sam Goodman & Kieron Heath
Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham, B18 6NF
ChemistryFactsheets may be copied free of charge by teaching staff or students,
provided that their school is a registered subscriber.
No part of these Factsheets may be reproduced, stored in a retrieval system, or
transmitted, in any other form or by any other means, without the prior
permission of the publisher. ISSN 1351-5136

3
 Chem Factsheet
April 2001 Number 15

Organic Chemistry I - Nomenclature

To succeed with this topic you need to Exam Hint - The ability to name carbon compounds correctly is
• Learn thoroughly the terms introduced in this Factsheet fundamental to any question on this topic. Remember – if you can
• Learn thoroughly the rules for nomenclature identify and name it you have solved half the problem. In addition, you
• Practice naming compounds until you are fully competent at gain marks for these “basic” skills.
applying the nomenclature rules
4. General formula (of a homologous series)
After working through this Factsheet you will be able to
• Identify the functional groups in compounds The general formula is the formula representing a
• Give the systematic names of the carbon compounds you will homologous series of a family of compounds.
meet at AS level
E.g.
Introduction
There are millions upon millions of carbon-based (organic) compounds,
Family General Formula Homologous
and thousands more are created (or discovered) every year.
(examples) series
In this context it is vital that an agreed world-wide system of naming these
Alkanes C nH 2n+2 CH4,
compounds is used so that scientists from different countries know which
C 2 H 6,
compound is which. This is called systematic nomenclature. This Factsheet
C3H8 etc
gives you the basics of this international system.
Alkenes C n H 2n C 2 H 4,
1. Functional group C 3 H 6,
C4H8 etc
The functional group is the reactive part of the molecule
Alcohols C nH 2n+1OH CH3OH,
C2H 5OH,
2. Family of compounds
C3H7OH etc
A family of compounds contains the same functional group
Exam hint - Learn the general formula for the hydrocarbons
(compounds containing only carbon and hydrogen) alkanes and
3. Homologous series alkenes.

A homologous series of compounds is one in which the

compounds belong to the same family and only differ by a –CH2 – i.e Questions will often give a formula – eg C7H14 – and expect you to spot
the length of the carbon chain that it matches CnH2n, so it is an alkene. Similarly, C8H18 is an alkane,
because it matches CnH2n+2

Systematic nomeclature
1. The length of the carbon chains
CH4 H CH 3OH H

C Name Number of carbons

H H H C OH
Meth- 1 C
H H Eth- 2 C2
Prop- 3 C3
C 2H 6 H H C2H5OH H H But- 4 C4
Pent - 5 C5
H C C H H C C OH Hex- 6 C6
H H H H Hept- 7 C7
Oct- 8 C8
C 3H 8 C 3H 7OH Non- 9 C9
H H H H H H Dec- 10 C 10

H C C C H H C C C OH Many of the terms you will remember from maths – eg pentagons have 5
sides, hexagons 6 side etc. Candidates usually remember meth- and eth- but
H H H H H H
it is prop- and but- that are most commonly mixed up!

1
Organic chemistry I - nomenclature Chem Factsheet

2. Functional Groups Worked example

H H OH Br H H
Family Functional Group Systematic Name
H C C C C C C H
Alkane C–C -ane Br I H H
Alkene C=C -ene 1. Six carbons in longest chain ⇒ hex
2. 5 functional groups. To get lowest numbers, start on the left of chain
Alcohol -OH -ol
3. Br ⇒bromo-; I⇒iodo- OH⇒ -ol; C=C ⇒ -ene
Halogenoalkane -Cl chloro- 4. The name is 3,4-dibromo-4-iodohex-1-ene-3-ol

-Br bromo- Note:

1. Two lots of Br ⇒”dibromo” (3 lots would be tribromo). Both numbers
-I iodo-
are given.
Ketone -one 2. Alphabetical so dibromo then iodo, and ene before ol.
C=O 3. The double bond (C=C) covers C atoms 1 and 2, but we only need to
give the 1.
H 4. “hex” not “hexan” because it has the alkene group C=C in it.
Aldehyde -al
C=O
Exam hint - Many candidates lose marks when using the nomenclature
OH system through a common error: it is not the longest straight chain of
Carboxylic Acid -oic acid carbon atoms, it is the longest chain. Remember that the displayed
C
O formula is a way of representing a 3 dimensional molecule, so it can
be written in different ways. This is used in questions to examine
whether or not a candidate understands this concept.
These functional groups are the ones in the AS-level course. More are
introduced in A2.
Study the following displayed formulae; they are all hexane!
Notice where the dash is on the systematic name. If it is behind eg bromo-,
then other names follow it, and the reverse if the dash is in front e.g. –ene. H H H H H H
H H
3. Naming Compounds – the method H C C C C C C H
Look at the example below: H C H H C H
H H H H H H H H
H H H H H
H H H C C C C H
5 4 3 2 1
H C C C C C OH H H H H
H C C H
H H H H Br H H
H H H H
the name is: 2 _ BROMOPENTAN_ 1_ OL
C C C H H C H H C C H
Prefix "2_bromo" H H H
Stem "Pentan" suffix "_1_ol" H C H
H
H C C C H
The functional group The longest carbon The functional
chain H H H
name going before group name going H
the stem after the stem
Before continuing, you should attempt questions 1 and 2 at the end of the
Notice particularly the numbering of the carbon chain. If it was numbered Factsheet to ensure you are confident with naming organic compounds
the other way, the compound would be 4-bromopentan-5-ol, so we number
it to get the lowest combination in the name. Branching of the carbon chain
When smaller carbon chains come off the longest carbon chain, they are
Also see how pent becomes “pentan” because there are only carbon-carbon called side-chains and the molecule is said to be branched. It is the ability
single bonds, like an alkane, so the “an” appears to reflect this fact. If there to have side-chains that is partly responsible for the large number of carbon
were only C=C bonds, the "an" would not appear compounds.

The box below shows the standard method for naming compounds The side chains are called alkyl groups and their names reflect their number
of carbon atoms:
Method
1. Find the longest carbon chain and so identify the stem name Number of carbons Alkyl group Name
2. Identify where the functional groups are on the chain and number 1 CH3- methyl
the chain based on their positions to get the lowest numbers
possible 2 C 2H 5- ethyl

3. Identify the names of the functional groups and whether they go 3 C 3H 7- propyl
before or after the stem name
4 C 4H 9- butyl
4. Write the name of the compound using the order: – stem, numbers 5 C 5H 11- pentyl
of prefixes and suffixes in alphabetical order

2
Organic chemistry I - nomenclature Chem Factsheet

Points about branching 2. C3H7OH has two structural isomers

1. The nomenclature method now has to be slightly changed to take in
side-chains as well as functional groups. H H H H OH H

Method: side chains are treated as functional groups in that they are H C C C OH H C C C H
prefixes, and go in the name alphabetically H H H H H H
H Propan-1-ol Propan-2-ol
e.g.
H C H
H H H
Exam Hint - A very common question at AS level is to give a formula
H C C C C OH e.g. C5H12 and ask you to give some structural isomers of it. This is
where the ability to name compounds really comes into its own
H H H H because if you correctly name the isomers you draw, you will avoid
duplicating the isomers.
is 2-methylbutan-1-ol

e.g. H Question 5 gives you some practice in drawing and naming structural
isomers
H C H
H H 2. Geometric isomerism
H C C C H
Geometric isomerism is caused by the presence of a carbon-
H Br H
carbon double bond (C=C). There is no rotation about the C=C because
rotating would require breaking the π bond. The two forms are called
is 2-bromo-2methylpropane stereoisomers.
2. Looking for the longest chain on a branched molecule must be done
very carefully But-2-ene, C4H8 is the smallest molecule showing geometric isomerism
H CH3 H 3C CH3
e.g. H H H H H
C C C C
H C C C C C H
H 3C H H H
H H H H
H C H Trans-but-2-ene Cis-but-2-ene

H C H The H-atoms are diagonally across The H-atoms are same side
(hence "trans") the double bond (hence "cis") the double bond
H
Geometric isomers can only form if both carbons involved in the double
is 3-methylhexane not 2-ethylpentane bond have two different groups attached to them.

Questions 3 and 4 will provide you with practice in naming branched Question 6 provides practice on geometric isomerism.
molecules
Condensed formula
Isomerism Examination questions and textbooks use a mixture of displayed formulae
Isomerism is the term used for compouds with the same molecular formula and 'condensed' formulae for example:
(i.e. the same number of atoms of each type) that have diferent arangements H OH H
of these atoms. The different forms are called isomers. At AS level there is
H C C C H CH3CH(OH)CH3
are two types of isomerism to learn about:
H H H
1. Structural isomerism
H Br O
Structural isomerism is when the same number and type of H C C C is CH3CH(Br)CO2H
atoms can be arranged in different ways to form structural isomers OH
H H
O O
Examples H H
1. C4H10 has two structural isomers C C is CH3CCH2I
H C I
H H H
H C H Exam Hint - You must be able to use condensed formulae and the
H H H H H H golden rule for all candidates is never try working out answers from
just “condensed” formulae – always convert condensed formulae to
H C C C C H H C C C H displayed formulae.The reason for this is that it is easier to see the
H H H H functional groups and the longest carbon chain for naming the
H H H
compound.
Butane 2-methylpropane
Question 7 provides practice on condensed and displayed formulae.

3
Organic chemistry I - nomenclature Chem Factsheet

Practice Questions 4. Draw the displayed formulae for the following componds:
Give the systematic names of these compounds: (a) 2-methylbutan-2-ol (b) 2,2-dimethylhex-3-ene
(c) 2-methyl-2-iodopropanoic acid (d) 3-bromo-3-ethylpentanal
1. (a) H H (b) Br H H (e) 2,3,4-trimethylpentane (f) 3-ethylhex-2-ene-1-ol
H
Br C C H Br C C C C H 5. C4H9OH has several structural isomers. Draw the displayed formulae
for all the isomers and give their systematic names..
H H H H H H
6. Pentene has two structural isomers called pent-1-ene and pent-2-ene.
H H H Only one of these isomers forms geometric isomers. Which isomer
(c) Cl Br H (d)
H C C C OH forms geometric isomers and what are their displayed formulae and
I C C C H
names?
H
H Br H
7. Draw the displayed formulae for the following compounds:
(e) (f) (a) CH3CH(OH)CH(Br)CH3
H O H H H H O
O
H C C C C H H C C C
OH (b) CH2(I)CH2CCH3
H H H H H
(c) CH3CH2CH2CH(OH)CH(OH)CO2H
H
(g) H (h)
H C H (d) CH2(OH)CH(Br)CH3
H C H
Cl O H C H 8. This question is about the molecule shown below.
H C C C H OH H
H OH H H H O
OH H C C C C H
H Br H C C C C C C H
Br H
Br H H
(a) Identify the four functional groups present in the molecule.
2. Draw the displayed formulae for these compounds
(a) Pentanoic acid (b) Butanone
(b) Draw the two geometric isomers of the molecule.
(c) 3-chloropentan-1-ol (d) 1,1,1-tribromoethane
(e) 1-iodobut-1-ene (f) 3-chlorohexanal
(g) 1-iodobutan1,2diol (h) hex-1-ene-3-ol

3. Give the systematic names of the following compounds

(a) H (b) H

H C H H C H
H H H H H H H
H C C C C C H H C C C C H

H H H H H H H H
H C H
H
(c) H (d) H
H C H H C H
H C H H H
H H H H C C C H
H C C C C H H H
H C H
H H H H
H
H
(e) (f)
H C H
H H H O H H
H H O
H C C C C C C H
H C C C C
OH H H
H H H
H C H

H C H
H
4
Organic chemistry I - nomenclature Chem Factsheet

Answers 5. H H H H H H OH H
1. (a) bromoethane (b) 1,2-dibromobutane
H C C C C OH H C C C C H
(c) 1-chloro-2,2dibromo-1-iodopropane
(d) prop-1-ene-1-ol (e) butanone H H H H H H H H
(f) propanoic acid (g) 2-bromobutanic acid butan-1-ol butan-2-ol
(h) 3-bromohex-1-ene-2-ol
H H
2. (a) (b) H C H H C H
H H H H O H O H H H H H H
H C C C C C H C C C C H H C C C OH H C C C H
H H H H OH
H H H H H H H OH H
(c) (d) 2-methylpropan-1-ol 2-methylpropan-2-ol
Br H
H H Cl H H
6. pent-2-ene
C C C C C OH Br C C H
H
H3C CH2 CH3 H 3C H
H H H H H Br H
C C C C
(e) (f) H H H CH 2 CH 3
H H H H H H H Cl H O Cis Trans
I C C C C H H C C C C C C
H H H H H H Pent-1-ene does not form geometric isomers because one of the carbons
H H
(g) (h) involved in the double bond has two identical groups (hydrogen atoms)
OH OH H H joined to it
H H OH H H H
I C C C C H C C C C
H C C H 7. (a) H OH Br H (b)
I H O H
H H H H H H H H
3. (a) 2-methylpentane (b) 2,3-dimethylbutane H C C C C H H C C C C H
(c) 3-methylpentane (d) 2,2-dimethylpropane H H H H
(e) 2-methylbutanoic acid (f) 4-ethylhex-1-ene-3-one H H H

4. (a) (b) (c) (d) H Br H

H H H OH OH O
H
H OH H H H C C C C C C HO C C C H
H C H
H C C C C H H H H H H OH H H H
H H H H H
H H H
H C C C C C C H
H C H 8. (a) bromoalkane (Br)
H H H alcohol (OH)
H H C H alkene (C=C)
O
H aldehyde (_C )
(c) (d)
H H
H H Br H O
H H
H C H H C C C C (b)
C OH
H O 'Cis' H C C
H H H H C H
H C C C H C H C C O
OH H H H
H I C
H C H Br
H
H H 'Trans' H
(e) H H
H
H C HH C H H C H C
Br OH
H H C H
C C C H
H C C H
C C
H
H H H H H H C O
H C
(f) H
H C H H
Acknowledgements:
H C H This Factsheet was researched and written by Sam Goodman & Kieron Heath
H H H H H Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham, B18 6NF
ChemistryFactsheets may be copied free of charge by teaching staff or students, provided
HO C C C C C C H that their school is a registered subscriber.
No part of these Factsheets may be reproduced, stored in a retrieval system, or transmitted,
H H H H in any other form or by any other means, without the prior permission of the publisher. ISSN
1351-5136

5
 Chem Factsheet
April 2001 Number 16

Organic Chemistry II - Reactions I

To succeed with this topic you need to Exam Hint - Unfamiliar compounds are used in questions but the
• Be able to name and draw organic molecules (Factsheet 15) secret is to leam how the family of compounds reacts. You identify the
• have revisited Factsheet 5 (‘Bonding’) and Factsheet 06 family the unfamiliar compound belongs to, remember how the family
(‘Structure of elements and compounds’) so you understand the reacts and then apply this to the compound. Again, being able to name
bonding and shapes of organic molecules. organic compounds is essential.

After working through this Factsheet you will

• Know the reactions of the families alkanes, alkenes and Reactions in organic chemistry
halogenoalkanes.
• Know the conditions and reagents for the reactions
• Understand how the bonding in the compounds influences their
reactions Substitution – When an atom or ‘group’ in a molecule is replaced by
• Know some of the terms used in reaction mechanisms. another atom or ‘group’

Addition – When two molecules react to form a single product.

Reaction Mechanisms
When compounds or elements react then bonds are broken and bonds are Elimination – When a simple molecule e.g. HCl, HBr, H2O, is removed
formed in the chemical reaction. from a molecule and not replaced.

Hydrolysis - When water reacts with a molecule and the molecule is

The reaction mechanism is the method used to show the bond making and split into two parts.
breaking processes by explaining what happens to the electrons involved
in bonding.

N.B. A2 Units require a much more detailed use of reaction mechanisms. Alkanes
First let us revise what we covered in Factsheet number 15 about alkanes.
• Alkanes are hydrocarbons (made of carbon and hydrogen only).
Definition of Terms • In an homologous series (differ from one another by only –CH2).
• Alkanes have a general formula of CnH2n+2.
Term Definition Example
• Alkanes are saturated compounds (Contain only single carbon bonds
. .
i.e. C–C).
Free A species with Cl2 → Cl + Cl
Radical a single unpaired the . on the Cl Reactions
electron represents the unpaired Alkanes are relatively unreactive because of the strength of the C – C and
electron C – H bonds they contain. The two reactions all alkanes undergo are :
1. Burning in excess oxygen to form carbon dioxide and water
Nucleophile A donator of a lone pair _ +
e.g. C2H6 + 3½O2 → 2CO2 + 3H2O
(literally 'liking of electrons (which so HO : C
the nucleus/ forms a new covalent Or 2C2H6 + 7O2 → 4CO2 + 6H2O)
positive charge') bond)
HO C Reaction type : combustion

Electrophile An acceptor of + 2. React with Cl2 or Br2 in the presence of UV light/sunlight to form a
(literally 'liking a lone pair of The C
complex mix of halogenoalkanes and hydrocarbons.
electrons/ electrons (so
negative charge') forming a new in the example above UV Light
Cl2 + C2H6 C2H5Cl, C2H4Cl2, C2H3Cl3, etc + HCl
covalent bond)
Reaction type: substitution
When a bond breaks A .x B Mechanism: free radical
Homolytic
Fission and one electron goes
Alkenes
to each atom (forming
Unsaturated hydrocarbons (i.e. C=C) with a general formula of CnH2n.
free radicals) Ax + .B
The C=C bond is
X
C . C
Heterolytic When a bond breaks A x. B X
.
Fisson and both electrons go
to one atom (forming _
+ The double bond contains a π-bond and a σ-bond. The σ– bond is strong
ions) A x. + B
(the bond pair is in the plane between the two carbon nuclei) But the π-
bond is weaker (the bond pair of electrons lies outside the plane of the
nuclei). The π-bond will break so other atoms / groups add on to the C–C link.
1
Organic chemistry II - reactions I Chem Factsheet

Reactions
1. Burning in excess oxygen to form carbon dioxide and water. Markovnikov's Rule
‘When a hydrogen halide is added to a double bond, the hydrogen
e.g. C2H4 + 3O2 → 2CO2 + 2H2O always goes to the C atom with the most H atoms on it already’.
H
Reaction type: combustion
H C C C H + HBr
2. Alkenes and hydrogen react when mixed over heated nickel catalyst
H H H
H H H H H H
Ni
H C C C H + H2 heat H C C C H H Br H H H Br
H H H H H C C C H H C C C H
alkene alkane
H H H H H H
Reaction type: Addition
correct wrong
Condition: Heat + Ni
Mechanism: Electrophile
Exam Hint - This is very commonly tested in examinations
3. Alkenes react with bromine / chlorine (halogens)
H H H H

H C C H + Br2 H C C H
Halogenoalkanes (haloalkanes )
Br Br The general formula is CnH2n+1 X, where X = Cl, Br or I.
alkene halogenalkane This means the functional group is a halogen atom.

Reaction type: Addition All halogenoalkanes react in the same way with the same reagents, but
Mechanism: Electrophile the different halogens do affect the rates of reaction. The difference in the
rate is explained by the bond energies shown below:
A solution of bromine in hexane (or trichloromethene) without C–Cl 338 kJ mol –1
heating, decolourises when added to a compound containing a C=C or C–Br 276 kJ mol –1
triple bonds. This is an important test used for dectecting unsaturation. C–I 238 kJ mol –1
NB. if bromine water (solution of bromine and water) is used, the
solution is also decolourised, but a different product is formed. Cl is a more electronegative atom that bromine which in turn is more
electronegative than iodine, so creating dipoles,
H H H H
δ+ δ δ+ δ δ+ δ
_ _ _

H C C H + Br2/H2O → H C C H + HBr C Cl C Br C I
Br OH The C–Cl bond is stronger than C–Br, which means more energy is needed
2-bromoethanol to break it so chloroalkanes will react slower than bromoalkanes,
i.e. rates of reactions, C–I > C–Br > C–Cl

4. Alkenes add hydrogen halides (e.g. HCl, HBr, etc) Reactions

In the following examples ‘X’ is used for the halogen because Cl, Br and
H H H H H H H H I will all react in the same way.
H C C C C H + HCl → H C C C C H
1. Reaction with aqueous sodium (or potassium) hydroxide to form an alcohol.
H H H H Cl H
CH3CH2X + NaOH → CH3CH2OH + NaX
alkene halogenoalkane
haloalkane alcohol
Reaction type: Addition
Reaction type: Substitution
Mechanism: Electrophile
Conditions: Aqueous + boil under reflux
Mechanism: Nucleophilic
5. Oxidation by alkaline potassium manganate(VII) solution
(KMnO4(aq)) 2. Reaction with potassium cyanide to form a nitrile (or cyanide).
H H H H H H
CH3X + KCN → CH3CN + KX
H C C C H + [O] + H2O → H C C C H haloalkane cyanide (nitrile)
H H OH OH Reaction type: Substitution
alkene
alcohol (diol) Conditions: KCN in water/ethanol + boil under reflux
Reaction type: Addition Mechanism: Nucleophilic
Condition: Alkaline
Mechanism: Electrophile

The decolourisation of an alkaline potassium manganate(VII)

solution is another test for C=C bonds/unsaturation.

2
Organic chemistry II - reactions I Chem Factsheet

3. Reaction with ammonia to form amines. 5. 2–bromopropene will react with each of the following:
(i) KCN
X NH 2 (ii) KOH (aq)
CH3 CH CH3 + 2NH3 → CH 3 CH CH3 + NH4X (iii) NH 3
For each reaction give the
haloalkane amine (a) balanced chemical equation
Reaction type: Substitution (b) reagents and conditions
Conditions: NΗ3 in ethanol + heat
Mechanism: Nucleophilic 6. Give the name and structural formula of the organic product in each
reaction.
(a) CH3CHICH3 NaOH(aq) A
4. Reaction with ethanolic potassium hydroxide to form alkenes.
H H H H ethanolic
(b) CH3 CH2 Br B
H C C H + KOH → H C C H + KX + H2O KOH

H X HBr
(c) CH 3 CH CH 2 C
Reaction type: Elimination
Conditions: KOH in ethanol + boil under reflux H2
(d) CH2 CH2 D

Tests for functional groups Answers

1. (a) UV Light / Sunlight
Group/Family Test Result (b) HBr, C3H7Br, C3H6Br2, C3H5Br3, etc
(c) Substitution
Alkene C=C Shake with bromine Colour of bromine
water, Br2(aq) solution goes from brown 2. (a) C3H6 + 4½O2 → 3CO2 + 3H2O (or ‘doubled’)
to colourless (b) C8H18 + 12½O2 → 8CO2 + 9H2O (or ‘doubled’)
(c) C4H10 + 6½O2 → 4CO2 + 5H2O (or ‘doubled’)
Chloroalkane 1. Warm with NaOH(aq) White precipitate -
C-Cl soluble in dil.NH3(aq) 3. (a) alkane (b) alkene (c) alkene (d) alkane

Bromoalkane Cream precipitate - 4. (i) CH3CH2CH=CH2 + HI → CH3CH2CHCH3

2. Add dilute HNO3 Condition: goes at room teperature
C-Br until just acidic soluble in conc. NH3(aq)
(ii) CH3CH2CH=CH2 + Br2 → CH3CH2CHICH2
Iodoalkane 3. Add AgNO3(aq) Yellow precipitate - Condition: Br2 in hexane at room temperature
C-I insoluble in conc. NH3(aq)
(iii) CH3CH2CH=CH2 + [O] + H2O → CH3CH2CHBr-CH2Br
Condition: KMnO4 in alkaline soultion

(iv) CH3CH2CH=CH2 + H2 → CH3CH2CH2CH3

Exam Hint - Candidates will be expected to know the tests for functional Condition: Heat + Nickel catalyst
/family groups.Thorough knowlege of the reactions outlined in this
Factsheet may be expected. Br CN
5. (i) CH3-CH-CH3 + KCN → CH3-CH-CH3 + KBr
Condition: boil KCN dissolved in mixture of water and ethanol
Br OH
Practice Questions
1. Propane will react with bromine under the correct conditions. (ii) CH3-CH-CH3 + NaOH → CH3-CH-CH3 + NaBr
(a) What are the conditions used? Condition: boil under reflux with NaOH(aq)
(b) Give the formula of four compounds likely to be formed by the Br NH 2
reactions.
(iii) CH3-CH-CH3 + 2NH3 → CH3-CH-CH3 + NH4Br
(c) What type of reaction is this?
Condition: heat concentrated solution of NH3 in ethanol
2. Write the balanced chemical equations for the reaction of the following
6. A = CH3CHOHCH3 Propan-2-ol
compounds with oxygen.
(a) Propane (b) Octane (c) Butane
B = CH 2=CH2 Ethene
3. Which family do the following hydrocarbons belong to?
(a) C5H12, (b) C10H20 (c) C4H8 (d) C11 H24 C = CH3CHBrCH3 2-bromopropane

4. But–1–ene reacts with each of the following: D = CH 3CH3 Ethane

(i) HI (ii) Br2 (iii) KMnO4 (iv) H2
For each reaction give the Acknowledgements:
(a) Balanced chemical equation This Factsheet was researched and written by Sam Goodman & Kieron Heath
Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham, B18 6NF
(b) reactions and conditions
ChemistryFactsheets may be copied free of charge by teaching staff or students,
provided that their school is a registered subscriber.
No part of these Factsheets may be reproduced, stored in a retrieval system, or
transmitted, in any other form or by any other means, without the prior
permission of the publisher. ISSN 1351-5136

3
 Chem Factsheet
April 2001 Number 17

Organic Chemistry III - Reactions II

To succeed with this topic you need to e.g. Solid P with solid I2 to make PI3 ,
• Be able to name and draw organic molecules (Factsheet 15) 3C2H5OH + PI3 → 3C2H5I + H3PO3
• Know the reactions of alkanes, alkenes and halogenoalkanes reaction type: substitution
(Factsheet 16) mechanism: nucleophilic

After working through this Factsheet you will

halogenating Halogenalkane
Alcohol
• Know the reactions of alcohols agent
• Know some of the reactions of aldehydes, ketones and carboxylic
acids
• Know the ways in which the organic compounds of this Factsheet
and Factsheet 16 can be converted from one to another (i.e. Exam Hint - test for alcohols (i.e. the – OH group).
synthetic pathways) Add solid PCl5 in dry conditions. It is an alcohol if white ‘steamy’
fumes (of HCl) are seen. This is a very important test and, like the
bromine water test for a alkene, is a common examination question
Important
The question at the end of this Factsheet test not only the information in
it, but also the information in Factsheet 16. Factsheets 16 and 17 make up
the complete work on organic reactions. 2. Dehydration (i.e. the removal of H2O)
Add concentrated H2SO4 and heat to 170 0C,
Exam Hint - The secret to answering questions on organic chemistry
is not to be put off by the unfamiliar compounds used in the question. e.g. H OH
Always look for the functional groups / families of the compounds conc. H2SO4
Functional groups always react in the same way! H C C H H C C H + H2 O
heat to 170 oC
H H H H
Alcohols
dehydrating Alkene
Alcohols have the general formula, Cn H2n + 1OH, and the functional group Alcohol agent
is –OH. The ending of the name in –ol shows the presence of the –OH
group. If two –OH groups are present it is called a diol. The position of the
–OH group on the carbon chain of a molecule affects its properties, so you
need to be able to identify the three types of alcohols: 3. Oxidation (only primary and secondary not tertiary)
Potassium dichromate(VI), K2Cr2O7, in dilute H2SO4 with heating. This is
the oxidising agent and it is orange in colour, but changes to green as it is
Primary Secondary Tertiary reduced. N.B. remember this colour change !
H OH OH
C (i) Primary alcohols
OH C C C C C C
H H C e.g. Cr2O72-/ O
C2H5OH + [O] + CH 3 C + H2O
H
-OH on the 2 carbon atoms 3 carbon atoms H
end of the attached to the attached to the
carbon chain OH- carrying C atom OH- carrying C atom Then – if left, the aldehyde is oxidised further to the carboxylic acid ,

e.g. O O
Reactions
CH 3 C + [O] CH 3 C
1. Halogenation
Primay, secondary, tertiary alcohols behave the same way. The – OH H OH
groups is replaced by Cl , Br or I.
[O]
e.g. PCl5 in dry conditions. Alcohol Aldehyde
C2H5OH + PCl5 → C2H5Cl + HCl + POCl3
reaction type: substitution
mechanism: nucleophilic [O]
Aldehyde Carboxylic acid
e.g. Solid NaBr with concentrated H2SO4 are used to produce HBr,
C2H5OH + HBr → C2H5Br + H2O
reaction type: substitution
mechanism: nucleophilic

1
Organic chemistry III - reactions II Chem Factsheet

(ii) Secondary alcohols

N.B. In the A2 course these oxidation processes are shown to be
e.g. OH O capable of being reversed by a reduction process,

CH 3 C CH3 + [O] CH3 C CH 3 + H2O i.e. Carboxylic [H] [H] Primary

acid Aldehyde alcohol
H
Ketones cannot be oxidised further.
[H] Secondary
Ketone
alcohol
[O]
Secondary alcohol Ketone

Synthetic Pathways
Summary Of Reactions From Factsheet 16 & 17

Primary KOH(aq) K2Cr2O7 K2Cr2O7 Carboxylic

Primary Aldehyde
Halogenalkanes Alcohol H+ H+ Acid

KOH / ethanol HX

X2 Dihalogeno KOH(aq)
Alkene Diol
Alkanes

KOH / ethanol HX

Secondary KOH(aq) Secondary K2Cr2O7

Halogenalkanes Alcohol H+ Ketone

Practice Questions 3. An unknown liquid gives the following test results:

1. The molecule contains the – OH group in various positions: (a) Produces white steaming fumes with dry PCl5
(b) changes potassium dichromate(VI) in dilute sulphuric acid from
H
6 yellow to green when heated.
H C OH What family could the liquid belong to?
H H OH H
1 2 3 4 5 4. For each of the steps A – D give the regents and the conditions necessary
HO C C C C C H
to bring about the conversion:
H H OH H H OH
step A
CH 3 C CH3 CH2 C CH 3
Is the –OH in a primary, secondary or tertiary position in the carbon
atom numbered 1, 3, 4 and 6? H H
step B
2. Propan -1– ol is reacted with the following reagents under the conditions
shown. In each case give: Br
(i) The balanced chemical equation.
(ii) The systematic name of the organic product. CH 3 C CH 3
H
(a) Solid NaBr and concentrated sulphuric acid.
(b) Heating to 170 oC with concentrated sulphuric acid. step C
(c) Heating with potassium dichromate (VI) in dilute sulphuric acid.
O OH
step D
CH3 C CH 3 CH3 C CH 3
H
2
Organic chemistry III - reactions II Chem Factsheet

5. Compound A (C4H10O) is oxidised to compound B (C4H8O2) by

heating it with K2Cr2O7 and dilute H2SO4. A produces compound C
with P and I2 at room temperature. C is converted into D by reacting it
with ethanolic KOH.

Identify the compounds A, B, C and D by giving their structural

formulas and systematic names.

6. An unknown compound gives the following test results:

(a) decolourises bromine water
(b) produces a yellow precipitate when reacted with dilute nitric acid
followed by silver nitrate solution.
What functional groups does the compound contain?

Answers
1. C - primary, Cƒ - tertiary, C„ - secondary, C† - primary

2. (a) C3H7OH + HBr → C3H7Br + H2O

1-bromopropane

(b) C3H7OH → C3H6 + H2O

propene

(c) C3H7OH + [O] → C2H5CHO + H2O

propanal

Or 2C3H7OH + 3[O] → 2C2H5 COOH + H2O

propanoic acid

3. Primary or secondary alcohol (both need to be named)

4. A – conc. H2SO4 at 170 oC

B – HBr (from conc. H2SO4 / NaBr)
C – KOH(aq)
D – K2 Cr2 O7 / dil. H2 SO4 + heat

5. A H H H H
H C C C C OH butan-1-ol

H H H H

B H H H
O
H C C C C butanoic acid
OH
H H H

C H H H H
H C C C C I 1-iodobutane

H H H H

D H H H H
but-1-ene
H C C C C H
H H
Acknowledgements:
This Factsheet was researched and written by Sam Goodman & Kieron Heath
6. (a) alkene, C C Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham, B18 6NF
ChemistryFactsheets may be copied free of charge by teaching staff or students,
(b) iodide, -I provided that their school is a registered subscriber.
No part of these Factsheets may be reproduced, stored in a retrieval system, or
transmitted, in any other form or by any other means, without the prior
permission of the publisher. ISSN 1351-5136

3
 Chem Factsheet
April 2001 Number 18

Applied Chemistry
To succeed with this topic you need to understand that the chemistry Polymers
studied in the Factsheets has an impact on industry, everyday life Polymers are long chain molecules made by joining together many small
and global issues molecules (monomers).

After working through this Factsheet, you will be able to Polymers have a wide and varied array of properties such as strength,
• Discuss the advantages of both liquid and gaseous fuels flexibility and softening temperature.
• Understand how simple polymers are formed and be aware of
their uses Addition polymers
• Discuss the use of halogens in pesticides, polymers and Polyethene
refridgerants and their impact upon the environment
• Recall the use of ammonia, nitric acid and sulphuric acid in the H H H H H H
manufacture of fertiliser C C + C C + C C
.... H H H H H H ....
• Discuss the extraction of aluminium from bauxite
• Recall the production of chlorine and sodium chlorate (I) by the
electrolysis of sodium chloride solution

Liquid and gaseous fuels

H H H H H
A fuel is a substance which releases useful energy when combusted C C C C C
H H H H H
An ideal fuel would
• Be abundant The name is due to the addition across the double bond.
• Be easy to store and transport
• Produce a large amount of energy per unit mass This reaction is better represented as follows
• Be non-toxic
H H
• Release harmless combustion products H H
200 oC
Abundance n C C 1200 atm O2 C C
• The majority of industrial fuel is fractionally distilled from crude oil H H
(e.g. methane, butane, octane) and there are limited resources. H H
n
• Ethanol is a viable liquid fuel formed by fermentation of plant sugars.
• Hydrogen is plentiful, but too much energy is required for the Properties of polyethene:
electrolysis of water to separate it from oxygen. • Branched chains, will not pack closely, so readily melted and deformed.
Used for bags and squeezy bottles
Transport and storage • If produced using catalysts at low temperatures, a harder form is
Different fuels are obviously chosen for different purposes. Household produced with higher melting point and strength. High density
fuel for cooking and heating is often gaseous due to the ease with which polyethene is used for crates
gaseous fuel can be piped into the home. Cars, however, tend to run on
liquid fuel due to the ease of handling the fuel at filling stations. Whilst the Polypropene
transport of liquid fuel is dangerous, the transport of gaseous fuel is
CH3 H CH 3 H
potentially more dangerous as practically it must be pressurised.
n C C C C
Energy per unit mass
Where mass of fuel is important (prime example being aeroplanes) it is H H H H
necessary for a great deal of energy to be generated from a relatively low n
mass of fuel.
Well packed, similar properties to high density polyethene. Can be made
into fibres and used for ropes – it does not rot away.
Toxicity
It is an advantage for fuels to be non-toxic if you consider how much they
Polychloroethene (or polyvinylchloride PVC)
need to be handled, and the possible impact on the environment of a fuel
leak. H H
H H
Combustion products n C C C C
The extent and type of pollution produced needs to be considered.
• The quantity of greenhouse gases – specifically CO2 – produced H Cl H Cl
• The emission of oxides of nitrogen and sulphur, which can lead to acid rain n
• The emission of particles Used for coating fabrics, electrical insulation and vinyl records.

1
Applied chemistry Chem Factsheet

Polytetrafluoroethene Ammonia, nitric acid and sulphuric acid in the manufacture of

F F F F fertiliser
Nitrogen is a vital element in fertilisers – ammonium nitrate (“nitram”) is
n C C C C widely used as it has a high nitrogen content and is water soluble. It is
produced by reacting ammonia with nitric acid
F F F F
n NH3 + HNO3 → NH4NO3
ammonium nitrate ('nitram')
“Teflon” is a very stable, low friction (“non-stick”) polymer used on
kitchenware There are 3 types of nitrogen based fertiliser
(i) quick release (eg NH4NO3)
Problems with polymers – the environmental issue (ii) slow release (eg NH2CONH2, urea)
Simple polymers such as those given above are not broken down in normal (iii) natural (eg manure, compost)
environmental conditions – they are “non-biodegradeable” due to the The first two are water soluble, so rapid leaching from soils can occur.
strength of the bonds within the compounds. Consequently, discarded Natural fertilisers are difficult and unpleasant to apply, and have low
polymers will not naturally disappear. nitrogen contents.

Practical uses of organic halogen compounds, and their impact on Sulphuric acid is used in the manufacture of nitrogenous fertiliser
(ammonium sulphate, (NH4)2SO4 and phosphate fertilisers. Phosphates
the environment
are commonly too insoluble to be used, so sulphuric acid is used to produce
the more soluble dihydrogen phosphates.
1. Polymers, as discussed above. PVC and Teflon are commonly used
chemicals, but strong carbon-halogen and carbon-carbon bonds mean e.g. Ca3(PO4)2(s) + 2H2SO4(aq) → Ca(H2PO4)2(aq) + 2CaSO4(aq)
they are non-biodegradeable
The extraction of aluminium from bauxite
2. Pesticides and herbicides. DDT (dichlorodiphenyltrichloroethane) has Aluminium is manufactured by the electrolysis of molten aluminium oxide.
been widely used as an insecticide, for instance eliminating malaria This is obtained from bauxite – hydrated aluminium oxide containing
from several areas in the world. DDT has two major drawbacks: impurities like iron (III) oxide and silicon (IV) oxide.

i. Insects reproduce quickly, and resistant strains are now found The bauxite is first treated to produce pure aluminium oxide. The ore is
ii. DDT breaks down very slowly in the environment as it is very treated with a hot 10% solution of sodium hydroxide which reacts with the
stable due to strong bonding amphoteric aluminium oxide.

Complicated chlorine compounds such as 2,4 – D and 2,4,5-T are Al2O3(s) + 2NaOH(aq) → 2NaAlO2(aq) + H2O(l)
herbicides (or chemical weedkillers). They are also very stable
compounds so persist in the environment, the problem being that, like The basic Fe2O3 does not react, and only small quantities of SiO2 react due
pesticides, they may enter the water cycle and food chain, producing to its giant atomic structure. These solid impurities are filtered off.
adverse effects on wildlife
Carbon dioxide gas is blown through the sodium aluminate solution and
3. CFCs – refrigerants and propellants. Chlorofluorocarbons (CFCs) have aluminium hydroxide is precipitated – this is filtered and heated to make
been widely used as aerosol propellants and as the cooling medium in pure aluminium oxide.
refrigerators. They are so stable in air and water that when released
they diffuse all the way up to the stratosphere, and only then will they The electrolysis of pure aluminium oxide
be broken down by ultraviolet light. When decomposed by light, Pure aluminium oxide is an unsuitable electrolyte due to its high melting
chlorine radicals are produced which catalyse the destruction of ozone. point (2040 oC). To reduce costs, it is dissolved in cryolite (Na3AlF6) at
900 oC, and then electrolysed (Fig 1).
2O3(g) → 3O2(g)
Fig 1. Electrolytic cell for aluminium extraction
Consequently alternatives to CFCs are now being used.
porous crust of solid electrolyte
For the Contact process (manufacture of sulphuric acid) and the Haber
process (manufacture of ammonia) see Factsheet 09 – Equilibrium Carbon lining
and LeChatelier’s principle cathode adjustable carbon anodes
_ + + + +
Oxidation of ammonia to nitric acid
syphon
Ammonia and oxygen (from air) are heated to 900oC in the presence of a
platinum/rhodium catalyst:

4NH3(g) + 5O2(g) ž 4NO(g) + 6H2O(g)

The nitrogen (II) oxide reacts with more oxygen on cooling

4NO(g) + 2O2(g) ž 4NO2(g)

Nitrogen (IV) oxide and oxygen then react with water

molten electrolyte
4NO2(g) + O2(g) + 2H2O(l) ž 4HNO3(aq)
molten aluminium

2
Applied chemistry Chem Factsheet

At the cathode, aluminium ions are reduced Sodium chlorate (I) manufacture
If the chlorine gas and sodium hydroxide solution, as products of the
Al3+ + 3e → Al(l)
_
electrolysis of brine, are allowed to mix, they react to form sodium chlorate (I).
At the anode, oxygen ions are oxidised
Cl2(g) + 2NaOH(aq) → NaOCl(aq) + NaCl(aq) + H2O(l)
2_
→ O2(g) + 4e
_
2O 2 Note: recognise this as the dispropotionation of chlorine - see Factsheet 14
and react with the carbon anodes Sodium chlorate I is used as a bleach and a disinfectant

C(s) + O2(g) →CO2(g) Practice Questions

1. Briefly explain why there are concerns about the use of petrol as the
So the anodes gradually wear away and need moving and replacing regularly.
main fuel for cars in the future
2. Write the equation showing the formation of polychloroethene (PVC)
Aluminium is an expensive metal to manufacture, so the recycling of
from its monomer
aluminium makes economic sense. It is a commonly used metal, e.g. for
3. Explain how the use of chlorofluorocarbons as aerosol propellants has
drinks cans, kitchenware, window frames and foil.
contributed to “the hole in the ozone layer”
4. Show how ammonia and nitric acid can be used in the formation of
The manufacture of chlorine and sodium chlorate (I) fertiliser
This is done by the electrolysis of an aqueous solution of sodium chloride 5. Explain why pure alumium oxide cannot be used as an electrolyte in
(brine) (Fig 2). the industrial manufacture of aluminium.
6. Give the reactions at the anode and cathode during the electrolysis of
Fig 2. Diaphragm cell for electrolysis of NaCl(aq) brine.
7. Show how bleach (sodium chlorate) is produced from the products of
Cl2(g) H2(g) the electrolysis of brine.

Answers
1. Points to be mentioned
brine NaOH(aq) • Petrol is fractionally distilled from crude oil, a fossil fuel of which there
is a diminishing supply
• Combustion products include carbon dioxide – increasing levels in the
atmosphere contribute to global warming
• Pollutants from the engine include nitrous oxides, which contribute to
the formation of acid rain
_ H
+ 2. H H H
titanium steel
anode cathode n C C C C
porous asbestos H Cl H Cl
diaphragm n

3. The strong carbon-halogen and carbon-carbon bonds mean that CFCs

are very stable compounds and when released into the atmosphere
The solution contains the following ions: they stay intact until they reach the stratosphere, where they are
_
Na+(aq) Cl (aq) H+(aq) OH (aq)
_ broken down when irradiated by UV light and chlorine free radicals are
produced. These free radicals catalyse the decomposition of ozone to
At the titanium anode (+) it is the chloride ions which are oxidised oxygen in the stratosphere, decreasing the levels of ozone unnaturally.
_ _
2Cl (aq) → Cl2(g) + 2e 4. NH3 + HNO3 → NH4NO3
so chlorine gas is produced
5. Pure aluminium oxide has a very high melting point (2040 oC) and this
At the steel cathode (-), hydrogen ions are reduced would be a very expensive temperature to maintain, so a suitable solvent
was found – cryolite (Na3AlF6) which dissolves the aluminium oxide,
_
2H+(aq) + 2e → H2(g) and electrolysis can be carried out at the lower (and cheaper)
temperature of 900 oC
so hydrogen gas is produced.
_ _
_ 6. Anode: 2Cl (aq) → Cl2(g) + 2e
The remaining solution still contains the Na+(aq) and OH (aq) ions – hence _
cathode: 2H+(aq) + 2e → H2(g)
sodium hydroxide solution is produced.
7. Cl2(g) + 2NaOH(aq) → NaOCl(aq) + NaCl(aq) + H2O(l)
The porous asbestos diaphragm is necessary to keep the sodium hydroxide
from the chlorine gas formed in the anode compartment.
Acknowledgements:
This Factsheet was researched and written by Sam Goodman & Kieron Heath
Uses of chlorine gas (see also Factsheet 14) Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham, B18 6NF
• Water treatment ChemistryFactsheets may be copied free of charge by teaching staff or students,
• Bromine manufacture provided that their school is a registered subscriber.
• Organochlorine compound manufacture No part of these Factsheets may be reproduced, stored in a retrieval system, or
• PVC manufacture transmitted, in any other form or by any other means, without the prior
• Hydrochloric acid manufacture permission of the publisher. ISSN 1351-5136

3
 Chem Factsheet
September 2001 Number 19

The Periodic Table - Period 3

To succeed in this topic you need to:-
• understand the work in Factsheet 12 on Periodicity - Trends in Period 3
• understand work on bonding (Factsheet 05) and structure (Factsheet 06)
After working through this Factsheet you will:-
• know the reactions of Period 3 elements with oxygen, chlorine and water
• know the formulae and some characteristics of the oxides, hydroxides and chlorides of Period 3 elements.
The trends in the physical properties of the Period 3 elements are summarised in Table 1.

Table 1. Trends in physical properties across Period 3

Group 1 2 3 4 5 6 7 8

Element sodium magnesium aluminium silicon phosphorus sulphur chlorine argon

Symbol Na Mg Al Si P S Cl Ar
Giant
Structure Giant Metallic Molecular Atomic
Covalent
Metalloid/ Non - Metallic
Character Metallic
Non-metal

Melting Point General increase General decrease

Conductance General increase General decrease

First Ionization Energy General increase

Atomic Radius General decrease

Reactions of the Period 3 elements with oxygen Reactions of the Period 3 elements with chlorine
The oxide products are generally very stable, as oxygen is a very All of the Period 3 elements (except argon and chlorine itself) react directly
electronegative element – this means that the enthalpy of formation of the on heating with chlorine. Moving across the period from left to right, the
oxides are usually negative. reactions become less vigorous with less heat released on formation, and
the bonds formed become increasingly covalent in character.
As we move across the period the electronegativity differences become
smaller and the oxides become less stable. The change in behaviour is due to the increasing electronegativity across
the period. The s-block metals are very electropositive so form strong
Element Equation for reaction ionic bonds with the electronegative chlorine.
Sodium 4Na(s) + O2(g) → 2Na2O(s) (simple oxide)
and 2Na(s) + O2(g) → Na2O2(s) (peroxide)
Element Equation for reaction
Magnesium 2Mg(s) + O2(g) → 2MgO(s) Sodium 2Na(s) + Cl2(g) → 2NaCl(s)
Aluminium 4Al(s) + 3O2(g) → 2Al2O3(s) sodium chloride (white ionic solid)
Magnesium Mg(s) + Cl2(g) → MgCl2(s)
Silicon Si(s) + O2(g) → SiO2(s) magnesium chloride (white ionic solid)
Phosphorus P4(s) + 5O2(g) → P4O10(s) Aluminium 2Al(s) + 3Cl2(g) → 2AlCl3(s)
Aluminium chloride (yellow covalent solid).
Sulphur S(s) + O2(g) → SO2(g)
Dimerises to form Al2Cl6
Chlorine Does not react directly with oxygen Silicon Si(s) + 2Cl2(g) → SiCl4(l)
silicon chloride (colourless covalent liquid)
Argon No reaction with oxygen
Phosphorus 2P(s) + 3Cl2(g) → 2PCl3(l)
phosphorus (III) chloride (colourless covalent liquid)
Exam Hint: Candidates must be able to recall the equations for
oxide and chloride formation. Sulphur 2S(s) + Cl2(g) → S2Cl2(l)
sulphur chloride (pale yellow covalent liquid)

1
The Periodic Table - Period 3 Chem Factsheet

Reactions of the Period 3 elements with water

Element Reaction Equation

Sodium Vigorous reaction, sodium melts into sphere and darts about on surface of water; 2Na(s) + 2H2O(l) →2NaOH(aq) + H2(g)
hydrogen gas given off and resulting solution is alkaline.

Magnesium Extremely slow reaction with cold water; Mg(s) + 2H2O(l)→ Mg(OH)2(s)+ H2(g)
bubbles of hydrogen formed on surface of metal.

Reacts quickly with steam, metal glows red and white flame is seen Mg(s) + H2O(g)→MgO(s) + H2(g)
as solid white magnesium oxide is formed, and hydrogen evolved.

Aluminium No reaction with cold water, but will react with steam 2Al(s) + 3H2O(l) →Al2O3(s) + 3H2(g)
to give oxide if powdered and heated strongly

Silicon No reaction with H2O

Phosphorus No reaction with H2O

Sulphur No reaction with H2O

Chlorine Forms an acidic solution; hydrochloric acid and hypochlorous acid (a bleach) Cl2(g) + H2O(l) ž HCl(aq) + HOCl(aq)
formed as chlorine undergoes disproportionation.

The Oxides of Period 3 For example, sulphur dioxide combines with water to form the covalent
The acidic/basic nature of the oxide depends upon the properties of the molecule H2SO3; the polar bond between the oxygen and hydrogen means
Period 3 element. The more electropositive the element, the more basic the that this will dissociate readily to form hydrogen ions.
oxide, as the compound will be more ionic in character and the O2- ions can
accept hydrogen ions to form water. This lowers the concentration of O O O O O O
-
+
H+(aq), so solution is alkaline. → ž + 2H
S S H S
As we move from left to right across Period 3, elements become more HO H HO O-
electronegative, so the covalent character of the oxides increases, so there is
no oxide ion to receive protons. Instead covalent molecules with a tendency
to dissociate and donate hydrogen ions (i.e. acids) are formed.
Exam Hint: - Ensure you can link the behaviour of the oxides and
Exam Hint: - The trends in acidic and basic character of the oxides chlorides of the elements with the trend in electronegativity across
are frequently examined. However, an understanding of the trends the period.
must be backed up by a detailed knowledge of the equations for
reactions which demonstrate this acidic, basic or amphoteric character
- i.e. those with water or H+ or OH− ions.

Oxide Structure/Bonding Acidic/Basic character Reaction with water

sodium oxide Na2O giant ionic basic Reacts to form a strong alkali
Na2O(s) + H2O(l) → 2NaOH(aq)

magnesium oxide MgO giant ionic, basic, but less so than Na2O Reacts to form a weak alkali
polarised MgO(s) + H2O(l) → Mg(OH)2(aq)

aluminium oxide Al2O3 ionic, some amphoteric - reacts with No reaction

covalent character both H+ and OH− ions
Al2O3(s) + 6H+(aq) → 2Al3+(aq) + 3H2O(1)
Al2O3(s) + 2OH−(aq) + 3H2O(1) → 2Al(OH)4−(aq)

silicon(IV) oxide SiO2 giant covalent acidic - reacts with OH− ions No reaction
SiO2(s) + 2OH−(aq) → SiO32−(aq) + H2O(l)

phosphorus(V) oxide P4O10 molecular acidic Reacts to form phosphoric (V) acid
covalent solid P4O10(s) + 6H2O(l) → H3PO4(aq)

sulphur(IV) oxide (or dioxide) SO2 molecular acidic React to form sulphuric (IV)
sulphur(VI) oxide (or trioxide) SO3 covalent gas and sulphuric (VI) acids:
SO2(g) + H2O(l) → H2SO3(aq)
SO3(g) + H2O(l) → H2SO4(aq)

chlorine oxide(Cl2O) molecular acidic Reacts to form hypochlorous acid

covalent gas Cl2O(g) + H2O(l) → 2HOCl(aq)

2
The Periodic Table - Period 3 Chem Factsheet

Chlorides of Period 3

Chloride Structure/ Bonding Reaction with water

sodium chloride NaCl Giant ionic Dissolves to give a neutral solution

magnesium chloride MgCl2 Giant ionic Dissolves to give a weakly acid solution

aluminium chloride AlCl3 When anhydrous, covalent solid Anhydrous form reacts to produce hydrochloric acid
which exists as dimers Al2Cl6 AlCl3(s) + 3H2O(l) → Al(OH)3(s) + 3HCl(aq)

The hydrated form is an ionic solid Hydrated form is hydrolysed in water, forming acidic solution
[Al(H2O)6]3+(aq) + H2O(l) → Al[(H2O)5(OH)]2+(aq) + H3O+(aq)

silicon chloride SiCl4 molecular covalent liquid Reacts to produce hydrochloric acid
SiCl4(1) + 2H2O(1) → SiO2(s) + 4HCl(aq)

phosphorus chlorides molecular covalent liquid Reacts to form phosphoric and hydrochloric acids
PCl3 and PCl5 PCl3(1) + 3H2O(1) → H3PO4(aq) + 3HCl(aq)

sulphur chlorides molecular covalent liquid Reacts to form hydrochloric acid

S2Cl2, SCl2 and SCl4 2S2Cl2(1) + 2H2O(1) → 3S(s) + SO2(aq) + 4HCl(aq)

Why does magnesium chloride give an acid solution when it dissolves in water, but sodium chloride a neutral solution?
When ionic solids like sodium and magnesium chlorides dissolve in water, the metal ion becomes surrounded by water molecules, as illustrated below:
δ+ δ+
H H δ+ δ+
δ+ δ+
δ+ H H
H Hδ
_ +
H O
_ H δ
δ _
δ δ+ _
O _
δ+ O H δ+ δ δ δ+
H Oδ_ H + O_ Mg2+Oδ_ H +
Na + _
δ δ δ δ
Hδ
+

δ+H _ O H O O δ_ O H+
Oδ δ
Hδ
_
Oδ
+
H
δ+ δ+ δ+
H H H δ+ H
H δ+ H δ
+

Because the Mg2+ has a higher charge density than Na+ (as it is both smaller and more highly charged), it further polarises the already polar O − H
bonds in water, causing some deprotonation. The presence of the H+ ion in solution causes some acidity.

Practice Questions Answers

1. Period 3 elements Na→Cl react with oxygen: 1. a) 4Na(s) + O2(g) → 2Na2O(s) and 2Na(s) + O2(g) → Na2O2(s)
The oxide is basic because it reacts with water to form a strong
(a) Sodium reacts with oxygen to form basic oxides. Write equations alkali.
for both its reaction with oxygen and to illustrate the basic nature
of sodium oxide. Na2O(s) + H2O(1) → 2NaOH(aq)

(b) One of the Period 3 elements forms an amphoteric oxide. Write b) Aluminium oxide is amphoteric
equations which illustrate the amphoteric nature of this oxide. As a base: Al2O3(s) + 6H+(aq) → 2Al3+(aq) + 3H2O(l)
As an acid: Al2O3(s) + 2OH-(aq) + 3H2O(l) → 2Al(OH)4-(aq)
2. Write equations for the reactions of magnesium, chlorine and
phosphorus(III) oxide with water. In each case suggest a likely pH of 2. Mg with water: Mg(s) + 2H2O(1) → Mg(OH)2(aq) + H2(g)
the solution formed. pH of soln: ~ 8-9 (weak alkali)

3. Explain why sodium chloride forms a neutral solution, yet magnesium Cl with water: Cl2(g) + H2O(1) → HCl(aq) + HOCl(aq)
chloride forms a slightly acidic solution in water. pH of soln: ~ 1-2 (strong acid)

4. Explain why the heat evolved in formation of Period 3 chlorides P4O10 with water: P4O10 (s) + 6H2O(1) → 4H3PO4(aq)
decreases as we move from left to right across the period. pH of soln: ~ 2 (acid)

3. Sodium chloride dissolves to give Na+(aq) and Cl−(aq) ions in solution.

Magnesium chloride dissolves to give Mg2+(aq) and Cl−(aq).

Mg2+(aq) is smaller and more positive than Na+(aq) and causes some
deprotonation of water molecules, hence slightly acid solution.
Acknowledgements:
This Factsheet was researched and written by Kieron Heath 4. s-block metals are very electropositive, so form strong ionic bonds
Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham, B18 6NF with electronegative chlorine, releasing a great deal of energy.
ChemistryFactsheets may be copied free of charge by teaching staff or students, provided that their As we move across the period, bonds formed become more covalent in
school is a registered subscriber. No part of these Factsheets may be reproduced, stored in a retrieval
system, or transmitted, in any other form or by any other means, without the prior permission of the character and heat released on formation decreases.
publisher. ISSN 1351-5136

3
 Chem Factsheet
September 2001 Number 20

The Periodic Table - Group 4

To succeed in this topic you need to: Structure
• Understand atomic structure (Factsheet 01), bonding (Factsheet Carbon exists as two common allotropes (fig 1):
05) and structure of elements and compounds (Factsheet 06) Fig 1. Allotropes of carbon
• Understand oxidation numbers (Factsheet 11)
Diamond
After working through this Factsheet you will:
• Know the trends in physical properties of the Group 4 elements
• Know the relative stabilities of the +2 and +4 oxidation states
of the Group 4 elements
• Know key characteristics of Group 4 oxides and chlorides

Group 4 Elements
The electron configurations of Group 4 are shown below: • Giant covalent molecule.
Element Electronic Structure
• One of the hardest substances known, due to strong covalent bonds.
carbon 2.4 [He] 2s2 2p2 • Insulator.
silicon 2.8.4 [Ne] 3s2 3p2
germanium 2.8.18.4 [Ar] 3d10 4s2 4p2 Graphite
tin 2.8.18.18.4 [Kr] 4d10 5s2 5p2
lead 2.8.18.32.18.4 [Xe] 4f14 5d10 6s2 6p2

Group 4 elements are part of the p-block.

Trends within the group

As we go down Group 4:
• Atomic radius increases - as electrons go into higher energy levels
• Density increases - density depends on structure, atomic radius and
atomic mass. Larger atomic masses usually produce higher densities,
since the atomic radius does not increase as fast as the atomic mass.
• Melting point decreases - due to the change in structure from giant
molecular to metallic • Giant covalent layer lattice.
• Ionisation energy generally decreases - since the atomic radius
increases, meaning the outer electrons are further away from the nucleus, • Lubricant due to ability of layers to ‘slide’ across each other.
and there is an increased shielding effect due to the greater number of • High melting point due to strong covalent interatomic bonds.
electrons between outer electrons and the nucleus • Conductor (in plane of layers) due to presence of delocalised electrons.
• Metallic character increases - since an explanation of this requires
knowledge of oxide characteristics, further details are given at the end
of this Factsheet Silicon and Germanium have a structure similar to diamond.

Exam Hint: Questions on trends, their explanations and consequences Tin has three allotropes, whose stability depends on the temperature. The
are common. Candidates need to be able to explain the reasons for the allotrope stable at room temperature (white tin) has a metallic structure.
trends in atomic radius, ionisation energy and metallic character. However, the other allotropes, which are stable at other temperatures,
have different structures.

Lead has a metallic structure.

Table 1. Elements of Group 4

Element Symbol Appearance Melting pt Density Conductivity 1st I.E. Bonding Metallic
(oC) (gcm-3) (kJ mol-1) character
carbon (graphite) C shiny black solid 3652 2.26 fairly good 1086 giant molecular non-metal
carbon (diamond) C colourless solid 3730 3.51 non-conductor 1086 giant molecular non-metal
silicon Si shiny grey solid 1410 2.33 semi-conductor 787 giant molecular non-metal
germanium Ge shiny grey solid 937 5.32 semi-conductor 760 giant molecular metalloid
tin Sn silver solid 232 7.3 good 707 giant metallic metal
lead Pb silver solid 327 11.4 good 715 giant metallic metal

1
Periodic Table - Group 4 Chem Factsheet

Oxidation States of Group 4

We might expect group 4 to have a common oxidation state of +4 as it has So tin(II) will reduce lead(IV) to lead(II):
4 outer electrons. oxidation
However, there are two oxidation states for Group 4: +4 and +2 >
Sn2+(aq) + Pb 4+(aq) → Sn4+(aq) + Pb2+(aq)
Going down the group, the stability of the +4 oxidation state falls, and the
stability of the +2 oxidation state rises (fig 2).
>
reduction

Fig 2. Relative stability of +2 and +4 oxidation states in Group 4 We will see examples of both oxidation states in the Group 4 elements
when we look at their oxides and chlorides.

rel +4 state Valencies in Group 4 - an explanation

ati
ve The ground state for the outer electrons of the Group 4 compounds is
sta
bil as shown below: s p
ity
f all
s

Hence, to achieve a valency of four, one s electron must be promoted to

the vacant p orbital:
+2 state rises s p
t i v e s tability
rela
C Si Ge Sn Pb

Promotion of this electron requires energy, but the energy released in

Only lead has a more stable +2 state than +4 state forming the two extra bonds compensates for this.

As we go down the group, the bonding electrons are further from the
Consequently: nucleus, so the energy gained from forming the extra bonds becomes
• +2 oxidation state of C, Si, Ge, Sn are reducing agents less. The s electron therefore becomes less likely to be promoted. This
(ie want to be oxidised and lose 2 electrons). In carbon and silicon, the is known as the inert pair effect.
+2 state is extremely unstable, so such compounds are rarely met. Since silicon and the elements below it have vacant d-orbitals, they can
• +4 oxidation state of Pb is an oxidising agent show a covalency of up to 6.
(ie wants to be reduced and gain 2 electrons)

Oxides of Group 4
Monoxides (+2 oxidation state)
Monoxide Reducing agent? Bonding Character
CO Yes - important industrially covalent neutral
SiO Yes covalent amphoteric - react with both acids and alkalis
SnO Yes some covalent character With alkali: PbO(s) + 2OH−(aq) + H2O (l) → Pb(OH)42−(aq)
PbO No ionic With acid: PbO(s) + 2H+(aq) → Pb2+(aq) + H2O(l)

Dioxides (+4 oxidation state)

Dioxide State Bonding Structure Character

CO 2 gas covalent simple molecular acidic - reacts with aqueous alkalis
CO2(g) + 2 OH −(aq) → CO32−(aq) + H2O(l)
SiO2 solid covalent macromolecular (Fig 3) v. weakly acid - reacts with hot concentrated alkalis
SiO2(s) + 2OH−(l) → SiO3(aq) + H2O(l)
GeO2 amphoteric - react with both acids and alkalis
SnO2 solid some ionic character giant structure With alkali: SnO2(s) + 2OH−(aq) + 2H2O(l) → Sn(OH)62−(aq)
PbO2 With acid: SnO2(s) + 4H+(aq) → Sn4+(aq) + 2H2O(l)

Fig 3. Structure of silicon dioxide

Acidity of the oxides decreases down the group

Exam Hint: Candidates must be able to recall suitable equations

to demonstrate the amphoteric character of oxides.

Note that lead(IV) oxide is an oxidising agent, and will decompose on

= silicon = oxygen atom heating to give lead(II) oxide and oxygen.

2
Periodic Table - Group 4 Chem Factsheet

Chlorides of Group 4
Element dichlorides (+2 oxidation state) tetrachloride (+4 oxidation state)
bonding stability & hydrolysis bonding stability & hydrolysis
carbon covalent extremely unstable unreactive
CCl4 and SiCl4 have
silicon covalent extremely unstable tetrahedral structures hydrolyses
germanium covalent hydrolyses with oxidation (Fig 4) reversible hydrolysis
GeCl2(s) + 2H2O(l) → GeO2(s) + 4HCl(aq) All tetrachlorides
tin partially ionic reversible hydrolysis covalent liquids with reversible hydrolysis
SnCl2(s) + H2O(l) ž SnClOH(s) + HCl(aq) simple molecular
structures
lead ionic stable, insoluble unstable, rapidly hydrolysed

Unlike the other tetrachlorides, CCl4 will not hydrolyse in water. The
Fig 4. Structure of carbon and silicon tetrachlorides
reason for this can be seen by examining the mechanism for hydrolysis of
SiCl4. The reaction between silicon tetrachloride and water is:
Cl Cl
SiCl4 (l) + 2H2O (l) → SiO2 (s) + 4HCl (aq)

This reaction can occur because a lone pair of electrons on the oxygen in
C Si water is allowed to approach the central silicon atom in SiCl4 and form a
Cl Cl Cl dative bond, starting this reaction.
Cl
Tetrachloromethane, CCl4, does not hydrolyse in water, as carbon is
Cl Cl smaller than silicon, causing:
• C - Cl bonds to be shorter than Si - Cl bonds
• C - Cl bonds to be stronger than Si - Cl bonds
Note: the dichlorides become increasingly ionic down the group as the • Cl atoms to be more closely packed around central C atom, not
"inert pair effect" (page 2) becomes more pronounced. allowing water molecule to approach it.
• Carbon, unlike silicon, has no available d - subshell to accept electrons
Exam Hint: Candidates must describe the inert pair effect in full; and form a new active bond.
just saying "because of the inert pair effect" will not gain full marks.
Exam Hint: Explaining the stability of carbon tetrachloride is a
common examination question.

Metallic Character in Group 4 - Summary and Explanation Questions

"Metallic character" is judged from a set of properties: 1. Explain the trend in first ionization energies down Group 4.
2. State the two oxidation states exhibited by Group 4 elements in their
compounds, and indicate which is the most common.
Metals • Good conductors of electricity. 3. Describe the trend in acidity of the Group 4 oxides.
• Form ionic compounds by losing electrons to produce
4. Give examples to show that lead(II) oxide is amphoteric.
positive ions
• Form basic oxides. 5. Use the electronic structure of carbon and silicon to explain why
Non-Metals • Non-conductors of electricity (insulators) except graphite carbon tetrachloride does not hydrolyse.
• Form ionic compounds by gaining electrons to produce
negative ions, or form covalent compounds Answers
• Form acidic oxides. 1. First ionisation energies decrease going down Group 4. This is due to:
increase in atomic radius; less attraction between outer electrons and
nucleus; increased shielding effect as more electrons exist between outer
So metallic character in Group 4 is measured by: electrons and nucleus. Consequently outer electrons are easier to remove
Electrical conductivity - this depends on the structure of the element. from larger atoms such as lead.
With the exception of graphite, conducting solids (as opposed to 2. Oxidation states of group 4 are +2 and +4. +4 is more common.
semiconductors) have a metallic giant structure, with free electrons. Tin 3. Acidity of the oxides decreases down the group.
and lead are the only group 4 elements with such a structure.
4. PbO(s) + 2OH−(aq) + H2O(l) → Pb(OH)42−(aq)
Covalent or ionic nature of compounds. Since +4 compounds are covalent PbO(s) + 2H+(aq) → Pb2+(aq) + H2O(l)
(with the exception of a small number of lead(IV) compounds), the change 5. Hydrolysis of SiCl4 can occur because a lone pair on an oxygen atom in
in metallic character is best shown by examining: water forms a dative bond to the Si atom. This is possible because Si has
• the relative stability of +2 and +4 compounds the 3d subshell which can accept electrons. The outer electrons of carbon
This depends on the "inert pair effect" as described on page 2. are in the second energy level, which has no d subshell, so the dative
• the ionic or covalent nature of +2 compounds bond cannot be formed.
This depends on ionisation energy, which decreases down the group.

Nature of oxides. Although no Group 4 oxides are basic, a change in Acknowledgements: This Factsheet was researched and written by Kieron Heath. Curriculum Press, Unit 305B,
The Big Peg, 120 Vyse Street, Birmingham, B18 6NF ChemistryFactsheets may be copied free of charge by
character can be seen from acidic to amphoteric - i.e. becoming more basic teaching staff or students, provided that their school is a registered subscriber. No part of these Factsheets may
in character. This is due to the increasingly ionic bonding in the oxides. be reproduced, stored in a retrieval system, or transmitted, in any other form or by any other means, without
the prior permission of the publisher. ISSN 1351-5136

3
 Chem Factsheet
September 2001 Number 21

Chemical Equilibria: Kc
To succeed in this topic you need to:- Kc is a ‘concentration term’ so can only be used for solutions and gases.
• understand the concepts of ‘dynamic equilibrium’ and Le Chatalier’s You cannot have concentrations of solids, so these are ignored when writing
Principle (Factsheet 09) the Kc expression.

After working through this Factsheet you will be able to The following examples illustrate the Kc expression for homogeneous and
• understand the concept of ‘Kc’ and write its mathematical expression heterogeneous equilibria:
from the balanced chemical equation.
• work out the units of Kc
• perform calculations using the Kc expression Example 1: 2SO2(g) + O2(g) ž 2SO3(g)

(a homogeneous reaction i.e. all species in the same phase)

What is Kc ?
The ‘c’ in Kc stands for ‘concentration’ and it is always expressed in [SO3]eq2
Kc = units = mol-1dm3
mol dm-3 (moles/litre = moles/dm3). To show this square brackets,[ ], are [SO2]2eq × [O2]eq
used around the species involved.
Example 2: CaCO3(s) ž CaO(s) + CO2(g)
Kc is a constant numerical value for any equilibrium reaction but is always
quoted at a particular temperature. This is because only temperature (a heterogeneous reaction i.e. the species are in different phases)
affects the value of Kc . In other words, you can add or remove reactants
and products, change the pressure of the system or add a catalyst and the Kc = [CO2]eq units = mol dm-3
position of equilibrium will change (according to Le Chatalier’s Principle)
to keep Kc a constant value. (NB. CaCO3 and CaO are solids)

Exam hint:- The concept of Kc, and its mathematical treatment, is a

Exam hint:- What affects the Kc value is invariably tested in questions! fundamental part of the A2 course. Questions commonly try to ‘catch
out’ candidates by including equations of heterogeneous reactions
i.e. state symbols for solids and liquids which do not appear on Kc
Writing Kc expressions expressions.
Look at the example below:
wA+xB ž yC+zD Question 1 at the end of this Factsheet provides further practice on writing
Kc expressions and working out the units of Kc
[C]eq × [D]eq
y z

Kc =
[A]eqw × [B]eqx
Working with powers
The example illustrates the rules for writing Kc expressions: To work with powers, you need to know these rules:

Rules
• If something doesn't have a power, it means the power is 1
1. ‘Products over ‘reactants’ (right-hand side on top) e.g. mol = mol1
2. Numbers in front become powers • If you have a power in the bottom of a fraction, you can bring it to the
3. ‘+’ becomes’×’ top by changing the sign
e.g. 1/mol2 = mol-2 1/dm-3 = dm3
Another example: • Anything to the power 0 is 1
N2(g) + 3H2(g) ž 2NH3(g) e.g. mol0 = 1
• Multiply the numbers ⇒ add the powers
[NH3]2eq
Kc = e.g. dm-3 × dm-3 = dm-3 + -3 = dm-6
[N2]eq × [H2]3eq
• Divide the numbers ⇒ subtract the powers
Every Kc has its own unit and this must be worked out every time (see box e.g. mol2/mol3 = mol2 − 3 = mol-1
on working with powers). For the example above: • To find a power of a power, multiply the powers
-3 2
(mol dm ) -3 2
(mol dm ) e.g. (dm-3)2 = dm-3× 2 = dm-6
Kc = =
(mol dm-3) × mol dm-3)3 (mol dm-3)4 When simplifying an expression, it is usually easiest to work in this order:

1 1. Work out any powers eg (mol dm-3)2 = mol2dm-6

= = (mol dm-3)-2 = mol-2dm6
(mol dm-3)2 2. Simplify the whole of the top of the fraction, and the whole of the
bottom of the fraction eg moldm-3×moldm-3= mol1+1dm-3 +-3= mol2dm-6
Sometimes the expression cancels down to ‘1’ i.e. ‘no units’. You must 3. Divide the top of the fraction by the bottom, (i.e subtract powers)
write ‘no units’ in these cases or the examiner will assume you have e.g. (mol dm-3)/(mol2dm-6) = mol1−2dm-3 − -6 = mol-1dm3
not tried to work out the units.

1
Chemical Equilibria : Kc Chem Factsheet

Kc values and the effect of temperature Method 2

Since Kc is a number, its value tells you the about position of equilibrium. You need to work out the amounts at equilibrium first, then find Kc. This
is the most common type of question! The method is outlined below:
1. Low Kc value e.g. Kc = 2.4 × 10-1
[products] 1. Write out the equation
Since Kc =
[reactants] 2. Put the starting amounts under the equation
there must be more reactants than products so the equilibrium lies to 3. Put the equilibrium amount(s) from the question under the starting
the left amounts
4. Use the information from the equation to calculate the ‘missing’
2. High Kc value e.g. Kc = 36.7 equilibrium amount(s), and find the concentrations
5. Write the Kc expression
[products] 6. Substitute the equilibrium amounts (using concentrations)
Since Kc =
[reactants] 7. Calculate the Kc value and its units.
there must be more products than reactants so the equilibrium lies to
the right.
Example 1.
How the Kc value is changed by changes in temperature depends on whether This problem refers to the equilibrium : A(g) + B(g) ž C(g)
the forward reaction is exothermic or endothermic:
0.50 mol of A and 0.40 mol of B were mixed in a 10 dm3 container. At
e.g. N2 (g) + 3H2(g) ž 2NH3(g) !H = -92kJmol
-1
equilibrium there were 0.2 mol of A. What is the value of Kc?

The forward reaction is exothermic so if the temperature is raised the 1. A + B ž C equation

equilibrium moves to the left (Le Chatalier’s) i.e. more reactants, so the Kc
value gets less. The reverse is true if the temperature is reduced the 2. 0.50 0.40 - starting amounts
equilibrium moves to the right producing more products, so the Kc value 3. 0.20 ? ? equilibrium amounts
increases.
4. If only 0.20 mol of A remains then 0.30 mol has converted to C.
The same logic applies to endothermic reactions. Since A:B:C is 1:1:1 then 0.30 mol of B must also convert to C.
Question (2) at the end of this Factsheet provides practice on working out So 0.30 mol of C is produced, and 0.1 mol of B remains.
the effect of temperature on Kc values So we have
A + B ž C
Kc calculations 0.20 0.10 0.30
There are two general types of calculations using the Kc expression:
1. finding the value of Kc given the amounts of species present, Now find the concentrations by dividing by the volume (10dm3):
2. finding the concentrations of species given the Kc value. A: 0.020 B: 0.010 C: 0.030
[C]eq
5. Kc =
Finding the value of Kc [A]eq × [B]eq
Method 1
You are provided with the equilibrium amounts in the question. 0.030
6. Kc = 0.020 × 0.010
Example 1.
7. Kc = 150 mol-1 dm3
This question refers to the following system in equilibrium:

2A(g) + B(g) ž 2C (g)

Example 2.
At equilibrium there were found to be 3 × 10-3 mol of A, 2 × 10-3 mol of This problem refers to the equilibrium 2R(g) ž S(g) + T(g)
B and 6.2 × 10-3 mol of C with a total volume of 2 dm3
2 mol of R was allowed to decompose into S and T until equilibrium was
reached. At equilibrium there was 0.5 mol of S and the total volume was 2 dm3
1. Write the Kc expression:
[C]eq2 Answer 1. 2R ž S + T
Kc =
[A]2eq[B]eq 2. start 2 - -
3. eqm ? 0.5 ?
2. Substitute the values in
2 4. Since S : T is 1 : 1, we must have 0.5 moles of T at equilibrium.
 6.2 × 10 −3  Since R : S is 2 : 1, we need 1 mole of R to make 0.5 moles of S
 2 
Kc =
2
So there is 1 mole of R left
 3 × 10 − 3  ×  2 × 10 − 3 
 2   2  2R ž S + T
eqm 1 0.5 0.5
NB. [ ] = mol dm-3, hence the need to use the 2dm3 from the question
to obtain ‘per 1dm3’. 5. Kc = [S]eq × [T]eq
[R]eq2
3. Calculate the answer and units Kc = 4.27 × 103 mol-1 dm3
6,7 Kc = 0.5× 0.5/1= 0.25 (no units)

This type of calculation is fairly straightforward as long as the Kc expression

is written correctly and the conversion using the volume is remembered. Question (3) and (4) at the end of this Factsheet provides further practice
on finding Kc .

2
Chemical Equilibria : Kc Chem Factsheet

Finding equilibrium concentrations from Kc values Exam Hint:- You will never have to solve a quadratic equation using
This type of calculation involves being given the value of Kc and some data the quadratic equation formula. If you ever find yourself with such an
about the concentrations of the species in the equilibrium reaction. equation, you have made a mistake!

Method 1 Practice Questions

You are provided with the K c value and some of the equilibrium 1. For each of the following equilibrium reactions write the Kc expression
concentrations and calculate the units:
Example (a) 2NH3(g) ž N2(g) + 3H2(g)
This question refers to the following equilibrium system: (b) 2SO2(g) + O2(g) ž 2SO3(g)
N2O4(g) ž 2NO2(g) (c) C(s) + O2(g) ž CO2(g)
At 250 C, the Kc value is 13.7 mol dm-3, and in the equilibrium mixture
o (d) N2O4(g) ž 2NO2(g)
there is 0.4 mol dm-3 of N2O4. Calculate the concentration of NO2 in the (e) 2HI(g) ž H2(g) + I2(g)
equilibrium mixture. (f) MgCO3(s) ž MgO(s) + CO2(g)
(g) C2H5OH(l) + CH3COOH(l) ž CH3COOC2H5(l) + H2O(l)
1. Write the Kc expression 2. (a) The reaction: 2A(g) ž B(g) + C(g)
[NO2]eq2 has Kc = 2.67 × 10-2 at 350 K.
Kc = When heated to 450K the Kc value changes to 0.98.
[N2O 4]eq
What can be deduced about the equilibrium from this information?
2. Substitute the values from the question into the equation
[NO 2]eq2 (b) The question is about the reaction,
13.7 =
0.4 X(g) ž 2Y(g) ∆H = -15 kJ mol-1
-3
3. Calculate the answer, including the units The Kc value is 7.4 mol dm at 300K.
[NO2]eq2 = 0.4 × 13.7 = 5.48 If the temperature is increased how do the following change?
[NO2] = √5.48 = 2.34 mol dm-3 (i) The value of Kc
(ii) The rate of reaction
Method 2 3. Calculate the value of Kc for each of the following and its units
You are provided with the Kc value and the starting amount of a species. (a) For the reaction: 2HI (g) ž H2(g) + I2(g)
At equilibrium there are 1.8 × 10-2 mol dm-3 of hydrogen iodide and the
Example hydrogen and iodine are both at a concentration of 3.2 × 10-3 mol dm-3.
For the following equilibrium system, Kc = 0.1
(b) At the equilibrium position for the reaction,
X(g) ž Y(g)
W(g) ž X(g) + Y(g)
If 10 moles of X were allowed to reach equilibrium, how many moles of the amounts of W, X & Y are 0.25 moles, 0.01 moles of 0.17 moles
Y would there be in the equilibrium mixture? respectively. The total volume is 1.2 dm3.
1. Set the equilibrium amount of a product to be x. Work out the
(c) When equilibrium is reached for the reaction,
equilibrium amounts of all the other substances in terms of x.
2NH3(g) ž N2(g) + 3H2(g)
If x moles of Y are produced, then x moles of X must be used up. There are 0.020 mol NH3, 0.015 mol N2 and 0.050 mol H2
So we have: in a total volume of 750cm3.
X(g) ž Y(g)
start 10 0 4. For each of the following calculate the Kc value and give its units:
eqm 10 −x x (a) This question is about the reaction: N2O4 (g) ž 2NO2(g)
0.4 moles of N2O4 is allowed to decompose. At equilibrium there
2. Convert to concentrations is found to be 0.1 mole of N2O4 in the 0.5 dm3 gaseous mixture.
Since we do not know the volume, call it V. (b) In the reaction: 2SO2(g) + O2(g) ž 2SO3(g)
So: [X] = (10 − x)/V 2 mol SO2 and 2 mol O2 react together until the equilibrium position
[Y]= x/V is reached. In a total volume of 10 dm3 there is found to be 1 mole
of SO3.
3. Write the Kc expresion and substitute in:
[Y]eq (c) When 1 × 10-2 mol ethanoic acid reacts with 2 × 10-2 mol ethanol
Kc = according to the equation,
[X]eq
CH3COOH(l) + C2H5OH(l) ž CH3COOC2H5(l) + H2O(l)
x/V
0.1 = there is found to be 5 × 10-3 moles of water in the equilibrium
(10 − x)/V mixture.
4. Rearrange the equation to find x
(d) When 0.4 mol M is mixed with 0.4 mol N they react together
x
First cancel the Vs: 0.1 = according to the following equation : 2M(g) + N(g) ž 4P(g)
(10 − x) In a total volume of 2 dm3 there is found to be 0.3 mol.
Then multiply up: 0.1(10 − x) =x (e) This question is about the equilibrium : C(s) + O2(g) ž CO2 (g)
Expand brackets: 1 − 0.1x =x 1 × 10-2 mol oxygen reacts with carbon and the system reaches the
Rearrange to find x: 1 = 1.1x equilibrium position. In the total volume of 200 cm3 there are 7.5 × 10-3
x = 1/1.1 = 0.91 moles moles of carbon dioxide.

3
Chemical Equilibria : Kc Chem Factsheet

5. (a) Kc is 15.6 mol-1 dm3 at 370oC for the system 4. (a) 1.8 mol dm-3 ([N2O4]eq = 0.05, [NO2]eq = 0.3)
PCl3(g) + Cl2(g) ž PCl5(g) (b) 6.67 mol- dm3 ([SO2]eq = 0.1, [O2]eq = 0.15, [SO3]eq = 0.1)
At equilibrium, the concentration of PCl5 is 0.6 mol dm-3. What are (c) 0.33 no units (Kc = (0.5 × 10-2)2 / (0.5 × 10-2 × 1.5 × 10-2)
the concentrations of the PCl3 and Cl2 if there were equimolar
(d) 0.025 mol dm-3 ([M]eq = 0.15, [N]eq = 0.175, [P]eq = 0.1)
amounts of each at the start?
(e) 3.00 no units C is a solid so does not appear to Kc express.
(b) For the equilibrium system
([O2]eq = 1.25 × 10-2, [CO2]eq = 3.75 × 10-2)
A(g) ž 2B(g)

Kc = 0.02 mol dm-3 at 170o C. 0.6

5. (a) 15.6 =
At equilibriu,m the concentration of B is 0.12 mol dm-3. x2
What is the equilibrium conentration of A?
15.6x2 = 0.6
x2 = 0.6/15.6 = 0.03846
(c) Kc is 0.88 at 200oC for the system
x = √0.03846 = 0.196 moles
R(g) ž S(g) 0.122
(b) 0.02 =
If there were 2 moles of R at the start, how many moles of R would A
there be at equilibrium? 0.02A = 0.122
A = 0.122/0.02 = 0.72 moles
(d) For the system
x
(c) 0.88 =
F(g) + G(g) ž H(g) + J(g) 2−x
Kc = 1 at 120oC 0.88 (2 − x) = x
Six moles of F and six moles of G were used at the start. How 1.76 - 0.88x = x
many moles of J will there be at equilibrium? 1.76 = 1.88x
x = 1.76/1.88 = 0.936 moles
Answers
3 (d) At equilibrium, we have x moles of J and H
[N2]eq × [H2]eq 2 -6 and 6 − x moles of F and G
1. (a) Kc = mol dm
[NH3]eq2
x2
1 = (6 − x)(6 − x)
2
[SO3]eq
(b) Kc = mol-1dm3 (6 − x)(6 − x) = x2
[SO2]eq2 × [O2]e
q
36 − 12x + x2 = x2
36 = 12x
[CO2]eq x = 3 moles
(c) Kc = (C(s)!!) No units
[O2]eq

[NO2]eq2
(d) Kc = mol dm-3
[N2O4]eq

[H2]eq × [I2]eq
(e) Kc = No units
[HI]eq2

(f) Kc = [CO2]eq (solids!!) mol dm-3

[CH3COOC2H5]eq × [H2O]eq
(g) Kc = No units
[C2H5OH]eq × [CH3COOH]eq

2. (a) the forward reaction is endothermic

(b) (i) Decreases/gets less

(ii) Increases

3. (a) 3.16 × 10-2 no units

(b) 5.67 × 10-3 mol dm-3 Acknowledgements: This Factsheet was researched and written by Sam
(c) 8.2 × 10-3 mol2dm-6 Goodman. Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street,
Birmingham, B18 6NF. ChemistryFactsheets may be copied free of charge by
teaching staff or students, provided that their school is a registered subscriber.
No part of these Factsheets may be reproduced, stored in a retrieval system, or
transmitted, in any other form or by any other means, without the prior
permission of the publisher. ISSN 1351-5136

4
 Chem Factsheet
September 2001 Number 22

Chemical Equilibria: Kp
To succeed in this topic you need to:- (mol dm-3)2
• Understand the concepts of ‘dynamic equilibrium’ and Le Chatalier’s Units =
(mol dm-3) × (mol dm-3)3
Principle (Factsheet 09) mol2 dm-6
• Ensure you are fully competent with the work on Kc covered in Factsheet =
(mol dm-3) × (mol3 dm-9)
Number 21 2 -6
= mol dm
mol4 dm-12
After working through this Factsheet you will be able to:-
• understand the concept of ‘Kp’ and write its mathematical expression = mol-2 dm6
from the balanced chemical equation Now we repeat this for Kp:
• calculate partial pressure from the data given
(pNH3)eq2
• work out the units of Kp Kp = (pN ) ×(pH ) 3
• perform calculations using the Kp expression 2 eq 2 eq

(atm)2
Units =
Exam hint:- Do not think of Kp as something completely new - it's (atm) × (atm)3
basically an extension of the work on Kc, with the fundamental theory
(atm)2
of equilibria applying to both. =
(atm)4
= atm-2
What is Kp ?
The ‘p’ in Kp stands for ‘pressure’. Kp only applies to gases. Exam Hint:- Pressure is quoted in a range of different units: -
atmospheres (atm), pascals (Pa), kilopascals (kPa), megapascals
(MPa) and mmHg or cmHg.
Exam Hint: -Watch out for heterogeneous reactions (those that It doesn’t matter – you just use whichever units are used in the question!
involve gases and solids or liquids) - Kp only applies to gases! So in the above example, if we'd started with Pascals, the final unit
would be Pa-2 etc.

Kp (like Kc) is a constant numerical value for any equilibrium but is always
quoted at a particular temperature. This is because only temperature Question 1 at the end of the Factsheet provides further practice on writing
affects the value of Kp expressions for Kp and working out units.

In other words you can add or remove reactants or products, change the Mole fractions and partial pressures
pressure or add a catalyst and the value of Kp does not change. This is Before we go to Kp calculations there is some new work to be done about
because the equilibrium, adjusts its position (according Le Chatalier’s gases. This theory is based on the Gas Laws - but you do not need to know
Principle) to keep Kp a constant value. anything about the Gas Laws for this!

Exam Hint:- The effect of changing conditions on the value of Kp is If you have a mixture of two or more gases then the mixture will exert a
invariably tested in questions. You should note very carefully what has total pressure. This total is made up of the individual contributions from
been covered so far! each of the gases in the mixture. These are called partial pressures.

Total Pressure = Sum of the Partial Pressures

Writing Kp expressions
of a gas mixture of the gases in the mixture
The same rules apply to writing Kp expressions as to Kc:
P = pA + pB + pC + ......
Rules where A, B, C, etc represent the gases.
1. ‘Products’ over ‘Reactants’ (right hand side on top)
2. Numbers in front become powers
3. ‘+’ becomes ‘×’. To find Partial Pressures, we use mole fractions:
4. Only gases are included
moles of that gas
Mole Fraction of a gas =
The difference to Kc is that pressures are used, not concentrations. This total number of moles of gas
affects the symbol used - Kc used [ ] ≡ mol dm-3, while Kp uses a letter ‘p’. The mole fractions must always add up to 1
The worked example below shows the rules being applied:

Example: For the reaction N2(g) + 3H2(g) ž 2NH3(g), write expressions

for Kp and Kc and give their units Partial pressure = Mole Fraction × Total
[NH3]eq2 of gas A for gas A Pressure
Kc =
[N2]eq×[H2]eq3

1
Chemical Equilibria: Kp Chem Factsheet

4. Calculate the equilibrium partial pressures

Example 1: What is the partial pressure of each gas if 2 moles of A and
3 moles of B have a total pressure of 4 atm? N2O4: (0.1/0.3)× 0.5 = 0.167 atm
NO2: (0.2/0.3)× 0.5= 0.333 atm
Mole fraction for A = 2/(2 + 3) = 0.4
Mole fraction for B = 3/(2 + 3) = 0.6 5. Calculate Kp
(pNO2)eq2
So: Kp =
(pN 2O4)eq
Partial pressure of A = 0.4 × 4 = 1.6 atm
0.3332
Partial pressure of B = 0.6 × 4 = 2.4 atm = = 0.66 atm
0.167
Check: pA + pB = 1.6 + 2.4 = 4 atm = total pressure
Example 2
4 moles of SO3 was heated to 150oC. At equilibrium there was found to
Example 2: 0.4 moles of C, 0.2 moles of D and 1.0 moles of E have a
be 0.5 moles of O2, and the total pressure was 2 atm.
total pressure of 200 Pa. Find the partial pressure of each gas.
2 SO3(g) ž 2 SO2 (g) + O2(g)
Mole fraction for C = 0.4/(0.4 + 0.2+1.0) = 0.25 What is the value of Kp?
Mole fraction for D = 0.2/(0.4 + 0.2+1.0) = 0.125
Mole fraction for E = 1.0/(0.4 + 0.2 + 1.0) = 0.625 1. 2 SO3(g) ž 2 SO2 (g) + O2(g)
4 0 0
Partial pressure of C = 0.25 × 200 = 50 Pa
Partial pressure of D = 0.125 × 200 = 25 Pa 2. At equilibrium, there are 0.5 moles O2. From the equation:
Moles SO2 produced = 2× moles O2 produced
Partial pressure of E = 0.625 × 200 = 125 Pa
Moles of SO3 used = 2 × moles O2 produced
Check: pC + pD + pE = 50 + 25 + 125 = 200 Pa = total pressure So moles SO2 produced = 1. Moles SO3 used = 1.
3 moles of SO3 are left
2 SO3(g) ž 2 SO2 (g) + O2(g)
Check you are happy using mole fractions to calculate partial pressures by equm moles 3 1 0.5
attempting Question 2 at the end of this Factsheet before moving on.
3. Mole fractions: SO3: 3/ 4.5 SO2: 1/4.5 O2: 0.5/ 4.5
Calculating Kp
The method for this is: 4. Partial pressures: SO3: (3/ 4.5)× 2 = 1.333 atm
SO2: (1/ 4.5)× 2 = 0.444 atm
Method O2: (0.5/ 4.5)× 2 = 0.222 atm
1. Write the equation, putting in the start moles
(pSO2)eq2 (pO2)eq 0.4442× 0.222
2. Calculate the equilibrium moles from the data given. 5. K p = 2 = = 0.024 atm
(pSO3)eq 1.3332
3. Change equilibrium moles into mole fractions.
4. Calculate partial pressures for the gases (mole fraction × total
pressure). In some examples, you may not be given the actual number of moles at the
start, but instead the percentage of dissociation. The approach is very
5. Substitute the partial pressure values into the Kp expression and similar - we just imagine that we start with 1 mole!
calculate the Kp value.

Example 3
Example 1 In the gas phase, PCl5 undergoes thermal dissociation:
0.2 moles of N2O4 was heated to 100oC in a flask. At equilibrium 50% of PCl5(g) ž PCl3(g) + Cl2(g)
the N2O4 has dissociated and the total pressure was 0.5 atm. At a certain temperature, and a total pressure of 3 atm, 60% of the PCl5
originally present has dissociated when equilibrium is attained.
N2O4(g) ž 2NO2(g)
Calculate the partial pressures of the three gases at equilibrium, and
What is the value of Kp?
hence the value of Kp at this temperature.
1. Write the equation. Put in the moles at the start 1. PCl5(g) ž PCl3(g) + Cl2(g)
N 2 O 4 ž 2 NO2 1 0 0
0.2 0
2. 60% dissociated means 0.6 moles of PCl5 are used up, so 0.4 remain.
2. Work out the moles at equilibrium,using the data in the question Moles PCl3 produced = moles Cl2 produced = moles PCl5 used = 0.6
50% of 0.2 moles is 0.1 moles PCl5(g) ž PCl3(g) + Cl2(g)
From equation, 1 mole N2O4 produces 2 moles NO2 equm moles 0.4 0.6 0.6
So 0.1 moles N2O4 produces 0.2 moles NO2 3. Mole fractions: PCl5: 0.4/1.6 PCl3: 0.6/1.6 Cl2: 0.6/1.6
So at equilibrium, we have
N 2O 4 ž 2 NO2 4. Partial pressures: PCl5:(0.4/ 1.6)× 3 = 0.75 atm
equm moles 0.1 0.2 PCl3: (0.6/ 1.6)× 3 = 1.125 atm
O2: (0.6/ 1.6)× 3 = 1.125 atm
3. Calculate the mole fraction for each substance at equilibrium
N2O4: 0.1/0.3 NO2: 0.2/0.3 (pPCl3)eq(pCl2)eq 1.125 × 1.125
5. K p = = = 1.69 atm (3SF)
(pPCl5)eq 0.75
Exam Hint:- Do not round at this stage - if you do you may end up with
rounding errors later. Before moving on, attempt Question 3 to make sure you are confident
with calculating Kp values.

2
Chemical Equilibria: Kp Chem Factsheet

Calculating partial pressure values at equilibrium Example 3.

If the value of Kp is given for a simple binary system (i.e. only two species
For the equilibrium system : N2O4(g) ž 2NO2(g)
involved) you may be required to calculate the partial pressures of the
at 100oC, Kp = 0.66 atm.
gases involved.
One mole of N2O4was placed in a sealed flask, and heated to 100oC. The
total pressure was 2 atm. Find the partial pressure of NO2 at equilibrium.
There are two types of calculation here; the first is simply the reverse of
the previous calculations on Kp where partial pressures were used to find 1. Equation and start moles
the value of Kp. N2O4(g) ž 2NO2(g)
1 0
Example 1.
For the equilibrium system 2. Equilibrium moles in terms of x
N2O4(g) ž 2NO2(g) Suppose that x moles of N2O4 have been used at equilibrium
at 340K, Kp = 3.90 atm. Since 1 mole of N2O4 is required to produce 2 moles of NO2,
moles of NO2 produced = twice moles of N2O4 used = 2x
If, at the equilibrium position, the partial pressure of the NO2 was found to So at equilibrium, we have:
be 0.80atm, calculate the partial pressure of the N2O4 and the total pressure. N2O4(g) ž 2NO2(g)
1. Write the Kp expression equm moles 1 − x 2x
(pNO 2) eq2 3. Mole fractions, in terms of x
Kp = Total moles = 1 − x + 2x = 1 + x
(pN2O4)eq
So mole fractions are
N 2O 4 : (1 − x)
2. Substitute in what you know
NO 2: 2x
(0.80)2 (1+ x) (1+ x)
3.9 = 4. Partial pressures, in terms of x
(pN2O4)eq
N 2O 4 : (1 − x) × 2 = (2 − 2x)
3. Rearrange the equation: (1+ x) (1+ x)
3.9 × (pN2O4)eq = (0.80)2
2x 4x
(0.80)2 NO2: ×2=
(1+ x) (1+ x)
(pN2O4)eq = = 0.164 atm
3.9
5. Write down expression for Kp, and substitute in:
Total pressure = sum of partial pressures = 0.164 + 0.80 = 0.96atm (2DP)

Exam Hint:- When you are multiplying a fraction by a whole

Example 2. number, just multiply the top of the fraction by the number
For the equilibrium system 2
N2O4(g) ž 2NO2(g)  4x 
(pNO2)eq2  
1+ x 
= 
at 340K, Kp = 3.90 atm.
Kp = 0.66 =
If the equilibrium partial pressure of the N2O4 was 0.60atm, calculate (pN2O4)eq 2 − 2x
the partial pressure of the NO2 and the total pressure. 1+ x
6. Rearrange
2
(pNO2)eq
1. Kp = Exam Hints:-
(pN2O4)eq
1. To square a fraction, square the top and square the bottom
2
(pNO2)eq 2. To divide a fraction by a fraction, turn the one on the bottom
2. 3.90 = upside down and multiply them
0.60
3. To multiply two fractions, multiply the tops and multiply the bottoms
3. 3.90 × 0.60 = (pNO2)eq2
(pNO2)eq = √(3.90 × 0.60) = √2.34 = 1.53atm (2DP) 16 x 2

0.66 =
(1 + x )2
Total pressure = 1.53 + 0.60 = 2.13atm (2DP) 2 − 2x
1+ x
16x 2 × 1 + x
0.66 =
In the second type of calculation, neither of the equilibrium pressures are (1 + x )2 2 − 2x
16x 2 (1 + x )
known. The examples below illustrate how to approach this; the method is
similar to the one for calculating Kp
(1 + x )2 (2 − 2x )
=

Method 16 x 2
(1 + x )(2 − 2 x )
1. Write the equation, putting in the start moles = (cancelling out the 1 + x)
2. Call the number of moles of reactant used up at equilibrium "x" 16 x 2 = 16 x
2
(multiplying out brackets)
=
Work out the number of moles at equilibrium of all the other substances 2 + 2x − 2x − 2x2 2 − 2x2
in terms of x. Now multiply up:
3. Find mole fractions, in terms of x 0.66(2 − 2x2) = 16x2
4. Find partial pressures, in terms of x 1.32 − 1.32x2 = 16x2
5. Write down expression for Kp and substitute in. 1.32 = 17.32x2
x2 = 1.32/17.32 = 0.0762...
6. Rearrange to find x, and hence the required partial pressure
x = √0.0762.. = 0.276
4x
So partial pressure of NO2 = (1+ x) = 0.87atm (2SF)

3
Chemical Equilibria: Kp Chem Factsheet

Practice Questions
Example 4. 1. For each equilibrium write the Kp expression and the units (the units of
For the equilibrium system partial pressure are given in brackets).
PCl5(g) ž PCl3(g) + Cl2(g) (a) 2X(g) ž 2Y(g) + 2Z(g) [atm]
at a temperature T, Kp = 1.69 atm.
(b) BaCO3(s) ž BaO(s) + CO2(g) [kPa]
One mole of PCl5(g)was placed in a sealed flask, and heated to
(c) 3R(g) ž 2S(g) + 3T(g) [Pa]
temperature T. The total pressure was 3 atm. Find the partial pressure of
PCl5 at equilibrium.
2. Calculate the partial pressures of the gases in the following mixtures at
equilibrium.
1. PCl5(g) ž PCl3(g) + Cl2(g) (a) 2 mol A, 2 mol B, 3 mol C. Total pressure = 2 atm
1 0 0 (b) 0.25 mol D, 0.25 mol E, 1 mol F. Total pressure = 150 Pa
2. If x moles of N2O4 have been used at equilibrium, x moles of each of 3. What is the Kp value for each of the following equilibria?
PCl3 and Cl2 will be produced
(a) PCl5(g) ž PCl3(g) + Cl2(g)
So at equilibrium, we have:
2 mol PCl5 is heated to 200oC. The PCl5 50% dissociates at
PCl5(g) ž PCl3(g) + Cl2(g)
equilibrium, and the total pressure is 100 kPa
equm moles 1−x x x
(b) S(s) + O2(g) ž SO2(g)
3. Total moles = 1 − x + x + x = 1 + x At the start there are 0.4 mol O2. At equilibrium there are 0.1 moles
So mole fractions are: of SO2, with a total pressure of 0.5 atm.
PCl5: (1 − x) PCl3: x x
Cl2: (c) 2A(g) ž B(g) + 2C(g)
(1+ x) (1+ x) (1+ x)
A sample of A is heated to 125oC in a flask. At equilibrium the gas
4. Partial pressures: A has 25% dissociated, and there is a total pressure of 2 atm.
(1 − x) (3 −3x)
PCl5: ×3= (d) N2(g) + 3H2(g) ž 2 NH3(g)
(1+ x) (1+ x)
0.5 moles of H2 and 0.4 moles of N2 are allowed to reach equilibrium.
x 3x At equilibrium there are 0.2 moles H2. The total pressure is 200 Pa.
PCl3 and O2: ×3=
(1+ x) (1+ x)
4. (a) Kp = 2.4 atm-1 at 400K for the following equilibrium system:
 3 x  3 x 
   2A(g) ž B(g)
(pPCl3)eq(pCl2)eq 1 + x  1 + x 
5. Kp =1.69 = =  At equilibrium, the partial pressure of A is 0.6 atm.
(pPCl5)eq 3 − 3x
Find the partial pressure of B and the total pressure at equilibrium.
1+ x
9x2

6. 1.69 =
(1 + x )2 (b) Kp = 0.53 atm at 350 K for the equilibrium system:
3 − 3x (CH3COOH)2(g) ž 2CH3COOH(g)
1+ x At equilibrium, the partial pressure of CH3COOH is 1.1atm.
Find the partial pressure of (CH3COOH)2 at equilibrium.
9 x2 × 1 + x
=
(1 + x )2 3 − 3x (c) For the system A(s) ž B(s) + C(g), Kp = 0.8 atm at 200oC.
Find the equilibrium partial pressure of C(g)
9 x2
=
(1 + x )(3 − 3x ) (d) For the system D(g) ž E(g) + F(g), Kp = 1.6 atm at 350 K
Given that there was initially 1 mole of D, and that the total
9x2 = 9x 2
2 pressure at equilibrium is 1 atm, find the equilibrium partial
=
3 + 3x − 3x − 3x 2
3 − 3x pressure of E.

1.69(3 − 3x2) = 9x2 Answers

5.07 − 5.07x2 = 9x2 1. (a) (pY)eq2 × (pZ)eq2 / (pX)eq2 atm2
14.07x2 = 5.07 (b) (pCO2)eq kPa
x2 = 5.07/14.07 = 0.360... (e) (pS)eq2 × (pT)eq3 / (pR)eq3 Pa2
x = 0.600
(3 −3x) 2. (a) A = 0.57 atm B = 0.57 atm C = 0.86 atm
Partial pressure of PCl5 = = 0.75atm (b) D = 25 Pa E = 25 Pa F = 100 Pa
(1+ x)
3. (a) pPCl5 = pPCl3 = pCl2 = 33.3 kPa Kp = 33.3 kPa
(b) pO2 = 0.375 atm pSO2 = 0.125 atm Kp = 0.33 No units
Exam Hint:- If you get to a stage of trying to solve a quadratic
equation – YOU HAVE MADE AN ERROR SOMEWHERE (solving (c) pA = 1.33 atm pB = 0.22 atm pC = 0.44 atm Kp = 0.024 atm
quadratic equations is not in the syllabus!) (d) pN2 = 85.7Pa pH2 = pNH3 =57.1 Pa Kp = 0.000204 Pa-2

4. (a) 2.4 = pB/0.602. So pB = 2.4 × 0.602 = 0.864 atm

(b) 0.53=1.12/p(CH3COOH)2 So p(CH3COOH)2 =1.12/0.53 = 2.28atm
Acknowledgements: This Factsheet was researched and written by Sam Goodman. (c) Kp = pC(g) So pC(g) = 0.8 atm
Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham, B18 6NF. (d) Equilibrium moles: D: 1 − x; E: x F: x
ChemistryFactsheets may be copied free of charge by teaching staff or students, provided pD = (1 −x)/(1+x) pE = pF = x/(1 + x)
that their school is a registered subscriber. No part of these Factsheets may be reproduced,
stored in a retrieval system, or transmitted, in any other form or by any other means, without Kp = 1.6 = x2/ (1 − x2)
the prior permission of the publisher. ISSN 1351-5136 x = 0.784 so pE =0.44atm

4
 Chem Factsheet
September 2001 Number 23
How To Answer Questions on Titration Calculations
Titration calculations are one of the most unpopular calculation types Example 1.
with many A-level students. This Factsheet aims to supply a method for A fertiliser contains ammonium sulphate and potassium sulphate. When
these calculations which will allow students to tackle them confidently, 0.50g of the fertiliser was warmed with sodium hydroxide solution,
even when the context is unfamiliar. ammonia gas was evolved. The ammonia required 15.0cm3 of 0.2 M
hydrochloric acid to neutralise it. What is the percentage by mass of
Before starting this Factsheet, you should review the formulae connecting ammonium sulphate in the fertiliser?
moles with masses, volumes and concentrations (Factsheets 2, 3 and 7).
Method
Approaching calculations 1. Produce the flowchart:
The commonest comment from students is ‘I didn’t know where to start
on it!’. The key point in overcoming this is to recognise that despite their (NH4)2 SO4/K2SO4 NaOH
appearances, all titration calculations involve the same processes, and once NH3+ 15.0cm3 0.2 M HCl
you recognise this you will succeed in solving them. 0.50g

Success in titration calculations not only requires the manipulation of 2. The equations are:
numbers - familiarity with reactions and an ability to write balanced (NH4)2SO4 + 2NaOH ! 2NH3 + Na2SO4 + 2H2O
chemical equations are also vital. Ratio 2 NH3 : 1 (NH4)2 SO4
NH3 + HCl ! NH4Cl
Exam Hint: Few marks will be gained from calculations from an incorrect Ratio 1 NH3 : 1 HCl
chemical equation. Take time checking your equations are balanced.
4. We know cm3 and M for HCl. So we start at the end of the flowchart
we can use:
cm3 × M on the HCl amounts,
moles =
The Method 1000
1. Read the question and produce your own flowchart of the information given.
Decide whether any parts are not relevant to the calculation. So moles HCl = 15 × 0.2 = 0.003
1000
2. From the equation(s) (either given in the question or the ones you
have to write for yourself) write down the ratio of reacting amounts 5. Working backwards:
needed If we know the moles of HCl then the moles NH3 is the same (1:1)
So moles NH3 = 0.003
3. Remember the following equations:
We know 2 NH3 : 1 (NH4)2 SO4
g So if we half the NH3 moles we get the moles of (NH4)2 SO4
moles =
Ar or Mr So moles (NH4)2SO4 = 0.003/2 = 0.0015
cm3 × M The question asks about % by mass, so we need this answer as a mass.
moles =
1000 So we need to change moles to grams i.e.
mass of pure substance × 100 g
moles =
percentage purity = Mr
mass of impure sample
To use this, we need Mr((NH4)2 SO4) = (18 × 2) + 32 + (4 × 16) = 132
4. Look at the flowchart and decide where, and to what, you can apply
So mass (NH4)2SO4 = moles × Mr
the equations in step 3 above. Look for something you know two
= 0.0015 × 132
pieces of informaton about that occur in the same equation - for example,
= 0.198g
both moles and cm3, or both mass (g) and Mr.
5. Work back through the flowchart to the answer asked for in the g × 100
So percentage (NH4)2 SO4 =
question. 0.50
0.198 × 100
=
0.50
= 39.6%
Understanding how step 4 works is the key to overcoming the "where do
I start?" problem. If you know two pieces of information about the same Before you go on to the next example you should make sure you understand:
thing - for example, the volume and concentration of a solution - then you • how the flowchart was produced
can use one of the equations listed in step 3 - you cannot get anywhere
with only one piece of information!
• why the calculation started with HCl,
• the process of working back to (NH4)2SO4 via the ratios from the
equations

1
How To Answer Questions on Titration Calculations Chem Factsheet

Example 2. Example 3
A piece of iron wire of mass 2.3g was reacted with heated dilute sulphuric In an experiment to find the value of n in (NH4)2SO4.FeSO4.nH2O, 16.98g
acid until it had all reacted and dissolved. After cooling the solution, it of the salt were dissolved in a mixture of water and dilute sulphuric acid.
was made up to 250cm3 in a volumetric flask. The solution contained The solution was made up to 250cm3 in a volumetric flask. 25.0cm3 of
only Fe2+ ions, not Fe3+ ions. 25.0 cm3 of the iron solution was acidified this solution was titrated with potassium manganate(VII) of concentration
and titrated with a 0.015 moldm-3 solution of potassium dichromate (VI) 0.030 mol dm-3. 22.5cm3 of this solution was required.
of which 30.0cm3 was required. The reaction is:

MnO4− + 8H+ + Fe2+ ! Mn2+ + 5Fe3+ + 4H2O

The reaction is:
What is the value of n in the salt?
Cr2O72− + 14H+ + 6Fe2+ ! 2Cr3+ + 6Fe3+ + 7H2O
This solution is written out only in minimum detail. Construction of the
Calculate the percentage of iron in the wire.
flowchart is left as an exercise for the student.
Method 5 Fe2+ : 1 MnO4−
1. The flowchart is,
22.5 × 0.003
Wire H2SO4 Moles MnO4− = = 0.000675
1000
2.3g Fe2+ ! 250cm3 ! 25cm3 Fe2+ + 30.0cm3 0.015 M
Fe2+ Cr2O72- Moles Fe2+in 25cm3 = 0.000675 × 5
= 0.003375
2. From the equation, 6 Fe2+ : 1 Cr2O72- Moles Fe2+ in 250cm3 = 0.003375 × 10 = 0.03375
cm3
4. We know cm3 and M for Cr2O72− So we can use moles = ×M
1000 1 Fe2+ : 1 (NH4)2 SO4.FeSO4.nH2O
on the Cr2O72− in the flowchart to find its moles
Moles (NH4)2 SO4.FeSO4.nH2O = 0.03375
30 × 0.015
Moles Cr2O72− = = 0.00045
1000 So 0.03375 = 16.98/ Mr
So Mr = 16.98/0.03375 = 503.1
5. 6 × Cr2O7 ! moles Fe in 25cm
2- 2+ 3

(18 × 2) + 32 + (4 × 16) + 56 + 32 + (4 × 16) + 18n = 503.1

So moles Fe2+ in 25cm3 = 0.00045 × 6
= 0.0027 284 + 18n = 503.1
18n = 503.1 – 284 = 219.1
Moles Fe2+ in 25cm3 × 10 ! moles Fe2+ in 250cm3 n = 219.1/18 = 12.17
So moles Fe2+ in 250cm3 = 10 × 0.0027 = 0.027 But n must be a whole number
So n = 12
1 Fe ! 1 Fe
2+

So moles Fe = 0.027
Practice Questions
We need mass of Fe, since question is about % purity. 1. A marble chip of mass 5.0g required 40cm3 of 1.5 mol dm-3 hydrochloric
g acid to react with all the calcium carbonate it contained. What is the
So use moles =
Ar percentage of calcium carbonate in the marble chip?
So mass of Fe = Ar × moles
2. 13.73g of sodium carbonate crystals were dissolved in 1 dm3 of water.
= 56 × 0.027 = 1.512g
25cm3 of the solution were neutralised by 24cm3 of 0.10 mol dm-3
hydrochloric acid. What is the value of n in the formula Na2CO3 . nH2O
Now find % purity
for sodium carbonate crystals?
1.512× 100
Percentage Fe = = 65.74%
2.3 3. A piece of iron wire weighs 2.8g. it is dissolved in acid and converted to Fe2+
ions. The solution reacts with 40cm3 of 0.2M potassium dichromate (VI)
Answers solution. The reaction is:
1. 60% Cr2O72− + 14H+ + 6Fe2+ ! 2Cr3+ + 7H2O + 6 Fe3+
moles HCl = 0.06; moles CaCO3 = 0.03;
Mass CaCO3 = 100 × 0.03 = 3g What is the percentage of iron in the sample of wire?

2. n = 10 4. A 0.50g sample of potassium(V) iodate, KIO3 is dissolved in water and

moles HCl = 0.0024 moles Na2CO3 (in 1 dm3) = 0.048 made up to 250cm3. A 25.0cm3 sample of this solution is added to an
Mr = 3.73/0.048 = 286 Na2CO3 = 106, so n = (286 − 106)/18 = 10 excess of potassium iodide in sulphuric acid solution. The reaction is:
3. 96% IO3− + 5I− + 6H+ ! 3I2 + 3H2O
moles Cr2O72- = 0.008; moles Fe2+ = 6 × 0.008
mass Fe = 0.048 × 56 = 2.688g The iodine formed requires 20.0cm3 of sodium thiosulphate solution
% = 2.688× 100/2.8 for titration. The reaction is:

4. 0.072 mol dm-3 2Na2S2O3 + I2 ! Na2S4O6 + 2NaI

moles KIO3 in 250cm3 = 0.5/Mr = 0.5/214 = 0.00234 What is the concentration of the sodium thiosulphate solution?
moles KIO3 in 25cm3= 0.00234 /10 = 0.000234
mole I2 = 0.000234 × 3 Acknowledgements: This Factsheet was researched and written by Sam Goodman. Curriculum Press, Unit 305B,
The Big Peg, 120 Vyse Street, Birmingham, B18 6NF ChemistryFactsheets may be copied free of charge by
moles Na2S2O3 = 0.000234 × 2 = 0.00144 teaching staff or students, provided that their school is a registered subscriber. No part of these Factsheets may
M = 0.00144 × 1000/20 be reproduced, stored in a retrieval system, or transmitted, in any other form or by any other means, without
the prior permission of the publisher. ISSN 1351-5136

2
 Chem Factsheet
September 2001 Number 24
Laboratory Chemistry: Making Observations and Inferences
In practical exams or assessments students are commonly asked to carry out chemical tests, record observations and draw conclusions
(inferences) from these observations. The focus of this Factsheet is on the language and background knowledge required to make clear,
accurate observations and inferences.
Recording Observations
Observations are made using all of the senses - you must record what is seen,smelled, heard and felt (e.g. temperature changes). You must use the correct
chemical language to describe these observations clearly and concisely. Table 1 gives some common key words (with their meanings) used in making
observations, with examples of how this information would be used. The table above shows the most common types of observations that are made, but
if you notice anything else occurring you should certainly record it. Some reactions can be identified by observations peculiar to them (i.e. silver mirror
formed on inside of test tube, or brown ring formed at interface) so everything should be written down.
Table 1. Basic descriptive terms
Key Word Description Example Observation
No observable Use this phrase when there is no evidence of a reaction occurring. Place a strip of copper No observable reaction.
reaction Never write ‘Nothing happened‘, as it may just be that the reaction metal into a test tube and
cannot be seen happening. add 4-5 cm3 of water.

Solid A chemical in the solid state. Gently heat copper powder A black powdered solid is formed.
State: • The colour. in a test tube.
• Whether powdered, ash, metallic, crystalline (shape of
crystals?) or gelatinous.
Solution A clear (i.e. transparent) liquid where a solute in dissolved in a solvent. Place a small amount of A blue solution is formed.
State: • The colour (or colourless) copper(II) sulphate into a
test tube and add 4-5 cm3 of
water.
Precipitate Precipitation occurs when the mixing of aqueous solutions leads to Place 2-3 cm 3 sodium A white precipitate is formed.
the formation of an insoluble substance. chloride solution in a test
State: • The colour tube and add silver nitrate
solution dropwise.

Immiscible Liquids which do not mix, separated at the interface. Place 3-4 cm 3 iodine The two liquids were immiscible, the
State: • Descriptions of both upper and lower layers. solution in a test tube and colourless hexane on the surface of the
add hexane dropwise. dark brown iodine solution.
On shaking, the lower aqueous layer
decolourised, and a purple solution was
formed in the upper organic layer.

Flame Description of flame when carrying out a flame test. Carry out a flame test on a The compound produces an
State: • The colour sample of barium chloride. apple-green flame.

Combustion The burning of a chemical, the exothermic reaction with oxygen. Using tongs, heat a Magnesium burns quickly with a bright
State: • The rate at which combustion occurs. magnesium strip in a Bunsen white flame, leaving a solid white ash.
• A description of the flame. flame.
• The appearance of any observable reaction products.

Endothermic/ Whilst we would always expect combustion reactions to be exothermic Place 5-6 cm3 water in a test Colourless solution formed, in an
Exothermic (so it would not be worth mentioning) sometimes a change of tube and carefully add exothermic reaction.
temperature may occur more unexpectedly, and therefore should be concentrated sulphuric acid
noted. dropwise.
State: • Whether reaction is endothermic (temperature drop) or
exothermic (temperature rise).

A gas is given off. Place 2g of magnesium Pungent dense brown fumes evolved
Fumes/vapour State: • The colour. nitrate in a test tube and which turn moist universal indicator
evolved • Whether fumes are dense (cloudy) or not dense (misty). heat. Test products for the paper red. A glowing spill re-ignited when
• If they have a pungent or choking smell. presence of oxygen. placed in the test tube. A white
• The pH, using moist indicator paper. powdered solid remained in the bottom
• Check for condensation of vapour (or solid, for of the test tube.
sublimation) on side of test tube, and describe it

Bubbles of gas moving through a liquid. Place 1 or 2 chips of calcium Effervescence, clear gas evolved which
Effervescence State: • The colour. carbonate in a boiling tube caused moist universal indicator paper
• Check pH of gas using moist indicator paper and record and add 5-6 cm dilute
3 to turn green/orange. Lime water
colour change. hydrochloric acid. Check for changed from colourless to cloudy
presence of carbon dioxide white when gas was bubbled through.
in products.

1
Laboratory Chemistry: Making Observations and Inferences Chem Factsheet

Tests for gases and ions

At AS and A2 level there are several simple practical tests for simple ions (Table 2) and gases (Table 3) which you are expected to know.
These tests are given below, along with the expected observations.
Table 2. Tests for ions
Anion Test Observations:

Chloride (Cl−) To a solution, add dil. HNO3, then AgNO3(aq). White ppt. of AgCl going
curdy; greying in bright light.
Bromide (Br−) To a solution, add dil. HNO3, then AgNO3(aq). Pale cream ppt. of AgBr
going curdy; greying in bright light.
Iodide (I−) To a solution, add dil. HNO3, then AgNO3(aq). Yellow ppt. of AgI going curdy;
greying v. slowly in bright light.
Nitrate (NO3−-) (a) ‘Brown ring‘ test. Brown ring formed at interface.
To soln add cold FeSO4(aq). Then pour
conc. H2SO4 carefully down inside of test tube
to form lower layer.
(b) To cold soln or solid add a few copper turnings Brown oxides of nitrogen
and then conc. H2SO4. Warm. obtained and a blue soln obtained.
Carbonate (CO32−) And To solid or soln. add dil. HCl Effervescence; colourless
Hydrogen Carbonate (HCO3−) gas turning lime water cloudy white.
To differentiate between CO32- and HCO3-: (a) A white ppt indicates CO32−.
To the unheated test soln add a drop of MgSO4. (b) No ppt indicates HCO3−.
Sulphate (SO42−) And To soln add dil. HCl and then BaCl2(aq). White ppt of BaSO4.
Hydrogen Sulphate (HSO4−)
To differentiate between SO42- and HSO4-:
(i) Heat the solid. (a) Dense white choking fumes of SO3
obtained readily indicates HSO4−
(b) SO3 fumes only on strong
heating indicates SO42−
(ii) To soln add Na2CO3. (a) Vigorous effervescence of CO2 indicates HSO4−
(b) Slight or no effervescence indicates SO42−
Sulphite (SO32−) To solid or soln add dil. HCl and warm. Pungent SO2 evolved (turning
acid dichromate green) but no S pptd
Ammonium (NH +) Warm gently a little soln or solid with a slight excess Ammonia evolved (turning red litmus blue).
4
of NaOH (aq).
Sodium (Na+) Flame test. Yellow flame.
+
Potassium (K ) Flame test. Lilac flame. (crimson viewed through blue glass)
Calcium (Ca+) Flame test. Brick-red flame.
Barium (Ba+) Flame test. Apple-green flame.

Table 3. Tests for simple gases

Gas Description Test Observations:

Hydrogen (H2) Colourless, odourless Ignite using a splint. ‘Squeaky pop‘.

Burns with a pale blue flame.
Oxygen (O2) Colourless, odourless Glowing splint. Ignites or glows much brighter.
Carbon Dioxide (CO2) Colourless, odourless Bubble through lime water. Turns cloudy white.
Ammonia (NH3) Colourless, pungent Moist red litmus paper. Turns red.
Chlorine (Cl2) Yellow-green, pungent (a) Moist litmus paper. Turns red then bleached white.
(b) Bubble through KBr(aq). Solution turns yellow or orange.
Nitrogen Dioxide (NO2) Brown, pungent Bubble through water, then add Colourless solution; no change on
a little NaOH(aq) to this solution addition of alkali.
Sulphur Dioxide (SO2) Colourless, pungent Bubble through acidified Turns from orange to green, but no precipitate
(dil. H2SO4) dichromate solution

2
Laboratory Chemistry: Making Observations and Inferences Chem Factsheet

Making Inferences.
After recording careful observations inferences must be made. These may Exam Hint: - Whilst there is a time limit in practical exams and many
require the use of data, or may be based upon the tests in tables 2 and 3. practical assessments, you also need to be aware that:
The inferences may lead to the complete identification of the unknown • Some reactions take a little time to occur.
• Some reactions occur in two or more observable stages, and if
compound, but sometimes only specific ions within the compound are
rushed you will only observe the first stage.
identified. Table 4 below provides examples of observations and inferences.

Table 4. Observations and inferences

Observations Inferences
On adding dilute nitric acid and silver nitrate solution to a solution of chemical X, a white Chemical X contains chloride (Cl−) ions.
precipitate was formed which later turned grey.

On heating a solution of X with sodium hydroxide solution, a pungent gas is evolved which turns The gas produced is ammonia. X contains NH4+
damp red litmus paper blue. ions

On heating solid X, it sublimes X is ammonium chloride (since it contains ammonium

ions, chloride ions and is one of the few substances to
sublime)

On carrying out a flame test, chemical Y produced an apple-green flame. Chemical Y contains barium ions

When hydrochloric acid is added to solid W , effervescence of a colourless gas occurs. The gas is hydrogen. Solid W is a metal above
The colourless gas produced burns with a squeaky pop sound. copper in the reactivity series.

Effervescence was observed on addition of dilute hydrochloric acid to solid Z, and the colourless Solid Z is either a hydrogen carbonate or a
gas produced turned lime water cloudy white. carbonate.

On adding a drop of magnesium sulphate to a solution of Z, there was no observable reaction. Solid Z is a hydrogen carbonate.

During a flame test on solid Z, a yellow flame was produced. Solid Z contains sodium.
Solid Z is sodium hydrogen carbonate.

Practice Questions Answers.

1. If two chemicals are added and nothing appears to happen, what 1. No observable reaction.
observation should be recorded?
2. How would you describe the following common chemicals? 2. (a) White crystalline solid.
(a) Sodium chloride. (b) Oxygen. (b) Colourless gas.
(c) Water. (d) Copper. (c) Colourless liquid.
(e) Blackcurrant juice. (d) Shiny pink/brown metallic solid.
(e) Purple solution.
3. What is an insoluble substance called if formed from a mixture of
aqueous solutions? 3. A precipitate.
4. Can a solution be described as cloudy?
4. No, solutions are clear.
5. What test should always be carried out if a gas is produced in a chemical test?
5. A pH test using moist indicator paper.
6. Write inferences for the following observations.
(a) A colourless gas was produced in the reaction which turned moist
6. (a) The gas is oxygen.
indicator paper green and ignited a glowing splint.
(b) The solid contains calcium.
(b) A flame test was carried out on the solid, and the flame burned
(c) Solid Q contains the iodide ion (I−) and the potassium ion (K+).
brick red.
Solid Q is potassium iodide.
(c) A solution was made up of white solid Q, and a yellow precipitate
was made on the addition of dilute nitric acid and silver nitrate. A
7. (a) Nitrogen dioxide and oxygen gases were evolved.
flame test on solid Q produced a lilac flame.
(b) Solid K is a nitrate.
7. Infer what you can from the observations of these tests on solid K. (c) Solid K contains calcium ions (Ca2+).
(a) Solid K was placed in a test tube and heated. Brown pungent Solid K is calcium nitrate, Ca(NO3)2.
fumes were evolved which turned moist indicator paper red, and
when a glowing splint was put into the test tube it ignited. A white
solid was left in the test tube.
Acknowledgements: This Factsheet was researched and written by Kieron
(b) A few copper turnings were added to solid K and then 2-3 cm3 Heath. Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham,
concentrated sulphuric acid. The mixture was carefully heated and B18 6NF. ChemistryFactsheets may be copied free of charge by teaching staff
brown pungent fumes were evolved which turned moist indicator or students, provided that their school is a registered subscriber. No part of
paper red, a blue solution was left in the test tube. these Factsheets may be reproduced, stored in a retrieval system, or transmitted,
in any other form or by any other means, without the prior permission of the
(c) A flame test on solid K produced a brick red flame colour. publisher. ISSN 1351-5136

3
 Chem Factsheet
January 2002 Number 25

Acid-Base Equilibria I - pH, Kw and Ka

To succeed in this topic you need to be able to: Generally, the conjugate base of a weak acid will show weak basic character,
• understand the writing of Kc expressions and their units (covered whilst the conjugate base of a strong acid will not show basic character.
in Factsheet No.21);
Usually there are two acid/base pairs:
• use your calculator to convert numbers into ‘logarithms to the
base 10 (log10) using the lg key;
e.g. HCl + NH 3 → NH 4+ + Cl−
• turn log10 values back into numbers using the inverse of log10 i.e. acid 1 base 2 acid 2 base 1
the 10x key (or second function above the lg key).

After working through this Factsheet you will be able to:

• use the A2 level definitions of acids and bases (Br∅nsted-Lowry e.g. H2SO 4 + H 2O → H3O+ + HSO4−
theory) and identify conjugate acid/base pairs; acid 1 base 2 acid 2 base 1
• define pH and perform calculations using its mathematical
expression;
• understand how to use the ionic product of water, Kw, to calculate
the pH of a base; This is ‘chase the H+’ because it is not seen as a separate entity in the
• understand the difference between the terms weak, strong, equation although it is being donated and accepted.
concentrated and dilute as applied to acids and bases;
The 1 and 2 used have no significance except to identify which acid goes
• write Ka expressions for weak acids and perform calculations with which base.
using these expressions.
For practice on conjugate acid-base pairs go to question 1.
Exam Hint:- Questions tend to be based on:
• learning the definitions for acids/bases, pH, pOH, Kw and Ka
• performing calculations on them
The calculations all involve using the lg and 10x keys on the calculator Using acid and base terms
and being able to input ‘powers to the 10’ e.g. 1.2 x 10-3, 5 x 10-6 - this Strong - acid or base which undergoes 100% dissociation as shown by
usually involves using the EXP key - eg 1.3 EXP -2 = 1.3 x 10-2 (be →
careful where you put the minus!)
e.g. HNO3 → H+ + NO3−
* Many marks are lost in examination questions on this topic by NaOH → Na+ + OH−
candidates who cannot use their calculators for these purposes. you
must practice this until you are competent!* N.B. At A2 level there are only
four strong acids: HCl, HNO3, H2SO4 and H3PO4
two strong bases: NaOH and KOH
Br∅nsted-Lowry Theory
At GCSE level you were taught that acids needed water to be present to Weak - acid or base that only partially dissociates so it has the equilibrium
show their acidic properties, and that they produced H+ ions. The Br∅nsted- sign ž
Lowry Theory takes this one step further:
e.g. CH3COOH ž CH3COO− + H+
NH4OH ž NH4+ + OH−
Acids are species that donate protons/H+
Bases are species that accept protons/H+ N.B. At A2 level organic acids e.g. methonoic, ethonoic, proponoic, etc
are weak, but NH3(aq) / NH4OH is the only weak base.

Monobasic acids (e.g. HCl, HNO3) donate one H+, dibasic acids (e.g. H2SO4) Concentrated/dilute
donate two H+ and tribasic acids (e.g. H3PO4) donate three H+ These terms refer to the ratio of moles to volume i.e. mol dm-3 of the
solutions of acid and bases,
Acids and bases are linked by the H+ as this example shows:-
i.e. 2 mol dm-3 (2M) would be considered ‘dilute’ and 6 mol dm-3 (6M)
HCl → H+ + Cl− ‘concentrated’.
acid conjugate base
There is no ‘cut-off’ value between ‘dilute’ and ‘concentrated’ as
The HCl and Cl- are a conjugate acid/base pair. descriptions of acids and alkalis – and it will not give you any problems.

Note that this new definition of bases includes species such as Cl− that So it is possible to have a concentrated weak acid and a dilute strong
would not have been regarded as bases at GCSE, and do not show basic acid.
character.
1
Acid Base Equilibria I Chem Factsheet

pH
You will know the term pH from the ‘pH scale’ and its link to Universal Indicator colours (Fig 1).

Fig 1. pH scale
pH 1 2 3 4 5 6 7 8 9 10 11 12 13 14

strong weak neutral weak strong

acid acid base base

At A2 level the numbers 1 – 14 are a logarithmic scale linked to the The reason Kw is introduced to be able to calculate the pH of bases which
mathematical expression below. lie in the range of pH 8 – 14 at 25oC

e.g. Q. What is the pH of 0.1 mol dm-3 NaOH?

Definition of pH
A. NaOH → Na+ + OH −
pH is the minus log to the base 10 of the hydrogen ion concentration.
0.1 → 0.1 + 0.1
pH = - log10 [H+] Kw = [H+] × [OH−] = 10-14
[H+] × 0.1 = 10-14
+ 10 −14
[H ] = = 10-13
For practice on pH and [H+] calculations using the calculator (lg and 10x 0.1
keys) go to question 2 and 3.
pH = -log10 [H+] = - log10 [10-13]
What are logs (or logarithms)? ∴ pH = 13
Logs are related to powers:
log10100 = log10102 = 2 For further practice on calculations involving pH of strong bases go to
log100.1 = log1010-1 = -1 question 4.
So if log10(0.63) = -0.201, then 0.63 = 10-0.201
The pH of weak acids and Ka
On your calculator, the key for "log10" will be called "log" or "lg" A weak acid only partially dissociates, so the concentration of hydrogen
ions, [H+] cannot be calculated from the concentration, mol dm-3, as it can
The pH of strong acids for strong acids.
Strong acids undergo 100% dissociation so the concentration (mol dm-3 or
molarity, M) is all that is needed to calculate its pH. Since a weak acid only partially dissociates there is an equilibrium set up:
e.g. Q. What is the pH of 0.1 mol dm-3 HCl ? HA ž H+ + A−
A. HCl → H+ + Cl−
0.1 → 0.1 + 0.1 and you can write the Kc expression,
pH = -log10 [H+] = - log10 [0.1]
∴ pH = 1 [H+] × [A−]
Kc =
[HA]
e.g. Q. What is the pH of 0.05 mol dm-3 H2SO4 ? For acids, we use Ka (where a = acid) instead of Kc
A. H2SO 4 → 2H+ + SO42−
0.05 → 0.1 + 0.05
[H+] × [A−]
pH = -log10 [H+] = - log10 [0.1] Ka =
[HA]
∴ pH = 1
Note that Ka is not defined for strong acids, because there will be no
The ionic product of water, Kw undissociated acid left.
Water partially ionises, H 2 O ž H+ + OH-
[H+] × [OH−] Since 1 HA → 1 H+ + 1 A− every time HA dissociates (according to the
Writing the Kc expression Kc =
[H2O] moles in the equation):
[H+] = [A−]
We can rearrange this to give:
Kc × [H2O] = [H+] × [OH−]
Since [H2O] is very large it can be considered a constant, we define: If the degree of dissociation is very small (which is the case for weak acids)
Kw = [H+] × [OH−] (the w stands for water) then [H+] is very small compared to [HA]. This means we can use:
[HA] – [H+] ≈ [HA]
This gives us Kc × [H2O] = Kw i.e. we can assume that the concentration of [HA] remains at its original
At 25oC, Kw = 10-14 mol dm-3 value.

Notice that if [H+] = [OH−] the solution is neutral, then: The equation now becomes,
[H]2 = Kw = 10-14, so [H] = √10-14 = 10-7
∴ pH = -log10(10-7) = 7 [H+]2
Ka =
[HA]
You will see the link between ‘neutral’ and a pH of 7 (although this is only Units = mol dm-3
true at 25oC - at higher temperatures Kw increases, and so does the pH of
water.)
2
Acid Base Equilibria I Chem Factsheet

The two types of calculation, using the equation are now:

1. Finding Ka - given pH and concentration of the acid.

Method Q. 0.1 mol dm-3 solution of HA has a pH of 5.10. What is its Ka value?
(1) Calculate the [H+] from the pH value A. p H = - log10 [H+]
5.10 = - log10 [H+]
[H+] = 10-5.10 = 7.94 × 10-6

(2) Use the Ka expression where [H+] = [A−] [H+]2

Ka =
[HA]

(3) Substitute the values for [H+] and [HA] (7.94 × 10-6)2
Ka =
0.1
(4) Calculate the answer and give units. = 6.3 × 10-10 mol dm-3

2. Finding pH - given Ka and the concentration of the acid.

Method Q. 0.1 mol dm-3 CH3CO2H has a Ka = 1.7 × 10-5 mol dm-3. What is its pH?

(1) Write the Ka expression for the acid given i.e. CH3CO2H A. [H+ ]2
Ka =
[CH3COOH]
[H+]2
(2) Substitute in the values for K and acid concentration 1.7 × 10-5 =
a 0.1

(3) Calculate the [H+] value [H+] = √1.7 ×10-5 × 0.1

= 1.3 × 10-3 mol dm-3
(4) Substitute into the pH expression and calculate the answer. pH = -log10 [H+]
= -log10 (1.3 × 10-3)
= 2.9

For further practice on Ka calculations go to question 5 and 6 Answers

1. a) base 1 + acid 2 ž acid 1 + base 2
Questions b) base 1 + acid 2 → acid 1 + base 2
1. Identify and label the two conjugate acid/base pairs in the following c) acid 1 + base 2 → base 1 + acid 2
reactions: d) acid 2 + base 1 ž acid 1 + base 2
a) NH3 + H2O ž NH4+ + OH- or base 1 + acid 2
b) H2O + HCl → H3O+ + Cl- e) acid 1 + base 2 → acid 2 + base 1
c) HNO3 + OH -
→ NO3- + H2O
d) H2O + H2O ž H3O+ + OH- 2. a) 7 b) 4 c) 3 d) 0.6 e) 4.7
e) HSO3- + H2O → H3O+ + SO32- f) 7.35 g) 3.15 h) 1.1 i) 5.49 j) 6.19

2. What is th pH of solutions with the following [H+] in mol dm-3? 3. a) 10-4 b) 10-6 c) 5.01 × 10-12 d) 1.99 × 10-3
a) 10-7 b) 10-4 c) 10-3 d) 0.25 e) 1.25 × 10-7 f) 7.9 × 10-14 g) 3.9 × 10-8 h) 3.16 × 10-2
e) 2.0 × 10 -5
f) 4.5 × 10 -8
g) 7.0 × 10-4 h) 7.9 × 10-2 i) 1.58 × 10-13 j) 3.98 × 10-4
i) 3.2 × 10 -6
j) 6.4 × 10 -7
4. a) 9 b) 11 c) 12.5 d) 5.7 e) 13.0
3. What is the [H+] in mol dm-3 for the following pH values? f) 7.8
a) 4 b) 6 c) 11.3 d) 2.7
e) 6.9 f) 13.1 g) 7.4 h) 1.5 5. a) 1.65 × 10-5 b) 1.65 × 10-4 c) 8.7 × 10-8 d) 1 × 10-7
i) 12.8 j) 3.4 e) 4.5 × 10-12

4. What is the pH of strong bases with the following [H+] in mol dm-3? 6. a) 4.72 b) 5.62 c) 2.68 d) 2.88 e) 1.97
a) 10-5 b) 10-3 c) 0.035 d) 5.4 × 10-9
e) 9.9 × 10-2 f) 7.1 × 10-7

5. Calculate the Ka of the following weak acids:

a) pH = 3.40 [HA] = 0.010 mol dm-3
b) pH = 2.40 [HA] = 0.10 mol dm-3
c) pH = 4.03 [HA] = 0.10 mol dm-3
d) pH = 4.00 [HA] = 0.10 mol dm-3
e) pH = 5.70 [HA] = 0.885 mol dm-3

6. What is the pH of the following weak acids?

a) Ka = 3.7 × 10-8 mol dm-3 [HA] = 0.01 mol dm-3 Acknowledgements: This Factsheet was researched and written by Sam Goodman. Curriculum
Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham, B18 6NF. ChemistryFactsheets
b) Ka = 5.8 × 10-10 mol dm-3 [HA] = 0.01 mol dm-3 may be copied free of charge by teaching staff or students, provided that their school is a
c) Ka = 5.6 × 10 mol dm
-4 -3
[HA] = 0.01 mol dm-3 registered subscriber. No part of these Factsheets may be reproduced, stored in a retrieval
d) Ka = 1.74 × 10-5 mol dm-3 [HA] = 0.10 mol dm-3 system, or transmitted, in any other form or by any other means, without the prior permission
of the publisher. ISSN 1351-5136
e) Ka = 5.62 × 10-4 mol dm-3 [HA] = 0.20 mol dm-3
3
 Chem Factsheet
January 2002 Number 26
Acid-Base Equilibria II - Buffer Solutions,
Titrations & Indicators
To succeed in this topic you need to: Calculations on buffer solutions
• Ensure you understand Le Chatalier’s Principle and the effect The calculations depend on a mathematical formula,
of changing conditions on the position of equilibrium (covered in
Factsheet No.21) [acid]
pH = - log10 Ka - log10
[base]
• Review the work in Factsheet No. 25 because it is the first part of
or
the whole work covering Acid-Base Equilibria
[acid]
• be able to use your calculator to convert numbers into logarithms pH = pKa - log10
[base]
to the base 10 (log10) using the lg key
After working through this Factsheet you will be able to: In examination questions you may be given the Ka or the pKa value,
• define buffer solutions and explain how they operate
pKa = - log10 Ka
• perform calculations on buffer solutions
in the same way that
• sketch the pH graphs for titrations of acids and bases
• identify which indicators to use for particular acid/base titrations pH = - log10 [H+]

You must learn both the variations of the formula.

Buffer Solutions
The two types of buffer solution calculations are:

A buffer solution is one whose pH hardly changes on the addition of 1. Finding pH - given the Ka value and the concentrations of the
small amounts of acid or base acid and base.

What is the pH of a buffer solution of 0.10 mol dm-3 propanoic acid

What are they? (C2H5CO2H) and 0.20 mol dm-3 sodium propanoate (C2H5CO2Na)?
A buffer solution is a weak acid or base and its salt i.e. an acid/base Ka for propanoic acid is 1.34 × 10-5 mol dm-3.
conjugate pair.
Answer [acid]
e.g. CH3COOH/CH3COO− Na+ (which gives a pH in the acidic range) pH = - log10Ka − log10
[base]

e.g. NH3/NH4Cl (which produces a pH in the basic range) [0.1]

pH = - log10 1.34 × 10-5 − log10
[0.2]
How do they work?
If we look at the example of ethonoic acid and sodium ethonoate then the p H = 4.87 −log10 0.5
salt is fully ionised: = 4.87 + 0.30 = 5.17

CH3COO−Na+ → CH3COO− + Na+ 2. Finding Ka - given the pH value and the concentrations of the
acid and the base.
The weak acid partially ionises,
0.01 mol dm-3 ethonoic acid is mixed with 0.117 mol dm-3 sodium
− ethanoate to produce a buffer solution of pH = 5.8.
CH3COOH ž CH3COO + H +

What is the Ka of the ethonoic acid?

The CH3COO− from the salt mixed in the equilibrium mixture means
[CH3COO−] is large and pushes the equilibrium to the left making Answer
[CH3COOH] large as well. the [H+] determines the pH of the buffer since [acid]
pH = - log10Ka − log10
pH = -log10[H+]. [base]

[0.01]
If an acid is added i.e. H+, then almost all of the H+ ions are removed by the 5.8 = - log10Ka − log10
[0.117]
CH3COO−,
5.8 = - log10Ka − log10 0.0855
CH3COO− + H+ → CH3COOH
5.8 = - log10Ka + 1.068
leaving the [H+] hardly changed (the [CH3COO−] is large). log10Ka = -4.732
Ka = 1.85 × 10-5 mol dm –3
If a base is added the CH3COOH reacts with the OH-.
If log10Ka = -4.732, you need to use
CH3COOH + OH− → CH3COO− + H2O SHIFT LOG -4.732 to find K a

but the [CH3COOH] hardly changes because it is large.

1
Acid Base Equilibria II Chem Factsheet

Titration curves
In the titration of an acid and a base, the pH changes during the course of Fig 2. Strong acid/strong base (eg HCl(aq)/NaOH(aq))
the titration. In the laboratory the titration is stopped when the indicator
changes colour at the end point. In titration curves the pH is measured as 14
the acid and base are added together, and this continues past the end point.
12
We will consider here only monobasic acids and bases - i.e. acids (HA) that
have only one hydrogen ion and bases (BOH) that have only one hydroxide 10
ion - the titration curves for other kinds of acids are substantially more
pH 8
complicated.
6
What does a titration curve look like?
For the sake of simplicity, it will be assumed that the acid and base are of 4
the same concentration, and that 25cm3 of the acid is used initially. The
equivalence point (the point at which the acid and base exactly neutralise 2
each other) will then be when 25cm3 of the base has been added.
0
Fig 1 below shows a general titration curve, which shows how the pH 25 volume of NaOH/cm3
varies with the volume of base added.
pH start vertical range end point final
Fig 1. Titration curve reading 1 3 - 10 7 13

$ Fig 3. Strong acid/weak base (eg HCl(aq)/ NH3(aq))

pH
# 14

12

" 10
!
pH 8
25cm3 Volume of base added
6
! No base added, so pH is the pH of the original acid
" Start of vertical portion of curve - close to equivalence point 4
# Equivalence point - moles of OH− = moles of H+ .
2
This is in the middle of the near-vertical portion of the curve.
$ End of vertical portion of curve
0
% Base is in excess, so final pH ≈ pH of base. 25 volume of NH3(aq)/cm3

pH start vertical range end point final

If instead the titration involves adding the base to the acid the graph is
reading 1 3 - 7 5 11
reversed:
pH

Fig 4. Weak acid/strong base (eg CH3OOOH(aq)/NaOH(aq))

14
volume
12
There are three curves you need to learn and be able to draw yourself:
1. Strong acid/strong base (Fig 2) 10
2. Strong acid/weak base (Fig 3)
3. Weak acid/strong base (Fig 4) pH 8

For each of these, you need to know approximate figures for: 6

• The pH at the start and end of the titration
4
• The pH range for the vertical part of the graph
• The equivalence point (note: this is only pH 7 for a strong acid and 2
strong base)
0
NB. There is no titration between a weak acid and a weak base because 25 volume of NaOH(aq)/cm3
there is no vertical range so no sharp end point (indicators do not show a pH start vertical range end point final
clear colour change.) reading 3 7 - 11 9 13

2
Acid Base Equilibria II Chem Factsheet

Why do titration curves have that shape? Indicators

• At the beginning of the titration, there is very little base compared to Indicators are weak acids and have the general formula, HIn. As with other
the acid, so the pH does not change much. weak acids they form an equilibrium in water where the anion, In−, has one
colour and the undissociated acid, HIn, another colour,
• As the equivalence point approaches, there are comparatively few
H+ ions remaining, so the addition of a small amount of OH− ions can HIn ž H+ + In−
cause the pH to change a great deal.
colour A colour B
• Once the base is present in excess, addition of further OH- ions only
causes a small change in pH. when H+ is added the equilibrium moves to the left and colour A is seen,
adding a base produces colour B.
This shape can also be verified using pH calculations. The examples At equilibrium: [HIn] = [In−]
below show how to do them for a titration between 25cm3 0.1 M so the colour of the indicator is a 50%:50% mixture of colours A and B.
hydrochloric acid and 0.1M sodium hydroxide. Note: you will not have
to work out the shape using calculations in the exam. Different indicators are used for different combinations of strong and weak
acids/bases. See Fig 5.
(a) To calculate pH before equivalence point:
Fig 5. Indicators
When 24.9cm3 of NaOH has been added, we have:
0.025 × 0.1 = 0.0025 moles of H+
0.0249 × 0.1 = 0.00249 moles of OH−
contained in 25 + 24.9 = 49.9cm3
So we have 0.0025 − 0.00249 = 0.00001 moles of H+ ions left
contained in 49.9cm3 A
This gives [H+] = 0.00001/0.0499 = 0.0002M pH
So pH = -log10(0.0002) = 3.7 B

(b) To calculate pH after equivalence point: C

When 25.1cm3 of NaOH has been added, we have:
0.025 × 0.1 = 0.0025 moles of H+ D
0.0251 × 0.1 = 0.00251 moles of OH−
E
contained in 25 + 25.1 = 50.1cm3
So we have 0.00251 − 0.0025 = 0.00001 moles of OH− ions
contained in 51.1cm3
This gives [OH−] = 0.00001/0.0511 = 0.000196M
volume of acid
Using [H+][OH−] = Kw = 10-14:
[H+] = 10-14/0.000196 = 5.11 × 10-11
pH = 10.2
The best indicator is C because it is closest to the mid point of the vertical
If you are happy with Excel Spreadsheets, you could use them to produce pH change, but B and D would work as well. A and E will not change
a titration curve for this example by putting the volume of sodium hydroxide colour because they are outside the range of pH change. (Table1)
added in the first column, and in the second column, entering the formula
Table 1. Suitable indicators
"=log((2.5 - 0.1*A1)/(25 + A1))" for volumes before the equivalence
point, and "=14 + log(0.1*A1 - 2.5)/(25 + A1))" for volumes above the
equivalence point. Combination vertical change suitable
in pH indicator

Why do weak acid/strong base and strong acid/weak base titrations strong acid/strong base 3 – 10 methyl orange
have equivalence points that are not neutral? or phenolphthalein
Consider a weak acid (ethanoic acid) titrated against a strong base (sodium
hydroxide). strong acid/weak base 3–7 methyl orange

First note that for a weak acid like CH3COOH, its conjugate base weak acid/strong base 7 – 10 phenolphthalein
(CH3COO-) will be weakly basic.

Since CH3COOH is a weak acid, it only partially dissociates:

CH3COOHž H+ + CH3COO− Exam Hint: - You may be given the pH range over which a number of
indicators change colour, and be asked to identify which would be
suitable for a specific titration. This requires you to be able to:
During the titration, the H+ ions will quickly be neutralised, causing the
equilibrium above to shift to the right. At the equivalence point, there • Identify weak and strong acids and bases
will be CH3COO− in solution, causing the pH to be slightly basic. • Recall the pH range for the vertical portion of the corresponding
titration curve.
Similarly, for a weak base/strong base titration, since the conjugate acid
of a weak base is slightly acidic, the equivalence point will have an acid
pH.

3
Acid Base Equilibria II Chem Factsheet

Questions 5. a) 14
1. a) What is a buffer solution?
b) How is a buffer solution made? 12

10
2. For each of the following buffer solutions calculate its pH.
a) [acid] = 0.1 mol dm-3 [base] = 0.05 mol dm-3 pH 8
Ka = 1.3 × 10-5 mol dm-3
6
b) [acid]/mol dm-3 [base] mol dm-3
i. 1.0 1.0 4
ii. 2.0 1.0
iii. 2.0 0.5 2
iv. 0.5 2.0
The Ka = 1.5 × 10-5 mol dm-3 in each case. 0
20 volume of CH3CO2H/cm3
b) 14
c) [acid]/mol dm-3 [base] mol dm-3
i. 0.10 1.0 12
ii. 2.0 0.2
iii. 0.50 2.5 10
iv. 0.85 2.1
The Ka = 1.6 × 10-4 mol dm-3 in each case. pH 8

6
3. What is the Ka of the acid in each of the following questions?
a) 0.10 mol dm-3 ethanoic acid with 0.10 mol dm-3 sodium ethonoate 4
having a pH = 4.73?
b) 2.0 mol dm-3 butonoic acid with 0.50 mol dm-3 sodium butonoate 2
having a pH = 4.22?
c) 1.6 mol dm -3 propanoic acid with 1.2 mol dm-3 potassium 0
propanoate, having a pH of 4.75? 20 volume of HNO3/cm3

4. Explain why a mixture of hydrochloric acid and sodium chloride does c)

14
not act as a buffer soulution, but a mixture of ethanoic acid and sodium
ethanoate does. 12

5. Draw the titration curves for each of the following: 10

a) 20 cm3 0.1 mol dm-3 NaOH with 0.1 mol dm-3 CH3CO2H
b) 40 cm3 0.1 mol dm-3 KOH with 0.1 mol dm-3 HNO3 pH 8
c) 25cm3 0.1 mol dm –3 HNO3 with 0.1 mol dm-3 NH3(aq)
6
6. Litmus is an indicator which is purple, and shows two colours red
4
(with acids) and blue (with bases). Explain how litmus works.
2
Answers
1. (a) A solution whose pH hardly changes when small amounts of acid 0
3
or base are added to it. 25 volume of NH3/cm
(b) A mixture of a weak acid and its salt, e.g. CH3COOH/CH3COONa
6. Litmus is a weak acid, HIn ž H+ + In−
2. (a) 4.6 red blue
(colours must be this way round)
(b) i. 4.8
ii. 4.5
iii. 4.2
iv. 5.4

(c) i. 4.8
ii. 2.8
iii. 4.5
iv. 4.2

3. (a) 1.86 × 10-5 mol dm-3

(b) 1.5 × 10-5 mol dm-3
(c) 1.33 × 10-5 mol dm-3 Acknowledgements: This Factsheet was researched and written by Sam Goodman. Curriculum
Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham, B18 6NF. ChemistryFactsheets
may be copied free of charge by teaching staff or students, provided that their school is a
4. Hydrochloric acid is a strong acid, and so fully dissociates - there is no registered subscriber. No part of these Factsheets may be reproduced, stored in a retrieval
equilibrium between HCl and its ions system, or transmitted, in any other form or by any other means, without the prior permission
of the publisher. ISSN 1351-5136

4
 Chem Factsheet
January 2002 Number 27

Organic Chemistry 1 - Key concepts and

Optical Isomerism
To succeed in this topic you need to:
• Understand organic nomenclature (covered in Factsheet 15 - Organic chemistry I - Nomenclature);
• Be able to name and draw organic molecules;
• Learn the reaction equations, conditions and mechanism names for the organic reactions met at AS-level (Factsheets 16 and 17).

After working through this Factsheet you will:

• Have recapped the chemical terminology learnt in AS-level;
• Have revised the organic reactions introduced at AS-level;
• Have revised structural and geometric isomerism;
• Understand how optical isomerism arises and be able to state whether or not it is present in a given molecule.

Key definitions: Functional Groups

These functional groups are the ones introduced in the AS-level course.
• Functional Group - the reactive part of a molecule.
• Family of compounds - contain the same functional group. Family Functional Group Systematic Name
• Homologous Series - a series in which the compounds belong to
the same family and only differ by a -CH2- group in the length of Alkane C–C -ane
the carbon chain.
Alkene C=C -ene
• General Formula - represents a homologous series of a family of
compounds. Alcohol -OH -ol
e.g. C n H 2n+2 - alkanes.
Halogenoalkane -Cl chloro-
C n H 2n+1OH - alcohols.
-Br bromo-

-I iodo-
IUPAC Nomenclature
The agreed international system of naming organic compounds, or Ketone -one
C=O
‘systematic nomenclature‘, is explained in detail in Factsheet 15. Candidates
must have a good understanding of this, and be able to name simple and
complex organic molecules. Aldehyde H -al
H C=O

e.g. CH4 H C H Methane Carboxylic Acid OH -oic acid

C
O
H
Nitrile -CN -nitrile
e.g. CH2CHCBrOHCBrICH2CH3

H H OH Br H H
Amine -NH 2 -amine
H C C C C C C H

Br I H H

3,4-dibromo-4-iodohex-1-ene-3-ol
Exam Hint: Candidates should ensure they are adept at switching
between the systematic name of a compound and its structure. This
Refer to Factsheet 15 for the method of naming organic compounds, worked skill will usually be assumed in A2 work.
examples, and questions.

1
Organic Chemistry 1 - Key Concepts Chem Factsheet

The following terms are used in describing and classifying reactions

Glossary of terms
Free radical A species with an unpaired electron. Substitution When an atom or ‘group‘ in a molecule is replaced by
another atom or ‘group‘.
Nucleophile A donator of a lone pair of electrons (to form a new
covalent bond). N.B. Nucleophile means 'nucleus Addition When 2 molecules react to form a single product.
(+ve charge) lover'. Elimination When a simple molecule (e.g. HCl, HBr, H2O) is
Electrophile An acceptor of a lone pair of electrons (to form a removed from a molecule and not replaced.
new covalent bond). N.B. Electrophile means Hydrolysis When water reacts with a molecule, and the molecule
'electron lover'. is split into two parts.
Homolytic fission When a covalent bond breaks and one electron goes Oxidation Loss of electrons, gain of oxygen or loss of hydrogen.
to each atom (forming free radicals).
Reduction Gain of electrons, loss of oxygen or gain of hydrogen.
Heterolytic fission When a covalent bond breaks and both electrons go
to one atom (forming ions). Polymerisation Formation of polymer molecules from monomers.

The diagrams below summarise the organic reactions from AS Chemistry - Exam Hint:
Factsheets 16 and 17 cover the full details and equations. Candidates must learn the following about each organic reaction.
• Reaction equation.
• Reaction conditions.
Fig. 1 Alkane reactions • Reaction type and mechanism.

carbon dioxide O2 halogen

Alkanes halogeno alkane Fig. 4 Alcohol reactions
+ water heat UV light

combustion free radical

bromo-alkane
substitution
nucleophilic substitution
chloro-alkane iodo-alkane
Fig. 2 Alkene reactions NaBr(s) +
nucleophilic H2SO 4(conc.) nucleophilic
substitution to make HBr substitution
CO2 + H2O combustion

alkane O2 Heat dry PCl5 P(s) + I2(s)

H2 to make PI 3
electrophilic
Heat, Halogen di-halogenoalkane
addition Alkenes
Ni catalyst electrophilic halogenation
addition
alkaline
KMnO4(aq) hydrogen
halide
halogenoalkane
diol electrophilic Alcohol
oxidation addition
electrophilic addition dehydration
oxidation

heat to primary
Fig. 3 Halogenoalkane reactions conc. H2SO4
170 o C alcohols
secondary
nitrile alcohol alcohols
nucleophilic KCN in nucleophilic Cr2O72−(aq) H+(aq)
substitution water/ethanol NaOH(aq) substitution alkene Cr2O72−(aq) H+(aq)
heat under
heat under reflux
reflux ketone
Halogenoalkane aldehyde
NH3 in KOH in further oxidation
ethanol ethanol
heat heat under Cr2O72−(aq) H+(aq)
amines reflux alkene
nucleophilic nucleophilic
substitution elimination carboxylic
acid

2
Organic Chemistry 1 - Key Concepts Chem Factsheet

Once these reactions have been learnt, candidates should then begin to see how organic compounds can be inter-converted, as ‘synthetic pathways‘ can
be understood.

Fig 5. Synthetic pathways summary

Primary KOH(aq) K2Cr2O7 K2Cr2O7 Carboxylic

Primary Aldehyde
Halogenalkanes Alcohol H+ H+ Acid

KOH / ethanol HX

X2 Dihalogeno KOH(aq)
Alkene Diol
Alkanes

KOH / ethanol HX

Secondary KOH(aq) Secondary K2Cr2O7

Halogenalkanes Alcohol H+ Ketone

Tests for functional groups 1. Structural Isomerism

Candidates are expected to know the following tests for functional groups Structural isomerism is when the same number and type of atoms can be
in practical exams / assessments and modular exams. arranged in different ways to form structural isomers.
e.g. C4H10 has 2 structural isomers.
Group / Family Test Result CH3
CH3CH2CH2CH3 and
CH3CHCH3
Alkene Shake with bromine water, Colour of bromine
C=C Br2(aq) solution goes from Exam Hint: A common exam question is for candidates to be given
brown to colourless. a formula and to be asked to work out a number of different structural
isomers, so practise this!
Chloroalkane 1. Warm with NaOH(aq) White precipitate,
C-Cl soluble in dilute
NH3(aq). 2. Geometric Isomerism
Geometric isomerism is caused by the presence of a carbon-carbon double
Bromoalkane 2. Add dilute HNO3(aq), Cream precipitate, bond (C=C). There is no rotation about the C=C because rotating would
C-Br until just acidic soluble in conc. require breaking the pi-bond. The two forms are called stereoisomers.
NH3(aq).
e.g. But-2-ene, C4H8, is the smallest molecule showing geometric isomerism.
Iodoalkane 3. Add AgNO3(aq) Yellow precipitate,
insoluble in conc. H CH 3 H 3C CH 3
NH3(aq).
C C C C

H3C H H H
Isomerism
Isomerism is the term used for compounds with the same molecular formula Trans-but-2-ene Cis-but-2-ene
(i.e. the same number of atoms of each type) that have different arrangements The H atoms are diagonally The H atoms are the same
of these atoms. across (“trans”) the side (“cis”) of the
At A2-level there are 3 types of isomerism to learn about: double bond. double bond.

Geometric isomers can only occur if both carbon atoms involved

in the double bond have two different groups attached to them.

3
Organic Chemistry 1 - Key Concepts Chem Factsheet

3. Optical Isomerism 6. (a) Mark the chiral centre in the following molecule.
H OH H
Optical isomers are defined as isomers of which one is the non-
superimposable mirror image of the other. Such molecules are said to be HO C C C C C NH 2
chiral molecules.
H Cl H H H
This can be caused by a carbon atom having 4 different groups attatched (b) Explain why chiral molecules are said to have ‘optical‘ isomers.
to it. This carbon atom is called the chiral centre. (c) What is a racemic mixture?
e.g. The optical isomers of lactic acid. Answers.
OH OH 1. (a) H H H H H H H H
C C H C C C C H H C C C C
HOOC H H
H COOH H H H H H
CH 3 CH3
imaginary H C H
mirror H H
They are known as ‘optical' isomers, as a single optical isomer has the H C C C
ability to rotate the plane of polarisation of plane-polarised monochromatic H
light. H
(b) (i) Lack of rotation about the double (π) bond.
Isomers which rotate the plane to the right (clockwise) are (ii) H CH 3 H 3C CH 3
dextrorotatory and given the prefix (+).
Isomers which rotate the plane to the left (anticlockwise) are C C C C
−).
laevorotatory and given the prefix (−
H 3C H H H
If a solution contains equal amounts of 2 optical isomers (e.g. 1 mole of
(+)-alanine and 1 mole of (−)-alanine) it is said to be a racemic mixture, Trans-but-2-ene Cis-but-2-ene
and will show no rotation, as the effects of each optical isomer cancel 2. (a) CH3CH=CH2
out. (b) CH3CH 2CH2CHOHCH3
(c) CHI3
Geometric and optical isomerism are both forms of stereoisomerism. (d) CH3CCl2CH=CBrCHOHCH3

Practice Questions 3. (a) A species with an unpaired electron.

1. (a) Give the formula of the three structural isomers of C4H8 which are (b) An acceptor of a lone pair of electrons (to form a new covalent
non-cyclic. bond).
(c) When an atom or group in a molecule is replaced by another atom
(b) One of these structures shows a type of stereoisomerism. or group.
(i) Explain what causes the existence of stereoisomerism. (d) When water reacts with a molecule, which is split into 2 parts.
(ii) Give the two structures of the stereoisomers and name them.
4. (a) (i) CH2=CH2 + H2 → CH3CH3
2. Draw the structures of the following organic compounds. Conditions: Heat over a nickel catalyst.
(a) Propene (ii) CH3CH3 + Cl2 → CH3CH2Cl + HCl
(b) Pentan-2-ol Conditions: UV light.
(c) Triiodomethane (b) Free radical substitution.
(d) 2,2-dichloro-4-bromohex-3-ene-5-ol
5. (a) (i) CH3CH=CH2 + HBr → CH3CHBrCH3
3. Define the following terms. Conditions: Room temperature.
(a) Free radical. (ii) CH3CHBrCH3 + KCN → CH3CHCNCH3 + KBr
(b) Electrophile. Conditions: KCN in water/ethanol, heat under reflux.
(c) Substitution. (b) Nucleophilic substitution.
(d) Hydrolysis.
H OH H
6. (a)
4. The question relates to the following reaction scheme. *
HO C C C C C NH 2
step1 step 2
CH2CH2 CH3CH3 CH3CH2Cl
H Cl H H H
(a) Give the conditions and equations for
(b) A single optical isomer has the ability to rotate plane-polarised
(i) Step 1.
monochromatic light.
(ii) Step 2.
(b) What is the type and mechanism of the reaction in step 2? (c) A solution containing equal amounts of two optical isomers. A
racemic mixture will show no rotation of plane-polarised light as
5. The question relates to the following reaction scheme.
the effect of the two optical isomers cancel each other out.
step 1 step 2
CH3CHCH2 CH3CHBrCH2 CH3CHCNCH3
Acknowledgements: This Factsheet was researched and written by Kieron Heath. Curriculum
(a) Give the conditions required and the equation for: Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham, B18 6NF. ChemistryFactsheets
may be copied free of charge by teaching staff or students, provided that their school is a
(i) Step 1. registered subscriber. No part of these Factsheets may be reproduced, stored in a retrieval
(ii) Step 2. system, or transmitted, in any other form or by any other means, without the prior permission
(b) What is the type and mechanism of the reaction in step 2? of the publisher. ISSN 1351-5136

4
 Chem Factsheet
January 2002 Number 28
Energetics - Lattice Enthalpy and
Born-Haber Cycle
To succeed with this topic you need to : Lattice Enthalpy (LE)
• Ensure you understand the AS work on enthalpy cycles and Hess’s Lattice Enthalpy (LE) is the energy produced when 1 mole of
Law (covered in Factsheet No. 8); a solid ionic compound is made from its gaseous ions under standard
conditions (298K, 1 atmosphere pressure).
• Ensure you understand the terms ionisation energy and electron
affinity (covered in Factsheet No. 1.). i.e. M+(g) + X−(g) → MX(s) !H = LE
is the general equation for LE.
After working through this Factsheet you will:

• have met the new enthalpy terms of Lattice Enthalpy and Standard
These are further specific examples:
Enthalpy of Atomisation;
Na+(g) + Cl−(g) → NaCl(s)
• be able to write Born-Haber cycles for any ionic compound; 2+
Mg (g) + O2−(g) → MgO(s)
+
2K (g) + O2−(g) → K2O(s)
• be able to use these cycles for calculation work; Ca2+(g) + 2Cl−(g) → CaCl2(s)
• understand the significance of variations in Lattice Enthalpy
values and what this tells us about the ions in a compound; For practice on writing L.E. equations go to question 2.

• be able to explain trends in Lattice Enthalpy values.

Remember : - all L.E. values are negative and given in kJ mol-1

This Factsheet introduces the Born-Haber cycle, and Factsheet No. 29 • This unit is the standard one for enthalpy changes.
(‘How to Answer Questions on Born-Haber Cycles’) goes into the details • The negative value shows the L.E. is exothermic.
of examination questions and calculations. • This is because it is bond making i.e. gaseous ions coming together
to make a compound.
Exam Hint: - Candidates should be aware that:
• There are ‘easy marks’ available for any candidate who learns
and can write the definition for Lattice Enthalpy and standard
enthalpy of atomisation; Born-Haber Cycles
• If a Born-Haber cycle calculation is worth 5 marks, 3 marks will
be for writing the correct cycle; Standard enthalpy of formation !H298.f° :
• State symbols are important – if omitted from the cycle marks are
deducted;
Elements in their standard state forming 1 mole of a compound under
• The differences in LE values is invariably tested and, once standard conditions.
understood by candidates, should give some ‘easy marks’.

The Born-Haber cycle is based on Hess’s Law. The general form of the
cycle is:
Standard Enthalpy of Atomisation, !H298.at
°
Elements ∆H 298.f
° Ionic
° ) is the energy
Standard enthalpy of Atomisation (!H298.at (in their standard state) solid
required to produce 1 mole of gaseous atoms of an element under
standard conditions (298K, 1 atmosphere pressure).
∆H1 ∆H = LE
!H298.at
° needs to be looked at carefully as these following examples show:
!H298.at
° [Na(s)] Na(s) → Na(g) Gaseous ions

!H298.at
° [Mg(s)] Mg(s) → Mg(g)
Using Hess’s Law: !H1 + LE = !H298.f
°
!H298.at
° [½Cl2(g)] ½Cl2(g) → Cl(g)

!H298.at
° [½O2(g)] ½O2(g) → O(g) It is !H1 that is a composite of various terms that need to be written out
in full: elements → gaseous atoms → gaseous ions
You need to see the differences between solids converting to gases, and
diatomic gaseous elements converting to gaseous atoms. These equations
are all based on producing 1 mole of gaseous atoms.

For practice on writing !H298.at

° equations go to question 1.
1
Energetics - Latice Enthalpy and the Born-Haber Cycle Chem Factsheet

Example 1. The Born-Haber Cycle for NaCl Example 3. The Born-Haber Cycle for MgBr2

∆H298.f
° [MgBr2] MgBr2(s)
Mg(s) + Br2(g)
∆H298.f
° [NaCl] NaCl(s)
Na(s) + ½Cl2(g)

∆H1 LE[MgBr2]
∆H1 LE[NaCl]
Mg2+(g) + 2Br−(g)
Na+(g) + Cl−(g)
L.E. + !H1 → !H298.f
°
!H1 is made up of the following 4 parts:
!H1 is made up of the following 5 parts:
!Hat° 1st I.E. !Hat° nd
Na(s) Na(g) Na+(g) Mg(s) Mg(g) 1st I.E. Mg+(g) 2 I.E. Mg2+(g)

!Hat° 1st E.A. 2 ×!Hat° 2 ×1st E.A.

½Cl2(g) Cl(g) Cl−(g) Br2(g) 2Br(g) 2Br−(g)

I.E. = ionisation energy E.A. = electron affinity

N.B. Note the doubling of the values for Br2 because the definitions are
all based on 1 mole, and here there are 2 moles.
So, in full, Hess’s law gives:
For further practice on writing Born-Haber cycles go to question 3
L.E.[NaCl] + !Hat° [Na(s)] + !Hat° [½Cl2(g)]
+ 1st I.E.[Na] + 1st E.A.[Cl(g)] = !H298.f
° [NaCl(s)] Enthalpy level diagrams
Another way of presenting Born-Haber cycles is as enthalpy level diagrams.

Remember - In practice the !H1 is dealt with separately to give a In these the direction of arrows indicate exothermic (↓) or endothermic (↑)
single numerical value from the separate parts. You do not need to write
the Hess’s law out as above in full so long as elsewhere in the question Look at the following example:
you show the ∆H1 in full.

Mg2+(g) + 2Cl(g)
Example 2. The Born-Haber Cycle for K2O.

∆H298.f
° [K 2O] K 2O(s)
d
2K(s) + ½O2(g)
Mg2+(g) + Cl2(g) e

∆H1 LE[K2O]
c
2K+(g) + O2−(g) Mg+(g) + Cl2(g) Mg2+(g) + 2Cl−(g) *

L.E. + !H1 → !H298.f

°
b
!H1 is made up of the following 5 parts:
2 ×!Hat° Mg(g) + Cl2(g)
2K(g) 2 × 1 I.E.
st
2K(s) 2K+(g)
f
!Hat° st
1 E.A. nd
2 E.A. a
½O2(g) O(g) O−(g) O2−(g)
Mg(s) + Cl2(g) *
N.B. Notice the need to double the values for K because 2 moles are
involved.
g
Exam Hint: - Since we are dealing with an ionic solid, ∆H1 will always
involve the enthalpies of atomisation (i.e. converting each element to MgCl2(s) *
gaseous ions) and appropriate ionisation energy(ies) and electron
affinity(ies) to convert to ions. Compare the cycle we have been using with the parts labelled with an * -
can you see the link? The * indicates elements, ionic solid and gaseous ions
Marks are often lost be ignoring the multiples of each of these required. as in the previous form of the cycle. Factsheet 29 covers how to use these
In particular, note O2(g) →2O(g) ∆H = 2 × ∆Hat°
diagrams to answer questions.
since two moles of gaseous atoms are formed.

Accurate knowledge of definitions is therefore vital for success. For further practice on enthalpy diagrams go to question 4.

2
Energetics - Latice Enthalpy and the Born-Haber Cycle Chem Factsheet

Trends in L.E. values Exam Hint: - Candidates may be:

Look at the following series of L.E. values (Table 1). • asked to calculate L.E. values via a Born-Haber cycle
• given theoretical values of L.E. and asked why they are different
Table 1. L.E. Values

Series (A) LE/kJmol-1 Series (B) LE/kJmol-1 Series (C) LE/kJmol-1

NaF -902 Mg(OH)2 -2382 Li2O -2814

NaCl -771 Cl(OH)2 -2093 Na2O -2478

NaBr -733 Sr(OH)2 -1895 K 2O -2232

NaI -684 Ba(OH)2 -1768 Rb2O -2161

In all three series A, B and C the L.E. values become less exothermic
Questions
down the Groups 1 and 2. Why is this?
1. Write the equation for the standard enthalpy of atomisation for the
As any metallic group is descended the cations become larger and so the following elements:
charge density decreases – this is the cause of the L.E. values becoming a) !H298.at.
° [½I2(s)]
less exothermic.
b) !H298.at.
° [Hg (l)]
L.E. values are exothermic because of bond making when the gaseous c) !H298.at.
° [Zn(s)]
ions come together to make the ionic solid,
d) !H298.at.
° [½N2(g)]
M+(g) + X−(g) → MX(s)
2. Write the equation for the Lattice Enthalpy of the following compounds:
The ions are attracted together because of their opposite electrostatic
a) ZnO(s)
charges, and the stronger the attraction between them the more energy is
b) K2S(s)
released.
c) SrCl2(s)
If you compare series A with C, then C is larger because more ions are d) CsF(s)
involved so more energy released.
3. Write the Born-Haber cycle for the following compounds:
Charges in charge density affect the value of L.E. a) ZnI2(s)
b) SrO(s)
c) CaCl2(s)
Experimental and Theoretical L.E. Values
The L.E. values calculated by the Born-Haber cycle are based upon values 4. a) Identify each of the enthalpy terms labelled a to g.
for I.E, E.A, !Hf °and !Hat° found by experimentation. These L.E. values b) In terms of letters a to g what is the Hess’s Law cycle?
are ‘experimental’.
Mg2+(g) + 2Cl(g)
However, because L.E. is about charged spherical ions coming together it is
possible to calculate a theoretical L.E. value based on the attractive charges
involved and the distribution of charge on the spheres (Table 2.) d

Table 2. Theoretical and experimental L.E. values Mg2+(g) + Cl2(g) e

Theoretical L.E./ Experimental L.E./

kJ mol-1 kJ mol-1
c
NaCl 766 776
Mg+(g) + Cl2(g) Mg2+(g) + 2Cl−(g)
NaBr 730 741
AgCl 767 890
b
AgBr 759 878
Mg(g) + Cl2(g)
NaCl and NaBr show good agreement, the silver salts do not. Why? f
a
Differences in theoretical and experimental LE values indicate
the level of distortion of the anion ie. the degree of polarisation of the Mg(s) + Cl2(g)
anion

Good Agreement both ions are spherical i.e. _

+ g

Poor Agreement the anion is distorted and so _ MgCl2(s)

polarisation has taken place i.e.
++

3
Energetics - Latice Enthalpy and the Born-Haber Cycle Chem Factsheet

Answers c)
1. a) ½ I2 (s) → I(g)
b) Hg (l) → Hg(g) ∆H298.f
° [Al2O3] Al2O3(s)
2Al(s) + 1½O2(g)
c) Zn (s) → Zn(g)
d) ½N2 (g) → N(g)

2. a) Zn2+ (g) + O2- (g) → ZnO(s) ∆H1 LE[Al2O3]

b) 2K+ (g) + S2- (g) → K2S(s)
c) Sr2+ (g) + 2Cl- (g) → SrCl2(s)
d) Cs+ (g) + F- (g) → CsF(s) 2Al3+(g) + 3O2−(g)

!H1
3. a)
2 × !Hat°
2Al(g) 2 × 1 I.E. 2Al+(g) 2 × 2 I.E.
st nd
2Al(s) 2Al2+(g)
∆H298.f
° [ZnI2] ZnI2(s)
Zn(s) + I2(s)
2 × 3rd I.E.

2Al3+(g)
∆H1 LE[ZnI2]
3 ×!Hat°
3O(g) 3 ×1 E.A. 3O−(g) 3 ×2 E.A. 3O2-(g)
st nd
1½O2(g)
Zn2+(g) + 2I−(g)
4. a) a = !Hat° [Mg(s)]
!H1
!Hat° 2nd I.E. b = 1st I.E.[Mg]
Zn(s) Zn(g) 1st I.E. Zn+(g) Zn2+(g)
c = 2nd I.E.[Mg+]
2 ×!Hat° 2 ×1 E.A.
st
I2(g) 2I(g) 2I−(g)
d = 2 × !Hat° [½Cl2(g)]
b) e = 2 × 1stE.A.[Cl]
∆H298.f
° [SrO] SrO(s) f = L.E.[MgCl2]
Sr(s) + ½O2(g)

g = !Hf° [MgCl2]
∆H1 LE[SrO] b) a + b + c + d + e + f = g

Sr2+(g) + O2−(g)

!H1
!Hat° 1st I.E. 2nd I.E.
Sr(s) Sr(g) Sr+(g) Sr2+(g)

!Hat° 1st E.A. 2nd E.A.

½O2(g) O(g) O−(g) O2-(g)

c)

∆H298.f
° [CaCl2] CaCl2(s)
Ca(s) + Cl2(g)

∆H1 LE[CaCl2]

Ca2+(g) + 2Cl−(g)

!H1
!Hat° 1st I.E. 2nd I.E.
Ca(s) Ca(g) Ca+(g) Ca2+(g)

2 ×!Hat° 2 ×1st E.A. Acknowledgements: This Factsheet was researched and written by Sam Goodman. Curriculum
Cl2(g) 2Cl(g) 2Cl−(g) Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham, B18 6NF. ChemistryFactsheets
may be copied free of charge by teaching staff or students, provided that their school is a
registered subscriber. No part of these Factsheets may be reproduced, stored in a retrieval
system, or transmitted, in any other form or by any other means, without the prior permission
of the publisher. ISSN 1351-5136

4
 Chem Factsheet
January 2002 Number 29
Answering Questions On Born-Haber Cycles
To succeed in this topic you need to thoroughly understand how to write Born-Haber cycles (covered in Factsheet No. 28)

After working through this Factsheet you will know and understand:
• how to convert Born-Haber cycles into numerical answers given the relevant data;
• how the data given is used to test the understanding of definitions by candidates;
• the relationship between the marks for a question and the balance between writing the cycle and calculating an answer;
• the use of enthalpy level diagrams to test the understanding of candidates of definitions and Born-Haber cycles.

Questions on Enthalpy Level Diagrams 2. Calculating a numerical answer given all the other values and the diagram
There are two types of questions on these diagrams:
1. Identifying enthalpy changes
2. Calculating a numerical answer from given values on a diagram Ca2+(g) + O2−(g)

1. Identifying enthalpy changes X

Ca2+(g) + O(g)
Zn2+(g) + 2Br(g)
+250 KJ mol−1
c Zn2+(g) + Br2(g) b 2+
Ca (g) + ½O2(g)
d Zn+(g) + Br2(g) Zn2+(g) + 2Br−(g)
+1150 KJ mol−1 -3512 KJ mol−1
e Zn(g) + Br2(g) a Ca+(g) + ½O2(g)
f Zn(s) + Br2(g)
g +590 KJ mol−1
ZnBr(s)
Ca(g) + ½O2(g)
Example 1
+192 KJ mol−1
Question: Identify the stages a – g
Ca(s) + ½O2(g)
Method
For each arrow look to see what has changed. It is then a matter of -635 KJ mol−1
deciding which definition it matches and how many moles. CaO(s)

Answer: Question What is the value of X?

a = gaseous ions to ionic solid = L.E.
b = 2Br(g) → 2Br−(g) = 2 × 1st E.A. Method: Either convert to an enthalpy cycle:
c = Br2(g) → 2Br(g) = 2 × !H°at [½Br2]
d = Zn+(g) → Zn2+(g) = 2nd I.E. Identify each of: elements, compound and gaseous ions, then draw the
e = Zn(g) → Zn+(g) = 1st I.E. diagram:
f = Zn(s) → Zn(g) = !Hat°[Zn(s)] ∆Hf°
Elements Compound
g = elements → compound = !Hf° [ZnBr2(s)]
∆H1 L.E.
Gaseous ions
Example 2
Question: How are a – g linked by Hess’s Law? !H1 + L.E. = !Hf°
Method: Identify on the diagram: elements, compound and gaseous ions Identify the components in the diagram and put in the values.
∆Hf°
Elements Compound Answer -635 = + 192 + 590 + 1150 + 250 + X - 3512
-635 = X – 1330
∆H1 L.E. X = + 1330 – 635 = +695 kJ mol-1
gaseous ions
Or follow the diagram round, starting and finishing with the elements:
So: !H1 + L.E. = !Hf° 192 + 590 + 1150 + 250 + X + (-3512) − (-635) = 0

Answer: f + e + d + c + b + a = g Note: The direction of the arrow tells us whether to add or subtract. We are
going in the direction of the arrow for the -3512, so we add (-3512).
Or alternatively, "follow the diagram round" - starting and finishing with
the elements. If you go in the same direction as an arrow, you add the X − 695 = 0 so X = +695 kJmol-1
corresponding value; if in the opposite direction, subtract the value.
Finally, equate to zero: f + e + d + c + a − g = 0 For practice on this type of calculation, go to question 1.

1
Answering Questions On Born-Haber Cycles Chem Factsheet

Further calculations using Borh-Haber Cycles

All of these use the enthalpy cycle below (or the enthalpy level diagrams Questions
- whichever you prefer). You may be required to find enthalpies of formation, 1. a) Identify s, t, u, v, w, x and y in the following cycle:
electron affinities etc, but the approach in each case is identical.
Ca2+(g) + 2Br(g)
∆Hf°
Elements Ionic solid v
Ca2+(g) + Br2(g) u

∆H1 L.E. w
Gaseous ions Ca+(g) + Br2(g) Ca2+(g) + 2Br-(g)

x
!H1 + L.E. = !Hf°
Ca(g) + Br2(g) t
Method
1. Draw the Born-Haber Cycle – including all parts of !H1, which will y
include enthalpies of atomisation and appropriate ionisation energies
Ca(s) + Br2(g)
and electron affinites
2. Substitute the values given s
3. Calculate the ‘missing’ value and so the answer CaBr2(s)
Exam Hint: - Candidates should be aware that all the definitions for
I.E, E.A, ∆Hat°, ∆Hf° and L.E. are based on 1 mole. Watch out for the
, b) What is the relationship between s – x?
following ‘data traps’ that are used to test whether you know the
definitions are for 1 mole
You will need the following data to answer questions 2 to 7
a) Cl2(g) → 2Cl−(g) ∆H = + 244 kJmol-2 (all values in kJ mol-1):
i.e. you have been given 2 x ∆Hat [½Cl2]. The question means you
have to use +244/2 if the cycle uses ½Cl2 → Cl(g) Cl2(g) → 2Cl(g) = -242 Cl(g) → Cl−(g) = -364
b ) Mg(g) → Mg (g) ∆H = + 2289 kJmol
2+ -1
½O2(g) → O(g) = +249 O(g) → O−(g) = -141
i.e. you have been given the total of the 1st I.E. + 2nd I.E. for Mg
O−(g) → O2−(g) = +798 K(s) → K(g) = +90
c) Suppose you are asked to find the E.A. of Cl from a cycle involving
MgCl2(s). K(g) → K+(g) = +418 Mg(s) → Mg(g) = +148
When you put in all the values you find the answer for 2Cl(g)→ 2Cl−(g). Mg(g) → Mg+(g) = +738 Mg+(g) → Mg2+(g) = +1451
The answer needs ÷ 2 because E.A. is for 1 mole! This is a
½Br2(g) → Br(g) = +112 Br(g) → Br−(g) = -325
common way of catching out candidates.
Zn(s) → Zn(g) = +131 Zn(g) → Zn2+(g) = +2639
Look out for these ‘data traps’ as you attempt Question 3. onwards – they I2(g) → 2I(g) = +214 I(g) → I−(g) = -314
are marked in the answers in order to help you out. Sr(s) → Sr(g) = +164 Sr(g) → Sr+(g) = +550
Sr+(g) → Sr2+(g) = +1064 Ca(s) → Ca(g) = +178
∆Hf° Ca(g) → Ca2+ = +1735 !Hf° [K2O(s)] = -361
Na(s) + ½Cl2(g) NaCl(s) !Hf° [MgBr2(s)] = -524 L.E. (ZnI2) (s) = -2605
L.E. (SrO) = -3223 !Hf°[CaCl2] = -796
∆H1 L.E.
+ -
Na (g) + Cl (g) 2. Using the cycle for K2O below calculate the L.E.
∆H 298.f
°
!H1 2K(s) + ½O2(g) K 2O(s)
∆H at° 1st I.E.
Na(s) Na(g) Na+(g) ∆H1 L.E.(K2O)
2+ 2−
K (g) + O (g)
∆H at° 1st E.A.
½Cl2(g) Cl(g) Cl−(g)
3. Using the cycle for MgBr2 below calculate the L.E.
!Hf ° = !H1 + L.E. ∆H 298.f
°
Mg(s) + Br2(g) MgBr2(s)
Question:What is the L.E. for NaCl(s)?

!Hf° [NaCl(s)]= -411 kJmol-1 !Hat° [Na(s)]= + 109 kJmol-1 ∆H1 L.E.(MgBr2)
2+ −
Mg (g) + 2Br (g)
!Hat°[½Cl2(g)] = +121 kJmol-1 1st E.A.Cl = -364 kJmol-1

1st I.E. Na = +494 kJmol-1 4. Write the Born-Haber cycle for ZnI2 and use it to find !Hf [ZnI2]

-411 = +109 +121 - 364 + 494 + L.E. 5. Write the Born-Haber cycle for SrO and use it to find the !Hf [SrO]

L.E. = -771 kJmol-1 6. What value for the E.A. of chlorine does the Born-Haber cycle for
CaCl2 produce?
For more practice on Born-Haber cycles try questions 2 – 6
2
Answering Questions On Born-Haber Cycles Chem Factsheet

Answers 6.
∆Hf°
1. a) s = !Hf° [CaBr2] t = L.E. (CaBr2) Ca(s) + Cl2(g) CaCl2(s)
u = 2 × E.A. (Br) v = 2 × !Hat° [½Br2]
w = 2nd I.E. (Ca+) x = 1st I.E. (Ca) ∆H1 L.E.[CaCl2]
y = !Hat° [Ca] 2+
Ca (g) + Cl (g)−

b) s = y + x + w + v + u + t
!H1
2. L.E. = - 1485 kJmol-1 ∆H at° 2nd I.E.
1st I.E.
Ca(s) Ca(g) Ca+(g) Ca2+(g)
-1
3. L.E. = - 2435 kJmol
+ 178 + 1735
∆Hf°
4.
Zn(s) + I2(g) ZnI2(s)
2 × ∆H at° 2 × E.A.
Cl2 (g) 2Cl(g) 2Cl−(g)
∆H1 L.E.[ZnI2] + 242 x
Zn2+(g) + 2I−(g)
N.B. Ca → Ca2+ is total value, and Cl2 → is given for 2 × !Hat°already.
!H1 !H1 = + 1671 + x
∆H at° 1st I.E.
nd
2 I.E.
Zn(s) Zn(g) Zn+(g) Zn2+(g) - 796 = + 1671 + x - 2258
+131 ∴x = - 796 – 1671 + 2258 = -209
+2639
2 × ∆H at° 2 × E.A. but this is 2 × E.A, so –209/2 = - 104.5 kJmol-1
I2(s) 2I(g) 2I−(g)
+214 2 × -314

N.B. Notice data changes for I2 and Zn/Zn2+

!H1 = + 2356

!Hf° = + 2356 = 2605

= - 249 kJmol-1

5. ∆Hf°
Sr(s) + ½O2(g) SrO(s)

∆H1 L.E.[SrO]
2+ 2−
Sr (g) + O (g)

!H1
∆H at° 1st I.E. 2nd I.E.
Sr(s) Sr(g) Sr+(g) Sr2+(g)
+ 164 + 550 + 1064

∆H at° 1st E.A. 2nd E.A.

½O2 (g) O(g) O−(g) O2−(g)
+ 249 - 141 + 798

!H1 = + 2684

!Hf° = + 2356 - 3223 = -539 kJmol-1

Acknowledgements: This Factsheet was researched and written by Kieron Heath. Curriculum
Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham, B18 6NF. ChemistryFactsheets
may be copied free of charge by teaching staff or students, provided that their school is a
registered subscriber. No part of these Factsheets may be reproduced, stored in a retrieval
system, or transmitted, in any other form or by any other means, without the prior permission
of the publisher. ISSN 1351-5136

3
 Chem Factsheet
January 2002 Number 30
Laboratory Chemistry - Separation &
Purification Techniques
After working through this Factsheet you will: This Factsheet mainly focuses on the practical techniques required once
• Have been introduced to a range of practical techniques; the initial reaction has been carried out, and the crude product has been
• Be able to give a short method describing each technique; formed in the reaction mixture.
• Understand how solid and liquid products can be isolated and
purified. These techniques are more general, as in most cases the crude product
must be:
Exam Hint: - Candidates should have a good knowledge of these
practical techniques, and be able to describe them concisely (with the
aid of diagrams if necessary). They are especially important when • Isolated - from the reaction mixture.
preparing for a practical exam or practical assessment of the “planning” • Purified - for use or identification.
skill, but may also be required in the written papers.
The practical techniques outlined in this Factsheet have been placed into
two groups - those associated with:
It is impossible to generalise about methods of preparation of crude chemical
products, as every compound is prepared in a slightly different manner.
1. isolation and purification of a solid product
Candidates should be aware, however, that examiners will ask about methods
2. isolation and purification of a liquid product.
of reactions covered elsewhere in the AS and A2 courses. Candidates
should be able to apply their existing knowledge to practical situations,
and will be given background information in the exam or assessment
question. 1. Isolation and Purification of a Solid Product
Once a solid product has been formed, the method, or plan, should commonly
One reaction condition worth mentioning here, however, is that of heating include three further steps:
under reflux, as it is very common in organic preparations (Fig 1).
a) Filtration
Reflux apparatus are necessary when a reactant has a low boiling point, or b) Recrystallisation
the reaction is slow at room temperature. The condenser prevents the c) Melting point determination.
escape of any volatile reagent or product.
a) Filtration
To isolate a crude solid product from a liquid, use suction filtration, using
Fig 1. Reflux apparatus a Buchner funnel (Fig 2).

Fig 2. Suction filtration

condenser
to sink
Buchner funnel
and flask

from tap suction

reaction mixture

heat A small amount of cold solvent should be used to wet the filter paper prior
to filtration, and to remove any solid remains from the reaction vessel - in
an effort to save as much of the solid product as possible.

1
Laboratory Chemistry - separation and purification Chem Factsheet

b) Recrystallisation - To purify the solid product 2. Isolation and Purification of a Liquid Product
A suitable solvent for recrystallisation will often be evident (e.g. the solvent There is slightly more to consider when planning how to extract a pure
from which the crude product was initially crystallised ), and should be a liquid product, as a liquid may be miscible or immiscible, acidic, or may
solvent which will not react with the solid. The solubility of the solid need drying.
should be high near the boiling point and low near room temperature.
Candidates should learn the method of recrystallisation. a) Separating Funnel - For use when separating immiscible liquids (Fig 4).

• Dissolve the solid in the minimum volume of hot solvent.

• Quickly filter the hot solution using preheated filter funnel and fluted
filter paper.
• Collect the filtrate and allow to cool and the solid to recrystallise.
• Use suction filtration (Buchner funnel) to collect the solid. solvent extraction or seperation
• Wash the solid with a small amount of cold solvent. of immiscible liquids
• Dry the solid product.

c) Melting Point Determination

The melting point of a solid is used to judge the purity of the product. A
solid should have a sharp melting point, and recrystallisation should be
repeated until this is obtained. Melting point should be determined using
melting point apparatus (Fig 3).

Fig 3. Melting point apparatus

capillary tube thermometer

If, after carrying out a reaction, candidates are left with a liquid product
which is immiscible with the rest of the reaction mixture, they must be able
to find out which layer (upper or lower) contains the product. This can be
electrically discovered by examining liquid density data - obviously the more dense
heated block liquid will be the lower layer.

The two layers, which meet at an interface, are physically separated by

running the lower layer out of the separating funnel (using the tap) and
retaining the upper layer in the funnel.

illuminated b) Neutralising Acidic Liquid Products

cavity Often acid conditions are required when preparing organic liquids, and the
acid should be neutralised by the addition of a solid base such as sodium
carbonate (Na2CO3), or sodium hydrogen carbonate (NaHCO3) solution.

The use of an indicator is not required as it is clear when the neutralisation

is complete as no further carbon dioxide gas is evolved on the addition of
the base.
sample
Care must be taken if sodium carbonate (or sodium hydrogen carbonate) is
added to a liquid and a stopper placed over the vessel so it can be shaken,
The sample is placed in a capillary tube, and the temperature increased as the pressure of the carbon dioxide gas formed must be periodically
slowly until it melts. released.

Melting points can also be used for identification purposes. Another by-product of the neutralisation reaction will be water, so an
aqueous layer may be formed. This can be removed using a separating
funnel and drying agent.

Example - Method for the preparation of Benzenecarboxylic acid.

Candidates would be given the background information in terms of the chemical reactions involved, and should be able to calculate reasonable quantities
of reactants. Focus here on steps 3, 4, 5 and 6 as they put the work covered so far in this Factsheet into a practical chemistry context.
(1) Add 40cm 3 of dilute sodium hydroxide solution to 1cm 3 of (4) Recrystallise the compound by dissolving the crystals in the minimum
ethylbenzenecarboxylate in a round-bottomed flask. Reflux for 30 amount of hot water and filtering the hot solution using preheated
minutes. filter funnel and fluted filter paper. Allow the filtrate to cool so that
crystals form.
(2) Transfer the mixture to a beaker and add dilute sulphuric acid until the
solution is just acidic. Use a glass rod and indicator paper to do this. (5) Use suction filtration to collect the crystals, wash with cold water
and let them dry.
(3) Use suction filtration (Buchner funnel and flask) to filter off crystals
of benzenecarboxylic acid. (6) When dry, weigh the solid product to calculate the yield, and determine
the melting point.

2
Laboratory Chemistry - separation and purification Chem Factsheet

c) Drying of Liquid Products - the Removal of Water Fractional distillation will be discussed in more depth in future Factsheets.
The anhydrous solids calcium chloride or sodium sulphate can be added to
the liquid product if it is necessary to dry it. After addition and agitation, For either type of distillation, knowledge of the boiling point of the liquid
the mixture should be allowed to stand for a few minutes and then filtered. product is important.
The dry liquid can then be collected as the filtrate.

Distillation
Preparation of a halogenoalkane
Distillation can be used when the boiling point of the product is significantly
2-chloro-2-methylpropane can be prepared from 2-methylpropan-2-ol
different to that of the rest of the reaction mixture.
and hydrochloric acid. The reaction will take place at room temperature
Distillation is used to purify a liquid by boiling it and then condensing it as tertiary alcohols undergo substitution readily.
away from its impurities (Fig 5).
Boiling point of product (2-chloro-2-methylpropane) is 50 oC.
Fig 5. Distillation apparatus
CH3 CH3

H 3C C CH 3 + HCl → H 3 C C CH 3 + H 2 O
Thermometer
CH 3 Cl
2-chloro-2-methylpropane and 2-methyl-propan-2-ol are flammable, and
both volatile liquids at room temperature. Concentrated hydrochloric
Thermometer pocket
acid is very corrosive.

Given this background information, candidates should be able to suggest

a reasonable procedure plan, with safety precautions.
Liebig condeser
Procedure
1. Measure 10cm3 2-methylpropan-2-ol into a measuring cylinder.
water
out 2. Pour the 2-methylpropan-2-ol into a 50cm3 separating funnel, and
water in reweigh the measuring cylinder to calculate the exact mass of liquid
poured.
Heat
Receiver 3. Add 20cm3 concentrated hydrochloric acid (excess) a few cm3 at a
time, taking care to mix the reactants after each addition by inverting
the stoppered funnel. Ensure that any build up of gas pressure is
Distillate
released.

4. Leave the reaction mixture in a fume cupboard for 15 minutes, gently

Fractional Distillation agitating the mixture at intervals.
Fractional distillation is most commonly used to separate two liquids (if 5. Allow the 2 layers in the separating funnel to separate, then run off
the boiling points are fairly close). Pure samples of each liquid can usually and discard the lower aqueous layer.
be obtained, unless the boiling points are too close (Fig 6).
6. Add sodium hydrogen carbonate solution 2cm3 at a time to neutralise
Fig 6. Fractional distillation apparatus the remaining organic layer. Shake the funnel carefully, being sure to
release the build up of gas pressure. Continue the addition until the
excess acid is neutralised.
Thermometer
7. Allow layers to separate and discard the lower aqueous layer.

Thermometer pocket 8. Run the organic product into a small conical flask and add 3 spatulas
of anhydrous sodium sulphate to dry it. Stopper and swirl the flask
for 5 minutes.
Liebig condeser
9. Decant the liquid into a small pear-shaped flask.
to vacuum pump 10. Distil the product, collecting the fraction in the range 47 to 53 oC into
water for distillation
Fractionating a pre-weighed flask.
out under reduced
column water in
pressure 11. Find the mass of the purified product.

Safety Precautions
Distillate • Keep flammable liquids away from flames.
• Carry out acid addition in fume cupboard.
Distillation flask • Keep stoppers on bottles as much as possible.
• Wear gloves and safety spectacles.

Exam Hint: - Take note of the style of language used when writing
out a method - it needs to be clear, accurate and concise. Name
the apparatus, calculate quantities to be used, and use diagrams if
Heat appropriate.

3
Laboratory Chemistry - separation and purification Chem Factsheet

Practice Question Answer

This is an example of a practical assessment task which. It is possible that (a) Conversion of 20 cm3 2-bromobutane to grams. (20 × 1.3 = 26g) 1
candidates would be given some general advice as to what areas to revise Conversion of grams 2-bromobutane to moles. (26/137 = 0.190) 1
and read about prior to the assessment, but notes and books would not be Recognise molar ratio 1:1, deducing moles of butan-2-ol. (0.190) 1
allowed whilst answering. Use 75% purity to calculate number of moles of butan-2-ol
required initially. (0.190/0.75 = 0.253 moles) 1
Planning the preparation of 2-bromobutane Deduce mass of butan-2-ol required initially (0.253 × 74 = 18.7g) 1
2-bromobutane is a liquid (density = 1.3gcm-3, Mr = 137) which is immisci- Converts grams to volume (cm3) of butan-2-ol required
ble with water. (18.7/0.8 = 23.4 cm3) 1

It is prepared from butan-2-ol (density = 0.8gcm-3, Mr = 74), by refluxing (b) Need for cooling / slow addition of conc. sulphuric acid. 1
it with solid sodium bromide, water and concentrated sulphuric acid. Reflux (for at least 30 minutes). 1
Diagram of reflux apparatus.
CH3CH2CHOHCH3 + Br − → CH3CH2CHBrCH3 + OH− (-1 for each error) 3

You are asked to plan a safe procedure for making 20 cm 3 of pure 2- Distillation 1
bromobutane, assuming a 75% yield. Made clear aim is to distil off upper organic layer. 1
Diagram of distillation apparatus. (-1 for each error) 3
Butan-2-ol dissolves in concentrated hydrochloric acid.
(c) Remove and discard upper aqueous layer. 1
The plan should include: Wash with concentrated hydrochloric acid to remove unreacted
butan-2-ol. 1
(a) The exact volume of butan-2-ol required (show your calculations). Collect lower layer. 1

(b) A description of the safe procedure of the preparation. Wash with an appropriate quantity of sodium hydrogen carbonate
Include: solution (2cm3 at a time) to remove excess acid. 1
• Diagrams of apparatus Remove stopper to ease pressure as gas is produced. 1
• Which layers are discarded and kept when immiscible liquids are Collect lower organic layer. 1
produced.
Dry using appropriate drying agent. 1
Filter or decant to remove desiccant. 1
(c) A description of all the steps in the purification process.
(d) Distil to further purify. 1
(d) A description of the final distillation of the pure product. Collection of distillate in temperature range (88-94 oC). 1
(N.B. there is no need to re-draw distillation apparatus).
(e) Identification of hazards 2
(e) All safety factors should be considered. e.g. corrosive nature of acid, exothermic reaction of concentrated acid
and water, ‘holding up‘ of vapour in reflux condenser.
Data:
Precautions 2
-3 e.g. gloves and goggles, gentle heating during reflux, no naked flame
Densities: Butan-2-ol = 0.8 gcm
near flammable solvents, careful addition of chemicals.
2-bromobutane = 1.3 gcm-3
Total = 30 marks.
Water = 1.0 gcm-3
Conc. Hydrochloric acid = 1.2 gcm-3
Sulphuric acid and water mix = 1.4 gcm-3

Boiling points: 2-bromobutane = 91 oC

2-chlorobutane = 78 oC

Acknowledgements: This Factsheet was researched and written by Kieron Heath. Curriculum
Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham, B18 6NF. ChemistryFactsheets
may be copied free of charge by teaching staff or students, provided that their school is a
registered subscriber. No part of these Factsheets may be reproduced, stored in a retrieval
system, or transmitted, in any other form or by any other means, without the prior permission
of the publisher. ISSN 1351-5136

4
 Chem Factsheet
April 2002 www.curriculumpress.co.uk Number 31
Organic Chemistry 2: Halogeno-compounds and Grignard Reagents
To succeed in this topic you need to:- Reactions of Grignard reagents
• Have a good understanding of AS-level Organic Chemistry The Grignard reagent is very reactive.
(Factsheets 15, 16, 17 and 27);
H
• Be confident in using organic nomenclature and structural
formulae. δ− δ+
CH 3 C Mg I
After working through this Factsheet you will:-
• Have reviewed the chemistry of the halogeno-compounds covered H
so far;
They contain a δ- carbon, which gives rise to the extremely reactive R−
• Know how Grignard reagents are formed;
species i.e. in the above example,
• Know how Grignard reagents are used in a variety of organic
preparations. H
Halogeno-alkanes
CH 3 C−
Fig 1 below summarises the reactions of the halogeno-alkanes.

Fig. 1 Halogenoalkane reactions H

The R− species is a strong nucleophile, which is capable of attacking δ+

nitrile alcohol
carbons in other molecules - hence carbon chain lengths can be increased.
nucleophilic KCN in nucleophilic
substitution water/ethanol NaOH(aq) substitution 1. Reaction with water to form alkanes
heat under
heat under reflux R−MgI + H2O → R−H + Mg(OH)I
reflux
Halogenoalkane Reaction type: Substitution.
NH3 in KOH in Mechanism: Nucleophilic.
ethanol ethanol
heat heat under This reaction shows why Grignard reagents must be prepared in dry
amine reflux alkene conditions.
nucleophilic nucleophilic
substitution elimination 2. Reaction with methanal to form primary alcohol.
Methanal gas is passed into the solution of the Grignard, and the mixture
is then hydrolysed with dilute hydrochloric acid.
R−MgI + CH2=O→ R−CH2−O−MgI (Nucleophilic addition)
Grignard Reagents
The main focus of this Factsheet is on the formation and use of a commonly Then:
examined set of reagents derived from the halogenoalkanes - Grignard R−CH2−O−MgI + H2O → R−CH2−OH + Mg(OH)I (Hydrolysis)
reagents. Reaction conditions: In dry ether, followed by addition of dilute acid for
Preparation of Grignard Reagents hydrolysis.
Grignard reagents are prepared by refluxing alkyl or aryl bromide or iodide
compounds, dissolved in dry ether, with small magnesium turnings. 3. Reaction with other aldehydes to form secondary alcohols.
R−Br + Mg → R−MgBr R R
'Grignard reagent' H 2O
R−MgI + R'CHO → CH−O−MgI CH−OH + Mg(OH)I
The Grignard reagent cannot be isolated - it must remain in etheral solution R' R'
for further reaction.
Reaction conditions: In dry ether, followed by addition of dilute acid for
Example of Grignard reagent preparation: hydrolysis.

C2H5I + Mg → C2H5MgI For example:

C 2H 5
Reaction type: Addition C2H5MgI + CH3CHO → CH−O−MgI
Conditions: Dry ether solvent
Reflux CH3
H 2O
Trace of iodine as catalyst
C 2H 5
C−OH + Mg(OH)I
CH3
Butan-2-ol

1
Halogeno-compounds and Grigand Reagents Chem Factsheet
www.curriculumpress.co.uk

Answers.
4. Reaction with ketones to form tertiary alcohols. H Br H
1. (a)
R1 R1
R1 H C C C H
H 2O
R−MgI + C=O → R−C−O−MgI R−C−OH + Mg(OH)I
R2 H H H
R2 R2
(b) H H Cl Cl
Reaction conditions: In dry ether, followed by addition of dilute acid for H C C C C H
hydrolysis.
H H H H
For example:
C2H5 H
C2H5 (c)
CH3MgI + C=O CH3−C−O−MgI H C H
H H H Br Cl
C3H 7
C 3H 7
H C C C C C C H

H 2O H H H H Br H
2. Because they contain a very unstable δ- carbon atom, an extremely
strong nucleophile.
C2H5

CH3−C−OH + Mg(OH)I 3. CH3I should be dissolved in dry ether

Magnesium turnings added
C 3H 7 Iodine catalyst
Heat under reflux

5. Reactions of Grignard with carbon dioxide to form carboxylic acid. 4. (a) CH3CH2CH2I + Mg → CH3CH2CH2MgI
Carbon dioxide is bubbled through (or solid CO2, ‘dry ice‘, is added to) Conditions: Reflux in ether
an etheral solution of a Grignard reagent. Iodine catalyst
H 2O
R−MgI + CO2 → R−C−O−MgI R−C−OH + Mg(OH)I (b) CH3CH2CH2MgI + CO2 + H2O → CH3CH2CH2COOH + Mg(OH)I
O O Conditions: Addition of CO2 in dry ether, then dilute acid for
hydrolysis
Reaction conditions: In dry ether, followed by addition of dilute acid for
hydrolysis. 5. (a) CH3CH2Br + Mg → CH3CH2MgBr
Conditions: Reflux in ether
Iodine catalyst
Questions
1. Write the structural formulae of the following compounds: (b) CH3CH2CH2MgI + CH3CHO + H2O → CH3CH2CHOHCH3 + Mg(OH)Br
Conditions: Dissolved in dry ether, then dilute acid for
(a) 2-bromopropane
hydrolysis.
(b) 1,2-dichlorobutane

(c) 2,2-dibromo-1-chloro-3-methylhexane

2. Explain why Grignard reagents are very reactive.

3. Explain clearly how the Grignard reagent CH3MgI would be formed

from CH3I.

4. This question relates to the following reaction scheme:

step 1 step 2
CH3CH2CH2I CH3CH2CH2MgI CH3CH2CH2COOH

Give the reaction equations and conditions for:

(a) Step 1.
(b) Step 2.

5. This question relates to the following reaction scheme:

Acknowledgements: This Factsheet was researched and written by Sam
step 1 step 2
CH3CH2Br CH3CH2MgBr CH3CH2CHOHCH3 Goodman and Kieron Heath. Curriculum Press, Unit 305B, The Big Peg, 120
Vyse Street, Birmingham, B18 6NF. ChemistryFactsheets may be copied free
Give the reaction equations and conditions for: of charge by teaching staff or students, provided that their school is a registered
subscriber. No part of these Factsheets may be reproduced, stored in a retrieval
(a) Step 1. system, or transmitted, in any other form or by any other means, without the
(b) Step 2. prior permission of the publisher. ISSN 1351-5136

2
 Chem Factsheet
April 2002 www.curriculumpress.co.uk Number 32
Organic Chemistry 3: Carboxylic Acids, Esters and Acyl Chlorides
To succeed in this topic you need to:-
2. Reaction with lithium tetrahydridoaluminate (III) - LiAlH4
• Have a good understanding of AS-level Organic Chemistry
Carboxylic acids can be reduced to alcohols by LiAlH4 dissolved in dry
(Factsheets 15, 16, 17 and 27);
ether.
• Be confident in using organic nomenclature and structural
H+
formulae. CH3COOH + 4[H] CH3CH2OH + H2 O

After working through this Factsheet you will:- The 4[H] are supplied by the LiAlH4.
• Have been shown the necessary reactions for the carboxylic acids, Reaction type: Reduction
esters and acyl chlorides; Conditions: LiAlH4 dissolved in dry ether, followed by hydrolysis
• Have tried practice questions to gain experience in how with H+(aq)
knowledge of the chemistry of these functional groups can be Mechanism: Nucleophilic
called upon in examinations.
3. Reaction with PCl5 to form acid chlorides
Carboxylic Acids Carboxylic acids can be converted to acid chlorides (or “acyl chlorides”)
Functional group by reaction with phosphorus pentachloride.
O The −OH group is replaced by a Cl− nucleophile.
R C
OH CH3COOH + PCl5 → CH3COCl + HCl + POCl3
Reactions of the carboxylic acids are not simply those of the − OH and ethanoyl chloride
C=O groups put together.
Reaction type: Substitution
The ionisation of the functional group is very significant. Conditions: Dry - observation of steamy white fumes (HCl)
O O Mechanism: Nucleophilic
CH3−C + H2O CH3−C + H3O+
OH O− 4. Reaction with sodium carbonate and sodium hydrogen carbonate
Note the acidic property of donating a proton. 2CH3COOH + Na2CO3 → 2CH3COO−Na+ + CO2 + H2O
The resulting anion is stabilised by π-electrons and lone pair electrons Reaction type: Neutralisation
(from the negative charge) forming a delocalised system. Conditions: Aqueous

O − The reaction between NaHCO3 and a carboxylic acid is a test for the
CH3 −COOH group.
C
O If NaHCO3 is added and CO2 gas is evolved, the -COOH group is present.
• The resulting structure is symmetrical; both C−O bonds are of equal CH3COOH + NaHCO3 → CH3COO-Na+ + CO2 + H2O
length and strength.
• The presence of the C=O group means that the carbon atom is Reaction type: Neutralisation
electrophilic in nature. Conditions: Aqueous

Reactions of Carboxylic Acids Esters

O
1. Reaction of carboxylic acids with alcohols (esterification) Functional group: R C
Carboxylic acid and an alcohol react to form an ester and water. O−R'
O heat, H+ O Where R and R' may be alkyl or aryl groups, and may be the same or
CH3CH2C + CH3OH CH3CH2C + H2 O different.
OH O−CH3
propanoic acid methanol methyl propanoate
Reaction type: Substitution Practical Hint: Esters are characterised by their sweet “gluey” aroma.
Conditions: Heat under reflux, add a few drops of conc. H2SO4
Mechanism: Nucleophilic

N.B. This rection is reversible - see later reactions of esters.

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Organic Chemistry 3: reactions of carboxylic acids, esters and acyl chlorides Chem Factsheet
www.curriculumpress.co.uk

Reactions of Esters Acid Chlorides - The Reactions of Ethanoyl Chloride.

Acid chlorides are derivatives of carboxylic acids.
1. Hydrolysis of esters with acids and alkalis
As shown earlier in this Factsheet, esters (and water) can be formed by the O
Functional Group: C
reaction of a carboxylic acid with an alcohol in acidic conditions. Cl
This is a reversible reaction, so can be looked at from the other direction, O
the hydrolysis of an ester to form a carboxylic acid and an alcohol. Ethanoyl chloride: CH3−C
Cl
The attainment of equilibrium in the system is catalysed by the presence
of concentrated acid. Theses are very reactive chemicals, prone to nucleophilic attack. The
electronegative Cl atom attracts electrons from the already δ+ C atom, so
H+
CH3CO2C2H5 + H2O CH3COOH + C2H5OH the C−Cl bond is relatively easy to break, with the positive carbon left
open to attack.
N.B. Using acid catalyst, equilibrium lies to the left in the above system,
esterification is favoured over hydrolysis. 1. Reaction of ethanoyl chloride with water.
A violent reaction occurs, the mixture boils and clouds of HCl gas are
The same equilibrium is also catalysed by alkaline conditions. evolved.
OH-
RCO2R` + H2O RCOOH + R`OH CH3COCl + H2O → CH3COOH + HCl
Ethanoic acid
When some RCOOH (acid molecules) have been formed, the OH− ions
react with them to form a salt. Reaction type: Substitution
Conditions: Room temperature
RCO2H + OH− → RCO2− + H2O Mechanism: Nucleophilic

(e.g.) CH3COOH + NaOH → CH3COO−Na+ + H2O

2. Reaction of ethanoyl chloride with alcohols.
Salt formation removes RCO2H from the equilibrium mixture. This moves A vigorous reaction at room temperature to form esters.
the position of equilibrium to the right, the hydrolysis reaction therefore
moving further towards completion in the presence of an alkali. CH3COCl + C2H5OH → CH3COOC2H5 + H 2 O
The alkali is not strictly a catalyst, as it gets used up in the reaction.
This is an excellent method of preparing esters, as unlike the reaction
between a carboxylic acid and an alcohol, this reaction is not reversible -
Alkaline conditions are favoured for ester hydrolysis it goes quickly to completion.

Reaction type: Substitution

Conditions: Room temperature
2. The formation of polyesters.
Mechanism: Nucleophilic
Polyesters are formed when an acid with two carboxyl groups and an
alcohol with two hydroxyl groups react to form a polymer.
3. Reaction of ethanoyl chloride with ammonia
A violent reaction at room temperature, with an aqueous solution of
HOCH2CH2OH + CH3OOC COOCH3 ammonia, producing ethanamide.

CH3COCl + NH3 → CH3CONH2 + HCl

Ethanamide
HOCH2CH 2OOC COOCH3 + CH3OH
Reaction type: Substitution
further reaction
Conditions: Room temperature, aqueous
on each end
Mechanism: Nucleophilic
OCH 2CH2OOC CO
n
4. Reaction of ethanoyl chloride with primary amines.
Again a readily occuring reaction at room temperature, producing an
Terylene: polyethane-1,2-diylbenzene-1,4-dicarboxylate amide.

Reaction type: Substitution, polymerisation CH3COCl + CH3NH2 → CH3CONHCH3 + HCl

Conditions: Acid N-methylethanamide
Mechanism: Nucleophilic
Reaction type: Substitution
Because H2O is liberated, this is called “condensation polymerisation”. Conditions: Room temperature, aqueous
Mechanism: Nucleophilic
Polyesters have great tensile strengh, and are used in fibre form in textiles.

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Organic Chemistry 3: reactions of carboxylic acids, esters and acyl chlorides Chem Factsheet
www.curriculumpress.co.uk

Questions
1. Explain:
(a) Why the −COOH group is acidic.
(b) Why the resulting anion (-COO−) is stable.

2. The following reaction is reversible:

CH3COOH + CH3OH CH3COOCH3 + H2 O

State the conditions which favour:
(a) Esterification.
(b) Ester hydrolysis.

3. For the following reaction scheme:

step 1 step 2
CH3COOH CH3COCl CH3CONH2

Give the reaction equations and conditions for:

(a) Step 1.
(b) Step 2.

4. For the following reaction scheme:

step 1
CH3CH2COOH CH 3CH2CH2OH

step 2
CH3CH2COONa

Give the reaction equations and conditions for:

(a) Step 1.
(b) Step 2.

Answers
1. (a) It is a proton (H+) donator.
(b) Delocalisation of electrons over the -COO - system means negative
charge is less localised, so the species is more stable.

2. (a) Acidic.
(b) Alkaline.

3. (a) CH3COOH + PCl5 → CH3COCl + HCl + POCl3

Conditions: Dry.

(b) CH3COCl + NH3 → CH3ONH2 + HCl

Conditions: Room temperature, aqueous.

4. (a) CH3CH2COOH + 4[H] → CH3CH2CH2OH + H2O

Conditions: LiAlH4 in dry ether, hydrolysis with dilute acid.

(b) CH3CH2COOH + NaHCO3 → CH3CH2COONa + CO2 + H2O

Conditions: Room temperature, aqueous.

Acknowledgements: This Factsheet was researched and written by Sam

Goodman and Kieron Heath. Curriculum Press, Unit 305B, The Big Peg, 120
Vyse Street, Birmingham, B18 6NF. ChemistryFactsheets may be copied free
of charge by teaching staff or students, provided that their school is a registered
subscriber. No part of these Factsheets may be reproduced, stored in a retrieval
system, or transmitted, in any other form or by any other means, without the
prior permission of the publisher. ISSN 1351-5136

3
 Chem Factsheet
April 2002 www.curriculumpress.co.uk Number 33
Organic Chemistry 4: Carbonyl Compounds
To succeed in this topic you need to:-
• Have a good knowledge and understanding of the organic
Chemical Tests
chemistry covered so far (Factsheets 15, 16, 17, 27 31 and 32); Exam Hint - Because these first four chemical tests are relatively
• Be confident in using organic nomenclature and structural easy to carry out, they are commonly asked about in both theory and
formulae. practical exam papers. It is important to be able to describe the
observations and recall the equations.
After working through this Factsheet you will:-
• Know the functional groups of aldehydes and ketones;
• Know how to test for the carbonyl group, and how to distinguish 1. Reaction with 2,4-dinitrophenylhydrazine (2,4-DNP) to give a
between aldeydes and ketones; red/orange precipitate.
• Have been given the required reaction types conditions and NO 2
HC
equations of the carbonyl compounds for the A2 exams. 3

C O NH 2 NH NO 2
Carbonyl Compounds - Aldehydes and Ketones H
2,4-DNP
The functional group is the carbonyl group: ethanal
in alcoholic solution,

C O Nucleophilic addition

H NO 2
Because oxygen is more electronegative than carbon, the electrons in the
double bond of the functional group tend towards the oxygen atom making CH 3 C NH NH NO 2
it δ-. The carbon atom becomes δ+, making it susceptible to nucleophilic
attack. OH
δ+ δ−
C O H2SO 4 Elimination (− H2O)

In this Factsheet we shall look at several reactions of the carbonyl NO 2

H
compounds, starting with common laboratory tests for these compounds.
CH3 C NH NH NO 2
There are two types of carbonyl compounds - the aldehydes and ketones.
ethanal 2,4-dinitrophenylhydrazine
(red/orange crystalline solid)
Aldehydes
Functional group of the aldehydes: The formation of a red/orange precipitate with 2,4-DNP is a test for
R carbonyl compounds - both aldehydes and ketones give a positive
C O test.
H
The reactions with 2,4-DNP are also used for the characterization and
The aldehydes are named using the suffix -al. identification of the aldehydes and ketones because the products are
For example: mostly crystalline solids. These are easy to handle, and the melting
CH 2 O methanal points of the derivatives are different enough for it to be possible to
CH 3CHO ethanal distinguish between the various carbonyl compounds - whereas several
CH 3CH 2CHO propanal of the pure carbonyl compounds have very similar melting points.

Ketones 2. The Silver Mirror Test.

The reaction with alkaline ammoniacal silver nitrate solution (Tollen's
Functional group of the ketones: reagent). This is a test for aldehydes.
R
C O Silver nitrate is dissolved in aqueous ammonia to form Tollen's reagent,
R' incorperating the complex ion: [Ag(NH3)2]+, diaminesilver (I) ion

The ketones are named using the suffix -one. When Tollen‘s reagent is warmed gently with an aldehyde, the aldehyde
For example: is oxidised to a carboxylic acid, and the silver (I) ions are reduced to silver
metal. This appears on the the inside of a test tube like a silver mirror.
CH3COCH3 propanone
CH3CH2COCH3 butanone 2Ag+ + RCHO + H2O → 2Ag + RCOOH + H+
CH3CH2CH2COCH3 pentan-2-one
Tollen's reagent has no effect on ketones.

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Organic chemistry 4: carbonyl compounds Chem Factsheet
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3. Reaction with Fehling's Solution. The remaining three reactions of the carbonyls are not chemical tests, but
A test for aldehydes. are important and need to be learnt.

Fehling's solution turns blue → red if warmed with an aldehyde. 5. Carbonyl compounds and hydrogen cyanide.
Aldehydes are oxidised to carboxylic acids by Fehling's solution, which
itself contains a blue copper (II) solution which is reduced to a red CH 3 CH 3 OH
precipitate of copper (I) oxide. KOH
C O + H−CN C
Again: CH3CHO + [O] → CH3COOH H H CN
ethanal 2-hydroxypropanonitrile
Note that Fehling's solution has no effect on ketones, as ketones cannot
be oxidised. OH
CH3 CH 3
KOH
C O + H−CN C
4. The Iodoform (or triiodomethane) Reaction. CH 3 CH3 CN
The reaction of carbonyls with iodine in the presence of alkali.
ethanal 2-hydroxy-2-methylpropanonitrile
This reaction gives a positive test (a yellow precipitate) if the following
group is present:
O Reaction type: Addition
where R is alkyl group
C or H atom Reaction conditions: HCN and a trace of KOH
CH 3 R (HCN and CN− must be present)
Reaction mechanism: Nucleophilic
This is not, therefore, a test for aldehydes or ketones, but rather for this
specific group. Note that this is a useful way of introducing one extra carbon atom into an
organic molecule.
If ethanal is warmed with iodine in alkaline solution, a two stage reaction
occurs. Ethanal reacts with the iodine to form triiodoethanal; this then
reacts with the alkali to form triiodomethane (or iodoform) - an insoluble Reduction of the carbonyl compounds
yellow solid with a characteristic ‘antiseptic‘ smell.
6. Reduction using sodium tetrahydridoborate (III) - sodium
H I borohydride, NaBH4.
O NaOH(aq) O
H C C + 3I2 I C C + 3HI
warm NaBH4 is a useful laboratory reagent. Dissolved in ethanol it reduces:
H H I H
Aldehydes → Primary alcohols
NaOH(aq)
warm
Ketones → Secondary alcohols

I NaBH4 in ethanol
O e.g. CH3CHO + 2[H] CH3CH2OH
I C H + H C Ethanal Ethanol
- +
ONa
I Reaction type: Reduction
Reaction conditions: NaBH4 dissolved in ethanol
Reaction mechanism: Nucleophilic

This reaction is specific to the following: 7. Reduction using lithium aluminium hydride, LiAlH4.

(a) Organic compounds containing a methyl group next to a LiAlH4 is an even more powerful reducing agent, which must be used in
carbonyl group. dry conditions (e.g dissolved in ether).
O
where R is alkyl Again:
C group or H atom
CH R Aldehydes → Primary alcohols
3
Ketones → Secondary alcohols
(b) Secondary alcohols that will oxidise under these conditions to
form a methyl group next to a carbonyl group. LiAIH4 in ether
e.g. CH3COCH3 + 2[H] CH3CHOHCH3
Propanone Propan-2-ol
H H H now gives positive
[O] O iodoform test Reaction type: Reduction
H C C OH H C C Reaction conditions: LiAlH4 dissolved in ether, dry
H Reaction mechanism: Nucleophilic
H H H

ethanol ethanal

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Organic chemistry 4: carbonyl compounds Chem Factsheet
www.curriculumpress.co.uk

Questions Answers
1. (a) Ethanal gives a positive iodoform test result. Give the reagents, 1. (a) CH3CHO + 3I2 + NaOH → CHI3 + HCOONa + 3HI
conditions and equation for the reaction.
Conditions: Alkaline, warm.
(b) Describe what is observed in a positive iodoform test result.
(b) Insoluble yellow solid / precipitate witgh characteristic (antiseptic)
(c) Draw the structures of the following chemicals, and state whether smell.
or not they would give a positive iodoform test result.
(i) Propanal. (c) (i) H H
(ii) Propan-2-ol. O
(iii) Hexan-3-ol. H C C C No
(iv) Butanone. H
H H
2. (a) Chemical X is a carbonyl compound. (ii)
Describe the product formed when X is reacted with H H H
2,4-dinitrophenylhydrazine (2,4-DNP) followed by concentrated
sulphuric acid. H C C C H Yes

(b) Describe a chemical test (and the possible results) which could H OH H
define X as either an aldehyde or a ketone. (iii)

3. Give the reaction equations and conditions for the reactions of propanal H H H H H H
with:
H C C C C C C H No
(a) HCN.
(b) LiAlH4.
H H H OH H H
(iv)
H H O H
H C C C C H Yes

H H H

2. (a) Red / orange (crystalline) solid / precipitate.

(b) Either:

Silver mirror test: or Fehlings:

Tollens reagent / ammoniacal AgNO3 Add Fehlings solution
Warmed Warmed
Aldehyde gives silver mirror Aldehyde causes blue to red
Ketone has no effect Ketone has no effect

3. (a) CH3CH2CHO + HCN → CH3CH2CHOHCN

Conditions: HCN and a trace of KOH.

(b) CH3CH2CHO + 2[H] → CH3CH2CH2OH

Conditions: LiAlH4 in dry ether

Acknowledgements: This Factsheet was researched and written by Sam

Goodman and Kieron Heath. Curriculum Press, Unit 305B, The Big Peg, 120
Vyse Street, Birmingham, B18 6NF. ChemistryFactsheets may be copied free
of charge by teaching staff or students, provided that their school is a registered
subscriber. No part of these Factsheets may be reproduced, stored in a retrieval
system, or transmitted, in any other form or by any other means, without the
prior permission of the publisher. ISSN 1351-5136

3
 Chem Factsheet
April 2002 www.curriculumpress.co.uk Number 34
Organic Chemistry 5: Compounds Containing Nitrogen
To succeed in this topic you need to:- Nitriles
• Have a good knowledge and understanding of the organic
chemistry covered so far (Factsheets 15, 16, 17, 27 31, 32 and 33); Functional group: C N:, which is also written as CN
• Be confident in using organic nomenclature and structural
formulae.
The lone pair on the electronegative nitrogen atom makes the nitrile group
After working through this Factsheet you will:- a strong nucleophile.
• Know the functional groups of amines, amides, nitriles and amino
acids; Nitriles can be prepared by reacting a haloalkane with KCN in aqueous
• Have been given the required reaction types conditions and ethanol (which increases the length of the carbon chain by one) - see
equations of the nitrogen containing compounds for the A2 Factsheet 16.
exams.
Reactions of the nitriles.
Amines 1. Hydrolysis of nitriles.
.. Nitriles can be hydrolysed by refluxing them with aqueous hydrochloric
Functional group: C−NH2 acid or aqueous sodium hydroxide.

(a) Hydrolysis with acid.

Like alcohols, amines can be primary, secondary or tertiary:
H R2 R2 The carboxylic acid is formed (via the amide as an intermediate).
R1 C NH 2 R1 C NH 2 R 1 C NH 2 CH3CH2CN + HCl + 2H2O heat
CH3CH2COOH + NH4Cl

H H R3 Reaction type: hydrolysis

primary secondary tertiary Conditions: acidic, heat under reflux
The lone pair of electrons on the nitrogen atom makes the amine group
both basic (an acceptor of protons, H+) and a nucleophile (a donator of (b) Hydrolysis with alkali.
electrons).
The carboxylic acid salt is formed (again via the amide intermediate).
Reactions of the amines. heat
CH3CH2CN + NaOH + H2O CH3CH2COO-Na+ + NH3
1. Reaction of primary amines with aqueous hydrogen ions (acids). Reaction type: hydrolysis
Amines are basic, so react with acids to form salts. Conditions: alkaline, heat under reflux
CH3CH2NH2 + HCl CH3CH2NH3+Cl−
2. Reduction of nitriles
Reaction type: addition
Conditions: acidic, aqueous Nitriles are reduced to amines by LiAlH4 dissolved in dry ether - a
Mechanism: nucleophilic powerful reducing agent.
LiAlH4
C2H5CN + 4[H] C2H5CH2NH2
2. Reaction of primary amines with acid chlorides.
Primary amines react quickly with acid chlorides to form substituted Reaction type: reduction
amides. Conditions: dry ether, followed by addition of dilute acid.
O O
C2H5NH2 + CH3C CH3C + HCl
Cl NHC 2H 5
Recation type: substitution
Conditions: aqueous, room temperature
Mechanism: nucleophilic

3. Formation of polyamides. H H O O H H
The above reaction between primary amines and acid chlorides can be ○ ○
N (CH2)6 N C (CH2) 4 C N (CH2)6 N ○ ○

used to form polymers if monomers are used with 2 amine groups and 2 H H Cl Cl H H
acid chloride groups present. O O

For example, the formation of nylon−6,6 − so called because both N (CH2)6 N C (CH2)4 C N (CH2)6 N
monomers contain 6 carbon atoms. H H H H
With HCl molecules being eliminated, this is a form of “elimination
polymerisation”.

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Organic chemistry 5: compounds containing nitrogen Chem Factsheet
www.curriculumpress.co.uk

Amino acids Amides

Functional group: Amino acids contain both -NH2 and - COOH O

Functional group: R C
groups (usually bonded to the same carbon atom).
H O NH 2
e.g. glycine
N C C
The amides are carboxylic acid derivatives.
NH 2 OH
They are formed by reacting ammonia with acyl chloride - see Factsheet 32.

Reactions of the amides

Exam Hint - Glycine is not a chiral molecule, but many amino acids 1. Dehydration of amides using phophorus (V) oxide.
are. Chirality will often figure in questions about amino acids, so
ensure that you understand this form of isomerism - see Factsheet 27. Amides are dehydrated to nitriles on heating with P4O10.
O
P4O10
CH3C CH3CN + H2O
Amino acids react as both acids and bases. NH 2
They are water soluble ionic solids because the molecules ethanenitrile
ethanamide
have ionic interactions.
Reaction type: dehydration (elimination)
Conditions: warm and distil off ethanenitrile
They form zwitterions, ions having both positive and negative charges
on them. CH3 O 2. Hoffmann degradation reaction with bromine and aqueous alkali.
CH3 O
(e.g.) N C C N C C Amides react with bromine in a solution of sodium hydroxide to give
- amines.
OH NH O
NH 2 3 O
+
CH3C + Br2 + NaOH → CH3NH2 + CO2 + 2NaBr + H2O
A "Zwitterion"
NH 2
Reactions of amino acids Conditions: Add liquid bromine to amide at room temperature, then
These reactions show that amino acids are amphoteric. add concentrated sodium hydroxide solution and warm.
The amine is then distilled off.
1. Reaction of amino acids with acids.
Note: The length of the carbon chain is decreased by one as CO2 is given off.
NH2CH3CHCOOH + H+ → NH3+CH3CHCOOH

2. Reaction of amino acids with bases.

NH2CH3CHCOOH + OH− → NH2CH3CHCOO− + H2O

The amphoteric nature of amino acids goes some way towards explaining Answers
why these compounds are commonly used in buffer solutions. 1. The lone pair of electrons on the nitrogen atom allows the group to
accept protons (H+), hence it is basic, and also to donate electrons to
Questions form dative covalent bonds with electron deficient species (hence a
1. The amine functional group is both basic and a nucleophile. Explain nucleophile).
why. 2.
2. Draw structural formulae for the following: (a) (b) (c)
(a) Propanamine. H H H H H H O H H
(b) Propanamide. H C C C N
H C C C N H C C C
(c) Propanenitrile.
H NH 2
H H H H H H H
3. (a) Draw the structure of NH2CH3CHCOOH, indicating the position
of the chiral centre.
3. (a) CH3
(b) Use equations to illustrate the amphoteric nature of
NH2CH3CHCOOH. NH 2 C* COOH * = chiral centre

4. The question refers to the following reaction scheme: H

step 1 step 2
(b) As a base:
CH3CONH2 CH3CN CH3CH2NH2 NH2CH3CHCOOH + H+ → NH3+CH3CHCOOH
step 3
CH3NH2 As an acid:
Give the reaction equations and conditions for: NH2CH3CHCOOH + OH− → NH2CH3CHCOO− + H2O
(a) Step 1.
4. (a) CH3CONH2 → CH3CN + H2O
(b) Step 2.
Conditions: P4O10, warm, and distil off ethanenitrile.
(c) Step 3
(b) CH3CN + 4[H] → CH3CH2NH2
Acknowledgements: This Factsheet was researched and written by Sam Goodman and Kieron Conditions: LiAlH4 in dry ether, followed by addition of dilute acid.
Heath. Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham, B18 6NF.
ChemistryFactsheets may be copied free of charge by teaching staff or students, provided
(c) CH3CONH2 + Br2 + 2NaOH → CH3NH2 + CO2 + 2NaBr + H2O
that their school is a registered subscriber. No part of these Factsheets may be reproduced,
stored in a retrieval system, or transmitted, in any other form or by any other means, without Conditions: Add Br2 at room temperature, then add
the prior permission of the publisher. ISSN 1351-5136 concentrated sodium hydroxide solution and warm.
2
 Chem Factsheet
April 2002 www.curriculumpress.co.uk Number 35
Answering Questions on Organic Pathways and Conversions
To succeed in this topic you need to:- The techniques and methods to answer flow diagram questions
• Have a good knowledge and understanding of the organic
chemistry covered so far (Factsheets 27, 31, 32, 33 and 34). Let us return to our original example:

After working through this Factsheet you will have covered: K2Cr2O7/H+ K2Cr2O7/H+
• the types of examination questions that are set on this topic; CH3CH2CH2OH CH3CH2CHO CH3CH2CO2H
heat and reflux heat and reflux
• what you need to know and understand to be able to answer the
questions;
Rule 1 - wherever possible re-write the pathway using DISPLAYED
• various techniques to help you answer these questions.
FORMULAE – this helps you to identify compounds.
This Factsheet assumes that you have the basic knowledge detailed above; H HH H HH H H OH
it concentrates on showing you how to use it. H−C−C−C−OH H−C−C−C=O H−C−C−C=O
H HH H H H H
What are ‘organic conversions’ and ‘pathways’?
Consider the reaction below: Rule 2 - (a) identify the FAMILIES
reagents (b) identify the REACTION TYPE
(c) name the SPECIFIC COMPOUNDS
K2Cr2O7/H+
CH3CH 2CH2OH CH3CH2CH O
heat and reflux oxidation oxidation
primary alcohol aldehyde carboxylic acid
original compound conditions product
propan-1-ol propanal propanoic acid
This is the basic conversion and shows all the facts about it:
Rule 3 - treat the pathway as a type of ‘crossword puzzle’. When
a) What are we starting with? you are doing a crossword puzzle you rarely do it in the order of the
b) What are the reagents used to convert it? clues i.e. 1 across, 5 across, etc.
c) What conditions are used?
d) What is made? You find a clue you can answer, put it in and use these letters to find
other word answers i.e. YOU START WHERE YOU CAN! - THIS
If we go one step further:
IS HOW YOU DO PATHWAY QUESTIONS. ( i.e. identify one of
K2Cr2O7/H+ K2Cr2O7/H+ the families/compounds and work back or forwards from it).
CH3CH2CH2OH CH3CH2CHO CH3CH2CO2H
heat and reflux heat and reflux The method is: (1) look at the pathway before the questions about it
(2) apply Rules 1+2+3 to see what you can find out
This is a pathway because it contains more than one step i.e. a⇒b⇒c not before looking at the questions.
just a conversion (a⇒b).

In this example the pathway shows CH3CH2CH2OH being changed to

CH3CH2CO 2H.

What happens in questions?

There are three types of question: c) These conversion/pathway questions will always have supplementary
(a) Conversions and pathways are always: parts to enable more marks to be given to a particular question:
reagents reagents e.g. (i) ‘How would you test for compound C?
compound A compound B compound C etc (Tests for compounds)
conditions conditions (ii) ‘Draw a structural isomer of compound B?
(Isomerism)
All the examiner has to do is give you some of the information in a
(iii) ‘Identify the asymmetric carbon atom in compound X’
pathway and ask you to find the ‘missing pieces’. To be successful in this
(Optical isomerism)
you need to have recognised which reactions are taking place.

This is the commonest type of question on conversions and pathways. These questions may draw upon all of the A2 Chemistry specification.
While these ‘supplementary parts’ are important, this Factsheet will not
(b) More difficult is the question which gives you the least amount of use them in its questions unless they provide information that helps to
information of all: complete the pathway.
e.g. ‘Starting with compound A how would you convert it into e.g. ‘Compound W decolourises bromine water’ i.e. we can deduce W is
compound X? You should show all the necessary reagents, unsaturated and so belongs to the family alkene.
conditions and intermediate compounds’

In effect the question is asking you to produce the type of flow-chart used
in part (a) above.

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How to answer questions on organic pathways and conversions Chem Factsheet
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Worked Examples

Consider the following reaction scheme: Answer the questions about the following organic conversions:
NH3 P4O10
C2H5COCl C3H7ON C3H5N C3H9N Step 1 Step 2 Step 3
A B D E CH3CH2OH CH3CH2Br W CH3CH2CO2H

(a) Suggest the structural formula of W

C2H7N (b) Give the reagents and conditions for:
C (i) Step 1
Compounds C and E have the same functional group. (ii) Step 2
(a) Draw the structural formulae of B and D (c) State the type of reaction taking place in:
(b) What is the functional group in C and E? (i) Step 1
(c) Give the reagents and conditions to convert (ii) Step 2
(i) D to E
(ii) B to C Method
Method H H H H H H OH
O O 1 2 3
H−C−C−OH H−C−C−Br X H−C−C−C=O
CH3−CH2−C CH3−CH2−C CH3−CH2−CN
H H H H H H
Cl NH 2
acyl chloride amide nitrile Primary alcohol Bromoalkane Carboxylic Acid
CH3−CH2−NH2 CH3−CH2−CH2−NH2 ‘Thinking process’
amine amine • the carboxylic acid has an ‘extra C’ atom in it
• how to go from bromoalkane to get ‘extra C’?
‘Thinking process’ • usually via nitrile i.e. –CN
• A is an acid chloride, so NH3 creates an amide (B) • so Step 3 would work i.e. –CN ⇒ CO2H
• counting atoms for B to D shows loss of 2H’s and 1O i.e. H2O,
dehydration so amide (b) to amine (C) Answer
• D to E shows 4H’s being added, reduction, so must be nitrile to amine (a) H H
• B to C shows loss of 1C and 1O, this must be decarboxylation, so
amide to amine. H−C−C−C≡N
H H
Answer
HH O HH
(b) Step 1 – KBr/ cone. H2SO4 + heat under reflux
(a) B = H C−C−C D = H C−C−C=N Step 2 – KCN/ethanol + heat under reflux
HH NH 2 HH
(c) Step 1 – nucleophilic substitution
(b) Amine i.e. –NH2
Step 2 – hydrolysis
(c) (i) anhydrous LiAlH4 (or NaBH4) + heat
(ii) P2O5/Br2 in aqueous alkali
Questions 1, 2 , 3 and 4 provide further practice on these types of problem.

Questions where only start and finish compounds are given Suggest a two step method by which ethanol could be converted into
These questions tend to be more complex for all candidates and there is ethanoyl chloride. (You should give reagents and conditions for each
much more of ‘trial and error’ involved in answering them. conversion)
Because of this there is only one rule and one method Method and ‘thinking process’
H H H O
• Rule - Create your own flow chart for the pathway using the H−C−C−OH 1 2
X H C−C
information provided in the question Cl
H H H
• Method - From the flow chart you have made use your knowledge of the ethanoyl chloride
reactions of the starting compound and when you have met the final • ethanoyl chloride is an acid chloride; these are usually made from the
compound to identify the intermediate compound(s). corresponding carboxylic acid
• ethanol is a primary alcohol, typical reactions are oxidation to
aldehydes and carboxylic acids
• X is probably a carboxylic acid i.e. CH3CO2H.
Answer
H H O H O
H−C−C−OH 1 2
H C−C H C−C
H H OH Cl
H
ethanol ethanoic acid ethanoyl chloride
Step 1 Oxidation of ethanol to ethonoic acid using potassium
dichromate (VI) in sulphuric acid and heating under reflux.
Step 2 Substitution by adding anhydrous PCl5 to ethanoic acid.
Questions 5 and 6 provide further practice on this type of problem.
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How to answer questions on organic pathways and conversions Chem Factsheet
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Questions 5. Outline how you would convert C2H5Br into C2H5CH2OH via a
1. This questions relates to the following scheme of reactions: Grignard Reagent.
Step 1 Step 2 Step 3 You should state clearly the reagents and conditions for the steps you
C3H 7Br C3H7CN C4H9NH2 C4H9OH
propose, as well as drawing structural formulae of any intermediate
(a) Give the reagents and conditions needed for: compounds.
(i) Step 1
(ii) Step 2 6. Outline a series of steps by which you could synthesise CH3 CH2 CH2
(iii) Step 3 NH2 from C2H5COCl.

(b) What type of reaction is taking place in Reagents and conditions for each step should be given as well as the
(i) Step 1 formulae of any intermediate compounds.
(ii) Step 2
Answers
2. Consider the following reaction pathway: 1. (a) (i) KCN in ethanol + heat/boil
(ii) LiAlH4 + anhydrous conditions
K2Cr2O7/H+ NaOH(aq) (iii) HCl and NaNO2 + room temperature
C3H7OCl C3H5O2Cl C3H5O3Na
A heat under B C (b) (i) nucleophilic substitution
reflux
I2/NaOH(aq) (ii) reduction
yellow 2. (a) H Cl H H Cl O H Cl O
precipitate C−C−C
A = H−C−C−C−OH B = H C−C−C C = H
H H H H H OH H H O − Na+
A reacts with PCl5 and produces steamy fumes, but A does not do this
with water. (b) Oxidation
B reacts with sodium hydrogen carbonate to form CO2.
(c) 2 – chloropropan –1-ol
(a) Write the structural formulae for A, B and C.
3. (a) H NH2 H
(b) What type of reaction is taking place when A converts to B. H Br H
W = H−C−C*−C−OH X = H C C C OH
(c) What is the name of compound A? H H H H H H
* chiral centre
H H H
3. This question is about the reaction scheme:
Y = H C C C OH
C3H9ON
NH 3 H
X
C3H 7OBr (b) alkene + alcohol.
W
4. (a) (i) KCN in ethanol + boil/heat
KOH/ ethanol C3H6O (ii) dilute acid
Y (iii) P2O5/Br2 in aqueous alkali

W is chiral, can be oxidised to an aldehyde and gives steamy fumes (b) H H H O

with anhydrous PCl5. butanoyl chloride
H C C C C
Y decolourises acidified potassium manganate (VII) solution. Cl
H H H
(a) Draw the structural formulae of W, X and Y
H H H
(b) Name the functional groups in Y. H H C O H H H
Mg H
H C C Br H C C MgBr H C C C OH
dry ether +dry ether
4. This question is about the following organic pathway: H H H H H H H
5.
Step 1 Step 2 Step 3
C4H 9Br C4H9CN C4H9COOH X O O
6. NH3(aq)
PCl5 CH3CH2C CH 3CH2C
Cl NH 2
NH3 Step 4 LiAlH4
Step 5 anhydrous
C4H9NH2 C4H9CONH2 H
CH 3CH2 C NH 2
(a) Give the reagents and conditions necessary for
(i) Step 1 H
(ii) Step 2
(iii) Step 5 Acknowledgements: This Factsheet was researched and written by Sam Goodman and Kieron
Heath. Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham, B18 6NF.
(b) Draw the structural formula of X and give its systematic name. ChemistryFactsheets may be copied free of charge by teaching staff or students, provided
that their school is a registered subscriber. No part of these Factsheets may be reproduced,
stored in a retrieval system, or transmitted, in any other form or by any other means, without
the prior permission of the publisher. ISSN 1351-5136

3
 Chem Factsheet
April 2002 www.curriculumpress.co.uk Number 36
Laboratory Chemistry - Continuous Practical Assessment
After working through this Factsheet you will: Observing and recording
• have met in more detail the skills that you will be assessed for in You gain marks by your ability to:
practical work; • record observations accurately of physical changes e.g. colour, gas
• have been given some examples of the experiments from A2 level formation, solubility, etc
that are helpful in preparing for assessments; • record accurately data readings
• have been offered specific advice on improving your performance • record observations/readings in an appropriate manner and use correct
in assessments. terminology
N.B. You need to be specific in your descriptions and use appropriate
Each Examination Board (or Awarding Body) for AS/A2 level Chemistry levels of accuracy for data readings.
publishes a specification, and this contains the precise details of the
Continuous Practical Assessment. Since there are slight variations between Interpretation and evaluation of results
the Boards, you must use the advice in this Factsheet in conjunction with This skill covers:
your specification and ensure you know the requirements of your • use correct equations for calculations
Examination Board. • use correct calculation methods
• use graphs
Assessing Practical Skills at A2 level • collate information to reach a correct conclusion e.g. identify a substance
Chemistry is a practically-based subject, and laboratory work is integral to • use and manipulate data, identify trends
both an understanding of the subject as well as developing your practical • identify anomalous results and experimental error and suggest
skills. improvements
• assess reliability of data
In continuous assessment, the school or college identifies various practicals • recognise the limitations of the procedure
throughout the year of the course to be assessed (often these are • estimates of errors
recommended by the Board, which also provides instruction sheets and
mark schemes.) The practicals are marked by your teacher/lecturer and the N.B. The ability to handle equations and data to ‘draw conclusions’ is
various marks kept on your individual Record Sheet. essential.

The skills to be assessed Put very basically, the skills are:

There are four skills assessed in continuous practical assessment. 1. Can you describe in detail how to perform a particular experiment so
that anyone else could use your instructions to get a successful result?
Planning (planning).
This is how to perform a practical and covers the following areas:
• method 2. Can you perform an experiment by following the instructions, using
• quantities of substances to be used apparatus correctly and so obtaining accurate results? (manipulation).
• apparatus needed
• use information to make choices of reagents, etc 3. Can you write down in a correct format e.g. a table, etc. all the correct
• safety issues observations and accurate readings generated by an experiment?
• control of variables (observing and recording).
N.B. Often you will be asked to perform the practical according to the
plan you have designed, then you are asked to comment on what changes 4. Can you use the results you obtain in an experiment to draw conclusions
you would make to the plan in the light of your experience. about what the experiment shows you and if there are problems with
any of the data? (interpretation and evaluation of results).
Manipulation
You are marked on the use of apparatus and the accuracy of your results. Over the year of the A2 course you will perform a number of assessments
It covers the following: and each one will cover one or at most two of the four skills. You may have
• handling apparatus and chemicals (including safety aspects) several opportunities to score well on each skill before submitting the final
• taking measurements and readings overall mark .
• performing common procedures without instructions being given eg.
filtering What are the practicals used?
• following a sequence of instructions It is impossible to say which of the hundreds of available practicals you
• specifically – preparing, purifying, qualitative will cover in your Continuous Assessment but here is a piece of advice:

N.B. Mark schemes for this skill reflect your level of accuracy i.e. the Exam Hint - When you are told you are about to do a Practical
closer you get to the correct answer the more marks are allocated. Assessment you will be told what skill it is to cover. Use your
specification to remind yourself of the experimental work you need to
know.

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Laboratory Chemistry: continuous practical assessment at A2 level Chem Factsheet
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Summary 3. Observing and recording

All of the following can be used for Practical Assessments: N.B. Remember - this goes with manipulation in many Assessments.

1. Titrations - acid/base, redox and ‘one off’ analysis examples. Key Issues:
(a) Physical changes - colours (be specific – is it dark blue/sky blue/red
2. Tests and compounds - if you do this to it and this happens what can /crimson/yellow/orange/etc) – see the textbooks ‘effervescence’
you tell about the compound?’ (‘fizzy’) i.e. production of bubbles/gas ‘colourless’ vs. ‘clear’ (they
are not the same )
3. Preparations and purification of an organic compound
• a liquid
• a solid Remember - you must describe:
(a) (i) what the two substances looked like before you mixed them
4. Kinetics/Equilibria - rates of reactions and ‘one off’ equilibria together
experiments. (ii) what they looked like after mixing them.

Specific Advice about skills (WAIT! – chemicals mixed together need at least 3-4 minutes
1. Planning to react before writing down your observation)
This is the most difficult of the skills! When you are given notice of the
Assessment you will probably be pointed towards other similar practicals (b) NO - ‘No Reaction’
that you have already done. It is very important that you do revisit these YES - ‘No Apparent Change’/’No Observable Change’
practicals.

In a planning exercise you must have the following:

(b) Readings from apparatus
(a) A clear sequence of events written as a set of instructions for another
• Electronic - 2 or 3 decimal places
student to follow e.g.
• Thermometers - 1 decimal place
(i) Collect a 50 cm3 pear-shaped flask, a connector and a condenser.
• Electronic meters - whatever the display shows e.g. pH = 3.5 or 3.54
(ii) Set the glassware up as shown in the diagram.
• Burettes - 20.15 or 20.10 i.e. nearest 0.05
(iii) Using a 10 cm3 measuring cylinder measure out 7.5 cm3 of ethanol
and pour into the pear-shaped flask etc.
4. Interpretation and evaluation of results
(b) Use labelled diagrams for any apparatus or procedures. As stated already, this is a skill that covers a wide range of practical
experiences, which makes offering specific advice difficult.
(c) Be specific about apparatus e.g. 25.0 cm3 pipette, 50 cm3 burette, 10 cm3
measuring cylinder, etc. However, this checklist will help you to obtain good scores for the skill.
You must be able to:
(d) Be specific about reagents e.g. dilute HCl, H2SO4, aqueous potassium
manganate (VII), solid Na2CO3, etc. (a) use your calculator to handle all the ‘powers’ and functions needed to
process results
(e) The calculation of amounts is vital!
Use this method: (b) plot results of experiments as graphs including connecting plotted
(i) write the equation points as ‘smooth curves’ or ‘straight lines’.
(ii) from the equation work out moles and masses of compounds
(c) comment on trends in numerical data or displayed in the form of a
(iii) convert masses to volumes for liquids (Density = mass ÷ volume)
graph.
(iv) work backwards from the amount of product you are supposed to
make (including ‘percentage conversion’) to calculate starting (d) identify from graph plots those results that do not fit the ‘curve’ or the
amounts. ‘straight line’ (anomalous results) and give a reason why they do not
fit the pattern
(f) Cover safety issues in your instructions i.e.
corrosive liquids/solids - (plastic gloves, safety goggles) (e) be able to substitute values into equations and rearrange the equation
gases/fumes evolved - (fume cupboard) to obtain the unknown value
(g) If you are asked to perform the experiment you must retrospectively (f) remember specific tests and results for
say what you would do to improve on your original plan (i) cations/anions
(ii) functional groups in organic compounds and be able to use these to
2. Manipulation
identify the compound
It is important to recognise that when a practical covers two skills it will
normally be manipulation + observing/recording. (g) understand that readings of 1 or 2 decimal places of data cannot produce
answers of 3-4 decimal places. This is called ‘level of accuracy’.
The reason for this is that if you perform an experiment (manipulation)
and obtain results/data, these will be written down (observing/recording). (h) be able to recognise where errors arise in practical work, BUT you
cannot use ‘human error’!
When you hand in your work for marking the accuracy of your results/
observations will reflect how well you have performed the procedures.

This is why the markscheme will give 3/2/1 marks for results in
manipulation – accuracy of titrations are a classic example of this! Acknowledgements: This Factsheet was researched and written by Sam
Goodman and Kieron Heath. Curriculum Press, Unit 305B, The Big Peg, 120
Remember - your marks will come from two sources: Vyse Street, Birmingham, B18 6NF. ChemistryFactsheets may be copied free
1. Observations by your teacher/lecturer as you do the practical (usually of charge by teaching staff or students, provided that their school is a registered
recorded on a checklist sheet), subscriber. No part of these Factsheets may be reproduced, stored in a retrieval
system, or transmitted, in any other form or by any other means, without the
2. The level of accuracy of your results.
prior permission of the publisher. ISSN 1351-5136

2
 Chem Factsheet
September 2002 Number 37
Redox Equilibria I: Standard Electrode
Potentials and Cells
To succeed with this topic you need to: When a metal is placed into a solution of its own ions an equilibrium is set
• be familiar with the concept of equilibrium (Factsheet 09); up. Zn Cu
• be able to assign oxidation numbers to elements (Factsheet 11).

After working through this Factsheet you will:

• understand the link between cells and oxidising and reducing powers
(redox reactions);
• have met the Standard Hydrogen Electrode and why it is needed; Zn2+(aq) Cu2+(aq)
• know the definition for Standard Electrode Potential (SEP) and its
symbol E ; Zn2+(aq) + 2e Zn(s) Cu2+(aq) + 2e− Cu (s)
• be able to use SEP values to find values for different cells;
• know how SEP values affect reducing and oxiding powers. You will recognise the half equations – the diagrams show the half cells.

Examination questions and techniques on SEPs and cells are covered NB: In this work, half equations are always shown with electrons on the
separately in Factsheet 41. left.

If these two half cells are connected then the same reaction takes place as
Redox – revision when a piece of zinc is put into a copper solution:
When a piece of zinc is placed in a copper salt solution the copper
wire
ions are displaced – zinc is more reactive than copper ions:
Zn Cu
salt
Zn(s) + Cu (aq) ➝ Zn (aq) + Cu(s)
2+ 2+
bridge

You will recognise this from the reactivity series of metals at

GCSE level.

If we now apply oxidation numbers to the same equation: Zn2+(aq) Cu2+(aq)

oxidation reduction Electrons move from the zinc cell to the copper cell and so the zinc electrode
will dissolve and the copper electrode will increase in size – this is called
Zn + Cu2+ ➝ Zn2+ + Cu short-circuiting the cell.
O.N. 0 +2 +2 0
reducing oxidising However, if a high-resistance voltmeter is connected so electrons cannot
agent agent flow through, the voltmeter gives a reading – it measures the difference in
electrode potential between the zinc and copper cells.
ie. Zn is being oxidised by the Cu2+ which is the oxidant (oxidising V
agent). Cu2+ is being reduced by the Zn which is the reductant Zn Cu
(reducing agent).

We can now separate the half equations from the full equation to
show the transfer of electrons:

Zn ➝ Zn2+ + 2e− oxidation – loss of electrons (increase in ON) Zn2+(aq) Cu2+(aq)

Cu2+ + 2e− ➝ Cu reduction – gain of electrons (decrease in ON)

The salt bridge used to connect the two half cells is a piece of
filter paper soaked in saturated potassium nitrate solution.
• The salt bridge is needed to complete the circuit
Cells
Let us stay with the zinc and copper solution displacement reaction. • Potassium nitrate is chosen to prevent preciptiation of salts when
it is dipped in the solution (nitrates are soluble). If precipitation
The full equation shows zinc is more reactive than copper (displacement occurred, the concentrations of the solutions would decrease,
method) but doesn’t tell us how much more reactive – this is where cells altering the electrode potentials.
come into the work.

1
Redox Equilibria I: Standard Electrode Potentials and Cells Chem Factsheet

Since the reading on the voltmeter would change depending on the two half Every half-cell has its own SEP.
cells involved and the concentrations, we need to define standard conditions
to ensure comparability: e.g. Cu2+ + 2e− Cu E = +0.34V

The standard hydrogen electrode NB. (1) Electrons shown on the left of the half equations
All half cells are compared to this cell to give the voltmeter reading. (2) You do not need to learn E values, except that the value for the
standard hydrogen electrode is 0.00V
(3) E values may be positive or negative. Always put the sign on!

V Half cells without a solid metal

Half cells also exist for non-metals (eg I2 + 2e− 2I−) and for equilibria
between two different aqueous ions (eg Fe3+ + e− Fe2+).
H2(g) 1 atm
A standard half cell for Fe3+ + e− Fe2+ is shown below:
Note the 1mol dm-3 of both solutions at 25oC.

1M H+(aq) V
Pt

temperature 25oC 1M Fe2+ (aq)/ 1M Fe3+ (aq)

Notation: Standard half cells are often written in the form

Pt Fe2+ | Fe

Exam Hint: - Recall of the hydrogen electrode is commonly tested.

All details of the diagram need to be learnt thoroughly. Combining half cells
When two half cells are combined, one electrode becomes the anode (positive
electrode), and one the cathode (negative electrode).
Standard electrode potential (SEP) E • At the anode, the reaction goes in the forward direction - reduction
The E stands for EMF (electromotive force) and is the electric potential takes place.
between standard cells (hence the use of ). It is measured in volts (V). • At the cathode, the reaction goes in the reverse direction - oxidation
takes place.
The hydrogen electrode is defined as having a standard electrode potential
of 0.00 V.
So when looking at a cell,
The standard electrode potential Eê for a half cell is when a • the species that is more readily reduced- the stronger oxidising agent
standard half cell (1 mol dm-3, 25oC) is connected to a standard - will be the anode,
hydrogen electrode ( 1 mol dm-3H+, 25oC, 1 atmosphere • the species that is more readily oxidised - the stronger reducing
pressure) using a high resistance voltmeter. agent - will be the cathode.

Considering the copper and zinc example from page 1: we know zinc is the
The diagram shows how this definition translates into the practical set-up stronger reducing agent, so it will be the cathode, making copper the anode.
for a standard zinc cell:

V The table of E values below can be used to determine which will be the
anode and which the cathode in a cell - and hence which species is oxidised
high resistance voltmeter and which reduced.
Zn
H2 (1 atm) salt bridge Table of E values

Half Equation E /V
Mg2+ + 2e− Mg -2.37
Al3+ + 3e− Al -1.66
Zn 2+ + 2e− Zn -0.76
Fe2+ + 2e− Fe -0.44
V2+ + 2e− V -0.26
Ni2+ + 2e− Ni -0.25
Pt
Temperature: 25o C 1M Zn2+(aq) 2H+ + 2e− H2 0.00
1M H+(aq) Cu2+ + 2e− Cu +0.34
The reading on the voltmeter would be –0.76V. This is shown as: I2 + 2e− 2I− +0.54
Fe + e−
2+
Fe2+ +0.77
Ag+ + e− Ag +0.80
Zn2+ + 2e− Zn E = -0.76V.
Cl2 + 2e− 2Cl− +1.36

2
Redox Equilibria I: Standard Electrode Potentials and Cells Chem Factsheet

Using E Values
Questions
1. Identifying the cathode and the anode 1. (a) Explain why the salt bridge is necessary in an electrochemical cell.
When two half cells are combined, the one with the smaller (= more negative
or less positive) SEP value is the cathode. (b) Explain why potassium nitrate is used in this bridge
2+ −
eg Zn + 2e Zn E = - 0.76V 2. Define standard electrode potential.
Fe2+ + 2e− Fe E = - 0.44V
3. A cell is produced by combining these two half cells.
Zn is therefore the cathode. Cu2+ + 2e− Cu E = + 0.34V
Ag+ + e− Ag E = + 0.80V
2. Finding the overall reaction (a) State which is the anode
Once we know which is the cathode and which the anode, we know in
which direction each reaction is proceding. (b) Write down the half-equations for the reaction taking place at the
anode and the cathode, stating clearly which is which.
The reaction at the anode goes in the forward direction - so we have:
Fe2+ + 2e− ➝ Fe (c) Find the overall reaction taking place in the cell

The reaction at the cathode goes in the reverse direction, so we have: (d) Calculate E cell
Zn ➝ Zn 2+ + 2e−

Combining these two gives the overall cell reaction: 4. Use the table of E values on page 2 to answer the following questions:

Zn + Fe2+ ➝ Fe + Zn2+ (a) Which is the stronger reducing agent, vanadium or nickel?

(b) A student looked up F2 + 2e− 2F− in a table of E values.

3. Calculating E cell He wrote down the value +1.20 V.
The difference in values between two electrodes (half cells) gives the E of Explain why this cannot be correct.
the cell i.e. the reading you would see on the high resistance voltmeter.

The equation is:

Answers
E cell = E (reactant being reduced) − E (reactant being oxidised)
1. (a) To complete the circuit
e.g. Zn2+ | Zn E = -0.76V
(b) To prevent salts being precipitated (as nitrates are soluble)
Cu2+ | Cu E = +0.34
2. The standard electrode potential E for a half cell is when a standard
Zn — cathode is OXIDISED half cell (1 mol dm-3, 25oC) is connected to a standard hydrogen electorde
Cu2+ — anode is REDUCED ( 1 mol dm-3 H+, 25oC, 1 atmosphere pressure) using a high resistance
voltmeter.
E cell = +0.34 − (-0.76)
= +0.34 + 0.76 = + 1.10V 3. (a) Silver

(b) Anode: Ag+ + e- ➝ Ag

4. Oxidising/ Reducing Power Cathode: Cu ➝ Cu2+ + 2e-

• The more positive the E value, the stronger the (c) 2Ag+ + Cu ➝ 2Ag + Cu2+
oxidising agent.
• The more negative the E value, the stronger the (b) 0.46V
reducing agent.
4. (a) Vanadium

(b) Fluorine is the strongest oxidising agent

So its E value must be the most positive.
This value is less than that for chlorine.

Acknowledgements:
This Factsheet was researched and written by Sam Goodman
Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham,
B18 6NF
ChemistryFactsheets may be copied free of charge by teaching staff or students,
provided that their school is a registered subscriber.
No part of these Factsheets may be reproduced, stored in a retrieval system, or
transmitted, in any other form or by any other means, without the prior
permission of the publisher. ISSN 1351-5136
3
 Chem Factsheet
September 2002 Number 38
Transition Metals 1: Definitions and Properties
To succeed in this topic you need to: Note that the configurations for chromium and copper appear slightly
• Be able to produce full electronic configurations for atoms and ions; anomolous:
• Understand the principle of oxidation numbers; • for chromium the 3d orbital has half shell stability, so this electron
• Understand types of bonding and molecular shapes; configuration is preferable.
• Have an understanding of atomic structure.
• for copper, the 3d orbital enjoys full shell stability, hence the given
After working through this Factsheet you will: electron configuration is more favourable.
• Be able to produce full electronic configurations for d-block atoms
and common ions; The change in chemistry cross the d-block series is very slight, as all have
• Know the definition of ‘transition metal’; two electrons in their outermost shell (except for chromium and copper).
• Know the common properties of the transition metals;
• Be able to write the formulae and represent the shapes of complex The atomic radius and ionisation energies also vary little across the series
ions; as increased nuclear charge is offset by increased shielding of the outer
• Have an understanding of why many transition metal compounds are electrons.
coloured;
• Know some common uses of transition metals in industry. Ions of d-block elements
In ion formation, 4s electrons are lost before 3d electrons even though 4s
Definition and electronic configurations fills before 3d when assigning electrons. This is because when the 3d
orbital does start to fill, the 4s electrons are repelled further away from the
The transition metals are d-block elements, which can form one nucleus.
or more stable ions with partially filled d-orbitals. Some electron configurations of d-block metal ions and oxidation states.

The d-block elements are situated between the s-block and p-block elements Ion/Oxidation State s p d configuration
on the periodic table. Sc 3+
[Ar]
2+
Ti [Ar] 3d2
Ti3+ [Ar] 3d1
2+
V [Ar] 3d3
V3+ [Ar] 3d2
s-block d-block p-block
Cr2+ [Ar] 3d4
You need to be able to produce the electron configuration of d-block atoms. Cr3+ [Ar] 3d3
You will always be given the atomic number (on the periodic table!) and
Cr (VI) [Ar]
should use the standard procedure for working out electron configuration
2+
(see Factsheet 01 - Atomic Structure). The configurations are given below. Mn [Ar] 3d5
Mn 3+ [Ar] 3d4
Element s p d configuration Electrons in boxes configuration
3d 4s Mn (VII) [Ar]

Sc [Ar] 1
3d 4s 2 Ar Fe2+ [Ar] 3d6
3+
Fe [Ar] 3d5
Ti [Ar] 3d2 4s 2 Ar
Cu2+ [Ar] 3d9
V [Ar] 3d3 4s 2 Ar Zn 2+ [Ar] 3d 10

Cr* [Ar] 3d5 4s 1 Ar

Mn [Ar] 3d5 4s 2 Ar The ions of scandium and zinc do not have partially filled
d-orbitals
Fe [Ar] 3d6 4s 2 Ar • Sc3+ has no electrons in the d-orbital

Co [Ar] 3d7 4s 2 Ar • Zn2+ contains a full d-orbital

Therefore, scandium and zinc are NOT transition metals
Ni [Ar] 3d8 4s 2 Ar
Exam Hint: - Assuming that all d-block elements are transition
Cu* [Ar] 3d 10 4s 1 Ar metals is a common mistake. Learn the definition and recall that
scandium and zinc are not transition metals.
Zn [Ar] 3d 10 4s 2 Ar

1
 Transition Metals I: Definitions and Properties Chem Factsheet

Properties of Transition Metals.

The coordination number of a complex is the number of
surrounding ligands (i.e. usually 6 in octahedral complexes).
Transition metals have the following four properties:-
1. Exist in a variety of oxidation states.
2. Form complex ions. Some complexes have coordination number 4 (e.g. those of Ni2+).
3. Form coloured ions.
4. Display catalytic properties. −
NC Br−
CN−
Ni2+ 123
Ni2+
123○
123 ○

1. Existence in a variety of oxidation states. −

NC CN− 123 ○ −
Br
Transition metals have electrons of similar energy in their 3d and 4s Br− Br−
subshells. Electrons from both subshells can be removed to form a variety [Ni(CN)4] 2−
square planar [NiBr4] 2−
tetrahedral
of oxidation states.

All transition metals (so Sc and Zn not included) exhibit two or more
oxidation states, so have ‘variable valency’. The possible oxidation states Some complexes have coordination number 2 (e.g. Ag+) and are linear in
for the d-block elements are shown below; the more common (stable) shape.
states are shown in bold italic. −
NC Ag + CN−
−
[Ag(CN)2]
7
6 6 6 Naming complexes.
5 5 5 5 5 This is the procedure for naming complexes
4 4 4 4 4 4 4
3 3 3 3 3 3 3 3 3 I State the number of coordinating ligands
2 2 2 2 2 2 2 2 2 (2 = di-, 4 = tetra-, 6 = hexa-).
1 1 1 1 1 1 1 1
Sc Ti V Cr Mn Fe Co Ni Cu Zn II Identify the ligands.
Anion names end in -o, neutral ligand names do not.
Exam Hint: - Candidates need to be able to write out the full electronic e.g. H 2 O ‘aqua’
configuration of the stable transition metal ions. NH 3 ‘ammine’
Cl− ‘chloro’
CN− ‘cyano’

2. Complex ion formation. III Name the transition metal.

Ions (and sometimes atoms) of the transition metals can be surrounded and Use the english name for a positively charged complex.
bonded to a number of molecules or ions called ligands. Use the latin name and the suffix ‘-ate’ for a negatively charged complex.

• Ligands must have a lone pair of electrons - they are ‘electron rich’ IV Indicate the oxidation number of the transition metal using
and therefore anions or neutral. roman numerals.
• Dative covalent (coordinate) bonds are formed, binding the ligands to
Examples:
the transition metal.
• The complexes formed owe their stability to the energy released on [Cu(NH3)4]2+ tetraamminecopper (II) ion
formation of the dative bonds.
[Cu(CN)4]2- tetracyanocuprate (II) ion
Common ligands include:
[Fe(CN)6]4- hexacyanoferrate (II) ion
• Halides F−, Cl−
• Sulphide S2− [Ag(NH3)2]+ diamminesilver (I) ion
• Cyanide CN−
• Hydroxide OH − Ligand binding strength.
• Water H 2O Some ligands bond more strongly than others. When a transition metal
compound is dissolved in water the ‘aqua’ ligands will bind to the transition
• Ammonia NH 3
metal ion, but H2O is quite a weak ligand.
There are commonly six ligands and six coordinate bonds arranged in an
If a stronger ligand (or its compound) is added to the aqueous solution a
octahedral shape in a complex ion - eg hexa aquachromium (III) ion
ligand substitution (or ‘ligand exchange’) will occur.
[Cr(H2O)6]3+
H2O
E.g. [Fe(H2O)6]2+ + 6CN− ! [Fe(CN)6]4− + 6H2O
H2O OH2
Cr3+ Some ligands in order of binding strength:

H2O OH2 H 2O OH − NH 3 Cl− NH2 CH2CH 2NH 2 EDTA

H2O
increasing strength
2
Transition Metals I: Definitions and Properties Chem Factsheet

3. Coloured Complex Ions. Questions.

By definition transition metals have incomplete d-subshells. The d-subshell 1. Write full electron configurations for the following species:
contains 5 electron orbitals, each of which can contain 2 electrons. (a) Mn
(b) Cu
(c) V3+
(d) Fe2+
• When a complex is formed ligands donate electrons (they form dative
bonds) into vacant higher orbitals. 2. List three common properties of transition metals.
• Because each of the d-orbitals points in a different direction in space,
they interact with the ligand electrons to varying extents. 3. Draw the shapes of the following complex ions:
• This causes a splitting of the d-orbitals into 2 higher energy and 3 (a) [Cu(H2O)6]2+
slightly lower energy orbitals. (b) [Ag(H2O)2]+

4. Name the following complex ions:

(a) [Cu(H2O)6]2+
E ∆E (b) [Ag(H2O)2]+
(c) [Fe(NH3)6]3+
Before splitting After splitting (d) (Fe(CN)6]4-

5. Name the catalysts used in:

(a) The Haber process.
• When white light is shone on the substance a d-electron is moved from (b) The Contact process.
the lower to the higher energy level.

• The frequency of light that causes this ‘jump’ is in the visible range.
This frequency is absorbed (removed) from the white light, so the Answers.
complex appears coloured. 1. (a) [Ar] 3d54s2
(b) [Ar] 3d104s1
• The colour depends on the size of the energy gap ∆E which varies with (c) [Ar] 3d2
the metal ion and ligand type - hence each complex has a different (d) [Ar] 3d6
colour.
2. Three from:
Existence in a variety of oxidation states
4. Catalytic Properties.
Form complex ions
A catalyst increases the rate of a chemical reaction, but it is not consumed
Form coloured ions or compounds
in the process. They work by providing an alternative reaction route or
Catalytic properties
mechanism which has a lower activation energy.
Paramagnetism.
The catalytic properties of transition metals are often associated with the
3. (a) octahedral (b) linear
variable oxidation states of the elements and available space in electron H2O
orbitals. H2O Ag + OH2
H2O OH2
Examples:
Cu2+
Haber Process - the production of ammonia. H2O OH2
3H2 (g) + N2 (g) ž 2NH3 (g)
H2O
Fe catalyst, 400 atm, 350oC.
4. (a) hexaaquacopper (II) ion (b) diaquasilver (I) ion
(c) hexaaquairon (III) ion (c) hexacyanoferrate (II) ion
Hydrogenation of alkenes.
RCH=CHR' + H2 ž RCH2−CH2R' 5. (a) Iron.
Ni catalyst, 150oC. (b) Vanadium (V) oxide.

Contact Process - manufacture of sulphuric acid.

2SO2 (g) + O2(g) ž 2SO3(g)
V2O5 (vanadium (V) oxide) catalyst, 1.5 atm, 400oC.

Acknowledgements:
This Factsheet was researched and written by Kieron Heath
Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham,
B18 6NF
ChemistryFactsheets may be copied free of charge by teaching staff or students,
provided that their school is a registered subscriber.
No part of these Factsheets may be reproduced, stored in a retrieval system, or
transmitted, in any other form or by any other means, without the prior
permission of the publisher. ISSN 1351-5136

3
 Chem Factsheet
September 2002 Number 39
Reactions of Benzene and its Compounds
To succeed in this topic you need to: Derivatives of benzene
• Have a good understanding of AS-level Organic Chemistry (Factsheets Derivatives of benzene are formed by substitution reactions which will be
15, 16,17, and 27); electrophilic in nature due to the high concentration of electrons in the
• Be confident in using organic nomenclature and structural formulae. delocalised system of benzene.

After working through this Factsheet you will: H

• Be able to explain the structure of benzene; H H
• Know the names and structures of common substituent products of High concentration of electrons.
benzene; Benzene attracts electrophiles. H
• Know the necessary reactions of benzene and its compounds. H
H
Benzene, C6H6, is an aromatic hydrocarbon, or an arene. When the formula
was first found, the structure proposed initially was: The group C6H5-, derived from benzene with one H atom having been
substituted, is known as the phenyl group.
H
H H Listed below are some common substituent products.

Substituent group Systematic name

H H
H Methyl -CH3 Methylbenzene
This structure would have resulted in bonds having different lengths; double Chloro -Cl Chlorobenzene
bonds are shorter than single bonds, due to the greater attractive forces. Nitro -NO 2 Nitrobenzene
Hydroxyl -OH Phenol
If this had been the correct structure, two equivalent forms would have Amino -NH 2 Phenylamine
existed: Carboxylic acid -COOH Benzenecarboxylic acid
H H
H H H H Reactions of benzene
Candidates are expected to be able to recall the following reactions, in
terms of reagents and reaction conditions.
H H H H
H H 1. Nitration of benzene.
Benzene reacts with a mixture of concentrated nitric acid and concentrated
However, where equivalent bond structures can be written for a compound
sulphuric acid (called a nitrating mixture) at 50oC to form nitrobenzene.
neither exist. Instead, all bond lengths will be equal as the available electrons
are shared equally amongst the atoms involved. NO 2
conc H2SO4
+ HNO 3 50o C + H2 O
The benzene ring consists of 6 C-C single bonds and the remaining electrons
exist in a delocalised system.
Reaction type: Substitution
Conditions: Conc. H2SO4, 50oC
The structure of benzene is often written:
Mechanism: Electrophilic

Exam Hint: - This is a commonly examined reaction. Candidates

should pay careful attention to the mechanism of this reaction – see
In this representation the H atoms need not be shown. The C-C bonds are Factsheet 40.
somewhere between single and double bonds, as illustrated by the following
bond length data:
2. Bromination of benzene.
C-C single bond length in cyclohexene = 0.15 nm Bromine reacts with benzene in the presence of an iron wire catalyst in dry
C=C double bond length in cyclohexene = 0.13 nm conditions at room temperature and pressure.
But Br
C-C bond length in benzene = 0.14 nm
Fe
+ Br 2 + HBr
Dry
Benzene is a clear colourless liquid at room temperature and pressure. It is
relatively unreactive due to the strong bonding within its structure
Reaction type: Substitution
Benzene used to be used as a non-polar organic solvent, but this is no Conditions: Fe catalyst, dry, room temp.
longer the case due to its carcenogenic (cancer causing) properties. Mechanism: Electrophilic

See Factsheet 40 for the reaction mechanism.

1
 Reactions of Benzene and its compounds Chem Factsheet

3. Alkylation of benzene (Freidel-Krafts Reactions). 1. Reaction of phenol with sodium hydroxide.

Benzene reacts with chloroalkanes in the presence of anhydrous aluminium The -OH group in phenol is more acidic (proton donating) than in straight
chloride to give an alkyl benzene. chain alcohols. Phenol is not very soluble in water, but forms a colourless
C 2H 5 solution with aqueous sodium hydroxide.
AlCl3 OH O−
+ C2 H 5Cl + HCl
Dry
(s) + OH−(aq) (aq) + H2O(l)
phenate
Reaction type: Substitution
ion
Conditions: Anhydrous AlCl3, dry, possible heat under reflux.
Mechanism: Electrophilic Conditions: Aqueous NaOH at room temp.

A similar reaction takes place with acid chlorides, benzene and aluminium Note how phenol has acted as an acid, donating a proton to neutralise the
chloride to give ketones. hydroxide ion.
CH 3 O
C
O
AlCl 3 2. Reaction of phenol with bromine water.
+ CH 3 C Dry + HCl
Cl Substitution of the hydrogen atoms on the benzene ring is made easier by
the presence of the -OH group.
Reaction type: Substitution
Conditions: Anhydrous AlCl3, dry, possible heat under reflux. OH OH
Mechanism: Electrophilic Br Br
(aq) + 3Br2(aq) (s) + 3HBr(aq)
Again, see Factsheet 40 for the reaction mechanism.
Br

Reaction type: Substitution

4. Oxidation of side chains on arenes. Conditions: Bromine water added - no catalyst required.
If an arene (i.e. benzene) with a carbon-containing side chain (with the C Mechanism: Electrophilic
atom bonded directly to the ring structure) is heated under reflux with
alkaline potassium manganate (VII) solution, benzenecarboxylic acid is This reaction is easily observed as the red/brown bromine water decolourises
formed. and a white precipitate is formed.
CH3 COOH
KMnO4
+ H2O 3. Reaction of phenol with acid chlorides.
OH−
Phenol reacts with acid chlorides to form esters, but alkaline conditions are
necessary as phenol does not react as readily as straight chain alcohols.
CH2CH2OH COOH O
KMnO4 CH 3 C
OH−
+ CO2 + 2H2O O
OH
O
+ CH 3 C + HCl
CH2COOH COOH Cl
KMnO4
+ CO2 + H2O Conditions: Aqueous NaOH
OH −

The carbon-containing side chain (whatever it is) is oxidised to –COOH.

Nitrobenzene
Reaction type: Oxidation Nitrobenzene C6H5NO2 is another common benzene derivative.
Conditions: KMNO4 in alkali, heat under reflux NO 2

Reactions of phenol. The reduction of nitrobenzene to an amine using tin and

Phenol, C6H5OH is a common derivative of benzene. concentrated hydrochloric acid.
OH Tin and concentrated hydrochloric acid are used as reagents to form an
intermediate tin complex, then large quantities of alkali are required to
release the amine after the initial reaction.
+ +
Phenol is an alcohol, but whereas straight chain alcohols have just the -OH NO 2 NH 3 NH 3 NH 2
2−
functional group, phenol has the -OH group and the electron- rich benzene Sn NaOH
ring. 2 conc HCl
SnCl6 2

Care must be taken when using phenol, a white crystalline solid, as it is

both corrosive and an anaesthetic. Reaction type: Reduction
Conditions: Tin, conc. HCl, then large quantities of NaOH.

Note: This reaction will work for other aromatic nitro-compounds.

Other reducing agents (e.g. LiAlH4) can work.
2
Reactions of Benzene and its compounds Chem Factsheet

Phenylamine Answers.
Phenylamine C6H5NH2 is produced from nitrobenzene, as described above.
1. Strong carbon-carbon bonds due to delocalised system of electrons
NH 2 througfhout the ring structure.

2. Electrophiles. They are attracted to the electron rich delocalised system.

Amines, being basic, usually react with acids to form salts. The following 3. Benzene is carcenogenic.
reaction, however, is different.
4. (a) reagents: conc. HNO3
(i) The reaction between phenylamine and nitrous acid conditions: conc. H2SO4, 500C
First the unstable nitrous acid (HNO2) is produced in situ by reacting
sodium nitrite with hydrochloric acid. (b) reagents: Br2 (l)
conditions: Fe catalyst, dry
NaNO2 (aq) + HCl(conc.) ! HNO2 (aq) + NaCl(aq)
(c) reagents: CH3Cl
conditions: anhydrous AlCl3, dry, heat under reflux
(ii) The diazotisation reaction
Phenylamine then reacts with the nitrous acid and HCl to form 5. Phenol is more acidic than ethanol, it donates protons more readily.
benzenediazonium chloride.
+ − O
N NCl 6.
NH 2 CH 3 C
low temp OH O
+ HNO2 + HCl + 2H2O O
+ CH3 C + HCl
Diazonium ions are important intermediates. Cl

(iii) The coupling reaction of benzenediazonium ions with phenol.

Azo-dyes are formed as diazonium salts react with phenol.
+ −
N NCl OH
low temp
+ N N OH + HCl
yellow precipitate
(diazo compound)
There are many diazo compounds with different colours, and they can be
used in textile dyes.

Questions

1. Explain the stability of the benzene ring structure.

2. State what sort of species will attack the benzene ring, and why.

3. State why care should be taken when handling benzene.

4. Give reagents and conditions for the following conversions:

(a) (b) (c)

NO 2 Br CH 3
Acknowledgements:
This Factsheet was researched and written by Kieron Heath
5. State why phenol reacts more readily with sodium hydroxide than Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham,
B18 6NF
ethanol. ChemistryFactsheets may be copied free of charge by teaching staff or students,
provided that their school is a registered subscriber.
6. Show how phenol can be used to form an ester. No part of these Factsheets may be reproduced, stored in a retrieval system, or
transmitted, in any other form or by any other means, without the prior
permission of the publisher. ISSN 1351-5136

3
 Chem Factsheet
September 2002 Number 40
Reaction Mechanisms
To succeed in this topic you need to:
Exam Hint: - Reaction mechanisms are commonly examined. As
• Have a good knowledge of the AS and A2 level organic chemistry
well as learning the standard examples given here, you need to practise
reactions covered so far; applying the mechanisms to other similar reactions.
• Be confident in using organic terminology, nomenclature and structural
formulae.
After working through this Factsheet you will: 2. Homolytic Free Radical Addition.
• Be able to represent movement of electron using the “curly arrow” Example: Polymerisation of ethene.
convention;
• Have been shown the key reaction mechanisms. The initiator is a free radical, R.(which could be a peroxide radical from
the oxygen catalyst).
All chemical reactions involve the movement of electrons, and reaction H H
Stage 1 - Initiation.
mechanisms allow us to display these movements and understand more H
about how a reaction occurs. R.
H
C C R C C.
H H
In this Factsheet you will meet organic reactions which you have come H H
across before. You should already be able to recall the overall reaction The new radical formed can then react with further ethene molecules to
equations and conditions required. The reaction mechanisms, which also lengthen the polymer chain.
require learning, often split these reactions up into several steps, each step Stage 2 - Propagation.
involving the movement of electrons. This should give an insight into how H H H H H H
H
C C C C.
a reaction occurs. . H
R C C C C R
H H
You need to be able to represent the movement of electrons using the H H H H H H
“curly arrow” convention: Termination can occur when two radical chains meet, or when a radical
chain attacks an established chain.
represents the movement of an electron pair Stage 3 - Termination.
H H H H H H H H
represents the movement of a single electron. n C C . .C C n n C C C C n

H H H H H H H H
When using curly arrows it is vital that you position each end of the arrows
carefully, so that you clearly show the examiner that you know where the The end product, polyethene, consists of long chain molecules (of varying
electrons are moving from and to. length) which are branched.

1. Homolytic Free Radical Substitution Stage 3 - Termination

These reactions involve free radicals, very reactive species which have
a single, unpaired electron. Cl . .Cl Cl Cl

Example: Alkanes with chlorine. Cl . .CH3 Cl CH 3

The reaction between methane and chlorine occurs in 3 stages. Free radicals are used up and not regenerated, causing the reaction to
eventually stop.
Stage 1 - Initiation
The overall reaction equation is as follows:
Cl . + Cl .
uv light
Cl Cl
uv light
The Cl-Cl bond is broken homolytically to form two chlorine free radicals. CH4 + Cl2 CH3Cl + HCl
Energy is required to break the bond, hence the reaction only begins in the
presence of UV light. But be aware that “by-products” are also formed in such reactions, e.g.
the formation of ethane (when chloromethane is the target molecule).
Stage 2 - Propagation
H H CH3 + CH3 C 2H 6
H C H Cl H C. + HCl
Most free radical reactions are extremely unstable and explosive. This
H H
reaction between methane and chlorine is controlled using subdued UV
H3C . Cl Cl H3C Cl + Cl . light.

Any such reaction caused by a free radical, where “replacement” free

radicals are produced by the reaction, hence the reaction process continues
unaided.

1
Reaction mechanisms Chem Factsheet

3. Heterolytic Electrophylic Addition Note the formation of a carbocation (C + ) intermediate. The most stable
Example: Alkenes with halogens or hydrogen halides. position for the carbocation will be the carbon with the least hydrogen
atoms around it.
Consider the addition of bromine to propene.
H H H H H
H
H3C C C H hence CH 3 C C H was formed, not CH 3 C C H
+ +
δ +

Br Br Br
δ− Br There is a similar reaction mechanism for the addition of hydrogen halides
to alkenes.
The electrons in the double bond repel the electrons in the approaching
Br2 molecule, causing a dipole. H H H H H
H
The δ+ end of the halogen molecule is electrophilic, and can attack the CH 3 C C → CH 3 C C H → CH 3 C C H
H +
electron rich π-bond. δ+ H H Br H
−
Meanwhile, the δ end of the halogen molecule will accept both of the
− :Br
bond pair of electrons, forming a negative anion. δ − Br

H H H H H
H Markownikov’s Rule
CH 3 C C H → CH3 C C H → CH 3 C C H
+ When a hydrogen halide is added to a C=C double bond, the hydrogen
Br − Br Br Br atom is added to the carbon atom that already carries more hydrogens.
:Br
Br

4. Heterolytic Electrophilic Substitution (b) Bromination of benzene

Examples: Reactions of benzene (see Chem Factsheet 39). Bromine reacts with benzene in the presence of an iron wire catalyst in
(a) Nitration of benzene dry conditions at room temperature.
Benzene reacts with a mixture of conc. nitric acid and conc. sulphuric Br
acid at 50oC to form nitrobenzene.
Fe cat. + HBr
conc. H 2SO4 Br2 +
+ HNO3 0 NO 2 + H2 O
50 C

Nitrobenzene The electrophile Br+ must be generated to attack the benzene ring.
The reaction of benzene with nitric acid alone is slow and pure sulphuric 2Fe + 3Br2 → 2FeBr3
acid at 500C has little or no effect on benzene.
+ −
Therefore, sulphuric acid must react with nitric acid forming a species Br Br FeBr3 Br FeBr4
which will attack the benzene ring. Then:
Br Br
Evidence suggests that this is the NO2+ species - an electrophile formed + +
Br H + H
by the removal of OH − from HNO3. +
HNO3 + 2H2SO4 → NO2+ + 2HSO4- + H3O + Bromobenzene
Note that the nitric acid is acting as a base (proton acceptor) in the Bromobenzene is formed and the H + is the removed by FeBr4 − to regenerate
presence of a stronger acid. the FeBr3.
The NO2+ ion is a strong electrophile, so attacks the delocalised π- + −
H + FeBr4 HBr + FeBr3
electron system in the benzene ring.
First a “loose” association is formed. (c) Alkylation of benzene with chloroalkanes or acyl chlorides
+ +
Benzene reacts with chloroalkanes in the presence of anhydrous aluminium
+ NO2 → NO 2 chloride to give an alkylbenzene.
C2H5
AlCl 3
NO2+ then attacks a C atom, forming a bond and distrupting the + C2H5Cl + HCl
delocalised π-system. NO 2
+
The mechanism is as follows:
+ H
NO 2 → H H +
CH 2CH3 −
C Cl AlCl3 + AlCl4
Note that a considerable amount of energy is required to disrupt the H
CH 3
very stable π-system, therefore this step has a very high activation
energy.
CH2CH 3 + HCl + AlCl3
The intermediate cation will then break down to either reform benzene,
or form nitrobenzene. ethylbenzene
The delocalised system reforms, hence energy is released. A similar reaction mechanism occurs when benzene reacts with acid
+ chlorides and AlCl3 to give ketones.
NO 2 + NO2
+
O O
H or AlCl 3
NO 2 + CH 3 C + HCl
+ C
+ H Cl Cl
Nitrobenzene

2
Reaction mechanisms Chem Factsheet

5. Heterolytic Nucleophilic Substitution (2) SN2 mechanism

Example: Halogenoalkanes with hydroxide ions and cyanide ions. The mechanism involves the substitution of a nucleophile which is
This mechanism is associated with polar covalent bonds (e.g. carbon-halogen). second order (two molecules in rate determining step).
δ+ δ− The nucleophile attacks the Cδ+ and starts to form a covalent bond
C Br with it. At the same time the C δ+-Hal δ− bond starts to break
heterolytically.
The positive charge on the carbon allows attack by nucleophiles such
as :OH− or :CN− which have lone pairs to donate. This is one continuous process with the carbon-nucleophile bond
getting stronger and the carbon-halogen getting weaker.
There are two mechanisms for nucleophilic substitution, (1) SN1 and (2) SN2.
The “transition state” (corresponding to the activation energy peak)
is when both are of equal strength.
(1) SN1 mechanism CH 3 - CH 3
CH
This mechanism involves the substitution of a nucleophile which is - 3
-
HO : C Br HO C Br HO C : Br
first order (one molecule in rate determining step).
H H H H H
This mechanism occurs in two stages: H
transition state
Stage 1: (The rate determining step)
CH3 CH 3 The formation of the transition state represents the rate determining
- step. This step is first order with respect to the halogenoalkane and
CH 3 C CH3 C
+ + Br the nucleophile.
Br
CH3 CH 3 Rate = k[CH3CH2Br][OH − ]
Stage 2:
CH 3 CH 3 SN1 or SN2?
- To find out which mechanism is followed for such nucleophilic substitution
CH 3 C + + :OH CH 3 C OH reactions, the reaction rate must be followed by experiment and the rate
CH 3 CH3 order with respect to the nucleophile discovered.
The first stage is rate determining as the second stage occurs much faster. In general the mechanism depends on the stability of the carbocation.
Therefore the rate equation is: Alkyl groups are more “electron donating” than hydrogen atoms, so the
Rate = k[(CH3)3CBr] carbocation of a tertiary group is more stable than that of a primary
group. H R1 R1
The reaction is zero order with respect to the nucleophile (OH − ) as it
does not take part in the rate determining step. R C + R2 C + R2 C +
This mechanism involves the formation of an intermediate - the carbocation. H H R3
Primary Secondary Tertiary

favour SN2 favour SN1

Answers
6. Heterolytic Nucleophilic Addition
1. Homolytic fission is when a bond breaks with one electron going to
Example: Carbonyl compounds and hydrogen cyanide.
each of the bonded atoms forming two free radical species. Heterolytic
A nucleophile will attack the δ+ carbon in the C=O group. fission is when a bond breaks with both of the bond pair electrons
going to one of the bonded atoms, forming a cation and anion.
R - O: H+ R OH
R δ+ δ− R + - 2. (a) HNO3 + 2H2SO4 → NO2+ + 2HSO4− + H3O+
C O C O C C
R R - +
NO 2 NO 2
:CN R CN R CN + +
+ NO2 → NO 2 → + H → + H

(b) H H H H H
Questions. H
1. What is this difference between homolytic and heterolytic fission of C 2H 5 C C → C 2H 5 C C H → C2H 5 C C H
H +
bonds? H H Br H
−
2. Show the reaction mechanisms for the following reactions: :Br
(a) C6H6 + HNO3 → C6H5NO2 + H2O Br
(c)
C 2H 5 δ+ δ− C2H5 + - C2H 5 O: H+
(b) C2H5CHCH2 + HBr → C2H5CHBrCH3 C O → C O → C
CH 3 CH 3 - CH3 CN
(c) C2H5COCH3 + HCN → C2H5C(OH)CH3CN :CN

C2H5 OH
C
Acknowledgements:
This Factsheet was researched and written by Kieron Heath CH 3 CN
Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham, B18 6NF
ChemistryFactsheets may be copied free of charge by teaching staff or students, provided that their school is a registered subscriber.
No part of these Factsheets may be reproduced, stored in a retrieval system, or transmitted, in any other form or by any other means, without the prior permission of the publisher. ISSN 1351-5136

3
 Chem Factsheet
September 2002 Number 41
Answering Questions on Electrochemical Cells
This Factsheet assumes you know and understand the basics of cells and Worked Example
standard electrode potentials (covered in Factsheet 37). It will concentrate What is the cell reaction when the following half cells are combined?
on applying that knowledge to examination questions on cells.
V3+ + e− ¾ V2+ Eê = -0.26V
There are three main types of question on electrochemical cells. Actual Ni2+ + 2e− ¾ Ni Eê = -0.25V
examination questions will usually contain more than one of these.
Method Answer
(1) Recall of basic facts Identify the cathode V2+| V3+ is the more negative electrode so it is the
cathode
You can be asked to give the following:
Reverse the equation V2+ ¾ V3+ + e−
(a) a drawing/description of the standard hydrogen electrode. for the cathode.

(b) the definition for a standard electrode potential. Write down the Ni2+ +2e− ¾ Ni
equation for the anode
(c) a drawing of the apparatus used to measure standard electrode potentials
"Balance" the electrons There are two electrons in the nickel equation
(d) an explanation of why a high resistance voltmeter is used. in the two equations but only one in the vanadium equation.
So double the vanadium equation:
(e) an explanation of why potassium nitrate is used for the salt bridge. 2V2+ ¾ 2V3+ + 2e−

(f) a description and explanation of the trend in oxidising and reducing Combine the equations. Ni2+ +2e− + 2V2+ ¾ Ni + 2V3+ + 2e−
powers related to the Eê table of values. Replace ¾ by ➝ Ni2+ + 2V2+ ➝ Ni + 2V3+
Cancel the electrons
All of these are covered in Factsheet 37.
. Question 1 at the end of the Factsheet provides further practice on this
type of question.
Exam Hint: - Exam questions on this topic always include some
element of recall. Good candidates should be able to recall the
answers to all the above questions quickly and accurately.
(3) Calculating Eê cell

(2) Writing the overall cell reaction Eê cell = Eê (anode) − Eê (cathode)

This depends on identifying which is the cathode and anode from the Eê Clearly, this type of calculation depends on identifying the cathode and
values of the two electrodes. anode from the Eê values again.
The electrode with the smallest (meaning most negative or least
Note that the reactant at the anode is being (electrons are added) and that at
positive) Eê value is the cathode. the cathode oxidised (electrons removed), so this is equivalent to an
alternative form which is often seen:
The values of electrode potentials are usually given in a table, with the Eê cell = Eê (reactant being reduced) − Eê (reactant being oxidised))
most negative at the top and the most positive at the bottom, like this
Worked Example
Mg 2+ + 2e− ¾ Mg -2.37 What is Eê cell for V3+|V2+ combined with Ni2+|Ni?
Al3+ + 3e− ¾ Al -1.66
Zn 2+ + 2e− ¾ Zn -0.76 Answer
2H+ + 2e− ¾ H2 0.00 First, identify the cathode: here Vanadium is the cathode, as its Eê value is
Cu2+ + 2e− ¾ Cu +0.34 more negative.
I2 + 2e− ¾ 2I− +0.54
Then use the equation: Eê cell = Eê (anode) − Eê (cathode)
If the Eê values are given in this format, the higher of the two in the list Eê cell = (-0.25) − (-0.26)
is the cathode. = +0.01V
Take care with minus signs. Make sure you write all of them in your
Exam Hint: - Examiners willl not always give you the Eê in this working, and if you are unsure - use your calculator!
order. Many otherwise good candidates lose out through assuming
that "the one on top is the cathode" without checking the values are in Exam Hint: - The overall answer should be positive for a real cell.
the correct order first.

Question 2 provides further practice on this type of example.

1
 Answering Questions on Electrochemical Cells Chem Factsheet

Answers
Questions
1.
You will need information on Eê values (given in Factsheet 37) to answer (a) Mg + Cl2 ➝ Mg2+ + 2Cl−
these questions. (b) Al + 3Ag+ ➝ Al3+ + 3Ag
(c) Cu + 2Fe3+ ➝ Cu2+ + 2Fe2+
1. What is the overall cell equation when the following half cells are
(d) Fe + I2 ➝ Fe2+ + 2I−
combined?
(e) 2V2+ + 2H+ ➝ 2V3+ + H2
(a) Mg2+|Mg with Cl2|2Cl− (f) Mg2+ + Zn ➝ Mg + Zn 2+
(g) Fe + 2V3+ ➝ Fe2+ + 2V2+
(b) Al3+ |Al with Ag+|Ag (h) Fe2+ + Ag+ ➝ Fe3+ + Ag
(i) Cl2 + 2I− ➝ 2Cl- + I2
(c) Cu2+|Cu with Fe3+|Fe2+ (j) 3Zn2++ 2Al ➝ 2Al3+ + 3Zn

(d) I2|2I− with Fe2+|Fe

2.
(e) 2H+|H2 with V3+|V2+ (a) + 3.73V
(b) + 2.46V
(f) Mg2+|Mg with Zn2+|Zn (c) + 0.43V
(d) + 0.98V
(g) V3+|V2+ with Fe2+|Fe (e) - 0.26V
(f) + 1.61V
(h) Fe3+|Fe2+ with Ag+|Ag (g) + 0.18V
(h) + 0.03V
(i) Cl2|2Cl− with I2|2I− (i) + 0.82V
(j) + 0.9V
(j) Al3+|Al with Zn2+|Zn

3. high resistance voltmeter

2. Calculate Eê cell for each of the cells in question 1. (a)
V

3. (a) Draw the apparatus used to measure the standard electrode potential
for an Al3+|Al half cell. Al
H2 (1 atm) SALT BRIDGE
3+ −
(b) An Al |Al half cell and an I2|2I half cell are combined.
(i) State which reactant is oxidised in the resulting cell reaction

(ii) Calculate the Eê value for the resulting cell.

4. (a) What is meant by a standard electrode potential?

(b) Given the following standard electrode potentials:

1M H+(aq) 1M Al3+(aq)
Cu2+ + e− ¾ Cu+ Eê = + 0.15 V
Cu+ + e− ¾ Cu Eê = + 0.52 V Temperature: 25o C

(i) Give the resulting reaction from combining the two half cells (b) (i) Reactant at cathode is oxidised: Al
Cu2+|Cu+ and Cu+|Cu (ii) Eê cell = +0.54 − (-1.66) = 2.20V

(ii) Predict what would happen if copper (i) sulphate was added
to water. 4.
(a) The SEP of a half cell is when a standard half cell (1 mol dm-3, 25oC)
is connected to a standard hydrogen electrode (1 mol dm-3 H+ (aq),
1 atm, 25oC) using a high resistance voltmeter.

(b) (i) Cathode is Cu2+ + e- ¾ Cu+

Acknowledgements: So equations are: Cu+ ¾ Cu2+ + e−
This Factsheet was researched and written by Sam Goodman
Cu+ + e− ¾ Cu
Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham,
B18 6NF Combining: 2Cu+ ➝ Cu + Cu2+
ChemistryFactsheets may be copied free of charge by teaching staff or students,
provided that their school is a registered subscriber. (ii) It would disproportionate to give copper metal and
No part of these Factsheets may be reproduced, stored in a retrieval system, or copper II sulphate
transmitted, in any other form or by any other means, without the prior
permission of the publisher. ISSN 1351-5136

2
 Chem Factsheet
September 2002 Number 42
Critical Analysis of Experimental
Procedures and Levels of Accuracy
To succeed in this topic you need to: (4) Reaction kinetics – following a rate of reaction and changing variables
• be familiar with the concepts raised in Factsheet 36 (Laboratory to see the effect on the rate.
Chemistry – Continuous Practical Assessment) and the other
Factsheets mentioned in this topic; These experiments generate data which usually then need plotting as graphs.
• have a copy of your AS/A2 specification so that you can refer to the You are likely to be asked to:
specifics on ‘evaluation and interpretation of practical results’. • comment on the procedure
After working through this Factsheet you will:
• spot anomalous results.
• have met a range of issues about ‘accuracy’ relating to practical work;
• know the appropriate level of accuracy for practical results;
• be able to calculate ‘percentage errors’. Categories of questions

AS/A2 specification requirements (1) Anomalous results

The specifications list the following under ‘Interpretation and evaluation These are results that do not fit a pattern or trend. They are hard to see just
of experimental results’: from the raw figures but once plotted as a graph they stand out – as you
can see in the two examples below.
The ability to:
(1) evaluate critically experimental work i.e. experimental error,
anomalous results, suggest improvements.
(2) assess how reliable data is and the conclusions drawn from it
(3) recognise the limitations of various techniques
(4) calculate experimental error

Laboratory practical work

Although it is not possible to cover all the specific practical situations that
you may be presented with in an examination question, we can, however,
put experimental work into broad categories:

(1) Test on compounds – if you do this test and the substance reacts
like this what can you tell about the substance?

To answer questions on this type of situation you need to learn the specific
tests and reactions of compounds as given in your specification. Factsheet
24 gives the commonly asked tests.

(2) Titrations – acid/base, redox and ‘one off’ analysis examples e.g EDTA.

All titrations involve the generation of data by the use of very accurate
glassware and balances. Questions on titrations are the most common in
the area of evaluation and interpretation. This Factsheet has examples on
titration work; see also Factsheet 23.

(3) Preparation and purification of compounds – these are usually

organic compounds but occasionally inorganic compounds as well.
(2) Percentage yield
The methods are different for solids and liquids - see Factsheet 30. The equation is

Examination questions usually involve describing a method for a preparation mass obtained × 100
and purification of a compound then asking you what happens at specific Percentage yield =
mass expected from calculation
stages. Sometimes an error will be put into the procedure and often a
percentage yield calculation included. This involves, as for tests/inferences,
a thorough learning of the procedures from your specification and your
own practical work.
1
 Critical Analysis of Experimental Procedures and Levels of Accuracy Chem Factsheet

Worked example
(4) Percentage Errors
0.25 mol ethanol is converted into bromoethane as in the equation.
The equation is
C2H5OH + HBr ➝ C2H5Br + H2O
Percentage error = error amount × 100
If 18.30g of bromoethane is produced, what is the percentage yield? actual amount

Answer Explanation
Worked examples
(a) 0.25 mol bromoethane From equation 1 mol ethanol What is the percentage error in each of the following situations?
should be produced produces 1 mol bromoethene
(a) A student weighs out 0.80g instead of 0.70g
(b) Mr (C2H5Br) = 109 C = 12, H = 1, Br = 80
(0.80 – 0.70) × 100
Percentage error = 0.70 = 14.29%
(c) Mass C2H5Br = 109 × 0.25 0.25 mol expected if
= 27.25g 100% conversion (b) The Mr of a compound is calculated to be 125 from experimental data.
The actual Mr is 127.
(d) Percentage purity = 18.30 × 100 Use equation
Percentage error = (127 – 125) × 100
27.25
= 1.57%
= 67.16% 127

(3) Level of accuracy (c) A student leaves 0.30cm3 in a beaker after pouring out the 25.00cm3
he originally put in it.
(a) The rule is clear for all calculated answers – only 2 or 3 figures after
the decimal point. Percentage error = 0.30 × 100 = 1.20%
25.00
If we go back to the percentage yield calculation:

percentage yield = 18.30 × 100

27.25
the calculator answer was 67.15596g

Only 67.16g or 67.156g are acceptable.

Exam Hint: - Even strong candidates can be prone to lose marks

through giving the answer to an otherwise correct calculation to an
inappropriate numbers of decimal places. Always look back at your
answer!

(b) Titration work throws up many examples of levels of accuracy because:

electronic balances - 3 figures after the decimal point

burette readings - ___.___5 or ___.___0 is the level of accuracy
pipettes - 25.00cm3/50.00cm3 i.e. 2 decimal places

Worked example
A student produced the following results from a titration:

burette reading 1 2 3
final cm3 23.40 23.67 23.40
start cm3 0.00 0.05 0.05
volume used cm3 23.40 23.62 23.35

Mean titre = 23.40 + 23.62 + 23.35 = 23.4566 cm3

What are the three errors in the student’s work?

Answers Acknowledgements:
(a) 23.67cm3 is incorrect because the burette cannot be read to that This Factsheet was researched and written by Sam Goodman
level of accuracy. Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham,
B18 6NF
ChemistryFactsheets may be copied free of charge by teaching staff or students,
(b) 23.62cm3 should not have been used to calculate the mean titre provided that their school is a registered subscriber.
because it is not in the range of accuracy of the other two values. No part of these Factsheets may be reproduced, stored in a retrieval system, or
You need two titres that are the same or ± 0.10cm3 of each other. transmitted, in any other form or by any other means, without the prior
permission of the publisher. ISSN 1351-5136
(c) Too many significant figures in the mean titre answer.
2
 Chem Factsheet
January 2003 Number 43
Rate Equations, Orders & Constants
To succeed with this topic you need to: Finding the orders from experimental data
• Know and understand the AS material on kinetics - This following worked example is typical of what will be expected of you
♦ collision theory in an examination question.
♦ activation energy
♦ Maxwell-Boltzman graph The reaction: 2C + D + 2E → 3F + 2G
♦ Factors affecting rates of reaction products the following data
♦ Catalysts and energy profiles covered in Factsheet No. 10 (Kinetics I)
experiment concentrations / mol dm -3 initial rate / mol dm-3s-1
After working through the Factsheet you will be able to: number [C] [D] [E]
• understand the parts making up the rate equation (or expression);
• be able to find the orders for a particular chemical reaction from the 1 0.5 1.0 1.0 2
data given for it; 2 0.5 2.0 1.0 8
• be able to perform calculations based on the rate equation; 3 1.0 2.0 1.0 16
• be able to work out the units for the rate constant, k. 4 1.0 2.0 2.0 16

Rate expressions (equations) (a) What are the orders with respect to C, D and E?
(b) Write the rate equation for this reaction.
The balanced chemical equation (the stoichiometric
equation) can tell you nothing about the rate expression. Hint the process involves looking at the experiments for C ,D and E and
selecting two where only one of C, D or E changes - compare changes
The rate expression can only be worked out from the data provided in concentration with the effect on the rate.
by reaction rate experiments.

Let us consider a reaction of substances A, B and C where the equation is Working Out Answer
For C compare experiments 2 and 3 Rate ∝ [C] (NB. ∝ is the
A + B + 2C → 2D + E because only C changes. proportional sign)
The rate expression (or equation) works out to be When [C] doubles, the rate doubles rate = k[C] (NB. the rate constant,
i.e.directly proportional so is first k enables the ‘=’ sign to be put in).
rate constant [ ] = concentration i.e. mol dm-3 order.
For D compare experiments 1 and 2. rate ∝ [D]2
rate = k × [A]2 × [B]1

units of mol dm-3 s−1 'orders' when [D] doubles, the rate goes up rate = k[D]2
4 times i.e. 4 = 22, so 2nd order
In words:
The reaction is 2nd order with respect to A and 1st order with respect to B. For E compare experiments 3 and 4 rate ∝ [E]0
Overall, the reaction is 3rd order (2 + 1)

Note the following points about this example: when [E] doubles, the rate is rate = k[E]0
(1) We would mormally write [B], not [B]1. The 1 is put in to make it clear unchanged i.e. no effect so is zero
(2) C does not appear in the rate expression – it is ‘0 order’ and if shown order
would look like this [C]0
(3) the expression would normally be shown as Combine the answers in (a) (b) rate = k[C][D]2
or
rate = k[A]2 [B] rate = k[C][D]2[E]0
with the ‘×’ symbol removed.

Summary
0 order - changing the concentration has no effect on the rate

1st order - directly proportional relationship e.g. half concentration

and half rate, triple concentration and triple the rate.

2nd order - ‘squared factor’ involved e.g. triple concentration and rate
increases 9×, double concentration and rate increases 4×.

1
Rate Equations, Orders & Constants Chem Factsheet

Exam Hint - The initial rate data is a common place for questions to Questions
catch out candidates by using ‘powers of 10’ (standard form). 1. For the reaction between A, B and C the following results were obtained:
Look at this data:
rate experiment concentration / mol dm-3- initial rate / mol dm-3s-1
2 x 10-3 [A] [B] [C]
8 x 10-3 1 1 1 1 2.0 × 10-4
3.2 x 10-2 2 2 1 1 4.0 × 10-4
6.4 x 10-2
3 1 2 1 2.0 × 10-4
Comparing these is a problem!
4 2 1 2 1.6 × 10-3
Now do this conversion to 10-3 for all figures:
rate (a) What are the orders with respect to A, B and C?
2 x 10-3
8 x 10-3
E x 4 comparison (b) What is the rate expression for this reaction?
-2 -1 -2 -3 E x 4 are (c) Calculate the value for k. What are its units?
3.2 x 10 = 32 x 10 x 10 = 32 x 10
E
6.4 x 10-2 = 64 x 10-1 x 10-2 = 64 x 10-3 x 2 now possible
(check conversions on your calculator if you are unsure) 2. For the reaction between C and D the following results were obtained:

experiment concentration / mol dm-3- rate / mol dm-3s-1

[C] [D]
Finding the units of k 1 0.01 0.1 2.5 × 10-4
To do this you need to 2 0.01 0.2 2.5 × 10-4
(1) remember the units of : [ ] = mol dm-3 3 0.02 0.3 5.0 × 10-4
rate = mol dm-3 s-1
(a) Write the rate expression for this reaction.
(2) be able to rearrange the rate equation
(b) Calculate the value for k and give its units.
(3) Know how to combine powers
Powers 3. The following results were obtained for the reaction between E, F and G:
• Anything without a number by it is to the power 1.
• Multiply ⇒ add powers. experiment concentration / mol dm-3 initial rate / mol dm-3s-1
• Dividing ⇒ subtract powers. [E] [F] [G]
• Powers on the bottom change sign when you bring them to the top. 1 1 1 0.5 7.0 × 10-3
• If you are finding a "power of a power" you multiply. 2 1 2 0.5 1.4 × 10-2
e.g. (mol dm-3)3 = mol1×3dm-3×3 3 2 2 0.5 1.4 × 10-2
= mol3dm-9 4 2 2 1.5 4.2 × 10-2
• You can only simplify powers of the same thing
e.g. mol2 × mol = mol3, but mol dm-3 can't be simplified. (a) Write the rate expression for this reaction.
(b) Calculate the value for k and state its units.
Example 1 rate = k[A][B]
Answers
-3 -1 -3 -1 1. (a) rate = k[A]1 rate = k[B]0 rate = k[C]2
rate mol dm s mol dm s
k= = = (b) rate = k [A][C]2
[A][B] mol dm-3 × mol dm-3 mol dm-3mol dm-3
rate
(c) k =
s-1 [A][C]2
= = mol-1dm3s-1
mol dm-3 use experiment 1:
2.0 × 104
=
Example 2 rate = k[C]2[D] 1 × 12
= 2.0 × 10-4
rate mol dm-3s-1 mol dm-3 s-1
k= = =
[C]2[D] (mol dm-3)3 mol3 dm-9 mol dm-3 s-1
Units: =
mol dm-3 (mol dm-3)2
= mol dm-3 s-1 mol-3 dm9 = mol-2dm-6s-1 = mol-2 dm6 s-1

Finding the value of k

This is a relatively straightforward procedure: 2. (a) rate = k[C]
1. choose the values for any one of the experiments in the data table 2.5 × 10-4
(b) k =
2. substitute these values for [ ] and rate into the rate expression 0.01
3. rearrange the equation and calculate k. = 2.5 × 10-2s-1

You will find examples of this calculation in the questions at the end of this 3. (a) rate = k[F][G]
Factsheet. (b) k = 1.4 × 10-2 mol-1dm3s-1

Acknowledgements:
This Factsheet was researched and written by Sam Goodman
Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham, B18 6NF
ChemistryFactsheets may be copied free of charge by teaching staff or students, provided that
their school is a registered subscriber.
No part of these Factsheets may be reproduced, stored in a retrieval system, or transmitted, in any
other form or by any other means, without the prior permission of the publisher. ISSN 1351-5136

2
 January 2003
Chem Factsheet Number 44
Rate Expression Orders and Experimental Procedures
To succeed with this topic you need to:
• ensure you are fully competent in writing rate expressions from the experimental data provided (Factsheet No.43 (Kinetics II)).

After working through this Factsheet you will be able to:

• recognise which experimental techniques are available to provide ‘initial rate’ data for rates of reactions;
• know how particular graph plots provide information about orders of reactions;
• use the data from first order reactions to find half-lives.

You need to know three experimental methods for measuring rates Exam Hint : - To be able to answer questions in the examination and
1. Gas syringe - for reactions involving gases experimental procedures you need to be able to do the following
2. Colorimetry - for reactions involving a colour change things:
3. Sampling methods (1) use state symbols from the chemical equation provided
(2) use your own knowledge from your laboratory work about some
chemicals (colours particularly)
(3) remember the procedures that are given below

Experimental methods for rates of reactions

2. Reactions where there is a colour change
1. Reactions producing gases
Examples are,
Examples are:

CaCO3(aq) + 2HCl(aq) → CaCl2(aq) + H2O(l) + CO2(g) 2MnO4−(aq) + 16H+(aq) + 5C2O42−−(aq) → 2Mn2+(aq) + 8H2O(l) + 10CO2(g)

2H2O2 (aq) → 2H2O(l) + O2(g) (the purple colour of potassium manganate (VII) disappears to form a
colourless solution)
Mg(s) + 2HCl(aq) → MgCl2(aq) + H2(g)
CH3COCH3(aq) + I2(aq) → CH2I COCH3(aq) + HI(aq)
Equipment – gas syringe
Volume of gas collected in the syringe is measured at set time intervals
(the brown/orange colour of iodine solution disappears to form a colourless
solution)

Equipment – colorimeter which gives a reading of the light intensity of

the solution as it changes.

The readings are taken at set times or connected to a data logger or

computer which plots the graph.

Graph produced

Graph produced
The gradient at zero time is the initial rate

a
rate = gradient = a
concentration [ ]

b
b
volume/cm3

a b
a gradient =
b
a
b
b time
0 time/s
Tangents are taken and gradients measured to produce rates at various
concentrations (see later)

1
Rate Expression Orders and Experimental Propcedures Chem Factsheet

3. Sampling techniques using titrations Exam Hint : - Questions on 1st order/t½ fall into two categories:
The first two methods involve starting the reaction and taking readings as (1) “Show this reaction is 1st order by plotting the results below”
the reaction proceeds. (Method – plot concentration against time. Show that t½ are the
same so must therefore be 1st order).
This method involves: (2) “What is the half life for this reaction?”
(a) starting the reaction mixture (Method – plot graph and find t½ by method of concentrations
(b) at fixed times removing a fixed volume of the mixture going down by half)
(c) stopping the samples from reacting any further by putting them into
a liquid that ‘quenches’ or ‘freezes’ the reaction
(d) titrating the samples and calculating the concentration of the substance
Questions
Examples are: 1. What experimental method(s) could be used to follow the rate of
CH3CO2CH3(aq) + NaOH(aq) → CH3CO2Na(aq) + CH3OH(aq) reaction of each of the following reactions? (More than one method
may apply to each reaction).
(NaOH concentration found by titrating with HCl (aq)) (a) CH3CO2CH3 (aq) + H2O(l) ¾ CH3CO2H(aq) + CH3COH(aq)
CH3COCH3 (aq) + I2(aq) → CH2ICOCH3(aq) + HI(aq)) (b) CH3Br(aq) + NaOH(aq) → CH3OH(aq) + NaBr(aq)
(I2 concentration found by titrating with sodium thiosulphate solution, (c) Zn(s) + 2HNO3(aq) → Zn(NO3)2(aq) + H2(g)
Na2S2O3(aq))
(d) IO−4(aq) + 7I−(aq) + 8H+(aq) → 4I2(aq) + 4H2O(l)
This method is sometimes called ‘batch sampling’.
2. Show by graph plot that the following data for a reaction is 1st order.
The graph produced will look the same as for Method (2) and the tangents/
gradients found in the same way. initial rate / mol dm-3s-1 concentration / mol dm-3
3.6 × 10-2 0.5
7.3 × 10-2 1.0
Graphs and orders 14.8 × 10-2 2.0
A plot of concentration against rate from any of the results of the 22.9 × 10-2 3.0
experiment procedures above (finding gradients which are the rates),
enables you to find the order – as shown below Answers
1. (a) ‘Quenching’ and titrating the CH3CO2H with alkali (NaOH
2nd order (b) ‘Quenching’ and titrating the NAOH with acid (HCl)
(c) ‘Quenching’ and titrating the HNO3 with alkali (NaOH) OR
rate collecting H2 in a gas syringe
(d) (i) ‘Quench’ - titrate H+ with alkali (NaOH)
(ii) ‘Quench’ - titrate I2 with sodium thiosulphate
1st order (iii) Colorimeter – measure intensity of light as colour
changes to orange / brown due to formation of I2
0 order 2. Plot should show that it is of this form.

concentration
rate

First order reations and half life (t½)

First order reactions are exponential when you plot concentration against
time. concentration
This means when the concentration drops by half the time taken every
time for this is the same i.e. the half life, t½
concentration

0 t½ t½ t½ time
Acknowledgements:
This Factsheet was researched and written by Sam Goodman
Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham, B18 6NF
ChemistryFactsheets may be copied free of charge by teaching staff or students, provided that
their school is a registered subscriber.
No part of these Factsheets may be reproduced, stored in a retrieval system, or transmitted, in any
other form or by any other means, without the prior permission of the publisher. ISSN 1351-5136

2
 Chem Factsheet
January 2003 Number 45
Standard Electrode Potentials &
The Feasibility of Reactions
To succeed with this topic you need to:
• ensure you are fully able to write equations for cells and work of Eê ‘Feasibility’ - will these two substances react or not?
cell values (covered in Factsheets No.37 & 41).

After working through this Factsheet you will: Eê Values and Feasibility
• understand the concepts of ‘feasibility’ of a chemical reaction and The best example you can use to help you look at these key questions is
‘spontaneous change’; the cell made by combining zinc and copper.
• be able to use Eê data to decide if a chemical reaction is ‘feasible’ or not;
• have met the concept of the ‘anti-clockwise rule’ as one way of The Data
assessing if a reaction is ‘feasible’; (a) Zn2+ + 2e− ¾ Zn Eê = −0.76 V
• be able to write balanced chemical equations from half equations using Cu2+ + 2e− ¾ Cu Eê = +0.34 V
the ‘electron balance method;
• have met the concept of ‘disproportionation’; Using the data
• understand how ‘non-standard’ conditions affect the ‘feasibility’ of a (b) Zn/Zn2+ is above Cu/Cu2+ in the table i.e. zinc will be the cathode i.e.
reaction. the electron provider so needs to be written the other way round

Introduction Zn → Zn2+ + 2e i.e. oxidation

We need to pick out some key points from earlier work before we start: O.N. 0 +2

(Zn is the reducing agent because it is oxidised)

1. REDOX means reduction and oxidation
2. OXIDATION NUMBERS define whether reduction or oxidation Copper is the anode i.e. the electron acceptor so stays in the same
is taking place order as in the table
3. HALF EQUATIONS are equilibria and relate oxidised and reduced
forms Cu2+ + 2e → Cu i.e. reduction
4. SEP (Eê ) VALUES (+/-) show the tendency for oxidation or +2 0
reduction for a particular half equation
5. THE TABLE OF Eê VALUES below shows the trend in oxidising/
reducing power for particular half equations (Cu is the oxidising agent because it is reduced)
6. COMBINING HALF EQUATIONS based on reduction and
oxidation using Eêvalues (+/-) gives the BALANCED CHEMICAL Writing the overall equation (the cell reaction)
EQUATION (c) Zn → Zn2+ + 2e
Cu2+ + 2e → Cu
Table of E values Zn + Cu2+ → Zn2+ + Cu
Half Equation E /V
Mg2+ + 2e− Mg -2.37 NB. there are 2e− on each side - so on addition they are ‘cancelled out’ and
Al3+ + 3e− Al -1.66 do not appear in the final equation.
Zn 2+ + 2e− Zn -0.76
Fe2+ + 2e− Fe -0.44 Let us look at this cell and Eêvalues again if you were asked the question:
V2+ + 2e− V -0.26 Q. Will zinc react when put into copper sulphate solution?
Ni2+ + 2e− Ni -0.25
i.e. What is the feasibility of a reaction between Zn(s) and Cu2+(aq)?
2H+ + 2e− H2 0.00
Cu2+ + 2e− Cu +0.34
Before you go any further– can you answer the question: will Zn(s) react
I2 + 2e− 2I− +0.54
with Cu2+(aq)?
Fe2+ + e− Fe2+ +0.77
Not sure? Go back again – there is no other way. Sorry!
Ag+ + e− Ag +0.80
Cl2 + 2e− 2Cl− +1.36

You must keep these ideas at the forefront of your thinking as you work
through this Factsheet because all we are doing is putting them together in
a slightly different way to answer these key questions:
1. Will this substance react with that substance?
2. If they do react what is the final balanced chemical equation?
3. If they do not react – why not?
4. What could be done to make them react?

1
Standard Electrode Potentials & The Feasibility of Reactions Chem Factsheet

The Anti-Clockwise Rule Using Electrons to Balance Equations

Study the following way of showing what has been talked about with the We combine the half equations to give the chemical equation – we use the
Zn/Zn2+ and Cu/Cu2+ example. electrons to balance the equation.

oxidation These two examples show the principle involved:

Eêv
Example 1
Zn 2+
+ 2e ¾ Zn Will manganese react with tin (II) solutions?
-0.76 Mn2+(aq) + 2e− ¾ Mn(s) Eê = -1.19 V
Sn2+(aq) + 2e− ¾ Sn(s) Eê = -0.14 V

(Method – arranged like this i.e. electrons on the left and more negative
Eê over the less negative half cell we can say ‘yes’ – top right, Mn(s),
with bottom left, Sn2+(aq))
0 Mn(s) → Mn2+(aq) + 2e− (reversed)
Sn2+(aq) + 2e− → Sn(s)
Cu2+ + 2e ¾ Cu
+0.34 Mn(s) + Sn2+(aq) → Mn2+(aq) + Sn(s) (add – electrons cancel out)

reduction Example 2
Will Cu(s) react with Ag+(aq)?
Cu2+(aq) + 2e− ¾ Cu(s) Eê = +0.34 V
+3 +2 +1 0 -1
Ag+(aq) + e ¾ Ag(s) Eê = +0.80 V
i.e. bottom line left (Cu2+) reacts with top line right (Zn)
The answer is yes. (Can you explain why? Remind yourself of the
method shown in Example 1.)
These are the key points that you need to note:
Cu(s) → Cu2+(aq) + 2e− (reversed)
1. the anti-clockwise rule is just another way of presenting the answer
Ag+(aq) + 2e− → 2Ag(s) (doubled to get 2e− as for copper equation)
to the questions ‘Will Zn(s) react with Cu2+(aq)?’
2. the axes can be easily remembered: Cu(s) + 2Ag+(aq) → Cu2+(aq) + 2Ag(s) (add – electrons cancelled)
Eê
− Disproportionation
0 The use of Eê values explains this term.

+
Disproportionation is when the same species is simultaneously
+ − oxidised and reduced
0
Write it on your examination paper once given the instruction to ‘start’
to help you remember it. The best example to remember is copper:
Cu2+(aq) + e− ¾ Cu+(aq) Eê = +0.15 V
3. It's called the Anti-clockwise rule because if the ‘graph’ is presented Cu+(aq) + e− ¾ Cu(s) Eê= +0.53 V
like this (Eê/-/+ and ONs +/-) then: bottom left reacts with top right
Using the method,
If the graph is written on your paper according to these guidelines Cu+ → Cu2+ + e− (reversed)
you can use the data in a question on the paper Cu+ + e− → Cu
(i.e. Eê data are given – over +, and ions on left, metal on right (like
2Cu+ → Cu2+ + Cu (add – cancel electrons)
Zn2+ + 2e− ¾ Zn)
You can then say ‘bottom left with top right’ will work. The Cu+ has been oxidised to Cu2+ and reduced to Cu:
2Cu+ → Cu2+ + Cu
O.N. +1 +2 0
Exam Hint:- To test your understanding of this difficult concept the
examination question will often give you the data in the following way: oxidation
(1) Eê data with the (+) values over the (−) values
(2) ions on right, not the left. reduction

The Zn/Zn2+ and Cu/Cu2+ example would look like this:

Cu ¾ Cu2+ + 2e− Eê = +0.34 V
Zn ¾ Zn2+ + 2e− Eê = -0.76 V
Find a blank part of the paper and put it in a format you can use to
answer the question and re-write.
(a) ions (oxidised from on the left)
(b) put Eê (-) over Eê (+)

2
Standard Electrode Potentials & The Feasibility of Reactions Chem Factsheet

Non-Standard Conditions and Feasibility Answers

You need to keep in mind what Eê means! It is standard conditions i.e. 1. ✗
298K (25oC) and 1 mol dm-3 concentration.
2. ✓
1. If you change the temperature or the concentration you change the
Eê values so reactions that normally would not react (i.e. do not obey 3. ✓
the anti-clockwise rule) may react because their relative positions would
change. 4. ✓

2. If the Eê values of the two half equations are not very different then 5. ✗
they may not react even if they obey the rule. There is not enough
difference in Eê values. 6. ✓

Exam Hint:- These concepts are examined in two types of questions. 7. ✗

1. You are given two half equations with Eê values. The question
asks you if they are feasible – the answer will be ‘no’. 8. ✓
The questions tells you they will react if 2M acid (or a higher
temperature) is used and asks you to explain. You explain that 9. ✗
non-standard conditions are being used so Eê values change
so they may obey the anti-clockwise rule and so react. 10. ✓
2. You are give two half equations with Eê values and asked if they
are feasible – the answer will be ‘yes’. The question tells you they
do not react – explain. You will say there is not enough difference
between the Eê values for feasibility.

Questions
To answer these questions you need to use the data from the Eê table and
the additional half-equations given below:

Half Equation Eê/V

Mg2+ + 2e− Mg -2.37
Al3+ + 3e− Al -1.66
Zn 2+ + 2e− Zn -0.76
Fe2+ + 2e− Fe -0.44
V2+ + 2e− V -0.26
Ni2+ + 2e− Ni -0.25
2H+ + 2e− H2 0.00
Cu2+ + 2e− Cu +0.34
I2 + 2e− 2I− +0.54
Fe2+ + e− Fe2+ +0.77
Ag+ + e− Ag +0.80
Cl2 + 2e− 2Cl− +1.36

Mn2+ + 2e ¾ Mn Eê = +0.15v

Sn2+ + 2e ¾ Sn Eê = -0.14v

Cu2+ + e ¾ Cu+ Eê = +0.15v

MnO4− + 4H+ + 3e- ¾ MnO2 + 2H2O Eê = +1.70v

Are the following reactions feasible?

1. Cu+ with Sn 2. Sn2+ with Mn

3. Sn2+ with Zn 4. Cu+ with Ag+

5. Cl- with Ni2+ 6. V with I2

7. Cl2 with Zn2+ 8. Cu2+/Cu+ with Fe Acknowledgements:

This Factsheet was researched and written by Sam Goodman
9. Al3+ with Cu2+/Cu 10.Sn2+ with Mg Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham, B18 6NF
ChemistryFactsheets may be copied free of charge by teaching staff or students,
provided that their school is a registered subscriber.
No part of these Factsheets may be reproduced, stored in a retrieval system, or
transmitted, in any other form or by any other means, without the prior permission
of the publisher. ISSN 1351-5136

3
 Chem Factsheet
January 2003 Number 46
Transition Metals 2 - Compounds and Reactions
To succeed in this topic you need to: The reaction mechanism for this process is important and often examined.
• Understand the principle of oxidation numbers. When aquatic transition metal ion react with hydroxide ions the reaction
• Understand types of bonding and molecular shapes. mechanism is deprotonation.
• Understand the basics of Transition Metals (covered in Factsheet 38)
H 2O H2O
After working through this Factsheet you will: H 2O OH 2 H2O OH 2
3+ H - 3+ -
• Have more experience of transition metal compounds; Fe :O :O H → Fe :O + H2 O
• Recall the reactions of transition metal ions with hydroxides and ammonia; H 2O H 2O
H H
• Recall the oxidation states of vanadium, and how they can be
interconverted. H 2O H 2O

The following simple test tube reactions illustrate the behaviour of transition
further deprotonation
metal ions.
Notice how a H+ ion (a proton) is removed from the aqua ligand leaving a
Addition of aqueous alkali to transition metal ions hydroxide ion. Note that this is not a ligand exchange.

Practical 1 – Addition of sodium hydroxide solution As can be seen from the results, few transition metal ions react in excess
Dilute sodium hydroxide solution is added dropwise to aqueous transition sodium hydroxide.
metal ions. Initially a precipitate is looked for, then the sodium hydroxide
Most metal hydroxides are basic, so the metal hydroxide precipitates formed
is added to excess to find out if the precipitate will eventually re-dissolve.
in these reactions do not react in excess sodium hydroxide, itself a strong
base.
Ion Addition of NaOH (aq) Excess NaOH (aq) However, some metal hydroxides (e.g. Cr(OH)3) are amphoteric, so will
Cr3+ Green ppt Green solution react with NaOH.

Mn 2+ Buff ppt, darkens in air Precipitate does not dissolve Cr(OH)3(s) + 3OH−(aq) → [Cr(OH)6]3−(aq)
Deep green solution
Fe2+ Pale green ppt,
browns on surface Precipitate does not dissolve Practical 2 – Addition of ammonia solution
Fe 3+
Red brown ppt Precipitate does not dissolve Dilute ammonia solution is added dropwise to aquatic transition metal
ions. Initially a precipitate is looked for, then the ammonia solution is
2+
Co Blue ppt, turns brown in air Precipitate does not dissolve added to excess to find out if the precipitate will eventually re-dissolve.
2+
Ni Pale green Precipitate does not dissolve
2+
Ion Addition of NH3 (aq) Addition of excess NH3 (aq)
Cu Pale blue ppt Precipitate does not dissolve
3+
Cr Green ppt Precipitate does not dissolve
Zn 2+ White ppt Colourless solution
2+
Mn Buff ppt, darkens in air Precipitate does not dissolve
2+
The equations for these reactions are similar; each of the transition metal Fe Pale green ppt, Precipitate does not dissolve
ions should be written as the hexa-aqua ion, except for zinc which forms a browns on surface
tetra-aqua ion. In each case the precipitates formed are the simple hydroxide Fe3+ Red brown ppt Precipitate does not dissolve
compounds. 2+
Co Blue ppt, turns brown in air Precipitate does not dissolve
For example: Ni 2+
Pale green Blue sloution
[Mn(H2O)6]2+(aq) + 2OH−(aq) → Mn(OH)2 (s) + 6H2O (l)
2+
Cu Pale blue ppt Deep blue solution
[Fe(H2O)6]3+ (aq) + 3OH− (aq) → Fe(OH)3 (s) + 6H2O (l) Zn 2+
White ppt Colourless solution

and for zinc, On adding aqueous ammonia solution, it is hydroxide (OH-) ions, which are
again introduced and react with the transition metal ions.
[Zn(H2O)4]2+ (aq) + 2OH− (aq) → Zn(OH)2 (s) + 4H2O (l)
NH3(aq) + H2O(l) → NH4+(aq) + OH−(aq)

The precipitates which form are therefore the metal hydroxides again, just
as when sodium hydroxide was the aqueous alkali added.

It is when the ammonia solution is added to excess that the reactions vary
when comparing results to practical 1.
Ammonia is a weak base, too weak to react with the amphoteric metal
hydroxides (e.g. Cr(OH)3).
1
Transition Metals 2 - Compounds and Reactions Chem Factsheet

However, some transition metals will form complexes with ammonia as a Questions
ligand when it is added to excess. 1. Copper (II) nitrate crystals are dissolved in water and the solution is
split between two test tubes, A and B.
For example: Copper 2M sodium hydroxide solution is added to test tube A dropwise and
then to excess.
Stage 1 – NH3 (aq) added dropwise 2M ammonia solution is added to test tube B dropwise and then to
[Cu(H2O)6]2+(aq) + 2NH3(aq) → Cu(OH)2(s) + 2NH4+(aq) + 4H2O(l) excess.
pale blue
(a) Draw and name the aqua complex of copper formed when copper (II)
precipitate
nitrate crystals are dissolved in water.
A deprotonation reaction
(b) Describe the expected observations in:
Stage 2 - NH3 (aq) added to excess
(i) Test tube A.
(ii) Test tube B.
Cu(OH)2(s) + 4NH3(aq) + 2H2O(l) → [Cu(NH3)4(H2O)2]2+(aq) + 2OH- (aq)
Deep blue solution (c) Give equations for the chemical changes, and name the reaction
A ligand exchange reaction mechanisms, caused by the addition of the different alkalis in:
(i) Test tube A (1 equation).
The resulting solution is an ammine complex, where the NH3 ligand has (ii) Test tube B (2 equations).
taken the place of the H2O ligands (or at least some of them).
Answers
H2O 1. (a)

H 3N NH 3 H 2O
2+
Cu
H 2O OH 2
H 3N NH 3 Cu2+
H 2O H2O OH 2
The Chemistry of Vanadium H2O
Vanadium compounds exist in 4 oxidation states.
Hexaaquacopper (II) ions
Oxidation state Common ion Colour
V(+5) VO2+ Yellow (b) (i) Pale blue precipitate formed on addition of NaOH (aq).
2+ Precipitate does not dissolve on further addition of alkali.
V(+4) VO Blue
3+
V(+3) V Green (ii) Pale blue precipitate formed on addition of ammonia solution.
V(+2) V 2+
Lavender Precipitate dissolves to give deep blue solution on addition of
ammonia solution to excess.

Reduction by zinc (c) (i)

If zinc is added to a solution of sodium vanadate (VO2+ ions) in dilute [Cu(H2O)6]2+(aq) + 2OH−(aq) → Cu(OH)2(s) + 6H2O (l)
hydrochloric acid the +5 oxidation state is steadily reduced to the +2 pale blue
oxidation state, and the colour changes can be observed. precipitate

This is a deprotonation reaction.

VO2+ VO2+ V3+ V2+
yellow blue green lavender (ii)
[Cu(H2O)6]2+(aq) + 2NH3(aq) → Cu(OH)2(s) + 2NH4+(aq) + 4H2O(l)
Oxidation by potassium manganate (VII) pale blue
V2+ ions can be oxidised all the way to yellow VO2+ ions by the steady precipitate
addition of potassium manganate (VII), a strong oxidising agent. Again the
associated colour changes can be observed with careful addition.
This is a deproronation reaction
2+ 3+ 2+ +
V V VO VO2
Cu(OH)2(s) + 4NH3(aq) + 2H2O(l) → [Cu(NH3)4(H2O)2]2+(aq) + 2OH(aq)
lavender green blue yellow
Deep blue solution
More redox reactions of vanadium
Depending on the oxidising or reducing strengths of the vanadium species This is a ligand exchange reaction.
and the reagents reacting with them, the four oxidation states can be
interconverted.
Acknowledgements:
In an exam situation candidates would be expected to deduce different This Factsheet was researched and written by Kieron Heath
conversions between oxidation states given their Eê values and those of the Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham, B18 6NF
ChemistryFactsheets may be copied free of charge by teaching staff or students, provided that
reagents. See Factsheet 47 for the data and explanation required for these
their school is a registered subscriber.
questions, plus examples. No part of these Factsheets may be reproduced, stored in a retrieval system, or transmitted, in any
other form or by any other means, without the prior permission of the publisher. ISSN 1351-5136

2
 Chem Factsheet
January 2003 Number 47
Answering Questions on Transition Metals
To succeed in this topic you need to: Remember to use the periodic table, always available in exams, to check the
• Understand the principle of oxidation numbers; atomic number and therefore the number of electrons in a neutral atom.
• Understand the principle of redox reactions and the use of Eê values So the answers will be:
(Factsheets 37 and 45); 3d 4s
• Understand types of bonding and molecular shapes (Factsheets 04 and 06); Ni [Ar]
• Understand work so far on Transition metals (Factsheets 38 and 46).

After working through this Factsheet you will:

• Have more experience of questions based on transition metals; Ni2+ [Ar]

Questions on transition metals are common in exams, as the examiners can

Sc3+ [Ar]
use them as a theme to incorperate several different strands of chemistry in
one question. To succeed candidates must have a solid understanding of
topics such as electronic configuration, molecular shapes, redox reactions, Understand the effect of the addition of ligands on electronic structure
standard electrode potentials, acid-base character and the work covered Each ligand donates an electron pair into the outer orbitals of a transition
specifically on transition metals and their compounds and complexes. metal as it forms dative covalent bonds.

Example: The electronic structure for the Cr3+ ion.

1. Learn the definition
3d 4s 4p
Ensure that you have learned the definition of transition metals, and that
you can explain why scandium and zinc are d-block metals, but not transition Cr3+ [Ar]
metals.
Now the electronic structure of Cr3+ in the aqua complex [Cr(H2O)6]3+:
Definition - Transition metals are d-block elements, which 3d 4s 4p
can form one or more stable ions with partially filled d-orbitals.
[Cr(H2O)6] 3+ [Ar]

2. Learn the properties

4. Names of transition metal complexes
Properties of transition metals are commonly asked for, so learn:
Factsheet 38 gives the set of rules candidates must learn to be able to name
(a) Exist in a variety of oxidation states.
complex ions. If given a formula or a structural diagram of a complex ion
(b) Form complex ions.
candidates should be able to give the name.
(c) Form coloured ions or compounds.
(d) Catalytic properties of elements and compounds. For example: [Cu(H2O)6] 2+ hexaaquacopper (II) ion

Evidence of understanding may also be required. 6 aqua ligands, hence “hexaaqua”. Metal is copper, and overall charge of
complex ion is positive, hence “copper”. Oxidation state of metal is +2,
3. Electronic configurations hence “(II)”.
You should be able to produce the electron configurations of the first row [Cu(CN)6]4− hexacyanocuprate (II) ion
(period 4) of d-block elements and those of their common ions. Be sure to
be confident in using arrows in boxes notation. 6 nitrile, or cyano, ligands, hence “hexacyano”. Metal is copper, overall
charge on complex ion is negative, hence Latin “cuprate”. Oxidation state
Example: Complete the electronic structure of the following. of metal is +2, hence “(II)”.
When completing these remember that when electrons are removed from
atoms (i.e. when forming cations) they are removed from the outermost 5. Shapes of transition metal complexes
orbital first. The 4s electrons are removed before the 3d electrons, despite Most complex ions have 6 ligands surrounding the central metal ion, so the
most common shape is octahedral.
3d 4s
Some complexes have fewer ligand bonds, and therefore different shapes.
Ni [Ar] Those complexes with 4 ligands will be tetrahedral or square planar, and
those with just 2 ligands will be linear in shape.

Candidates should be able to represent the shapes of complex ions in 3-D

Ni2+ [Ar] where appropriate.

For example: H2O

Sc3+ [Ar]
H 2O OH 2
the fact that when filling orbitals we fill the 4s before the 3d. Fe 3+
hexaaquairon(III) ions
H 2O OH 2
H 2O

1
Answering Questions on Transition Metals Chem Factsheet

6. Reactions of complex ions Worked example of reduction

Candidates should be aware that different ligands bind to transition metal Question: What effect would a solution of iron (II) ions have on an acidified
ions with different strengths. Simple substitution reactions (ligand exchange solution of sodium vanadate (V)?
reactions) will occur if a stronger binding ligand is introduced to a solution
of metal ions surrounded by weaker bound ligands. Answer: Iron (II), Fe2+, is a reducing agent. By using the anti-clockwise
rule, it can be seen that it is powerful enough to reduce vanadate (V) ions to
Candidates are expected to know the expected observations of the reactions the +4 oxidation state:
of transition metal ions with aqueous sodium hydroxide and aqueous
ammonia (Factsheet 46). Take time to learn about these tests, and be able Eê/V
to identify where deprotonation has taken place, and where ligand exchange Fe3+(aq) + e− ¾ Fe2+(aq) +0.77
has occurred.
VO2+(aq) + 2H+(aq) + e− ¾ VO2+(aq) + H2O(l) +1.00
7. The oxidation states of vanadium
Questions on the chemistry of vanadium are common. Already covered in anti-clockwise rule
Factsheet 46 are the reactions with zinc and potassium manganate (VII),
which are able to display all of vanadium’s common oxidation states and
the associated colours. On further examination of the Eê data, it can be seen that further reduction
of the VO2+ (oxidation state +4) is not possible with the Fe2+ ions.
Ion VO2+ VO2+ V3+ V2+
oxidation state +5 +4 +3 +2 Colour changes in this case may be difficult to observe, but candidates
colour yellow blue green lavender should recognise that the vanadium ions are going from yellow (+5) to blue
(+4), whist Fe2+ (green) changes to Fe3+ (brown).
reduction (zinc)
Eqn: VO2+(aq) + 2H+(aq) + Fe2+(aq) → VO2+(aq) + H2O(l) + Fe3+(aq)
oxidation (KMnO4)
Questions
Other reducing or oxidising agents can be used, but depending on their 1. Write out the electronic configuration of:
strength may not reduce the +5 state all the way to +2, or oxidise +2 all the (a) Cu atom.
way to +5.
(b) Cu2+ ion.
Given Eê data, candidates should be able to predict the effect of various
chemicals on the different oxidation states of vanadium. 2. Complete the following:
Reduction Half Equations 3d 4s
Eê/V Zn [Ar]
Zn2+(aq) + 2e− ¾ Zn(s) −0.76
V3+(aq) + e− ¾ V2+(aq) −0.26
SO42−(aq) + 4H+(aq) + 4e− ¾ H2SO3(aq) + H2O(l) +0.17 Explain why zinc is not a transition metal despite its position in the d-block.
VO2+(aq) + 2H+(aq) + e− ¾ V3+(aq) + H2O(l) +0.34
Fe3+(aq) + e− ¾ Fe2+(aq) +0.77 3. Name the following complex ions, and represent their shapes using 3-
VO2+(aq) + 2H+(aq) + e− ¾ VO2+(aq) + H2O(l) +1.00 D diagrams:
MnO4−(aq) + 8H+(aq) + 5e− ¾ 4H2O(l) + Mn2+ +1.51 (a) [Fe(H2O)6]2+
Candidates should be able to use the above data to predict equations, (b) [Cu(CN)4]2- (hint: not tetrahedral)
colour changes and so on.
4. A few drops of dilute sodium hydroxide is added to a solution of
Worked example of oxidation hexaaquachromium (III) ions.
Question: What effect would dilute sulphuric acid have on a solution of (a) Describe the product.
vanadium (II) ions?
(b) Write the equation for this reaction.
Answer: The sulphate ions present in the dilute sulphuric acid are oxidising
(c) What type of reaction has occured?
agents. By using the anti-clocwise rule it can be seen that they are powerful
enough to oxidise the V2+ to V3+ ions. (d) The product reacts further in excess NaOH(aq). Explain why.
Eê/V
V3+(aq) + e− ¾ V2+(aq) −0.26 5. A solution of hexaaquairon (III) ions reacts with the CN− ions in a
solution of potassium cyanide in a ligand exchange reaction.
SO42−(aq) + 4H+(aq) + 4e− ¾ H2SO3(aq) + H2O(l) +0.17 (a) Write an ionic equation for the reaction.

(b) Why does this reaction take place?

anti-clockwise rule 6. Zinc metal is added to an acidified solution of vanadate (IV), VO2+(aq), ions.
On further examination of the Eê data, it can be seen that further oxidation Describe the colour changes in the subsequent reactions.
of the V3+ ions is not possible with SO42− ions.

The colour change associated with this reaction will be the lavender of the
V(+2) solution to the green of the V(+3) solution.

Eqn: 4V2+(aq) + SO42−(aq) + 4H+(aq) → 4V3+(aq) + H2SO3(aq) + H2O(l)

2
Answering Questions on Transition Metals Chem Factsheet

Answers
1. (a) [Ar] 3d104s1

(b) [Ar] 3d9

2. 3d 4s
Zn [Ar]

Zinc is not a transition metal because it does not form any stable ions
which have an incomplete d-subshell of electrons.

3. (a) H2O H 2O 2+

H 2O OH 2 H2O OH 2
II
Fe 2+ or Fe
H2O OH 2 H 2O OH 2
H 2O H 2O

hexaaquairon(II) ions
(b)
2-
−
−
NC CN− NC CN−
II
Cu 2+ or Cu
− −
NC CN −
NC CN−

tetracyanocuprate (II) ion

4. (a) Green precipitate.

(b) [Cr(H2O)6]3+(aq) + 3OH−(aq) → Cr(OH)3(s) + 6H2O(l)

(c) Deprotonation

(d) Chromium hydroxide is amphoteric in nature, so reacts with a base.

5. (a) [Fe(H2O)6]3+(aq) + 6CN−(aq) → [Fe(CN)6]3−(aq) + 6H2O(l)

(b) The cyano ligand is a stronger binding ligand than the aqua ligand.

6. Zinc reduces the blue VO2+ ions (V+4) to green V3+ ions (V+3) and
then to lavender V2+ ions (V+2).

Acknowledgements:
This Factsheet was researched and written by Kieron Heath
Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham, B18 6NF
ChemistryFactsheets may be copied free of charge by teaching staff or students, provided that
their school is a registered subscriber.
No part of these Factsheets may be reproduced, stored in a retrieval system, or transmitted, in any
other form or by any other means, without the prior permission of the publisher. ISSN 1351-5136

3
 Chem Factsheet
January 2003 Number 48

Laboratory Chemistry - Organic Techniques

Before working through this Factsheet you should: 2. Distillation
• Have some practical experience in organic chemistry; Distillation can be used to isolate a liquid product if the boiling point of the
• Undersatnd the Organic Chemistry covered so far at AS and A2 (covered product is significantly different to that of the rest of the reaction mixture.
in Factsheets 15, 16, 17, 27, 31, 32, 33, 34, 35 and 39);
• Understand the laboratory techniques for separating and purifying Distillation is used to purify a liquid by boiling it and then condensing it
(covered in Factsheet 30). away from its impurities.

After working through this Factsheet you will:

• Have met and revised common practical techniques in organic chemistry;
• Be able to represent the relevant equipment with simple diagrams; Thermometer
• Be able to assess simple organic practicals in terms of safety.

As several of these techniques were discussed in detail in Factsheet 30, this

Factsheet is designed to be more of a focused revision aid. Thermometer pocket

It is necessary for candidates to display a familiarity with a variety of

practical techniques in organic chemistry when preparing for both written
exams and practical exams or assessment. Liebig condenser

1. Heating under reflux

Reflux apparatus are necessary when a reactant has a low boiling point, or water
the reaction is slow at room temperature. The condenser prevents the out
escape of any of the volatile reagent or product. water in
Heat
Receiver

Distillate
condenser
to sink
3. Fractional Distillation
Fractional distillation is most commonly used to separate two liquids if the
boiling points are quite close. Pure samples of each liquid can usually be
obtained, unless the boiling points are too close.

Thermometer
from tap

Thermometer pocket

reaction mixture Liebig condenser

to vacuum pump
water for distillation
Fractionating out
column water in under reduced
pressure
heat

Distillate

Distillation flask

Heat

1
Laboratory Chemistry - Organic Techniques Chem Factsheet

Candidates need to be familiar with the following types of graphs plotting 5. Recrystallisation
boiling points against composition. To purify the solid product.
A suitable solvent for recrystallisation will often be evident (e.g. the solvent
Chemical A must be separated from chemical B. Chemical A has a higher from which the crude product was initially crystallised), and should be a
boiling point than chemical B, so chemical B is a more volatile liquid. solvent which will not react with the solid. The solubility of the solid
should be high near the boiling point and low near room temperature.
Candidates should learn the method of recrystallisation.
Boiling
point A
• Dissolve the solid in the minimum volume of hot solvent.
T1 • Quickly filter the hot solution using preheated filter funnel and
T2 Boiling fluted filter paper.
point B • Collect the filtrate and allow to cool and the solid to recrystallise.
o
Temp. C • Use suction filtration (Buchner funnel) to collect the solid.
• Wash the solid with a small amount of cold solvent.
• Dry the solid product.

100% A composition 0% A 6. Melting Point Determination

0% B 100% B The melting point of a solid is used to judge the purity of the product. A
composition composition composition solid should have a sharp melting point, and recrystallisation should be
X Y Z repeated until this is obtained.

Consider a mixture of two chemicals A and B, of composition X. If it is Melting point should be determined using melting point apparatus.
heated it will boil at T1 oC to give a vapour of composition Y.

Note that Y is richer in the more volatile component than X. capillary tube thermometer
If Y is condensed and reboiled it will boil at a temperature T2oC, giving a
vapour of composition Z, where Z is richer in the more volatile component
B than Y was.
electrically
Eventually pure B will be distilled off from the top of the fractionating heated block
column and pure A will be left in the flask.

How the vapours are continuously condensed and reboiled will be discussed
in a later Factsheet, which will deal with the workings of fractional distillation
in even more detail.
illuminated
4. Filtration under reduced pressure cavity
To isolate a solid product from a liquid, suction filtration using a Buchner
(or Hirsch) Funnel is an effective method.

sample
Buchner funnel
and flask

The sample is placed in a capillary tube, and the temperature increased

slowly until it melts.
suction
Melting points can also be used for identification purposes.

7. Boiling point determination

Boiling points can also be used for identification purposes, and to check
the purity of a product. Boiling points are most commonly measured in the
process of distillation (see section 2).

A small amount of cold solvent should be used to wet the filter paper prior
to filtration, and to remove any solid remains from the reaction flask.

2
Laboratory Chemistry - Organic Techniques Chem Factsheet

8. Selecting an appropriate heat source

There are a variety of heat sources available in the laboratory, and heat is
often required for organic reactions to increase the rate of reaction or to
provide the activation energy to initiate the reaction.

Two things must be considered when selecting the type of heat source:
(a) The temperature or strength of heating required.
(b) Safety.

Consider the following options:

Bunsen burner
Direct, variable heat and accessible, but danger - do not use with flammable
reagents, solvents or products.

Electric heating mantle

No naked flame (so can be used with flammable chemicals), controllable
temperature, but a little cumbersome. Electricity, and necessary wiring,
obviously required.

Water bath
Useful when gentle heating required, as maximum temperature is that of
boiling water. Some water baths are electrically heated, whilst a simple
water bath is a beaker over a Bunsen flame, so candidates should be aware
if any flammable vapours may be produced.

organic chemial
water

heat

Oil bath
Same principle as water bath, but higher temperatures can be reached.
Take some time to reach required temperatures, and some time to cool
down again afterwards.

Exam Hint: - A note about safety during organic practicals.

Candidates should be able to make simple risk assessments
when it comes to practical work. A common type of exam question
will ask for safety precautions during a specified procedure. For
success in the exams and for your own personal safety, knowledge
of safe procedure is important.

It is assumed that students wear eye protection during practical

work, so the answer “wear goggles” will not suffice in response to
a question about safety.
Consider the following:
• Fume hoods should be used for all reactions involving toxic,
Acknowledgements:
irritant or carcinogenic chemicals.
• No naked flames should be used with flammable chemicals.
This Factsheet was researched and written by Kieron Heath
• The use of gloves is required when dealing with corrosive or Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham,
irritant chemicals such as concentrated acids. B18 6NF
ChemistryFactsheets may be copied free of charge by teaching staff or students,
provided that their school is a registered subscriber.
Use these ideas and common sense when answering questions about safety.
No part of these Factsheets may be reproduced, stored in a retrieval system, or
When carrying out practical procedures, be careful to follow the prescribed
transmitted, in any other form or by any other means, without the prior permission
method and pay attention to the risk assessment and safety notes.
of the publisher. ISSN 1351-5136
3
 Chem Factsheet
April 2003 Number 49
Rate Orders and Mechanisms of Chemical Reactions
Before working through this Factsheet you should:
• understand the principles of kinetics covered so far at AS and A2 ‘nucleophilic substitution’ reactions/mechanisms
(Factsheets 10, 43 and 44). Substitution - when an atom/group in a molecule is removed and then
• ensure you are fully competent in writing rate expressions and finding replaced by another atom/group. Basically – ‘swapping parts’.
orders of reactions. Nucleophile - ‘a donor of a lone pair of electrons’. Basically –
After working through this Factsheet you will be able to: ‘nucleophile’ means ‘positive liking’ (the nucleus is positive).
• identify the mechanism for the nucleophilic substitution of Nucleophiles are often (not always) negatively charged, so are attracted
halogenoalkanes by hydroxide ions from the rate expression and its order; to anions (+) or polarised atoms (δ+)
• write the two mechanisms for nucleophilic substitution and be able to Mechanisms - represents the movement of a pair of electrons when
explain how each type gives rise to its rate order; writing mechanisms.
• recognise which halogenoalkane is likely to undergo which type of mechanism;
• quote the Arrhenius Equation and explain its use in reaction kinetics. Cδ +—Brδ− shows Br is more electronegative than C so attracts the
electron bonding pair towards itself, hence producing a dipole (δ+/δ-)
and a polar bond.
Reaction kinetics
1. The balanced (stoichiometric) chemical equation can tell you nothing Homolytic fission of a covalent bond
about how fast or how slow (kinetics) the reaction will proceed – it
e.g. C—X → C!+ X! producing free radicals
has to be from experiments using the reactants.
(one electron to each atom)
2. The data from experiments is obtained by measuring the ‘initial
rate’ whilst varying the concentrations (mol dm-3) of the reactants. Heterolytic fission of a covalent bond
3. Only the reactants involved in the slowest step (the ‘rate determining e.g. C—X → C + + X − producing ions
step’) appear in the rate expression. (both electrons move to one of the two atoms).
4. The rate expression is of the form
Nucleophic substitution of halogenoalkanes and the order of reaction
rate = k × [A]a × [B]b When aqueous sodium hydroxide solution is added to a halogenoalkane a
nucleophilic substitution reaction takes place. The halogen atom (Cl/Br/I)
• k = rate constant is replaced by a hydroxide group (OH).
• a and b are called ‘orders’ CH 3 CH 3
• a + b = ‘overall order’ of the reaction
• the units of k need to be worked out for each expression H C Br + NaOH → H C OH + NaBr
(rate units = mol dm-3s-1, [ ] = mol dm-3)
CH 3 CH 3
sodium sodium
5. At A2 level ‘orders’ are 0,1 or 2 only. 2-bromopropane + → propan-2-ol +
hydroxide bromide
6. The Maxwell-Boltzmann curve shows that increasing the N.B. OH− is the nucleophile.
temperature speeds up the rate of reaction, not just because the
This reaction is written in its general form as:
number of collisions increase (particles moving faster) but more of
the particles have the minimum energy (activation energy = EA) to R  X + OH− → R  OH + X−
produce a reaction when they do collide. There are two ways in which this reaction could take place (the ‘mechanisms’).
Mechanism 1
H H This is heterolytic fission of
Exam Hint - The reason that this Factsheet concentrates only on First step: + − the C  X bond forming the
‘nucleophilic substitution of halogenoalkanes’ is because it is the quoted R C X → R C X carbocation and the halide ion.
example in A2 specifications. This is the SLOW STEP
H H
Beware – you may be presented with examples that do not look like
‘halogenoalkanes’ – remember they will always fit the principles shown Second step: H H The nucleophile (OH −)
in this Factsheet for halogenoalkanes for SN1 and SN2. + − forms a covalent bond with
R C OH → R C OH the carbocation by donating
Note SN1 = ‘substitution, nucleophilic, 1st order’
a lone pair of electrons.
SN2 = ‘substitution, nucleophilic, 2nd order’ H H This is the FAST STEP
Since the slowest step is the rate determining step, only the
halogenoalkane is involved in the rate expression. So it will be of the form:
rate k × [RCH2 – X]
This FIRST ORDER – so this mechanism is SN1

1
Rate Orders and Mechanisms of Chemical Reactions Chem Factsheet

The equation can be re-written as:

Mechanism 2
EA 1
lg k = lg A -
First step: H H X H 2.303R T

R C X → R C → R C OH This fits the equation for a straight line:

:OH −
OH H+ X
− y = c + mx
H H
If you plot lgk against 1 you will obtain a straight line with a negative
T
In this mechanism the nucleophile forms the covalent bond as the gradient.
lg k
heterolytic fission is taking place.

The transition state shows both the incoming OH and the leaving X ‘in lg A
contact’ with the carbon atom at one point in time.

The transition state is the rate determining step and since both the
halogenoalkane and the OH − are involved they appear in the rate expression.
So it will be of this form:
rate = k × [RCH2 – X] × [OH − ]
1
T
This is the SECOND ORDER - so the mechanism is SN2 - EA
gradient =
2.303R
SN1 - the mechanism is in TWO STEPS This enables you to calculate a value for EA.the activation energy.
- rate = k × [halogenoalkane]
Questions
SN2 - the mechanism involved a TRANSITION STAGE 1. The following data were obtained for the reaction:
- rate = k × [halogenoalkane] × [OH−]
R Br + OH− → R  OH + Br-
Exam Hint - Questions on this topic usually follow this format:
(a) using experimental data to write the rate expression Experiment Initial concentrations/mol dm-3 Initial rate/ mol dm-3s-1
(b) asking what the rate expression tells you about the mechanism RBr OH−
(c) asking you to draw and explain the mechanism 1 0.1 0.4 3.0 × 10-3
2 0.2 0.4 6.0 × 10-3
3 0.1 1.6 1.2 × 10-2
Which halogenoalkanes use which mechanism?
Primary Secondary Tertiary (a) What is the order of reaction with respect to
Halogenoalkanes Halogenoalkanes Halogenoalkanes (i) RBr?
H (ii) OH−?
R1 R1
(b) Write the rate expression for the reaction.
R C X R C X R C X
(c) Calculate the value of the rate constant.
H H R2
SN2 may be SN1 or SN2 SN1 (d) (i) What does the rate expression tell you about the mechanism of
or a mixture of both the reaction?
Remember this is a general rule – only the experimental data giving the (ii) Draw and explain the mechanism you stated in part (i).
order ensures which mechanism it will be. 2. The following data were obtained for the reaction:
NB. The choice of mechanism is decided by the stability of the R  I + OH− → R  OH + I−
carbocation.
Tertiary halogenoalkanes form more stable carbocations so Mechanism 1 Experiment Initial concentrations/mol dm-3 Initial rate/ mol dm-3s-1
where the carbocation is formed is the most likely for them. RI OH−
Primary halogenoalkanes usually go via the transition state because their 1 0.2 0.2 2.4 × 10-2
carbocations are less stable. 2 0.4 0.2 4.8 × 10-2
3 0.2 0.4 2.4 × 10-2
The Arrhenius Equation
At this level you need to know that following facts: (a) What is the order of reaction with respect to
Increasing the temperature increased the rate of reaction by increasing (i) RI?
the rate constant: (ii) OH−?

k = rate constant (b) Write the rate expression for the reaction.
EA = activation energy
−
EA
(c) Calculate the value of the rate constant.
k = Ae RT T = temperature in degrees Kelvin (273 + oC)
R = the gas constant (8.31 JK-1 mol-1)
(d) (i) What does the rate expression tell you about the mechanism of
A = a constant
the reaction?
e = a number that goes on for ever (like π)
(ii) Draw and explain the mechanism you stated in part (i).
It is about 2.72

2
Rate Orders and Mechanisms of Chemical Reactions Chem Factsheet

Answers
1. (a) (i) 1
(ii) 1
(b) rate = k × [RBr] × [OH−]
(c) 0.075 mol-1 dm3s-1

(d) (i) Because it is 2nd order overall it must go via a mechanism

involving a transition state i.e. both RBr and OH− are in the
rate determining step.
(ii) R  Br → R Br → R  OH + Br−
−
:OH
OH

As the OH− (nucleophile) donates a lone pair the Br comes

away through heterolytic fission. At a moment in time both
will be in contact with the carbon atom so forming the transition
state.

2. (a) (i) 1
(ii) 0
(b) rate = k × [RI]
(c) 0.12 s-1
(d) (i) Only RI appears in the rate expression so only RI is in the rate
determining step.
This means that it is a 2 step mechanism.
(ii) R  I → R + + I −  SLOW
(formation of the carbocations by heterolytic fission)
This is the rate determining step.

R + → R  OH  FAST

OH −
(nucleophile donating a lone pair of electrons to form a covalent
bond).

Acknowledgements:
This Factsheet was researched and written by Sam Goodman
Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham,
B18 6NF
ChemistryFactsheets may be copied free of charge by teaching staff or students,
provided that their school is a registered subscriber.
No part of these Factsheets may be reproduced, stored in a retrieval system, or
transmitted, in any other form or by any other means, without the prior permission
of the publisher. ISSN 1351-5136
3
 Chem Factsheet
April 2003 Number 50

Redox Equilibria III - Applications

Before working through this Factsheet you should ensure you understand The topics are in most other A2 textbooks – which you could (and should)
the redox equilibria covered so far at AS and A2 in Factsheets: use in conjunction with the Factsheet to help you gain a full understanding
• No. 9 (Equilibrium) – use of the ¾ sign. of the work.
• No. 37 (Redox Equilibria (I)) - cells and standard electrode potentials (E ê)
• No. 45 (Redox Equilibria (II) – using E êvalues to predict if reactions The presentation of these topics is designed to be a logical progression
will take place. from the other Factsheets already mentioned.

After working through this Factsheet you will: 1. Corrosion/rusting - its causes and prevention
• have met the concept of ‘corrosion/rusting’ and be able to explain the
processes involved using the Eê values and equilibrium processes Definitions
• have met the concept of ‘storage cells’ and seen it applied to the lead • Corrosion is when a metal is converted into its ions (forming a
acid battery (accumulator) as the specific example. compound). e.g. M(s) → M2+(aq) + 2e
• This process is OXIDATION (oxidation state change from O → + 2
Exam Hint:- In this area of the A2 specification you need to learn the
basic facts and equations so you can answer questions on the topic. • When iron undergoes this change it is called RUSTING.
There is no shortcut to learning thoroughly the information given!
• Corrosion/rusting is an ELECTROLYTIC PROCESS because
electron transfer is involved.

Rusting
Overall:
iron + water + oxygen → Fe2O3. x H2O (rust)

Air
1.
Even the smoothest-looking piece of iron has small pits or pieces of impurities on its surface.
Iron These cause small variations in the electrode potential of the iron when water comes into contact
with it.

Air
water
2.
Fe2+(aq)
At the anode area (+) the iron atoms dissolve to form iron ions (OXIDATION).
Anode Fe(s) → Fe2+(aq) + 2e−
e− area e−

O2(g)
3. 2+
Fe (aq) O2(g) The electrons travel through the iron to where oxygen and water meet the iron – the cathode area (-).
Hydroxide ions are formed
e− cathode
e− area ½O2(g) + H2O(l) + 2e− → 2OH−(aq)

4.
Fe(OH)2(s)
The Fe2+ ions react with the OH− ions to form a precipitate of iron (II) hydroxide.
Fe2+(aq) + 2OH−(aq) → Fe(OH)2(s)

At the surface of the water more oxygen converts the iron (II) hydroxide to brown iron (III) oxide.

5. 2Fe(OH)2(s) + ½ O2(g) → Fe2O3(s) + 2H2O(l)

(brown ‘rust’)

1
Redox Equilibria III: Applications Chem Factsheet

Questions
Methods of preventing rusting
1. State what is meant by corrosion of a metal
1. Barrier methods - Painting or greasing to prevent air/water reaching
the surface of the iron.
2. Galvanised iron consists of of iron covered by a layer of zinc. Even if
2. Sacrificial Protection - In this case the iron is covered by a layer the zinc is scratched, and the iron is exposed to the air, it does not rust.
of zinc (this is called GALVANISING). (a) Use the data below to explain why
When the zinc is scratched and the iron beneath exposed to air and
(b) Comment on the use of tin-plated iron cans for food
water, the iron does not rust. This is because of the standard
Zn2+ + 2e− ¾ Zn E ê = - 0.76 V
electrode potentials:
Sn2+ + 2e− ¾ Sn E ê = - 0.14 V
Fe ¾ Fe2+ + 2e− E ê = + 0.44 Volts Fe2+ + 2e− ¾ Fe E ê = - 0.44 V
Zn ¾ Zn2+ + 2e− E ê = + 0.76 Volts
3. The NiCad cell has overall cell reaction when discharged
Applying the anti-clockwise rule (‘bottom left’ i.e. Zn, with ‘top
right’ i.e. Fe2+) gives the reaction, NiO(OH)(s) + Cd(s) + 2H2O(l) → 2Ni(OH)2(s) + Cd(OH)2(s)
Zn + Fe → Zn + Fe
2+ 2+
State the substance forming the cathode, explaining your choice.
Note Zn that is oxidised i.e. corroded, not the iron.
The zinc has been ‘sacrificed’ to protect the iron. Answers
1. When a metal is converted into its ions/oxidised.
3. Tin Plating - ‘Tin cans’ for foodstuffs are made of iron covered by
2. (a) Considering the cell is made from zinc and iron we have:
a layer of tin.
Zn as the reacting agent Zn → Zn2+ + 2e−
Look at the standard electrode potentials:
Sn ¾ Sn2+ + 2e- E ê = +0.14 Volts Fe as the oxidising agent Fe2+ + 2e− → Fe
Fe ¾ Fe2+ + 2e- E ê = +0.44 Volts So overall Zn + Fe2+ → Zn2+ + Fe
so zinc is corroded, not iron
If the tin coating is scratched to expose the iron,
Fe + Sn2+ → Sn + Fe2+ ie. the iron is oxidised ie. rusts. (b) Since its Eê value is less negative, tin will not be corroded in
so don’t buy tins of food which are dented, the iron rusts so the preference to iron, so exposed iron will not be protected. So scratched
food will not keep! tin cans may rust.
3. Cadmium (Cd) because it is oxidised 0 → +2
Remember - ‘tin plating’is a barrier method (not sacrificial
protection).

2. Storage cells
Definitions
Cells or ‘batteries’ turn chemical energy → electrical energy.
There are two types:
(1) Disposable i.e. when the chemical reaction is over they have to be
replaced - these are based on non-reversable reactions.
(2) Rechargeable – these are called STORAGE CELLS.
In storage cells:
(a) the reactions involved in discharging and charging up the cell
must be fully reversible.
(b) the chemicals produced by the redox reactions must be insoluble.

The lead acid battery (accumulator)

The lead acid battery is the type used in motor vehicles. It continually
discharges (chemical energy → electrical energy) and is continually charged
up by the alternator (electrical energy → chemical energy).

Three are two redox reactions involved:

Pb(s) + SO42−(aq) ¾ PbSO4 + 2e− E ê = +0.36 V
PbSO4(s) + 2H2O(l) ¾ PbO2(s) + SO (aq) + 4H (aq) + 2e
4
2− + −
E ê= +1.69 V

Applying the anti-clockwise rule: Acknowledgements:

This Factsheet was researched and written by Sam Goodman
2PbSO4 + 2H2O → PbO2 + 2SO42− + Pb + 4H+ Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham,
This is the process of charging up. B18 6NF
Note the Pb disproportionates; it is both oxidised (+2 → +4) and reduced ChemistryFactsheets may be copied free of charge by teaching staff or students,
(+2 → 0) provided that their school is a registered subscriber.
No part of these Factsheets may be reproduced, stored in a retrieval system, or
In discharging, the reaction is reversed: transmitted, in any other form or by any other means, without the prior permission
PbO2 + 2SO42− + Pb + 4H+ → 2PbSO4 + 2H2O of the publisher. ISSN 1351-5136
2
 Chem Factsheet
April 2003 Number 51

Redox Equilibria IV - Redox Titrations

Before working through this Factsheet you should:
Exam Hint: - At A2 level you need to learn some of the specific half-
• Understand and be confident with titration calculations and using Eê
equations relevant to redox titrations – THESE HAVE BEEN MARKED
values (Factsheets No.23 and No. 45).
FOR YOU IN THIS FACTSHEET.
After working through this Factsheet you will:
• have met the specific reactions of potassium manganate (VII) and However, it would be a mistake to try to learn all the titration equations
sodium thiosulphate/iodine (which are the quoted examples for redox – you need to use the METHOD for working out the full equation using:
titrations); (a) Eê values and the anti-clockwise rule,
• be able to use the anti-clockwise rule and the ‘balancing equations (b) balancing equations using the ‘electron method’.
using electrons’ method to write titration reactions from half-equations;
• have revised the method for calculations involving titrations. Before we look at this ‘standardisation process’ we need to remind ourselves
of the TITRATION CALCULATION METHOD:
1) Potassium manganate(VII) titrations (1) The balanced chemical equation tells us the ratio of the species
N.B. Used to be called ‘potassium permanganate’. reacting together in the titration.
Potassium manganate (VII) is usually found in laboratories as purple (2) The following equations are used:
crystals which are then dissolved in water to form the solutions used in volume (cm3)
titrations. moles = × M(mol dm-3)
1000
The solution is a dark purple colour and is a strong oxidising agent.
However, if it is not acidified (with dilute sulphuric acid) it produces a grams mass of pure × 100
moles = % purity =
brown precipitate of MnO2 which makes accurate titrations impossible Ar/Mr mass of impure
(you cannot see the end-point).

You must learn this half equation Let’s see the method being used in the following two examples:
MnO4−(aq) + 8H+(aq) + 5e− → Mn2+(aq) + 4H2O(l)
Example 1
25.0cm3 of sodium ethanedioate solution (concentration of 0.20 mol dm-3)
Note the following points about the half-equation: was warmed and titrated with potassium manganate (VII) solution.
(a) MnO4− is the ion in KMnO4, potassium manganate(VII), which is purple. 19.60cm3 of the managate solution was required.
(b) In MnO4− the Mn has oxidation number = +7 (O = -2).
(c) 5e− are involved – this will be the number when we are balancing half- Calculate the concentration of the potassium managante (VII) solution.
equations to give the full equation.
Answer Explanation
(d) The Mn in MnO4− is REDUCED to Mn2+ (O.N. = +2) because it is
(a) MnO4− + 8H+ + 5e− → Mn2+ + 4H2O (x2) First find full equation
the OXIDISING AGENT.
C2O42− → 2CO2 + 2e− (×5)
N.B. Mn2+(aq) is faintly pink in colour but at the concentrations used in 2 MnO4− + 16H+ + 10e− → 2 Mn2+ + 8H2O
the titrations the solution appears colourless. 5 C2O42− → 10 CO2 + 10e−
_________________________________________________________________
In potassium manganate(VII) titrations there is no indicator added
2MnO4− + 16H+ + 5 C2O42− → 2Mn2- + 10CO2 + 8H2O
because the KMnO4 acts as a self-indicator.
___________________________________________
In the titration the purple KMnO4 solution is in the burette and as it is Use equation to find
i.e. 2MnO4− ≡ 5C2O42− ratio of reactants
added to the solution in the conical flask the purple colour is ‘absorbed’.
At the end-point one drop of KMnO4 solutions produces a pale pink 25 cm3
colour in the flask (a very slight excess of the KMnO4 solution). (b) Moles of Na2C2O4 = × 0.20 = 0.005 Moles = × M
1000 1000
Standardising potassium manganate (VII) solution 2
A ‘standardised solution’ is one whose concentration (mol dm-3) is known (c) Moles of KMnO4 = 0.005 × = 0.002 ratio is 2:5
5
accurately by titrating it against an accurately made-up solution.
0.002 × 1000 moles × 1000
KMnO4(aq) is standardised by titrating it with (d) Concentration = M =
19.60 cm3
sodium ethanedioate, Na2C2O4, solution. = 0.102 mol dm-3

You must learn this half equation

C2O42−(aq) → 2CO2(g) + 2e−

1
Redox Equilibria IV: Redox Titrations Chem Factsheet

Example 2 Example 4
A piece of iron weighs 0.368g. It is reacted with acid to dissolve it and then 5.65g of a copper (II) salt is dissolved in water and made-up to 250cm3. A
reduced to form Fe2+ ions. The resulting solution was titrated with potassium 25.0cm3 sample of solution is added to an excess of potassium iodide, KI.
maganate(VII) solution. 38.60cm3 of 0.02 potassium manganate (VII) The iodine formed by the reaction required 21.0cm3 of a 0.10 mol dm-3
solution were required. solution of sodium thiosulphate for its reduction.
What is the percentage purity of the iron? What is the percentage by mass of copper in the salt?
(Fe2+ → Fe3+ + e-)
Answer Explanation
Answer Explanation (a) 2Cu2+ + 4I- → Cu2I2 + I2 Reacting ratio.
(a) MnO4− + 8H+ + 5e → Mn2+ + 4H2O Finding the full so 2Cu2+ ≡ 1I2
Fe2+ → Fe3+ + e- (×5) equation by the
'balancing electrons' (b) 2S2O32- + I2 → S4O62- + 2I− Reacting ratio
MnO4− + 5Fe2+ + 58H+ → Mn2+ + 4H2O + 5Fe3+ method. so 2S2O32- ≡ 1I2
MnO4− ≡ 5Fe2+ Gives the RATIO of (c) Cu2+ ≡ S2O32- Combing (a) + (b) to
reactants. find thiosulphate to
38.6 × 0.02 cm3 copper ratio.
(b) Moles of MnO4− = = 0.000772 Moles = × M
1000 1000
21.0 cm3
(c) Moles Fe2+ = 0.000772 × 5 = 0.00386 ratio is 1:5 (d) Moles S2O32- = × 0.10 = 0.002 Moles = ×M
1000 1000
(d) Mass Fe2+ = 56 × 0.00386 = 0.216g Mass = moles × Ar (e) Moles Cu2+
= 0.002 Ratio from (c)
moles × 1000 in 25cm3
0.216 × 100 M =
(e) Percentage purity = = 58.70% cm3
0.368 (f) Mass Cu2+ Mass = moles × Ar
= 0.002 x 63.5 = 0.127g
in 25cm3 Ar for Cu = 63.5
2. Sodium thiosulphate / iodine titrations (ions have some mass
Sodium thiosulphate, Na2S2O3, is a REDUCING AGENT and is used to as the element.)
titrate iodine, I2.
(g) Mass of Cu2+ = 1.27g 25 → 250
You must learn this half equation in original solution (× 10)
2S2O32− (aq) + I2 (aq) → S4O62− (aq) + 2I− (aq)
1.27 × 100
(h) % Cu2+ = = 22.48%
5.65
The reacting ratio is 2S2O3 2−
≡ 1I2
In these titrations: 3. Other redox titrations
(a) I− (aq) reacts with a particular chemical species and I2 is produced, Although potassium manganate (VII) and sodium thiosulphate/iodine
(b) The amount of I2 produced is found by titrating it with sodium titrations are the ones quoted in A2 syllabuses they may not be the only
thiosulphate, ones you are questioned about.
(c) The amount of the original species can be found by the ratios of the
two reactions. For example, potassium dichromate (VI) solution is another oxidising agent
used in redox titrations.
When I2(aq) is produced by a reaction it produces a BROWN/ORANGE
COLOUR in the solution. As sodium thiosulphate is added from the Cr2O72− (aq) + 14H+ (aq) + 6e− → 2Cr3+ (aq) + 7H2O (l)
burette the colour fades to a yellow colour and will eventually go
colourless. However, it is impossible to see when a very pale yellow Exam Hint: - As long as the question gives you the relevant half-equations
goes to colourless (the ‘one drop’ change at the end-point). e.g. for K2Cr2O7, it is exactly the same method as for potassium manganate (VII)
– it is the process that matters i.e. balancing the equations using ‘electrons’
When the pale yellow stage is reached STARCH SOLUTION is added to find the reacting ratio then using the titration calculation equations.
as an indicator – it produces a DARK BLUE / PURPLE COLOUR. At
the end-point one drop of thiosulphate changes the blue colour to colourless.
Note Factsheet 59 (Redox V: Answering questions on redox titrations) will
Example 3 go into more details of the calculations as well as practice questions.
3.22g of iodine and 7g of potassium iodide are dissolved in distilled water From this Factsheet you should concentrate on:
and made up to 250cm3. A 25.0cm3 portion of this solution required 19.0cm3
of sodium thiosulphate solution in a titration. 1. learning the relevant half-equations;
2. understanding the processes in manganate (VII) and thiosulphate/iodine
What is the concentration of the sodium thiosulphate solution? titrations;
Answer Explanation 3. familiarising yourself with the four examples of calculations given.
(a) Moles I2 3.22 I = 127
= = 0.0127
in 250 cm3 2 × 127 mass
moles =
Mr
(b) Moles I2 0.0127 250 → 25
= = 0.00127
in 25cm3 10
(c) 2S2O32- ≡ 1 I2 Ratio
Moles S2O32- = 0.00127 × 2 = 0.00254
0.00254 moles × 1000
(d) Concentration (m) = × 1000 M =
19 cm3
= 0.134 mol dm-3
2
Redox Equilibria IV: Redox Titrations Chem Factsheet

Questions Answers
1. 25 cm3 of sodium ethanedioate solution was warmed and titrated with 1. 2MnO4− + 16H+ + 5C2O42− → 2Mn2+ + 10CO2 + 8H2O
potasium manganate(VII) solution. 17.20 cm 3 of potassium 2MnO4 − : 5C2O42−
manganate(VII) solution of concentration 0.05 mol dm-3 were required.
17.20
moles of MnO4- = × 0.05 = 0.00086 moles
Calculate the concentration of the ethandioate solution. 1000
5
2. 4.30 g of hydrogen peroxide solution was acidified, then titrated with moles of C2O42− = × 0.00086 = 0.00215 moles
2
potassium manganate(VII) solution of concentration 0.3 mol dm-3.
21.80 cm3 of potassium manganate(VII) solution were required. 0.00215 × 1000
concentration = = 0.125 moles
17.20
Calculate the percentage by mass of hydrogen peroxide in the solution.
(5O2− → 5O2 + 10e−) 2. 2MnO4− + 16H+ + 5O2− → 2Mn2+ + 8H2O + 5O2
2MnO4− : 5O2−
3. A commercial medication contains potassium iodate. 1.20 g of the
21.80
medication were dissolved in water and made up to 250 cm3. A 25 cm3 moles of MnO4− = × 0.3 = 0.00654
sample was added to an excess of potassium iodide, KI. The iodine 1000
formed by the reaction required 19.6 cm3 of a 0.05 mol dm-3 solution of 5
moles of O2− = × 0.00654 = 0.01635
sodium thiosulphate for its reduction. 2
What is the percentage by mass of potassium iodate in the medication? mass of O2 = 0.01635 × (2 × 1 + 2 × 16) = 0.5559 g
(K = 39, I = 127, O = 16) percentage by mass = 12.9 %
IO3− + 6H+ + 5e− → ½I2 + 3H2O
3. IO3− + 6H+ + 5I− → 3I2 + 3H2O
I− → ½I2 + e−
1IO3− : 3I2
2S2O32− + I2 → S4O62− + 2I−
4. A student weighs out 8.02 g of an unknown iron(II) salt and dissolves it
2S2O32− : 1I2
in distilled water. The solution is acidfied, then made up to 250 cm3.
25 cm3 of this solution were titrated with potassium dichromate solution. So 6S2O32− : 3I2
16.8 cm3 of the 0.4 mol dm-3 dichromate solution were required. So 1IO3− : 6S2O32−
Find the percentage by mass of iron in the unknown salt. (Fe = 56) 19.6
moles S2O32− = × 0.05 = 0.00098
Fe2+ → Fe3+ + e− 1000
Cr2O72−(aq) + 14H+(aq) + 6e− → 2Cr3+(aq) + 7H2O(l)
1
moles IO3− in 250 cm3 = × 0.00098 = 0.0001633
3 6
5. 25 cm of liquid bleach, in which the active ingredient is NaClO, are
made up to 250 cm3 with distilled water. 25 cm3 of this solution were moles IO3− in 250 cm3 = 0.001633
added to an excess of potassium iodide. The iodine formed by this mass of KIO3 in 250 cm3 = 0.001633 (39 + 127 + 3 × 16) = 0.3495 g
reaction required 20.30 cm3 of a 0.02 mol dm−3 solution of sodium so percentage by mass in medication = 29 %
thiosulphate for its reduction.
4. 6Fe2+ + Cr2O72− + 14H+ → 6Fe3+ + 2Cr3+ + 7H2O
Find the concentration of ClO− ions in the bleach.
6Fe2+ : 1Cr2O72−
2H+ + ClO− + 2e− → H2O + Cl−
16.8
moles of Cr2O72− = × 0.4 = 0.00672
1000
moles of Fe2+in 25 cm3 = 6 × 0.00672 = 0.04032
moles of Fe2+ in 250 cm3 = 0.4032
mass of Fe = 0.032 × 56 = 2.25792 g
percentage of Fe = 28 %

5. 2I− + 2H+ + ClO− → I2 + H2O + Cl−

2S2O32− + I2 → S4O62− + 2I−

1ClO− : 1I2 1I2 : 2S2O32−

So 1ClO− : 2S2O32−
20.30
moles 2S2O32- = × 0.02 = 0.000406
1000

0.000406
moles ClO− in 25 cm3 = = 0.000203
2
moles ClO− in 250 cm3 = 0.00203
moles ClO− in 25cm3 bleach = 0.00203
1000
Acknowledgements: [ClO−] = 0.00203 × = 0.0812 mol dm−3
This Factsheet was researched and written by Sam Goodman
25
Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham, B18 6NF
ChemistryFactsheets may be copied free of charge by teaching staff or students, provided that
their school is a registered subscriber.
No part of these Factsheets may be reproduced, stored in a retrieval system, or transmitted, in any
other form or by any other means, without the prior permission of the publisher. ISSN 1351-5136

3
 Chem Factsheet
April 2003 Number 52
Reactions of Functional Groups - A Summary
To succeed in this topic you need to: Reactions of alkenes
• Be able to recall and write out the functional groups represented
in this Factsheet; CO2 + H2O
• Have a thorough knowledge of the organic reactions and their Alkane
conditions (described in the Organic Chemistry Factsheets to H2 O2
electrophilic heat Di-halogenoalkane
date 27, 31, 32, 33, 34 and 39); heat,
addition
• Recognise the summarised versions of the equations in this Ni catalyst halogen electrophilic
Alkenes addition
Factsheet and be able to write them out in full under exam
conditions.
alkaline hydrogen
KMnO4(aq) halide Halogenoalkane
After working through this Factsheet you will: Diol
• Have revised the organic chemistry reactions that candidates electrophilic
oxidation addition
are required to learn for AS and A2 Chemistry modules. electrophilic addition
• Have a reference paper as you start to work through questions
on organic pathways and synthesis.
Reactions of alcohols
This Factsheet is designed to be used as a revision aid as candidates set
about the sometimes daunting task of learning all of the organic reactions bromo-alkane
required by the A2 Chemistry course.
nucleophilic substitution
These spider diagrams represent the reactions in a summarised version, in chloro-alkane iodo-alkane
a visual fashion that suits many learners. They should be used in NaBr(s) +
nucleophilic H2SO 4(conc.) nucleophilic
conjunction with Factsheets 27, 31, 32, 33, 34 and 39, which show the substitution to make HBr
reactions in a more detailed format. substitution

A good way of using this Factsheet to revise effectively would be as

dry PCl5 P(s) + I2(s)
follows: to make PI 3
1. Pick a group to revise (e.g. alkanes).
2. Pick a member of that group at random (e.g. propane). halogenation
3. Use the spider diagram to help you write out balanced chemical
reactions, with conditions, for the organic chemical you have chosen.

(e.g.) Propane and oxygen (combustion)

heat
Alcohol
C3H8 + 5O2 3CO2 + 4H2O
dehydration
Propane and chlorine (free radical substitution) oxidation

uv light
C3H8 + Cl2 C3H7Cl + HCl
conc. H2SO4 heat to primary
170 o C alcohols
In an exam, candidates are required to apply their knowledge of organic secondary
reactions to a wide variety of compounds, so the more of these you do, the alcohols
better!
Cr2O72−(aq) H+(aq)
Reactions of alkanes alkene Cr2O72−(aq) H+(aq)

aldehyde ketone
Carbon Dioxide O2 halogen Halogeno
Alkanes further oxidation
+ Water heat UV Light alkane
free radical Cr2O72−(aq) H+(aq)
combustion
substitution

carboxylic
acid

1
Reactions of Functional Groups - A Summary Chem Factsheet

Fig. 3 Halogenoalkane reactions Ester Reactions

Nitrile Alcohol
Carboxylic acid H 2O H 2O Carboxylic acid
nucleophilic nucleophilic
KCN in + Ester +
substitution NaOH(aq) substitution
water/ethanol Alcohol Alcohol
heat under acid alkaline
heat under reflux conditions conditions
reflux
Halogenoalkane
KOH in
NH3 in
ethanol
ethanol heat under Acyl Chloride Reactions
heat
reflux
Amines Alkene
nucleophilic nucleophilic Carboxylic
substitution elimination acid Ester
nucleophilic nucleophilic
Grignard Reagents substitution substitution

Preparation H 2O alcohol
Mg turnings
Grignard Reagent
Halogenoalkane Acyl
Dry ether solvent
"R-MgHal"
Chloride
Boil under reflux addition
primary
Reactions amine NH3

Primary
Alcohol N-substituted Amide
nucleophilic Amide
addition / hydrolysis nucleophilic
nucleophilic
substitution
substitution

methanal,
CH2=O(g) then use Secondary
Alkane Reactions of Aldehydes
+ H2O(l) dilute acid Alcohol
nucleophilic for hydrolysis
substitution nucleophilic
addition / hydrolysis Primary
H 2O H+(aq) Alcohol
Hydroxy-nitrile
aldehyde (not methanal) compound reduction Primary
Grignard Reagent + H2O(l)
"R-MgHal" nucleophilic addition Alcohol
CO2 (g) reduction
NaBH4 in
+ H2O(l) ketone H+(aq) trace of ethanol
H+(aq) + H2O(l) HCN
KOH LiAlH4
in ether
Carboxylic Tertiary
Aldehydes
Acid Alcohol 2,4-DNP in Fehlings
ethanol solution
nucleophilic nucleophilic H2SO4 silver
addition / hydrolysis addition / hydrolysis nitrate in
warm
2,4-DNP ammonia
warm
Derivative solution
Carboxylic Acid Reactions Positive Fehlings
nucleophilic Test
Polyester addition then Positive Silver redox
elimination Mirror Test
nucleophilic substitution /
Ester polymerisation redox

nucleophilic
Alcohol
substitution Diacid LiAlH4 reduction
alcohol + H+(aq) then
Diol H+(aq)
boil under reflux
conc. H2SO4 LiAlH4 in
dry ether
Carboxylic
Na2CO3 Acid
or NaHCO 3 PCl5
dry
aqueous
Sodium Salt + Acyl Chloride
CO2 + H2O nucleophilic
neutralisation substitution

2
Reactions of Functional Groups - A Summary Chem Factsheet

Reactions of Aldehydes Reactions of Amino Acids

Secondary acid alkali

Alcohol Salt Amino Acids Salt
Hydroxy-nitrile
compound reduction Secondary neutralisation neutralisation

nucleophilic addition Alcohol

reduction Reactions of Phenol
NaBH4 in
trace of HCN ethanol
KOH LiAlH4 2,4,6-
in ether
Phenate ion tribromophenol
Ketones
neutralisation electrophilic substitution
-
2,4-DNP in OH (aq)
H2SO4 Br 2(aq)
Phenol
2,4-DNP
Derivative
acyl chloride,
nucleophilic addition then
in NaOH(aq)
elimination

Reactions of Amines Ester

nucleophilic substitution
Substituted
Salts Amides
Reactions of Benzene
nucleophilic addition / nucleophilic
neutralisation substitution
Bromobenzene
acid electrophilic substitution
acyl chloride
Amines Br2 Fe cat.
dry
primary amines + acyl chlorides
if monomers contain 2 amine
groups and 2 acyl chloride groups Benzene

50o C conc
H2SO4 Fe cat. dry
Polyamides HNO3 Br2
nucleophilic substitution
polymerisation
Nitrobenzene Alkylbenzene
electrophilic substitution electrophilic substitution
Reactions of Nitrites
Sn, in alkali
Carboxylic alkali acid Carboxylic conc. HCL, KMnO 4 heat under
Nitriles NaOH reflux
acid salt acid
heat under heat under
hydrolysis reflux reflux hydrolysis
LiAlH4 Phenylamine Benzocarboxylic
in ether reduction acid
oxidation
Amine HNO2
+
reduction HCl

Benzenediazonium
Reactions of Amides
ions

Br2(l) +
P4 O10 NaOH(aq) Amine +
Nitrile Amides Acknowledgements: This Factsheet was researched and written by Kieron Heath
warm warm CO2
Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham, B18 6NF
dehydration
hydrolysis ChemistryFactsheets may be copied free of charge by teaching staff or students, provided that
their school is a registered subscriber. No part of these Factsheets may be reproduced, stored
in a retrieval system, or transmitted, in any other form or by any other means, without the
prior permission of the publisher. ISSN 1351-5136

3
 Chem Factsheet
April 2003 Number 53

Answering Questions on Organic Synthesis

Before working through this Factsheet you should:
1) The first step in tackling these questions is to identify the functional
• Have a good knowledge of the organic chemistry covered at AS and A2
groups in the starting molecule and the target molecule.
level;
• Have a good knowledge and understanding of the reagents and conditions 2) The next step is to ‘count the carbons’ in the starting molecule and
required to interconvert organic functional groups; the target molecule.
• Have worked through the organic chemistry Factsheets.
If the length of the main carbon chain:
After working through this Factsheet you will: • Remains the same, look simply to interconvert functional
• Have been shown the two common types of organic synthesis groups.
questions. • Increases by one, look at the introducing a nitrile group (CN)
• Have more experience in answering questions on organic synthesis. within the reaction scheme.

You may find it useful to have Factsheet 52 ( reactions of funtional groups) • Increases by more than one, consider including a Grignard
besides you when you work through this Factsheet. reagent.
• Decreases by one, consider the use of the Hoffman degradation
There are two common types of exam questions on organic synthesis.
reaction, converting an amide to an amine.
Factsheet 35 has covered the first, more straightforward, style of question.
It involves the conversion of functional groups from one type to another.

For example, given the reaction scheme: Example 1

step 1 step 2 step 3 Devise a reaction scheme, involving more than one step, to convert:
CH3CH2CH2Cl CH3CH2CH2OH CH3CH2COOH CH3CH2COCl
CH3COCl → CH3CH2NH2
A B C D
The examiner may test candidates’ knowledge of organic reactions by • Recognise the functional groups here, and acyl chloride (ethanoyl
asking for reagents and conditions, or even equations. chloride) must be converted to a primary amine (ethanamine).
• There is no change in the carbon chain length (2 carbons).
Step 1: CH3CH2CH2Cl + NaOH → CH3CH2CH2OH + NaCl
Conditions: Aqueous, heat under reflux • Recalling the reactions of ethanoyl chloride (Factsheet 32) one of
the reactions involves introducing nitrogen:
Step 2: CH3CH2CH2OH + 2[O] → CH3CH2COOH + H2O CH3COCl + NH3 → CH3CONH2 + HCl
Conditions: K2Cr2O7, acidified with conc. H2SO4 Ethanamide
Conditions: Room temp, aqueous.
Step 3: CH3CH2COOH + PCl5 → CH3CH2COCl + HCl + POCl3
Conditions: Dry. • The reactions of the amides must now be considered (Factsheet 34).
The second, more difficult, style of organic synthesis question requires Degradation of the amide (reducing the number of carbons) is not
candidates to produce their own reaction scheme, or ‘flow chart’. required, so:
P4 O 10
Using the above example, candidates may be supplied with less information. CH3CONH2 CH3CN + H2O
For example, devise a reaction scheme involving several steps to convert Ethanenitrile
compound A to compound D: Conditions: Warm and distil off Ethanenitrile.

CH3 CH2 CH2 Cl → CH3CH2COCl • Now consider the reactions of the nitriles (Factsheet 34) and the
A D nitrile can be converted to the target molecule:
LiAlH 4
The steps required for this are outlined in the previous example, but here CH3CN + 4[H] CH3CH2NH2
candidates are required to produce their own flow chart. Ethanamine
Conditions: Dry ether solvent, addition of dilute acid.
Exam Hint : - To be successful in answering such questions, candidates:
• Require a thorough knowledge of the reactions of all the functional The reaction scheme is now complete, and all reagents, conditions and
groups. equations can be supplied as necessary.
• Should understand that an element of ‘trial and error’ may be
necessary. CH3COCl → CH3CONH2 → CH3CN → CH3CH2NH2
• Should understand that there may be more than one way to convert
the starting molecule to the target molecule, but should look for the
simplest route.

1
Answering Questions on Organic Synthesis Chem Factsheet

Example 2 Questions
Devise a reaction scheme, involving more than one step, to convert: Devise reaction schemes, including reagents and conditions for each step,
for the following conversions.
CH3COCl → CH3NH2
1. C2H5 OH → C2H5ONH2
• A similar example to the first, converting ethanoyl chloride to a
Ethanol Ethanamide
primary amine, but notice the length of the carbon chain has decreased
by one. Use of the degradation reaction should be suspected. CH 3
2. CH3
First introduce nitrogen as required:
→
CH3COCl + NH3 → CH3CONH2 + HCl NO 2
Ethanamide
Conditions: Room temp, aqueous. methylbenzene 4-nitrobenzene

• Then use the Hoffman degradation reaction (Factsheet 34) with the (HINT: Factsheet 39)
amide.
Answers
CH3CONH2 + Br2 + 2NaOH → CH3NH2 + CO2 + 2NaBr + H2O 1. Reaction scheme:
Conditions: Add Br2 (l) at room temp, then add conc NaOH and warm.
CH3CH2OH → CH3COOH → CH3COCl → CH3CONH2
The target molecule has been attained in two steps. The reaction scheme is:
K Cr 2O 7
Step 1: CH3CH2OH + 2[O] 2 CH3COOH + H2O
CH3COCl → CH3CONH2 → CH3NH2 Conditions: H+, heat under reflux.

Step 2: CH3COOH + PCl5 → CH3COCl + HCl + POCl3

Example 3
Conditions: Dry, room temp.
Devise a reaction scheme, involving more than one step, to convert:

CH3CH2Br → CH3CH2CHClCH3 Step 3: CH3COCl + NH3 → CH3CONH2 + HCl

Conditions: Aqueous, room temp.
• Conversion of bromoethane to 2-chlorobutane.
• Note that the carbon chain length has increased by 2, so suspect the 2. CH 3 COOH COOH
use of a Grignard reagent (Factsheet 31).
• Since the starting molecule is a halogenoalkene, formation of the → →
Grignard reagent should be the first step. NO 2
CH3CH2Br + Mg → CH3CH2MgBr Step 1: CH 3 COOH
KMnO4
Conditions: Heat under reflux, ether solvent. + H2 O
OH −
• Recalling reactions of Grignard reagents, a halogenoalkane cannot heat under reflux
be formed directly. Looking at where the Cl atom is to be placed in
the target molecule, on the second carbon, it would be logical to move COOH COOH
Step 2:
to a secondary alcohol next. conc. H2SO4
• The Grignard reagent must be reacted with ethanal to achieve the + H2 O
50 oC
desired 4 carbons in total. NO 2

CH3CH2MgBr + CH3CHO + H2O → CH3CH2CHOHCH3 + Mg(OH)Br

Conditions: Dry ether solvent, hydrolysis with dilute acid.

• Knowledge of the reactions of the alcohols (Factsheet 17) gives a

rout to the target molecule:

CH3CH2CHOHCH3 + PCl5 → CH3CH2CHClCH3 + HCl + POCl3

Conditions: Dry.

The reaction scheme, therefore:

CH3CH2Br → CH3CH2MgBr → CH3CH2CHOCH3 → CH3CH2CHClCH3

Acknowledgements:
As these examples illustrate, a thorough knowledge of the organic reactions This Factsheet was researched and written by Kieron Heath
covered in the AS and A2 courses are required. Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham,
B18 6NF
ChemistryFactsheets may be copied free of charge by teaching staff or students,
provided that their school is a registered subscriber.
No part of these Factsheets may be reproduced, stored in a retrieval system, or
transmitted, in any other form or by any other means, without the prior
permission of the publisher. ISSN 1351-5136

2
 Chem Factsheet
April 2003 Number 54

Organic Analysis I : Infrared Spectroscopy

Before working through this Factsheet you should: The amount of IR radiation absorbed at different wavelengths by the sample
• Have a good knowledge of the organic chemistry covered at AS and A2 level. chemical is compared with a blank sample cell and quoted as a percentage.
• Understand covalent bonding.
• Be able to recognise functional groups within organic structures. If a sample absorbs IR at a certain frequency and wavelength, the IR will
not pass through the compound to the detector, so a low transmittance %
After working through this Factsheet you will: will be recorded.
• Be able to interpret simple Infrared spectra.
• Have a basic understanding of how an infrared spectrometer works.
Spectra
The A2 syllabus requires candidates to be able to interpret simple infrared An example of an IR spectrum is shown below (fig 3).
spectra. At first glance this can appear to be a daunting task - the spectra
themselves look complex, and background reading about how the spectra Fig 3. Example of an IR spectrum
are produced can sometimes be confusing.
transmittance /%
Do not fear infrared spectra - they are a tool to help chemists determine the 100
structure of organic chemicals. With a little experience and use of any data
supplied in an exam paper, scoring marks on questions involving IR spectra
is not as difficult as it may seem. 80

In this Factsheet the workings of the infrared spectrometer will be briefly

outlined - look to a textbook for a more detailed description if you are 60
interested. The main focus of the Factsheet is to give candidates the
necessary experience of IR spectra, and the expertise to pick up some
40
valuable exam marks.

Introduction 20
Infra-red spectroscopy depends on the fact that infrared radiation is
absorbed by certain molecular bonds and causes them to vibrate vigorously.
These vibrations involve stretching or bending (Fig 1). 4000 3500 3000 2500 2000 1500 1000 500
wave number / cm-1
Fig 1. Symmetrical, asymmetrical, bending effects Note the axis labels:
• wavenumber (cm-1) (x-axis)
H H H H H H • transmittance (a percentage) (y-axis)
C C C
The wavenumber is related to the wavelength of the IR absorbed:

symmetrical asymmetrical bending or 1

Wavenumber =
stretching stretching scissoring Wavelength

The transmittance shows the percentage of the IR that passes through the
Different bonds absorb IR of different wavelengths and frequencies, e.g. sample cell - so the lower it is, the more is absorbed.
C=O absorbs IR of a different wavelength to O-H.
Here is a data table showing some different IR absorption ranges of different
By looking at the frequencies at which a substance absorbs IR radiation, bonds:
we can therefore gain an idea of the bonds in it.
Bond Wavenumber Range (cm-1)
The apparatus used in this form of analysis, an infrared spectrometer, is C-O 1000 - 1300
based on a split-beam mechanism (Fig 2). C=O 1650 - 1750
Fig 2. Infrared spectrometer C-H (alkanes) 2850 - 3000
C-H (alkenes) 3000 - 3100
Sample cell O-H 2500 - 3500 broad peaks due
N-H 3300 - 3500 to H-bonding
Light
source Such data was compiled by comparing the IR spectra of related compounds.
Beam split Note that bonds (such as C-H) will absorb slightly different wavelengths
Prism Control cell Detector for
beam comparison depending on the surrounding atoms. This means that it is impossible to
assign a precise wavenumber to a bond. Nevertheless, we can identify
bands or ranges corresponding to specific bonds, as shown in the data
table.
1
Organic Analysis I : Infrared Spectroscopy Chem Factsheet

For the following IR spectrum of an ‘unknown’ organic compound, we can Peak Assigned Bond
assign different absorption peaks to particular bonds (using the data table)
and gain some information about the content and structure of the sample 2500 - 3500 cm-1 Broad O-H peak, characteristic shape
compound (Fig 4). 1700 - 1750 C=O
1250 - 1300 C-O
Fig 4. IR spectrum of unknown organic compound
The spectrum is in fact that of ethanoic acid, so the above bonds are
transmittance /% present:
H
100 O
H C C
O H
80 H

Remember that assigning peaks in IR spectra is not an ‘exact science’,

60 instead careful use of a data table and common sense is required.

40 Exam Hint: Ignore ‘interference peaks’, or ‘weak absorption peaks’,

and focus on strong peaks where transmittance drops to below 70%.

20
Assign peaks for the following spectrum (Fig 7):
4000 3500 3000 2500 2000 1500 1000 500
Fig 7.
wave number / cm-1
transmittance /%
100
Peak Assigned Bond
3100 - 3500 cm-1 O-H
2800 - 3000 cm-1 C-H 80
1050 - 1100 cm-1 C-O
60
Note that this information alone does not tell us what the unknown chemical
is, but helps to build a picture. We now know the following about the
sample: 40
• Not a carbonyl or carboxylic acid (no C=O).
• Not an amine, amide or amino acid (no N-H). 20
• O-H, C-O and C-H bonds are present.

The spectrum is actually that of ethanol, so all of the above-deduced 4000 3500 3000 2500 2000 1500 1000 500
information is correct. wave number / cm-1

Exam Hint: Look at the shape of the broad O-H absorption peak - it is
very distinctive and easy to spot (now you know what you are looking for!). Peak Assigned bond
3300 - 3500 cm-1 Broad N-H peak, ‘double pronged’ shape
The peaks given by O-H and N-H are usually broad owing to 2800 - 3000 cm-1 C-H
hydrogen bonding.
There are no other significant peaks that correlate with the data table.

The spectrum is that of propyl amine

Now look at this next spectrum and ‘assign’ the major peaks:
H H H
H
transmittance /%
H C C C N
100 H
H H H

80 As mentioned above, the shapes of N-H peaks and O-H peaks are different,
so usually can be told apart despite them being in the same region of the
spectra. The O-H peaks are broader, whilst the N-H peaks are often
60
‘double-pronged’ in shape.

40 Exam Hint: IR spectra are commonly used in conjunction with other

organic analysis techniques, such as UV spectrometry, mass
spectrometry and NMR, to identify unknown compounds.
20
The interpretation of simple IR spectra often forms part of an exam
question, as knowledge of these other forms of organic analysis are
also required - see later Factsheets.
4000 3500 3000 2500 2000 1500 1000 500
wave number / cm-1

2
Organic Analysis I : Infrared Spectroscopy Chem Factsheet

Questions Answers
Assign the peaks to bonds in the following spectra. In the answers you
will simply be given the structure of the compound from which the spectrum 1.
was generated, but with a little thought you can check to see if you have H H
O
assigned the correct bonds!
H C C C
1. H H H
transmittance /%
2.
100 H
O
H C C
80
N H
H
60 H

3.
40 H H
H
H C C O
20 C C
H H H

4000 3500 3000 2500 2000 1500 1000 500 O H

-1
wave number / cm

2.
transmittance /%

100

80

60

40

20

4000 3500 3000 2500 2000 1500 1000 500

wave number / cm-1

3.
transmittance /%
100

80

60

40

Acknowledgements:
20 This Factsheet was researched and written by Kieron Heath
Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham,
4000 3500 3000 2500 2000 1500 1000 500 B18 6NF
wave number / cm-1 ChemistryFactsheets may be copied free of charge by teaching staff or students,
provided that their school is a registered subscriber.
No part of these Factsheets may be reproduced, stored in a retrieval system, or
transmitted, in any other form or by any other means, without the prior permission
of the publisher. ISSN 1351-5136
3
 Chem Factsheet
www.curriculumpress.co.uk Number 55
Organic Analysis II- Mass Spectroscopy
Before reading through this Factsheet you should: Mass spectrometer traces (Fig 2) are used to identify atomic masses of any
• Have a good understanding of Atomic Structure (Factsheet 01); isotopes present and to provide the information to calculate relative atomic
• Have a basic understanding of the way in which a mass spectrometer mass.
works;
Note the axis labels:
• Have a good knowledge of the Organic Chemistry covered at AS and
• Relative abundance
A2 level;
• Mass/Charge ratio (or m/e)
• Understand covalent bonding and molecular structure (Factsheets 05
and 06). The relative abundance is self explanatory − the more common a particular
mass of particle, the higher the peak. Usually the highest peak (base
After working through this Factsheet you will be able to: peak) is given a value of 100, with the other peaks scaled accordingly.
• Interpret simple mass spectra;
An understanding of the mass/charge ratio is important. After electron
• Recognise mass spectra as useful tools in organic analysis.
bombardment, the majority of the ions formed have a +1 charge as just one
electron is removed.
Before we discuss the role of mass spectra in organic analysis, candidates
should remind themselves of the simplified appearance of a mass If the ion has a +1 charge then the mass/charge ratio is the
spectrometer (as shown below) and how the machine works. same as the mass.
23
e.g. Na+ m/e = 23/1 = 23
Fig 1. Mass Spectrometer
If a higher number of electrons are removed from a species, a different
+ peak will be generated on the spectrum.
1. 123456789012345
123456789012345 23
3. 123456789012345 e.g. Na2+ m/e = 23/2 = 11.5
123456789012345
123456789012345
123456789012345 However, it is worth reinforcing that the vast majority of ions formed
123456789012345
4.
○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○

123456789012345
12345678 have a +1 charge.
12345678
123456789012345
123456789012345
12345678
12345678
123456789012345
2. 123456789012345
12345678 Mass Spectra in Organic Analysis.
12345678
123456789012345
123456789012345
1. vaporisation
12345678
12345678
123456789012345 Mass spectra, like infrared spectra (Factsheet 54 Organic analysis I- Infrared
2. ionisation
To 123456789012345
12345678 Spectroscopy), are a useful tool in identifying organic molecules. The aim
vacuum pump
○

3. acceleration of this Factsheet is to give candidates the necessary experience in interpreting

○

(by electric field) mass spectra to be able to extract the relevant information from them. This
○

4. deflection information is likely to be used in conjunction with other data to identify

○

5.
5
(by magnetic field)
○

chemicals. In exam questions the mass spectrum of an unknown organic

5. detection compound is often supplied with the IR spectrum and results from chemical
tests. The skill of the analytical chemist is to piece together all of the
information.
The five stages listed on the above diagram are discussed in more detail in
Factsheet 01 – Atomic Structure. Exam Hint: Candidates should be aware that exam questions at A2
level may test knowledge and understanding of how mass spectra are
generated.
Examples of mass spectra observed at AS level will include those of
simple elements.

Fig 2. Mass spectrometer traces

Sodium Iron
100
(91.68%)
(100 %)
Relative Abundance / %

Relative Abundance / %

100
sodium (Na)
80

60 50

40

20 (2.17%)
(5.84%) (0.31%)
0 0
0 10 20 30 40 70 80 20 30 40 50 60 70 80
Mass / Charge Ratio Mass / Charge Ratio

1
55 - Organic Analysis II- Mass Spectroscopy Chem Factsheet

When an organic compound is placed into the mass spectrometer for There will be a variety of fragments formed from an organic compound, as
analysis, the initial reaction is for an electron to be removed – ionisation. each molecule can be fragmented in a variety of ways.
electron bombardment e.g. Some possible fragments of methane, CH4
M M+ + e-
Fragment m/e
M+ can be described as the molecular ion or the parent ion.
+
It is rare that the molecular ion is undetectable on a mass spectrum. CH4 16
CH3+ 15
+
Exam Hint: - When a candidate is presented with a mass spectrum, CH2 14
the first task should be to locate the peak associated with the molecular CH+ 13
ion. This will be the peak of significant relative abundance which has +
the largest mass/charge ratio. From this the relative molecular mass C 12
of the compound can be deduced. H+ 1

Some fragments will be more stable and therefore more likely to occur than
relative abundance /% others, hence different heights of relative abundance peaks are observed.
[43] CH3CH3CH2+
100
By assigning fragments to peaks on a spectrum, valuable information about
the structure of a molecule can be gained.

The assigning of peaks can be something of a ‘numbers game’ using relative

atomic masses, but bearing in mind that mass spectra are usually supplied
with other analysis data this is not a difficult task.
50 [29] CH3CH2+
The following data may be useful when assigning fragments to peaks on a
mass spectrum; these are examples of commonly occurring fragments:

[15] CH3+ parent ion [58] Fragment m/e

+
CH 3 15
0
0 10 20 30 40 50 60 CH3CH2+ or CHO+ 29
CH 2NH2 + 30
The RMM of the compound is 58 CH 2OH + 31
CH3CO+ or CH3CHCH3+ or CH3CH2CH2+ 43
relative abundance /% CONH2 + 44
[55] CH2CCH2CH3+
100 COOH+ or CH3CHOH+ 45
[69] CH2C(CH2CH3)CH2+
[41] CCH2CH3+ C 6H5+ 77
C 6H5 CH2+ 91
C6H 5CO+ 105
[29] CH3CH2+
50 [84] parent ion
The reason that these fragments are more common is that they are relatively
stable. This is well illustrated if we look at the mass spectrum and structure
of benzenecarboxylic acid: O
C
O H

relative abundance /% C6H5CO+ [105] [122] parent ion

0
0 10 20 30 40 50 60 70 80 90 100 100
[77] C6H5+
The RMM of the compound is 84

Candidates should be aware that there is the possibility of small, low

relative abundance peaks further up the spectrum than the peak for the
molecular ion. These peaks are due to the occasional presence of heavy 50
isotopes of elements (e.g. 14C, 18O, 2H) which can occur in organic molecules.
These peaks can be ignored.

When an organic compound is ionised by electron bombardment in the

mass spectrometer, not all of the molecular ions survive. Often the molecular
ions are broken up into smaller pieces by a process called fragmentation. 0
20 30 40 50 60 70 80 90 100 110 120 130
+
electron bombardment + .
e.g. CH3CH 3
CH 3
+ CH3
fragment ion radical by-product Note the large peaks at 77 (C6H5+) and 105 (C6H5CO+). The benzene ring
is especially stable due to the delocalised system of electrons, so it is
The fragment ions are detected and are responsible for all of the other unlikely to be fragmented. Consequently, if an analytical chemist observes
peaks on a mass spectrum. a peak at 77, the presence of a benzene ring is strongly suggested.
2
55 - Organic Analysis II- Mass Spectroscopy Chem Factsheet

For the worked examples and questions in this Factsheet, use the following Worked Example
data to help you. The following are mass spectra of simple alcohols.

Fragment m/e relative abundance /%

Spectrum A
[31] CH 2OH+
100
CH3 + 15
CH3CH2+ or CHO+ 29
CH2 NH2+ 30
CH2OH + 31
CH3CO+ or CH3CHCH3+ or CH3CH2CH2+ 43
50
CONH2+ 44
COOH+ or CH3CHOH+ 45
C 6H 5 + 77
C 6H5 CH2+ 91 [60] parent ion
C6H5CO + 105
0
10 20 30 40 50 60 70 80
Worked Example relative abundance /% Spectrum B
The following mass spectrum is of a hydrocarbon which does not react
[45] CH3CHOH+
with bromine water. 100

relative abundance /%

50

[60] parent ion

0
10 20 30 50 60 70 80
m/e
29 43 57 71 85 114 It can be seen from the spectra that both alcohols have relative molecular
masses of 60 (they are isomers).
• The first task is to use the molecular ion peak to give the relative
molecular mass, 114. The formulae of the molecular ions can then be ‘suggested’. Knowing
• The fact that the compound is a hydrocarbon which does not react that we are dealing with alcohols, the following elements will be present:
with bromine water suggests an alkane.
• Alkanes general formula is CnH2n+2, where the atomic masses are Element Atomic Mass
C=12 and H=1. C 12
• Hence suggested formula for the compound is: C8H18 H 1
O 16
The fragment peaks can be assigned as follows:
Knowledge of the general formula of the homologous series (CnH2n+1OH),
Fragment m/e chemistry ‘common sense’ and being aware that the RMM is 60 suggests
that the formula of each molecular ion will be: C3H8O+, as
C 2H 5 + 29
C 3H 7 +
43 (3×12) + (8×1) + (1×16) = 60.
C 4H 9 + 57 By now looking at fragments within each spectrum, some structural
C 5H 11 +
71 information can also be gained:
C 6H 13+ 85 In spectrum A the base peak is at m/e = 31. This could be due to the
presence of the CH2OH+ fragment. This fragment can only come from a
Note that suggesting a name for the compound is not straightforward, as primary alcohol:
it would be difficult to tell whether this is the mass spectrum of octane or .
an isomer, for example 3,4-dimethylhexane. e.g. R-CH2-OH fragmenting to give R and CH2OH+.

In spectrum B the base peak is at m/e = 45. This could be due to the
presence of the CH3CHOH+ fragment. This fragment can only come
Every species detected by a mass spectrometer is a positive ion. from a secondary alcohol:
Ensure that you always remember to include the + charge when writing .
the formula of a molecular ion or fragment. e.g. CH3-CHOH-R fragmenting to give R and CH3CHOH+.

These deductions are correct, as spectrum A is that of propan-1-ol

(CH3CH2OH) and spectrum B is that of propan-2-ol (CH3CHOHCH3).

3
55 - Organic Anaylysis II- Mass Spectroscopy Chem Factsheet

Practice Questions Answers

1. (a) 120
1. The mass spectrum of a liquid is given. The liquid is known to be an (b) C 8H 8 O
aromatic ketone with percentage composition C 80%, H 6.7%, O 13.3%. (c) Use information given from fragment peaks, e.g. peak at 77 suggests
presence of benzene ring, peak at 43 could be due to CH3CO+.
relative abundance /%
CH 3
C
O

Suggested formula (with RMM=120):

(d)
+
C or C6H5CO+
O

m/e
43 51 77 105 120 2. (a) C4H4O
(b) C8H8O2 (as RMM = 136, deduced from spectra).
(a) Use the mass spectrum to determine the relative molecular mass of (c)
the compound. m/e Fragment formula
(b) Combine this information with the percentage composition to 136 C 8H 8O 2 +
deduce the molecular formula. 105 C 7H 5O +
(c) Suggest a structure for the molecule. 91 C 7H7+
(d) What fragment is responsible for the peak at m/e 105? 77 C 6H5+

2. Two organic compounds, A and B are isomers with percentage (d)

composition C 70.5%, H 5.9%, O 23.6%.
A is moderately soluble in water, forming a solution of pH 5. O
CH 2 C
B is a pleasant smelling liquid. OH

(a) What is the empirical formula of A and B?

O
mass spectrum of compound A
100 C
90 138 O CH 3
80
70
relative abundance

60
50 65
40
30 39
20 45 51
10 77
28
0
20 40 60 80 100 120 140 m/e

mass spectrum of compound B

100 105
90
80 77
70
relative abundance

60 28
50
40
30 51 136
20 32
10 39
0
20 40 60 80 100 120 140 m/e Acknowledgements: This Factsheet was researched and written by Kieron
Heath. Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham,
B18 6NF. ChemistryFactsheets may be copied free of charge by teaching staff
(b) What is the molecular formula of A and B?
or students, provided that their school is a registered subscriber. No part of
(c) Give the formulae of the molecular fragments corresponding to the these Factsheets may be reproduced, stored in a retrieval system, or transmitted,
following peaks: m/e: 136; 105; 91; 77. in any other form or by any other means, without the prior permission of the
(d) Suggest structural formulae for A and B. publisher. ISSN 1351-5136

4
 Chem Factsheet
www.curriculumpress.co.uk Number 56
Maths for Chemists 1
This Factsheet concentrates on reviewing the basic mathematical techniques required for AS/A2 Chemistry. You will have already met the ideas involved
in GCSE Maths, but this Factsheet aims to provide some fool-proof methods for applying them in chemical contexts. The topics covered are:
• Ratios • Percentages • Standard form • Significant figures
Later Factsheets will cover work on rearranging formulae, graphs, and exponentials and logarithms.

Ratios Example 2. 5Fe2+ + MnO4− + 8H+→ Mn2+ + 5Fe3+ + 4H2O

Ratios are used in mole calculations. There are two stages in this part of Find the number of moles of Fe2+ required to react with 0.123 moles of
the calculation: MnO 4 −
1. Using a chemical equation to find the reacting ratio
Step 1: Fe2+ : MnO4−
2. Using the reacting ratio to work out moles.
5 : 1
Steps 2 & 3: ? : 0.123
Stage 1 just involves looking at the numbers in the equation!
Step 4: Moles of Fe2+ = 5 × 0.123 ÷ 1 = 0.615
eg: 4Al + 3O2 → 2Al2O3 The questions at the end of the Factsheet gives more practice on ratio
Reacting ratio of Al to O2 is 4:3 calculations

2NaOH + H2SO4 → Na2SO4 + 2H2O

NB: This is only part of the entire mole calculation! The rest of it will
involve converting between moles, masses, concentrations, volumes etc.
Reacting ratio of NaOH to H2SO4 is 2:1 For more details on moles calculations, see Factsheets 2, 3, 7 ,23 and 59.
You do have to be careful if you are looking for the reacting ratio for a
Percentages
particular ion rather than the entire compound. For example, 1 mole of
Percentages are used in:
H2SO4 contains 2 moles of hydrogen ions (because of the “H2” in the
• Yield Calculations
“H2SO4”). So in the equation 2NaOH + H2SO4 → Na2SO4 + 2H2O, the This relates to experiments involving preparing a particular substance.
reacting ratio of OH− ions to H+ ions is 2:2 (the same as 1:1) You never actually get as much of the substance as you’d theoretically
predict. The % yield is the amount you actually get as a percentage of
Stage 2 involves the actual calculation. There are several ways to do this – what you’d get theoretically
if you are confident and accurate with another method, you probably do • % purity (or % by mass) calculations
not need this one! But if you ever make mistakes, it’s worth taking a look. This relates to doing an experiment on a sample that’s only partly the
substance that’s reacting (eg a commercial “iron pill” is certainly not
Example 1. pure iron!) The % purity is the mass of the substance you’re interested
0.316 moles of aluminium react with oxygen to form aluminium oxide. in as a percentage of the total mass of the sample
Find the number of moles of oxygen gas used.

Exam Hint: We need the number of moles of O2, not moles of O, Note that all these types of calculation will involve other parts as well as
because oxygen normally exists as O2. finding the percentage!

Exam Hint: You will see percentages in empirical formula calculations

Step 1: Write down your reacting ratio from the equation too - but you just use them like masses - rather than calculating them.
Al: O2
4 : 3 Percentage calculations can be done in a similar way to ratio calculations,
using the cross method shown above. You draw a table, with one column
Step 2: Underneath the ratio, in the right order, write down the moles you for % and one for actual amounts (masses,moles etc). You can use the same
know and a ? for the moles you don’t. Line up the : to avoid mix ups method whether you are trying to find a percentage or an actual amount.
4 :3
0.316 : ? Example
In an experiment, 1.062g of compound X were produced. The theoretical
Step 3: Draw a cross: maximum yield was 1.231g. Find the percentage yield.
4 :3
0.316 : ? Step 1: Draw a table, with one column for % and one for mass, and put in
the data you know. The theoretical maximum is 100%
Step 4: Multiply the two joined numbers and divide by the other one to % mass
find ? 100 1.231
? = 3 × 0.316 ÷ 4 = 0.237 moles of O2 ? 1.062

Exam Hint: Make sure at the end of this part of your calculation that
Step 2: Draw a cross
the substance corresponding to the larger “ratio number” has the
larger number of moles Step 3: Multiply the two joined numbers and divide by the other one to
find ?
? = 100 × 1.062 ÷ 1.231 = 86.3%

1
56. Maths for Chemists 1 Chem Factsheet

Standard Form Standard form on your calculator

Standard form is a way of writing very large or very small numbers. You
need to be able to Entering numbers in standard form
• be confident with manipulating standard form numbers in a variety There is a special key used for entering standard form; it's usually
of contexts - e.g. when using data to determine the order of a reaction, labelled EE or EXP.
or when plotting a graph
You enter a number in standard form by typing in the first part of the
• enter these numbers into your calculator, and write the answer correctly
number, then hitting the EE or EXP key, then typing in the power
Working with standard form eg: 6.02 EXP 23 gives 6.02× 1023
Numbers in standard form look like this:
Take care with minus signs:
if you enter them before pressing the EE/EXP key, they'll be attached
to the number (eg -2 × 105)
This number is The power can be positive if you enter them after pressing the EE/EXP key, they'll be attached to
between 1 and 9.999... (large numbers) or negative the power (eg 2 × 10-5)

6.02 × 1023 (small numbers)

Reading off the answer
Most calculators display standard form numbers like this:
This is
always 10 6.02 23
The two small digits high up to the right show the power - so this
display means (and should be written as) 6.02 × 1023.
In GCSE maths, you will have done work on changing numbers in and out
of standard form. Now it is more important to be able to compare two
numbers in standard form - without having to convert them both to "normal" Significant figures
numbers. Specifications require that students quote their answers "to an appropriate
number of significant figures". This section reviews what is meant by
Comparing numbers is easy if they both have the same power of 10. For significant figures, and explains the rules for using them.
example, it's easy to see that
6 × 10-5 = 2× (3×10-5) What are significant figures?
But it's harder to compare, say, 1.2 × 10-5 and 3 × 10-6. Significant figures (SF) refer to the most “important” figures in a number
– the ones that represent the largest amounts.
For example, in the number 1425:
To compare numbers in standard form, convert them all
to the same power
• 1 is the most important – the 1st SF - it represents 1000
• 4 is the 2nd most important – the 2nd SF - it represents 400

This is how to convert standard form numbers to the same power: Similarly, in the number 0.00423:
• 4 is the 1st SF, because it represents 0.004
Method Example: 1.2 × 10-5 and 3 × 10-6. • 2 is the 2nd SF because it represents 0.0002
Choose the smaller power. The smaller power is 10-6 So you count from the left to find significant figures, ignoring initial zeros.
NB: It is only the initial zeros you ignore, not ones in the middle of the
Write: number - eg in 9806, 0 is the third significant figure.
no. in big = no. in small + something 10-5 = 10-6 + 1
power power
Rounding to a number of significant figures
To round to a particular number of SF:
Use the laws of powers (adding 10 = 10 ×10 -5 -6 1
• Count to that number of SF (eg for 4SF, find the 4th SF)
powers means multiply)
• Look at the next figure – if it’s 5 or above, round up, otherwise round
1.2 × 10-5 = 1.2 ×10-6 ×101 down
Substitute back
= 1.2 ×101 ×10-6 Working with significant figures
= 1.2 ×10 ×10-6 When doing a calculation, you will often need to decide how many significant
= 12 ×10-6 figures. You will need to consider:-
• The data given in the question (eg from a table, a graph…)
Do the comparison We can see that: o eg 2.10 is correct to 3SF but 2.1 is correct to 2SF
12 ×10-6 = 4 × (3 × 10-6) o be realistic about how accurately you can read a graph – usually
to the nearest small square on graph paper.
• What is required in the answer.
This sort of calculation might be required to compare rates of reaction o you may be asked for a specific number of DP or SF
when the concentration of a reactant is doubled, for example. o if not, give your answer to the same accuracy as the data in the
question, and state the number of SF you are using
To draw a graph using numbers in standard form, first convert them all to
the same power, following the procedure above. For example, you might Then, you should:
end up with 1 ×10-6, 2 ×10-6 ....., 14 ×10-6, , 15 ×10-6. . You'd work out a scale • Work to a greater accuracy than is required in the answer, to avoid
for these just like you would for the numbers 1 - 15. You must remember rounding errors (eg if 2SF is needed, you work to at least 3SF)
to put the "×10-6" in; it can either be written with the actual numbers in the • Keep intermediate answers in your calculator as far as possible
scale itself, or as part of the labelling (eg [H+1]/10-6). • Give the final answer to no greater accuracy than is given in the
question (eg if all data in the question are to 2SF, it would be silly to
give the answer to 3SF)

2
56. Maths for Chemists 1 Chem Factsheet

Questions

1. 0.53 moles of sodium react with oxygen to form sodium peroxide 5. In an experiment, 0.813g of a compound are produced. The theoretical
(Na2O2) mass expected was 1.02g. Calculate the percentage yield

(a) Write an equation for this reaction

6. A commercial iron pill of mass 0.87 g is found to contain 5.6% of iron
(b) Calculate the number of moles of oxygen required by mass. Calculate the mass of iron in one pill.

2. Iodide ions (I− ) react with iodate V ions (IO3−) in the presence of acid 7. Write the following pairs of numbers to the same power of 10
to produce iodine. (i) 2.3 × 10-5 and 3.68 × 10-4

5I− + IO3− + 6H+ → 3I2 + 6H2O (ii) 1.08 × 10-3 and 5.4× 10-4

0.821 moles of iodine are produced. (iii) 9.1 × 10-6 and 2.43× 10-4

Calculate the moles required of

(i) iodide ions 8. Use your calculator to find the following. Give your answers in standard
(ii) iodate ions form

(i) (2.91× 10-5 ) ×(5.81× 102 )

3. Iron II ions are oxidised by dichromate ions to form iron III ions in the (ii) (7.03× 104 ) ÷ (2.03 × 10-1 )
presence of acid

6Fe2+ + Cr2O72- + 14H+ → 6Fe3+ + 2Cr3+ + 7H2O 9. Write the following correct to the number of significant figures given

Calculate the moles of dichromate ions required to fully oxidise 0.0174 (i) 290300 3 significant figures
moles of iron II ions (ii) 0.9998 3 significant figures
(iii) 0.0368 2 significant figures

4. Dichromate ions oxidise iodide ions to iodine:

10. The following data are given in a question:
6I− + Cr2O72− + 14H+ → 3I2 + 2Cr3+ + 7H2O
Time (s) 0.0 5.0 10 15 20
The iodine liberated is titrated with sodium thiosulphate solution: Concentration (mol dm-3) 2.00 1.21 0.736 0.446 0.271

2S2O32− +I2 → S4O62− +2I− (a) How many significant figures are
(i) the times
0.105 moles of sodium thiosulphate are required. (ii) the concentrations
Calculate the moles of dichromate ions used. given to?

(b) A graph is to be plotted from this data. Suggest a suitable level of

accuracy to use for any measurements taken from this graph.

Answers

1. (a) 2Na + O2 → Na2O2 5. 0.813 × 100 ÷ 1.02 = 79.7%

(b) 0.53 × 1 ÷ 2 = 0.265 moles of O2
6. 5.6 × 0.87 ÷ 100 = 0.049g
2. (i) 0.821 × 5 ÷ 3 = 1.37 moles of I−
(ii) 0.821× 1 ÷ 3 = 0.274 moles of IO3− 7. (i) 2.3 × 10-5 and 36.8 × 10-5
(ii) 10.8 × 10-4 and 5.4× 10-4
(iii) 9.1 × 10-6 and 243× 10-6
3. 0.0174 × 1 ÷ 6 = 0.0029 moles of Cr2O72-
8. (i) 1.69× 10-2 (ii) 3.46 × 105
4. Moles of iodine = 0.105× 1 ÷ 2
Moles of dichromate = moles of iodine × 1 ÷ 3 9. (i) 290000 (ii) 1.00 (iii) 0.037
= 0.105× 1 ÷ 2 × 1 ÷ 3
10.(a) (i) 2 (ii) 3
= 0.0175 (b) 2 SF

Acknowledgements: This Factsheet was researched and written by Cath Brown Curriculum Press, Bank House, 105 King Street, Wellington, TF1 1NU
ChemistryFactsheets may be copied free of charge by teaching staff or students, provided that their school is a registered subscriber.
No part of these Factsheets may be reproduced, stored in a retrieval system, or transmitted, in any other form or by any other means, without the prior permission of
the publisher. ISSN 1351-5136

3
 Chem Factsheet
www.curriculumpress.co.uk Number 57

Answering Questions on Redox Titrations I

To succeed with this topic you need to: Before you start – remember this topic requires problem solving - so the
• Know and understand how to do AS titration calculations ( Factsheets method is a way of thinking, not just a recipe sheet. It's worth taking your
No. 7 (‘Moles and Volumetric Analysis’) and No. 23 (‘How to Answer time to make sure you really are happy with what is going on.
Questions on Titration Calculations’))
Understand the whole concept of Redox Equilibria (Factsheet No.37, Example 1
No.45, and No.50). Ammonium iron(II) sulphate crystals have the formula:
• Understand the basics of redox titrations (Factsheet No.51) U1
(NH4)2Fe(SO4)2 . x H2O.
U2
After working through this Factsheet you will have In an experiment to find the value of x, 4.25 g of crystals were dissolved
• met more examples of redox titrations in water and dilute sulphuric acid and made up to 250 cm3. U3
• seen the ‘method’ being used on a range of examples U4 U5
A 25.0 cm3 portion of the solution was titrated against 0.015 mol dm-3
potassium manganate(VII) solution of which 11.3 cm3 was needed.
U6
You may be given a problem that looks very different from ones you
The equation is: MnO4− + 8H+ + 5Fe2+ → Mn2+ + 5Fe3+ + 4H2O
have seen before. The way to deal with it is to remember the following
Only the iron(II) from the crystals react with potassium manganate (VII).
method:
What is the value for x?
(1) Write the EQUATION for the titration reaction (you may need to
combine half equations using numbers of e− to write the full Method
(1) + (2) I’ve been given the Answer
equation).
EQUATION 1 MnO4− ≡ 5 Fe2+
(2) Write down the REACTING RATIO from the balanced equation. so I need the
(3) Identify which of the reactants you can find the NUMBER OF REACTING RATIO
MOLES of using from it.

volume (cm3) × M(mol dm-3) (3) What can I find the ‘moles of ?
11.3
moles = U5 and U6 will work for MnO4− moles of MnO4−= × 0.015
1000 1000
cm3
(4) Combine answers from (2) + (3) to find the NUMBER OF MOLES in Moles = ×M = 1.695 × 10-4
1000
OF THE OTHER REACTANT.
(4) If I combine answers (2) + (3) Moles Fe2+ = 1.695 × 10-4 × 5
(5) Look at the question – WHAT DO YOU NEED TO FIND? I can work out the moles of Fe2+ = 8.475 × 10-4
This will dictate which equation to use next i.e. in 25.0cm3 (U4)
volume (cm3) × M(mol dm-3)
moles = (5) The question is about x. Moles ‘crystal’
1000
What have moles of Fe2+ got = 8.475 × 10-4 in 25.0cm3
grams
or moles = to do with it?
Ar/Mr
I have to look at the crystal (U1) Moles in 250cm3
mass of pure formula. It seems that there is = 8.475 × 10-4 × 10
or % purity = × 100
mass of impure one Fe2+ in the formula – so = 8.475 × 10-3
number of moles of crystals
Summary - you could remember the 5 stages as is no. of moles of Fe2+.
EQ → RR → Moles → ‘other moles’ → Q → A Must use the 250cm3 (U3)
(1) (2) (3) (4) (5) (6) so I will scale up by 10.

(6) Where now? I have used all the g g

Moles = Mr =
data except the 4.25g (U2) Mr moles
Exam Hint - there are some equations e.g. iodine/sodium thiosulphate in 250cm3. To find x I need 4.25
and some half equations e.g. MnO4− reduced to Mn2+ that YOU NEED Mr = = 501.5
the Mr value – I can add up 8.475 × 10-3
TO LEARN! In this Factsheet you will be given them – you may not be
given them in A2 examination papers! all the other parts and find x!

(NH4)2Fe(SO4)2 = 284
CHECK Seems o.k. – H2O = 18
In the following examples the questions are underlined at key places so the I’ve gone back over and checked
method can be explained e.g. U2 = the second underlined section. Underlining the ‘number work’. so 284 + 18x = 501.5
key points is often helpful in examination questions – and not just for the Double checked (4) – it is ×5 501.5 – 284
x = = 12.08
topic we are dealing with now - as it helps you focus your attention on the 18
not divide by 5 (common error)
key facts and figures. x = 12.08 x = 12
(must be a whole number
in a formula)

1
57 Answering Questions on Redox Titrations I Chem Factsheet

Example 2 U1
2.05g of potassium dichromate (VI), K2Cr2O7, is dissolved in water and Before we start on the example, think about this– on the face of it the
made up to 250cm3. U2 ‘method’ seems not easy to use e.g. two equations involved, and there are
U3
25.0 cm3 of this solution is mixed with an excess of acidified potassium no ‘mol dm3’ given so what calculation equation can we use?
iodide solution and iodine is formed by the reaction, It's important to take the time to work through the "thinking process"
Cr2O72− + 6I− + 14H+ → 2 Cr3+ + 3I2 + 7H2O equation [1] explained in the method, to help you deal with this type of demanding
question in the exam
The iodine produced is titrated with sodium thiosulphate solution and
21.5cm3 is needed. U4

2S2O32− + I2 → S4O62− + 2I− equation [2]

What is the concentration of the sodium thiosulphate solution? U5

Method Answer
(1) + (2)
I should be looking at the equation first but there are two! However, I2 is in both Cr O72− → 3I2
so I have nothing to lose by putting both reacting ratios down – I may need them. 2 S2O32− ≡ 1I2

(3) Where are the ‘moles’? There are no ‘mol dm-3 so how can I use any of my Mr(K2Cr2O7) = 294
calculation equations?

Let’s go for moles from grams (U1) grams 2.05

Moles = = = 6.97 × 10−3
Mr 294

6.97 × 10−3
This is in 250cm3 so I must go the 25cm3 for the moles I need to use later. (U2) Moles Cr2O72− = = 6.97 × 10−4
10

(4) I need to combine (2) + (3) to find the ‘other moles’. I have a problem here – what If 2S2O32− ≡ 1I2
‘other moles’? All the information seems to ignore ‘I2’ – why? then 3I2 ≡ 6S2O32−
so 6S2O32− ≡ 1Cr2O72−
Let’s revisit (1) + (2) – I need to sort out ‘reacting ratios’ – I need only one of (6:1)
them. ‘I2’ seems to be a bridge between Cr2O72- and S2I32- so let’s go that way for
‘reacting ratios’

I can use the answer from (3) to get the ‘other moles’ of S2O32- S2 O32− = 6.97 × 10−3 × 6
= 4.182 × 10−3

cm3
(5) What does the question want? (U4) ‘Concentration’ of S2O32- - so I need the Moles = × M
1000
equation involving M.

What do I know about S2O32- so far? 4.182 × 10−3 = 21.50 × M

I have moles (4.182 × 10-3) and a volume (21.50 cm3) so from my calculation 1000
equations I only have one with these in i.e.
volume(cm3) × M(mol dm-3) 4.182 × 10−3 × 1000
moles = so M =
1000 21.5
= 0.195 mol dm-3

(6) IS THIS THE ANSWER? It seems O.K. – I have followed the ANSWER - 0.195 mol dm−3
‘method’ and I have checked the mathematics using the calculator.
HOWEVER – have I checked the 6:1 ratio which is the commonest
error – should I divide or multiply?
Seems O.K.

Exam Hint - it is quite common to need to use a "bridging" substance, as in the example above. The bridging substance will be a product in the
first reaction that takes place and a reactant in the second reaction.

Although you can work with one equation at a time, and actually work out the moles of the bridging substance, this is not a very efficient way of doing
the calculation - it will waste time in the exam - and it may lead to rounding errors due to re-entering rounded data.

2
57 Answering Questions on Redox Titrations I Chem Factsheet

Practice Questions Answers

1. 2.50g of iodine was dissolved in potassium iodide solution and made 1. 2S2O32- ≡ I2
up to 250 cm3 with water.
Mr of I2 = 2 × 127 = 254
25.0 cm3 of the iodine solution was titrated against sodium thiosulphate 2.50
solution of which 22.0 cm3 was required. Moles of I2 in 250cm3 = = 0.00984
254

2S2O32− + I2 → 2I− + S4O62− 0.00984

The equation is: Moles I2 in 25.0cm3 = ≡ 0.000984
10

What is the concentration of the sodium thiosulphate solution? Moles Na2S2O3 = 0.000984 × 2
(Ar of I = 127) = 0.00197
cm3
Moles = × M
2. 1.1g of potassium dichromate (VI) was dissolved in water and made up 1000
to 250cm3. A 25.0cm3 portion of this solution was added to an excess 22.0
of potassium iodide solution and dilute sulphuric acid, and the iodine so 0.00197 = × M
1000
released was titrated with sodium thiosulphate solution, of which
0.00197 × 100
22.0cm3 was needed. so M = = 0.0895 mol dm-3
22.0
The equations involved are:
2. Cr2O72- ≡ 3I2
Cr2O72− + 14H+ + 6I− → 3I2 + 2Cr3+ + 7H2O 2S2O32- ≡ I2
so Cr2O32- ≡ 6S2O32-
2S2O32− + I2 → 2I− + S4O62−
1.1
Moles K2Cr2O7 in 250cm3 = = 0.00374
What is the concentration of the thiosulphate solution? 294
(Mr of K2Cr2O7 = 294) 0.00374
Moles K2Cr2O7 in 25.0cm3 = = 0.000374
10

3. 6.74g of an unknown iron (II) salt was dissolved in a mixture of water Moles S2O32- = 0.000374 × 6
and dilute sulphuric acid and made up to 250cm3. 25.0cm3 of this = 0.00224
solution was titrated against 0.04 mol dm-3 potassium dichromate (VI)
solution and 23.60cm3 was needed. cm3
Moles = × M
1000
The equations are: 22.0
0.00224 = × M
1000
Fe2+ → Fe3+ + e−
0.00224 × 1000
so M = = 0.102 mol dm-3
Cr2O 2−
+ 14H + 6e → 2Cr
+ − 3+
+ 7H2O 22.0
7

Calculate the percentage by mass of iron in the unknown iron (II) salt. 3. 6Fe2+ + Cr2O72- + 14H+ → 6Fe3+ + 2Cr3+ + 7H2O
(Ar of Fe = 56) 6Fe2+ ≡ 1 Cr2O72-
23.60
Moles Cr2O72- in 25.0cm3 = × 0.04
1000
= 0.000944

Moles Cr2O72- in 250cm3 = 0.00944

Moles Fe2+ in 250cm3 = 0.00944 × 6 = 0.05664

g
Moles =
Ar

g
0.05644 =
56
mass Fe = 0.05664 × 56 = 3.172g

3.172
% iron = × 100 = 47.06 %
6.74

Acknowledgements: This Factsheet was researched and written by Sam Goodman. Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire,
TF1 1NU. ChemistryFactsheets may be copied free of charge by teaching staff or students, provided that their school is a registered subscriber. No part of these
Factsheets may be reproduced, stored in a retrieval system, or transmitted, in any other form or by any other means, without the prior permission of the
publisher. ISSN 1351-5136

3
 Chem Factsheet
www.curriculumpress.co.uk Number 58

Applied Organic Chemistry

Before working through this Factsheet you should ensure that you 2. Nitrogenous fertilizers
understand all the organic chemistry covered so far on AS and A2 Plants need to take in nitrogen to produce proteins and nucleic acids.
Green plants can only do this by taking in the inorganic nitrate ion, NO3−.
This Factsheet concentrates on the uses of organic chemistry to produce:
• pharmaceuticals Fertilizers do not need to contain the nitrate ion if they contain the
• fertilisers ammonium ion, NH4+ because,
• esters, oils and fats oxidised by
• soaps and detergents NH 4 + NO3−
• polymers soil bacteria

After working through this Factsheet you will have met You need to remember the above basic facts as well as the fact that the
• the use and impact of fertilizers in modern agriculture nitrate ion needs to be dissolved in water for plants to be able to absorb it.
• the concept of pharmaceuticals being chemical compounds used in
medicine based on their structure Fertilizers are best remembered in three categories:
• examples and uses of esters, oils and fats (a) Natural organic fertilizers e.g. manure, compost, dried blood.
• the making of soaps These natural materials have been used for thousands of years and,
• some polymers, their impact on the environment and biodegradability apart from producing nitrates by being broken down by bacteria, they
also improve the quality of the soil.

• ADVANTAGES - slow release of the nitrate ion so no damage to

Exam Hint – In this area of the A2 specifications you need to learn the plants and they also improve soil quality generally.
basic facts – there is no shortcut to learning thoroughly the information
provided!
• DISADVANTAGES - low solubility in water; the time taken to break
them down to the nitrate ion; low nitrogen content.
1. Pharmaceuticals (Drugs used as medical treatments)
(b) Manufactured inorganic fertilizers e.g. potassium nitrate, KNO3;
Drugs need to be targeted to particular parts of the body and there are
ammonium nitrate, NH4NO3; ammonium sulphate, (NH4)2SO4.
two major groups to consider:
The need to produce more food because of increasing world population
(a) Water soluble - go into the blood and aqueous tissue of the body. led to the development of inorganic fertilizers. They could be made as
They are soluble because they have ionic groups (e.g. COO-Na+) powders or pellets for easy spreading over the ground.
or groups which form hydrogen bonds (e.g. -NH2, -OH).
• ADVANTAGES - higher nitrogen content and soluble in water (ionic)
They are called ‘hydrophilic’ groups (literally ‘water liking’). encouraging quick plant growth.

(b) Fat soluble - go into fatty tissue. • DISADVANTAGES - being very soluble, they can be washed through
They are soluble in fat because they have ‘lipophilic’ groups the soil (‘leached’) and cause ‘eutrophication’ (excessive plant growth
(literally ‘fat liking’) on the molecule (e.g. alkyl side chains – in rivers/ponds which leads to bacterial growth which lowers the
CH2CH2CH2CH2CH3). oxygen content and affects aquatic life) before they are broken down.

If they remain in the soil, they are released in ‘one dose’and can
damage the plant with a too high concentration of nitrate – they need
Exam Hint - In your revision, focus on learning the hydrophilic and to be applied in carefully measured amounts.
lipophilic groups so when presented with an unknown molecule you
will be able to say if it is soluble in water or fat. N.B. The slower breakdown of the ammonium ion, NH4+ by soil
-
bacteria has to be balanced against the ‘leaching out’ effect and
+
CO2 Na the concentration of the fertilizer applied.
e.g. Note the presence of the ionic
OCOCH 3 side-chain that will make the (c) Manufactured organic fertilizer e.g. urea, H2NCONH2
molecule water-soluble. Urea is an intermediate between the ‘natural organic’ and the
‘manufactured inorganic’ fertilizers. Urea is a manufactured organic
fertilizer.

e.g.
CH2CH2CH2CH2CH2CH2CH3
The long side chain makes
• ADVANTAGES - very soluble in water; high nitrogen content (47%)
this molecule soluble in fat. compared to other fertilizers; releases its nitrogen slowly by hydrolysis
(i.e. reaction with water) (NH2)2CO + H2O → 2NH3 + CO2

• DISADVANTAGES - its high solubility means it can be ‘leached

away’ by rainwater.
NO2

1
58. Applied Organic Chemistry Chem Factsheet

3. Esters, oils and fats 5. Polymers and biodegradability

There are two types of polymers:
Remember: Carboxylic acid + alcohol → ester + water
(a) Addition polymers
O O
CH 3 C + C2H5OH → CH 3 C + H2 O The monomers contain a double bond which undergoes electrophilic
OH O addition.
C 2H 5
e.g.
Oils and Fats are both naturally occurring esters. H H
heat/pressure
The difference is the source: C C C C

OILS - from vegetables and marine animals e.g. whales H H H H

n
FATS - from land animals
(b) Condensation polymers
CH 2 OH The commonest ester is based on the The monomers have different functional groups which react
alcohol propane – 1,2,3 – triol (glycerol), together to form the link in the polymer and release H2O or HCl.
CH OH
The triol then reacts with a variety of long-chain
Four examples need to be learned:
CH 2 OH carboxylic acids e.g. stearic acid, CH3(CH2)16CO2H.
1. carboxylic acid + alcohol → ester + water
O
The esters formed are commonly called glycerides.
HOOC COOH + HO OH → HOOC C O OH
Fats have higher melting points than oils. This is because the acids that
form the esters are saturated (no double bonds). These saturated chains + H2 O
ester link
can pack together easily so creating greater intermolecular forces and
increasing melting points.
2. acyl chloride + alcohol → ester + hydrogen chloride
If unsaturated acids are used to make the ester, geometric isomerism O O O
(cis and trans) is present but mainly the cis-form. This makes packing O
of side-chains less easy, leading to the lower melting points of oils. Cl C C Cl + HO OH → Cl C C O OH
The result of this is that: + HCl
ester link
FATS tend to be SOLIDS
3. carboxylic acid + amine → + water
OILS tend to be LIQUIDS
O O O O H
If acids forming the esters have more than one double bond, the ester is NH 2 → HO C
HO C C OH + H 2 N C N NH 2
described as ‘polyunsaturated’ – a term you will have heard in
connection with foodstuffs like margarines. peptide link
+ H2 O
4. Soaps and detergents 4. acyl chloride + amine → amide + hydrogen chloride
Soaps are directly linked to fats and oils because,
O O O O H
salt of a
oil sodium Cl C C Cl + H 2N NH 2 → Cl C C N NH 2
or + → propane-1,2,3-triol + carboxylic acid
hydroxide
fat SOAP peptide link
+ HCl
This is alkaline hydrolysis of esters.
The process is called saponification i.e. ‘soap-making’ From the above four examples, you will see how the molecules can
salt of a continue linking on to form the long polymer chains.
e.g. ester + alkali → alcohol +
carboxylic acid
This will form polyamides (e.g. nylon) and polyesters (e.g. terylene).
O
OR The disposal of polymers (e.g. plastics) has been a long-term problem!
CH 2 C CH 2 OH
O _
+
+ 3NaOH → CH OH + 3RCOO Na BURNING - produces poisonous fumes e.g. sulphur dioxide, and carbon
CH C OR dioxide i.e. contributes to the ‘greenhouse effect’ and so global warming.
O SOAP
CH 2 OH
OR LANDFILL SITES - plastics don’t ‘break down’ so provide bulk which
CH2 C
increases the amount of volume needed for landfill sites for waste disposal.
You make different types of soap depending on the oil or fat (the ester)
you start with. ‘Biodegradable polymers’ (i.e. those that are broken down by bacterial
attack when buried in the ground) have been developed. Research
Modern detergents have gradually replaced soaps over the past fifty
continues to address the problem of disposing of plastics.
years. This is because detergents are more soluble in water and do not
form scum in ‘hard’ water (as soap does). Detergents are made using acid
instead of alkali.
2
 Chem Factsheet
www.curriculumpress.co.uk Number 59

Titration Calculations:
Revision Summary
To succeed with this topic you need to know and understand the material
covered so far in Factsheets No. 7 (Moles and Volumetric Analysis), No.23 CATEGORIES OF TITRATION CALCULATIONS
(How to Answer Questions on Titration Calculations), No.51 (‘Redox • categories 1, 2, 3, 4 and 5 use examples from both redox and acid/
Equilibria (IV) : Redox Titrations’) No.57: Answering questions on Redox base titrations.
Titrations 1) • category 6 is usually only acid/base titration type.

The purpose of this Factsheet is to bring together all the different Type Example
types of titration calculations under various categories.
1 Finding concentration A standard solution is made and
By now you should be competent in titration calculations. If you can now of a solution used to find the concentration of
recognise a calculation problem as belonging to a particular category it will the other solution in the titration.
help you to get into the problem more quickly.
2. Finding the formula mass A standard solution is made of the
You should regard this Factsheet as a summary of all the four Factsheets (Mr) of a compound compound. It is titrated with the
listed above. We will re-visit the basic equations and terms, and then put in other solution and its
the categories. concentration, mol dm-3, formed.
g
Using: moles =
Mr
TERMS USED
the value of Mr is found.
Volumetric analysis - this is another way of saying TITRATION i.e.
adding reacting solutions together to find the exact point (the end- 3. Finding the percentage A standard solution of the impure
point) when the two solutions have completely reacted together. purity of a sample of impure solid is made. Titration with the
compounds other solution enables you to find
Standard Solution - a solution made by dissolving an accurate amount the mass of the pure solid and
of solid in, usually, water. The volume is usually 250cm3 so you can hence the percentage purity.
always calculate g dm-3. If the Mr is known, you can calculate mol dm-3
. 4. Finding the formula of a Exactly the same as (2) above, but
Titre - the final volume added from the burette in the titration. When compound the Mr value is used to find, for
a series of titrations are done, then titres in good agreement (concordant)
example, ‘the x in Na2CO3⋅ xH2O’
are averaged to give the volume used in calculations – the AVERAGE
TITRE. 5. Finding the percentage The method is the same as for (4)
Acid/Base Titration - as it says! An acidic solution reacting with a mass of an element in a above, but you find the mass of
basic solution (neutralisation). compound the element and hence the
percentage of it in the compound.
Redox Titration - the two half equations are combined to give the
balanced chemical equation (using the ‘electron balancing method’). 6. Using the 'back titration' Usually a solid is reacted with an
One of the half equations is a reduction process (electron gain) and the method excess of acid. The acid left after
other an oxidation process (loss of electrons) the reaction is found by titrating
with a base. It is therefore possible
to find how much acid reacted
EQUATIONS USED IN CALCULATIONS with the solid and so more about
the solid itself.
grams
moles =
Ar/Mr

volume (cm3) The examples on the next page review how to tackle each of these types of
moles = × M (mol dm-3)
1000 calculation - these include a mixture of acid-base and redox titrations. The
key approach is to make sure you understand what is going on at each
mass of pure
purity percentage = × 100 stage, rather than try to remember the method "parrot fashion".
mass of impure

mass of element Exam Hint - make sure you are confident rearranging the various
percentage by mass = × 100 equations used in these calculations. Factsheet 56 (Maths for
mass of compound
Chemists 1) gives some assistance on calculations involving
percentages, and a later Factsheet will review rearrangment of
formulae.

1
59. Titration Calculations: Revision Summary Chem Factsheet

Worked Examples
1. Finding Concentration 4. Finding the Formula of a Compound
0.95g of ethonedioic acid crystals, H2C2O4 . 2H2O, was dissolved Sodium carbonate crystals (13.91g) were dissolved in water and
in 250cm3 of water. A 25.0cm3 sample of solution required 33.0cm3 made up to 1.0 dm3 . A 25.0cm 3 portion of the solution was
of potassium manganate (VII) solution in a titration. neutralised by 24.4cm3 of 0.10 mol dm-3 hydrochloric acid solution.
What is the concentration of the manganate (VII) solution? What is x in Na2CO3. x H2O?
The equation is, Na2CO3 + 2HCl → 2NaCl + H2O + CO2
2MnO4− + 16H+ + 5C2O42−− → 2Mn2+ + 8H2O + 10CO2 1Na2CO3 ≡ 2HCl
Mr of acid crystals = 2 + 24 + 64 + 36 = 126 Moles HCl in 25.0cm3 = 24.4 × 0.1 = 0.00244
1000
Moles of acid crystals in 250cm3 = 0.95 = 0.00754 1000
126 Moles of HCl in 1 dm-3 = 0.00244 × = 0.0976
0.00754 40
3
Moles of acid crystals in 25cm = = 0.000754
10 Moles of sodium carbonate = 0.0976 = 0.0488
2 MnO4− ≡ 5C2O42− 2
g 13.91
Moles MnO4− = 0.000754 × 2 = 0.000302 Moles =
Mr
0.0488 =
Mr
5
Moles =
Vcm3
× M so Mr = 13.91 = 285.04
1000 0.0488
Na2CO3 ⋅ xH2O = 46 + 12 + 48 + 18x
0.000302 = 33.0 × M
1000 = 106 + 18x
0.000302 × 1000 285.04 = 106 + 18x
so M = = 0.0092 mol dm-3
33 so 18x = 285.04 - 106 = 179.04
x = 179.04 = 10
18
2. Finding a formula mass i.e. Na2CO3 ⋅ 10H2O
5.2g of compound X was dissolved in 250cm3 of water. A 25.0cm3
portion of the solution required 20.0cm3 of a 0.20 mol dm-3 of
potassium dichromate (VI) solution in a titration. The reacting
ratio is: 5 ≡ 1Cr2O72−− 5. Finding Percentage Mass
Brass is a mixture of copper and zinc. It dissolves in nitric acid to
What is the formula mass, Mr, of X ? form Cu2+ and Zn2+ ions. The Cu2+ ions can be found by using
iodide and sodium thiosulphate. The zinc ions do not react in the
Moles Cr2O72− = 20.0 × 0.20 = 0.004
1000 process.
Moles X in 25.0cm3 = 5 × 0.004 = 0.02 2.0g of a sample of brass was dissolved in nitric acid and after
Moles X in 250cm3 = 0.02 × 10 = 0.2 treating the solution formed to remove other materials excess
g potassium iodide was added.
Moles =
Mr
2 Cu2+ + 4I− → 2CuI + I2
g 5.2
so Mr = = = 26 The iodine reacted with 20.0cm3 of 1 mol dm-3 sodium thiosulphate
moles 0.2
solution,
2S2O32−− + I2 → 2I− + S4O62−−
3. Finding Percentage Purity What is the percentage by mass of copper in the brass sample?
A piece of iron wire has a mass of 0.62g. It is dissolved in acid,
then reduced from Fe3+ to Fe2+. The whole solution was titrated 2Cu2+ ≡ I2
with 0.04 mol dm-3 potassium dichromate (VI) solution of which
2S2O32- ≡ I2
42.5cm3 was required.

The equation is: so Cu2+ ≡ S2O32-

Cr2O72−− + 14H+ + 6Fe2+ → 2Cr3+ + 6Fe3+ + 7H2O Moles S2O32- = 20.0 × 1 = 0.02
1000
What is the percentage purity of the iron wire?
Moles Cu2+ = 0.02 Ar of Cu = 63.5

Moles Cr2O72− = 42.5 × 0.04 = 0.0017 g

Moles =
1000 Ar
so Mass = 0.02 × 63.5 = 1.27g
Moles Fe2+ = 0.0017 × 6 = 0.0102

Moles =
g
Ar of Fe = 6 Percentage purity = 1.27 × 100 = 63.5%
Ar 2.0

so mass = 0.0102 × 56 = 0.5712g

Percentage purity = 0.5712 × 100 = 92.13%

0.62

2
59. Titration Calculations: Revision Summary Chem Factsheet

6. Using a ‘Back Titration’ Method Answer

0.80g of impure chalk was reacted with 100cm3 of 1 mol dm-3 1. 2NaOH + H2SO4 → Na2SO4 + 2H2O
hydrochloric acid (an excess). The mixture was filtered into a
volumetric flask and made-up to 250cm3. NaOH: H2SO4 is 2:1

A 25.0cm3 portion of the solution required 8.5cm3 of 1 mol dm-3 Moles H2SO4 = 0.02785 × 0.0487
sodium hydroxide solution for neutralisation.
Moles NaOH = 2 × 0.02785 × 0.0487
What is the percentage of calcium carbonate in the impure chalk?
0.0487
Concentration NaOH = 2 × 0.02785 ×
CaCO3 + 2HCl → CaCl2 + H2O + CO2 0.025
= 0.109 mol dm-3
CaCO3 ≡ 2HCl
NaOH + HCl → NaCl + H2O 2. I2 : Cr2O72- is 3:1
NaOH ≡ HCl I2: S2O32- is 1:2

Moles NaOH in 25.0cm3 = 8.50 × 1 = 0.0085 So Cr2O72- : S2O32- is 1: 6

1000
Moles HCl in 25.0cm3 = 0.0086 Moles S2O32- used = 0.0244 × 0.102

Moles HCl in 250cm3 = 0.085 (the excess after the reaction) 0.102
Moles of Cr2O72- = 0.0244 ×
6
Moles of HCl used initially = 100 × 1 = 0.1
1000 0.0244 × 0.102
Moles HCl used in the chalk= 0.1 − 0.085 = 0.015 Concentration of Cr2O72- =
6 × 0.0250
Moles CaCO3 = 0.015 = 0.0075 = 0.0166 mol dm-3
2
Mr of CaCO3 = 40 + 12 + 48 = 100 3. H2C2O4 + 2NaOH → Na2 C2O4 + 2H2O
g
Moles = H2C2O4 : NaOH is 1:2
Mr
Moles NaOH = 0.0211 × 0.1
g
so 0.0075 =
100
0.1
so mass = 0.75g Moles H2C2O4 = 0.0211 × in 25cm3
2
Percentage = 0.75 × 100 = 93.75% 10
0.80 Moles H2C2O4 = 0.0211 × 0.1 × = 0.01055 in 250cm3
2
So 1.33g of H2C2O4.nH2O is 0.01055 moles
Practice Questions
1.33
1. In a titration with methyl orange as the indicator, 25.0 cm3 of sodium So Mr = = 126
0.01055
hydroxide solution required 27.85 cm3 of 0.0487 mol dm-3 sulphuric
acid to produce a colour change. Calculate the concentration of the So (2 × 1) + (2 × 12) + (4 × 16) + 18n = 126
sodium hydroxide solution.
90 + 18n = 126
3
2. 25.0 cm of potassium dichromate(VI) solution were acidified and n =2
treated with excess KI(aq). The liberated iodine was titrated with
4. NH4+ + OH- → NH3 + H2O
24.4 cm3 of 0.102 mol dm-3 Na2S2O3(aq). Calculate the concentration
NaOH + HCl → NaCl + H2O
of the K2Cr2O7(aq).
Cr2O72- + 14H+ + 6I- → 2Cr3+ + 7H2O + 3I2 Moles HCl = 0.101 × 0.02625
Moles NaOH reacting with HCl =0.101 × 0.02625
2S2O32- + I2 → S4O62- + 2I-
Moles NaOH originally added to ammonium salt = 1.04 × 0.01
3. 1.33 g of hydrated ethanedioic acid, H2C2O4.nH2O, were dissolved in
distilled water and the solution made up to 250 cm3 in a graduated So moles NaOH reacting with ammonium salt
flask. 25.0 cm 3 of this solution were titrated by 21.1 cm 3 of = (1.04 × 0.01) – (0.101 × 0.02625)
0.100 mol dm -3 NaOH(aq). How many molecules of water of
crystallisation are there in the hydrated ethanedioic acid? So moles NH4+ = (1.04 × 0.01) – (0.101 × 0.02625) = 0.00774875
Ar: H = 1; C = 12; O = 16.
So mass NH3 = 0.00774875 × 17

4. 0.414 g of an ammonium salt were boiled with 10.0 cm3 of 1.04 dm-3 So % by mass of NH3 = 0.00774875 × 17 × 100/0.414
aqueous sodium hydroxide until no more ammonia was evolved. = 31.8%
Afterwards the solution was titrated with 0.101 dm-3 hydrochloric
acid, 26.25 cm3 of which were needed to reach an end-point with Acknowledgements: This Factsheet was researched and written by Sam
methyl orange. Calculate the percentage of ammonia in the ammonium Goodman. Curriculum Press, Bank House, 105 King Street, Wellington,
salt. Ar: H = 1; N = 14. Shropshire, TF1 1NU. ChemistryFactsheets may be copied free of charge by
teaching staff or students, provided that their school is a registered subscriber.
No part of these Factsheets may be reproduced, stored in a retrieval system, or
transmitted, in any other form or by any other means, without the prior
permission of the publisher. ISSN 1351-5136

3
 Chem Factsheet
www.curriculumpress.co.uk Number 60

Laboratory Chemistry: Summary of

Organic Tests
Before reading through this Factsheet you should:
• Have gained practical experience of organic chemistry tests and Group: Hydroxyl group (in alcohols and carboxylic acids)
preparations. OH
• Have a good understanding and knowledge of organic functional groups Test: Add PCl5 to a dry sample of the compound.
and their reactions.
Observations: Steamy white fumes of hydrogen chloride.
After working through this Factsheet you will be able to:
• Give reagents, conditions and expected observations when carrying Notes: PCl5 causes nucleophilic substitution reaction of –OH
out chemical tests for common organic functional groups; group in alcohol, carboxylic acid or water (hence organic
• Use this information in a practical or written exam situation. compound must be dry).
Chemical testing is still commonly used in school laboratories for simple e.g. C2H5OH + PCl5 → C2H5Cl + HCl + POCl3
organic analysis because:
• The use of expensive modern spectroscopic equipment is not required; Reference Factsheet 17.
• It provides excellent opportunities to improve practical skills, such as
making observations and inferences.

Knowledge and understanding of common organic tests are required in

Group: Alcohols (Primary, Secondary and Tertiary)
practical and written examinations. The aim of this Factsheet is to provide
a summary of these tests, which candidates should be able to recall. H H

C OH C OH C OH

H
Group: Alkenes (and other unsaturated hydrocarbons) Test: Warm with potassium dichromate (VI) acidified with
dilute sulphuric acid.
C C
Observations: Primary and secondary alcohols cause orange
Test: Addition of bromine solution. dichromate (VI) ions to be reduced to green
chromium (III) ions. Tertiary alcohols do not react.
Observation: Orange bromine solution decolourises.
Notes: CH2=CH2 + Br2 + H2O → CH2BrCH2OH + HBr Notes: Potassium dichromate (VII) is an oxidising agent, as it is
Reference Factsheet 16 reduced.
The oxidation of alcohols can be summarised:

[O] [O]
Primary alcohol aldehyde carboxylic acid
Group: Halogenoalkanes
[O]
Secondary alcohol ketone X
C Cl C Br C I
Tertiary alcohol X
Test: Warm with NaOH (aq). To distinguish between primary and secondary alcohols
Add HNO3 (aq) until just acidic. the products of oxidation should be distilled off and
Add AgNO3 (aq) dropwise. tested for the presence of aldehyde or acid (inferring
primary alcohol) or ketone (inferring secondary alcohol).
Observations: Chloroalkanes- White precipitate, soluble in dilute
ammonia solution. Reference Factsheet 17.

Bromoalkanes- Cream precipitate, soluble in

concentrated ammonia solution. Exam Hint: Exam questions will commonly require you to combine
information from organic tests and spectroscopy to determine a
Iodoalkanes- Yellow precipitate, insoluble in compound's identity
concentrated ammonia solution.

Notes: Reference Factsheet 16.

1
60. Laboratory Chemistry: Summary of Organic Tests Chem Factsheet

Group: Carboxylic Acid.

Group: Methyl group next to carbonyl group, or secondary
O
C alcohol which would oxidise to such a group in these
OH conditions.
H
Test: Add to sodium hydrogen carbonate solution. O
C C CH
Observations: Carbon dioxide gas evolved, which turns lime water CH 3 OH
cloudy white.
Test: The Iodoform (tri iodomethane) Test.
Notes: CH3COOH + NaHCO3 → CH3COO−Na+ + H2O + CO2 Warm the compound with a solution of iodine and sodium
hydroxide.
Another possibility would be to test the pH of the (The reagents potassium iodide and sodium chlorate (I)
compound, which would be less than 7 for an acid. produce a similar effect).
Reference Factsheet 32. Observations: A yellow precipitate is formed with an antiseptic-like
smell.

Notes: The yellow precipitate formed is iodoform, CHI3.

Group: Carbonyl group (aldehydes and ketones).
O Reference Factsheet 33.
C C O
H Practice Questions:
Test: Add an alcoholic solution of 2,4-dinitrophenylhydrazine 1. What would the expected observation be upon the addition of bromine
(2,4-DNP) acidified with dilute sulphuric acid. water to the following chemicals:
(a) Hexane (b) Hex-2-ene
Observations: A red-orange precipitate produced. 2. What would the expected observation be upon the addition of
2,4-DNP to the following chemicals?
Notes: This test does not distinguish between the two types (a) Propanone (b) Propane (c) Propanal
of carbonyl compound, aldehydes and ketones.
3. Pentan-2-ol is warmed with potassium dichromate (VI) dissolved in
Reference Factsheet 33 dilute sulphuric acid and a reaction is observed. The resultant organic
product is distilled off and split into two parts. One part is tested with
To Distinguish between Aldehydes and Ketones: 2,4-DNP solution, and one part is tested with ammoniacal silver nitrate.
There are two tests which can be carried out.
Describe:
Test 1: Silver Mirror Test : A test for aldehydes. (a) The observation that was made which indicated that a reaction
Warm carbonyl compound with ammoniacal silver nitrate solution took place between the pentan-2-ol and acidified potassium
(Tollen’s reagent). dichromate (VI) solution.
(b) The observation made as the distillate was tested with 2,4-DNP.
Observations: If an aldehyde is present a silver mirror is formed on (c) The observation made as the distillate was tested with ammoniacal
the inside of test tube, or a grey-black precipitate. silver nitrate solution.
(d) Name the distillate.
Notes: The aldehyde is oxidised to a carboxylic acid, whilst
the silver (I) ions are reduced to silver metal. 4. Describe the observations if the following chemicals were warmed
with iodine solution and sodium hydroxide.
Ammoniacal silver nitrate has no effect on ketones. (a) Ethane (b) Ethanol (c) Ethanal (d) Propanone
Reference Factsheet 33 (e) Propanal (f) Hexan-3-one (g) Hexan-2-one

Test 2: Fehling’s Solution Test : A test for aldehydes. Answers

Warm the carbonyl compound with Fehling’s solution. 1. (a) Two immiscible layers, no observable reaction.
(b) Two immiscible layers, bromine water decolourises.
Observations: If an aldehyde is present Fehling’s solution turns from
blue to red. 2. (a) Red-orange precipitate.
(b) No observable reaction.
Notes: The aldehyde is oxidised to a carboxylic acid, whilst the (c) Red-orange precipitate.
blue copper (II) ions are reduced to a red precipitate of 3. (a) Colour change orange to green.
copper (I) oxide. (b) Formation of a red-orange precipitate.
(c) No observable reaction.
Fehling’s solution has no effect on ketones. (d) pentan-2-one.
Reference Factsheet 33.
4. (a) No observable reaction.
(b) Yellow precipitate, antiseptic smell.
Acknowledgements: This Factsheet was researched and written by Kieron Heath. Curriculum (c) Yellow precipitate, antiseptic smell.
Press, Bank House, 105 King Street, Wellington, Shropshire, TF1 1NU. ChemistryFactsheets
may be copied free of charge by teaching staff or students, provided that their school is a (d) Yellow precipitate, antiseptic smell.
registered subscriber. No part of these Factsheets may be reproduced, stored in a retrieval (e) No observable reaction.
system, or transmitted, in any other form or by any other means, without the prior permission (f) No observable reaction.
of the publisher. ISSN 1351-5136
(g) Yellow precipitate, antiseptic smell.

2
 Chem Factsheet
www.curriculumpress.co.uk Number 61

Organic Analysis III - Low

Resolution NMR Spectroscopy
Before reading through this Factsheet you should: Proton Magnetic Resonance
• Understand atomic structure (Factsheet 01); Some isotopes commonly found in organic molecules, such as 12 C and 16 O,
• Have a good knowledge of AS/A2 organic chemistry; do not have nuclei which possess the property of spin, so are not detected
• Understand covalent bonding and molecular structure. by NMR. The hydrogen nucleus (a single proton), however, does.
After working through this Factsheet you will be able to: Consequently, when identifying organic molecules, proton magnetic
• Be able to interpret simple low-resonance nuclear magnetic resonance resonance spectra, 1H NMR, are commonly studied. By studying these
spectra; spectra, an analytical chemist can gain information about the arrangement
• Recognise NMR spectra as useful tool in organic analysis. of hydrogen atoms within an organic molecule, and thus make deductions
about the structure.
Successful A2 Chemistry candidates should be able to interpret simple
low-resolution nuclear magnetic resonance (NMR) spectra. The aim of To ensure consistency between machines, NMR spectra are calibrated
this Factsheet is to provide candidates with the knowledge, understanding using the compound tetramethylsilane or TMS, (CH3)4Si, which contains
and experience to do this. 12 hydrogen nuclei (protons):
Whilst a brief description of how NMR spectra are produced is given, this
Fig. 2 Tetramethylsilane (TMS)
is background information which students can research in greater detail
from text books or other sources. Exam marks are gained from the
H
interpretation of NMR spectra; hence this is the focus of the Factsheet.
H C H
Formation of NMR Spectra H H
Any spinning electric charge generates a magnetic field. Atomic nuclei are H C Si C H
charged, so if they possess the property of spin, they have an associated
magnetic field. If such nuclei are placed in a strong magnetic field, they H H
H C H
behave like bar magnets and align themselves with that field. This would
H
be the stable, low energy arrangement.
If energy is applied, the nuclear magnets can be forced to ‘flip’, and oppose
the strong applied magnetic field. This would be the unstable, higher All 12 of the hydrogen atoms are in an identical environment, so will all
energy arrangement. The applied energy would be electromagnetic radiation have an identical resonant field. This will give one strong peak on an NMR
of radio frequencies. spectrum.

Fig 3. NMR spectrum

Fig. 1 Formation of NMR Spectra
'down - field' direction TMS
external
nuclear
magnetic
'magnet'
field ∆E (Energy to cause 'flip')
E

nuclear external
'magnet' magnetic
field 7 6 5 4 3 2 1 0
δ(ppm)

If a nucleus aligned with the external magnetic field is supplied with Notice that the axis at the base of the NMR spectrum is labelled δ(ppm).
electromagnetic radiation of the correct frequency, it will absorb the radiation The difference between the resonant field of a proton in a given compound
and ‘flip’ to the higher energy level. This is nuclear magnetic resonance. and that of the protons in TMS is known as the chemical shift, given the
The precise frequency of radiation that causes a nucleus to ‘flip’ depends symbol δ, and measured in parts per million (ppm).
not only on the type of nucleus, but also the environment of that nucleus NMR spectroscopes can work in two ways:
– that is to say the electrons and other nuclei adjacent to the nucleus in • Maintain a fixed strength magnetic field and vary the frequency of the
question. electromagnetic radiation.
By placing an organic sample in a strong magnetic field and measuring the • Vary the magnetic field strength and maintain the frequency of the
frequencies of radiation it absorbs, information can be gained about the electromagnetic radiation.
environment of the nuclei, i.e. how certain atoms are arranged within the Consequently, the analysis of NMR spectra is consistent if chemical shift
molecule. Such structural information is invaluable in organic analysis. is given, rather than specific frequencies or field strengths.
1
61. Organic Analysis III - Low Resolution NMR Chem Factsheet

As will be shown in the following examples and questions, the resonant Example 3
field peaks caused by protons in organic molecules appear to the left of the Use the following data and knowledge of 1H NMR to show which of the
TMS peak (which is δ=0). This direction of chemical shift is said to be spectra below is that of propan-1-ol, and which is propan-2-ol.
‘down-field’.
Spectrum A
The Analysis of Proton NMR.
Example 1
1
H NMR for methane, CH4:

When studying low-resolution proton NMR there are two things to

look out for:
• The number of peaks, which gives the number of different proton
environments.
• The area under each peak, which gives an idea of the number of 11 10 8 7 2 1 0
9 6 5 4 3
protons (hydrogens) in each environment. δ/ppm

There is one peak, as all four hydrogens are in an identical environment. Spectrum B

11 10 9 8 7 6 5 4 3 2 1 0
δ/ppm
6 5 4 3 2 1 0
δ/ppm
Group δ(ppm)
CH3-R 0.8-1.2
Example 2
1
H NMR for ethanol, CH3CH2OH: R-CH2-R 1.1-1.5
In this spectrum there are three peaks, as there are three different CH-R3 1.5
environments in which hydrogens exist. R-OH 1.0-6.0
R-CH2-OH 3.3-4.0
R2-CH-OH 3.2.-4.1

Propan-1-ol
H **** H *** H **
****H C C C O H*

H **** H *** H **
Group CH3−R R−CH2−R R−CH 2−OH R−OH
10 9 8 7 6 5 4 3 2 1 0
δ/ppm 0.9 1.2 3.5 2.3
δ/ppm
Number of H's 3 **** 2 *** 2 ** 1*
Remember that the areas under the peaks give an indication of the number
This has 4 different proton environments, so 4 peaks would be expected
of hydrogens in each environment. In this spectrum the ratio of areas
which match the peaks in spectrum A.
under the peaks is 2:1:3. Using this information each peak can be assigned
to an 1H environment. Propan-2-ol
H*** H* H ***
H H
***
'-OH' H C C C H ***
'-CH3' H C C O H
environment
environment H*** O H ***
H H
'-CH2' H **
environment Group CH3−R R−OH R2−CH−OH
• 2H in a ‘-CH2’ environment (3.7 ppm). δ/ppm 1.1 2.3 4.0
• 1H in a ‘-OH’ environment (2.7 ppm). Number of H's 6 *** 1 ** 1*
• 3H in a ‘-CH3’ environment (1.3 ppm). This has 3 different proton environments, so 3 peaks would be expected
which match the peaks in spectrum B. Note that there are 6 hydrogens in
identical environments in propan-2-ol.
Exam Hint: Often data will be supplied to assist in the assigning of
peaks to hydrogen environments. Candidates are not required to learn Careful examination of this example is worthwhile as it illustrates how two
any of this data, but should be able to use it when it is given. compounds with only slight structural differences can have marked
differences in their NMR spectra.
2
61. Organic Analysis III - Low Resolution NMR Chem Factsheet

Practice Questions Answers

1. The NMR spectrum of butane is shown. Relate this spectrum to the 1. 2 peaks due to 2 1H environments:
structure of the compound.
H H H H

H C C C C H

H H H H

• 1.0 ppm, rel. area 6, due to CH3 × 2.

• 1.3 ppm, rel. area 4, due to CH2 × 2.

2. Propanal:
H H O
H C C C
8 7 6 5 4 3 2 1 0
δ/ppm H H H

3 expected peaks:
2. The following NMR spectra are of the isomers propanal and propanone.
• 1H in –CHO
Show which spectrum belongs to each compound.
• 2H in -CH2-
Spectrum A: • 3H in –CH3
Hence match with spectrum A.
Propanone:
H O H

H C C C H

H H

1 expected peak:
• 6H in –CH3 (×2)

Hence match with spectrum B.

3. Chloroethane has structure:

Spectrum B:
H H

H C C Cl

H H

From this it can be seen that 2 different proton environments exist, 3H’s in
CH3-R and 2 H’s in R-CH2-Cl.

Hence an NMR spectrum containing 2 peaks would be expected, with

relative area under peak ratio 3:2.

11 10 9 8 7 6 5 4 3 2 1 0 e.g.
δ/ppm

3. Predict the appearance of the NMR spectrum for the compound

chloroethane.

11 10 9 8 7 6 5 4 3 2 1 0
δ/ppm

Acknowledgements: This Factsheet was researched and written by Kieron Heath. Curriculum
Press, Bank House, 105 King Street, Wellington, Shropshire, TF1 1NU. ChemistryFactsheets
may be copied free of charge by teaching staff or students, provided that their school is a
registered subscriber. No part of these Factsheets may be reproduced, stored in a retrieval
system, or transmitted, in any other form or by any other means, without the prior permission
of the publisher. ISSN 1351-5136

3
 Chem Factsheet
www.curriculumpress.co.uk Number 62
Answering Questions on Identifying
Unkown Organic Compounds
Before reading through this Factsheet you should: Information supplied in the question
• Have some practical experience of organic chemistry tests and
Exam Hint: Read the question carefully, assume any information
preparations (Factsheet 60); about the unknown chemical supplied is important and must be
• Have a good understanding of different spectroscopic techniques considered. "Tick off" the information to make sure you have used all
(Factsheets 54, 55 and 56); of it.
• Have a good understanding of AS/A2 organic chemistry;
• Have a good understanding and knowledge of organic functional groups Such problems on identifying unknown organic problems generally begin
and their reactions. by supplying the first ‘clues’. Often this will be information about the
composition:
After working through this Factsheet you will be able to:
• Identify unknown organic chemicals when supplied with the necessary E.g. Compound X contains carbon, hydrogen and oxygen only.
information in a written exam or practical situation.
Sometimes the molecular mass or even the molecular formula is supplied.
The aim of this Factsheet is to build on knowledge of organic chemical
testing and spectroscopic techniques to enable candidates to attempt a Results of Chemical Tests
specific type of question. In a practical exam or assessment, candidates may be given instructions to
carry out simple organic tests, or in a written exam results of such tests
Candidates are often asked to identify an organic compound having been may be described. Inferences must be drawn from these about the unknown
given some information about that compound. Sometimes all of the relevant compound.
information is supplied, and sometimes in practical situations candidates
are given instructions so as the necessary information can be discovered by Exam Hint: Do not treat each piece of information or test result in
chemical testing. isolation. Use all of the knowledge gained about the compound to
build a picture of the unknown structure.

The following table is not a definitive list of chemical tests (see Factsheet 60 for more information) but is included to help candidates make links between
test observations and inferences about unknown organic compounds.

Reagents Positive Test Result Possible Inferences about Unknown Organic Compound
Dry PCl5 solid Steamy white fumes of HCl -OH group present. Could be alcohol or carboxylic acid.

Sodium carbonate or Effervescence, CO2 produced Carboxylic acid.

sodium hydrogen carbonate

2,4-dinitrophenylhydrazine Red-orange crystalline precipitate C=O present. Aldehyde or ketone.

Ammoniacal silver nitrate Silver mirror or grey precipitate Aldehyde.

Fehling's solution Blue solution fades, red precipitate forms Aldehyde.

Iodine and sodium hydroxide Yellow precipitate, antiseptic smell. -COCH3 group or -CHOHCH3 group present.
(or potassium iodide and Triiodomethane – iodoform
sodium chlorate (I))

Acidified potassium dichromate (VI) Colour change orange to green. Oxidation occurs. Could be primary alcohol, secondary alcohol
or aldehyde.
Bromine water Colour change orange/brown to colourless. C=C present.
Sodium hydroxide, acidification White precipitate, soluble in dilute ammonia C-Cl present.
with nitric acid, then addition solution
of silver nitrate solution.
Cream precipitate, soluble in concentrated C-Br present.
ammonia solution.

Yellow precipitate, insoluble in concentrated C-I present.

ammonia solution.
Obviously if test results are negative, negative inferences can be made.E.g. If PCl5 is added to an unknown organic chemical and there is no observable
reaction, the unknown does not contain the –OH group. Similarly, if there is no colour change an addition of acidified potassium dichromate, the substance
will not oxidise - e.g. tertiary alcohol or ketone.
1
62. Answering Questions on Identifying Unkown Organic Compounds Chem Factsheet

Spectroscopic Data Worked Example 2

See Factsheets 54, 55 and 56 for more detail on interpreting mass, IR and Organic compound Y has the molecular formula C5H10O. The IR
simple NMR spectra. In questions involving unknown organic compounds spectrum is supplied:
it is essential that candidates can obtain the following information from
supplied spectra: IR spectrum
• Mass spectra can supply the molecular mass of the unknown compound transmittance /%
– the highest trace reading on the spectrum gives the mass of the 100
‘parent ion’ which is equal to the molecular mass.
• IR spectra supply information about types of bonds present such as 80
O-H and C=O. Use this information to when deducing the structure of
an unknown organic compound.
60

Worked Example 1
Organic compound X contains carbon, hydrogen and oxygen only. 40
Already certain organic chemicals can be ruled out – alkanes, alkenes,
halogenoalkanes or nitrogen containing compounds.
20
Chemical tests on X: C=O stretch
Addition of PCl5 – steamy white acidic fumes. 4000 3500 3000 2500 2000 1500 1000 500
X contains the –OH group, so is likely to be an alcohol or carboxylic wavenumber /cm-1
acid. The presence of a C=O group is confirmed here, so Y is an aldehyde or
ketone. Y cannot be an acid as only one O atom is present, and from the
X is added to acidified potassium dichromate (VI) solution and warmed number of C and H atoms present it can be concluded that there are no
– a colour change of orange to green is observed. further multiple bonds aside from the C=O.
X is oxidised, so cannot be a carboxylic acid, instead must be an alcohol.
Chemical tests on Y:
X is added to iodine and sodium hydroxide and warmed – a yellow Y is warmed with ammoniacal silver nitrate solution – no observable
precipitate with an antiseptic smell is formed. reaction.
X contains the –CHOHCH3 group (note that the previous tests discount Y is not an aldehyde, Y is a ketone. Care must still be taken here as there
the presence of the –COCH3 group!). are still a number of possibilities:
X is a secondary alcohol. e.g. pentan-2-one, pentan-3-one, 2-methylbutanone and so on.

Spectroscopic data: Y is warmed with sodium hydroxide and alkali – no observable reaction.
The mass spectrum of X has a highest peak of m/e=74. The -COCH3 group is not present in Y.
The molecular mass of X is 74. Now this structural information is available, the name and structure of Y
Bringing together all of this information – X is a secondary alcohol of can be deduced.
molecular mass 74, a name and structure can now be assigned to X: Y is pentan-3-one, CH3CH2COCH2CH3
X is butan-2-ol, CH3CH2CHOHCH3

Worked Example 3 Spectroscopic data:

Z is an organic compound containing the elements C, H and O only. Mass spectrum
[43] CH3CO+
Chemical tests on Z: 100
[45] COOH+
Addition of PCl5 – steamy white acidic fumes.
Z contains an –OH group, so is likely to be a carboxylic acid or an 80
alcohol.
relative abundance /%

[60] parent ion

Addition of Z to sodium hydrogen carbonate solution – effervescence, 60
gas produced turns lime water cloudy (carbon dioxide).
Z is a carboxylic acid.
40 [15] CH3+
The molecular mass of Z is that of the parent ion, RMM = 60.
The name and structure of Z, a carboxylic acid of RMM 60, can now be
20
deduced.
Z is ethanoic acid, CH3COOH
0.0
10 20 30 40 50 60 70
m/e

In summary, when attempting a question which requires the identification of an unknown organic compound:
• Use information supplied in the question introduction.
• Use information gained via chemical test results and spectra to build a picture of the chemical.
• Do not just use isolated pieces of information, but combine what you know from the various sources to gradually eliminate possibilities and then
deduce the correct answer.
2
62. Answering Questions on Identifying Unkown Organic Compounds Chem Factsheet

Practice Questions
1. Organic chemical A is a straight chain hydrocarbon.
On addition of bromine water to A there is no observable reaction.
The mass spectrum of A is supplied. Identify A.

mass spectrum
100

80
relative abundance /%

60

40

20

0.0
0 10 20 30 40 50 60

2. Organic chemical B contains the elements C, H and O only, with the carbons all positioned in a straight chain. The mass spectrum of B indicates that
B has a molecular mass of 72.
The following chemical tests were carried out on B.

Chemical test Observations

Addition of PCl5 No observable reaction.

Addition of 2,4-DNP solution Red/orange precipitate.

Addition of ammoniacal silver nitrate solution and warmed Silver mirror formed on inside of test tube.

Identify B

3. C, D and E are all organic chemicals containing C, H and O only. C, D and E all contain 3 C atoms and just one functional group each.
Identify C, D and E from the following test results:

Test C D E

PCl5 No observable reaction Steamy white acidic fumes No observable reaction

2,4-DNP Red/orange precipitate No observable reaction Red/orange precipitate

NaHCO3 solution No observable reaction Effervescence, CO2 No observable reaction

Heat with acidified K2Cr2O7 Colour change orange to green No observable reaction No observable reaction

Warm with I2/NaOH No observable reaction No observable reaction Yellow precipitate with antiseptic smell

E is propanone, CH3COCH3. Acknowledgements: This Factsheet was researched and written by Kieron
D is propanoic acid, CH3CH2COOH. Heath. Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire,
3. C is propanal, CH3CH2CHO. TF1 1NU. ChemistryFactsheets may be copied free of charge by teaching
2. Butanal, CH3CH2CH2CHO. staff or students, provided that their school is a registered subscriber. No part
1. Butane, CH3CH2CH2CH3. of these Factsheets may be reproduced, stored in a retrieval system, or
Answers transmitted, in any other form or by any other means, without the prior
permission of the publisher. ISSN 1351-5136
3
 Chem Factsheet
www.curriculumpress.co.uk Number 63
Answering Questions on Identifying
Unkown Inorganic Compounds
Before reading through this Factsheet you should:
• Be confident in assigning ionic formulae;
• Have gained practical experience of inorganic chemistry tests and preparations. (Factsheet 24);
• Know and understand the AS/A2 content on inorganic chemistry (Factsheets 13, 14, 19, 20, 38, 46, 47).

After working through this Factsheet you will be able to:

• Identify unknown inorganic chemicals when supplied with the necessary information in a written exam or practical situation.
The aim of this Factsheet is to provide candidates with the necessary information and experience to tackle questions involving the identification of
unknown inorganic compounds.

Such questions are commonplace in both written and practical exam situations, and also practical assessments. In practical situations candidates will most
likely be required to carry out simple chemical tests and make observations. In an exam situation the observations may be supplied, or the question may
involve selecting the correct reagents for particular situations.
This Factsheet will provides summaries of the common tests (see tables at the end of the Factsheet) and help in making inferences from the test results.
Strategy
Read the question carefully, assume any information about the unknown chemical supplied is important and must be considered. It is worth "ticking off"
the information to make sure you have used it all.

Unknown inorganic compounds are likely to be ionic - identification is usually achieved through chemical testing for both the anion and cation. Although
some pieces of information can be used in isolation - eg a flame test - be aware that you will often have to make deductions from the results of more than
one test - for example, a white precipitate with acidified barium chloride solution indicates a sulphate or hydrogen sulphate, but you will need to combine
this with a further test (addition of sodium carbonate solution) to distinguish between the two.
Chemical tests are not the only things to provide useful information. You should also note the colour of the compound, and whether it is soluble or not:-
Colour -
• a coloured compound suggests a transition metal,
• most group 1 and 2 compounds are white
Solubility
• alkali metal, ammonium salts and nitrates are soluble
• halides are soluble except for lead, mercury and silver
• sulphates are soluble except for calcium, strontium, barium, silver, mercury and lead
• carbonates and hydroxides are insoluble except for group 1 and ammonium compounds.
These can provide a useful check on the results of chemical tests - if you think you have a solution of copper carbonate, for example, you cannot be right,
as it is insoluble. Likewise, a blue compound is unlikely to be a sodium salt.
The example below indicates how conclusions can be drawn from each piece of information. Further examples are overleaf.

Information given Conclusion drawn

Inorganic compound P is a pale green solid. Suggests P contains transition metal cation

10cm3 of a solution of P was made up in a test tube. P is soluble - not a carbonate or hydroxide (it can't be a group 1 carbonate
or hydroxide)
Sodium hydroxide solution was added to 5cm3 of this solution Green ppt could be Fe2+, Cr3+, Ni2+. Insoluble in excess, so not Cr3+
A pale green precipitate was produced, which became brown on its surface Brown on surface ⇒Fe2+ (brown is from oxidation to Fe3+)
with standing. The precipitate did not dissolve in excess sodium hydroxide.

The mixture from the previous test was warmed. A gas was evolved Gas is ammonia ⇒NH4+ present
which turned damp red litmus paper blue

To the remaining 5cm3 of P, barium chloride solution was added dropwise, White ppt ⇒sulphate or hydrogen sulphate
followed by dilute hydrochloric acid. A white precipitate was observed.

On addition of sodium carbonate solution to this mixture, a very slight Only slight effervescence ⇒Fe2sulphate
effervescence was observed
Compound is ammonium iron (II) sulphate (NH4)2Fe(SO4)2

1
63. Answering Questions on Identifying Unkown Inorganic Compounds Chem Factsheet

Practice Questions Answers

1. Use the following information to identify inorganic chemical A: 1. Yellow-orange flame ⇒ sodium
Flame test: Yellow-orange flame. Silver nitrate test⇒ halide
To 3 cm3 of a solution of A was added 3 cm3 2M HNO3 and 0.1M cream ppt, soluble in conc NH3 ⇒ bromide
AgNO3 dropwise. Note that a cream ppt can be difficult to distinguish from white or
A cream precipitate was produced which would not dissolve in dilute yellow - the solubility in conc ammonia is essential to be certain it is
NH3 (aq), but did dissolve in concentrated NH3 (aq). bromide
A is sodium bromide (NaBr)

2. Use the following information to identify inorganic chemical B: 2. Sodium hydroxide test for cations
No ppt ⇒no cation with insoluble hydroxide present
4 cm3 of a solution of B was made up in a test tube. Sodium hydroxide
Gas given off is ammonia (alkaline gas)
solution was added, and the mixture warmed. A gas was given off
Ammonium ions present
which turned damp red litmus paper blue.
Another sample of B was dissolved in dilute nitric acid, and then Barium chloride test for sulphate or hydrogen sulphate
barium chloride solution was added dropwise. A white precipitate was No effervescence with sodium carbonate ⇒sulphate
observed. Note that if the barium chloride was not acidified, carbonates would
Sodium carbonate was added to a solution of B, and there was no also produce a white ppt
observable reaction.
B is ammonium sulphate (NH4)2SO4)

3. Use the following information to identify inorganic chemical C: 3. Lilac flame ⇒ potassium

Solid C gives a lilac colour in a flame test. Gas evolved is ammonia (from reduction of nitrate ion) ⇒ nitrate
A solution of C is boiled with sodium hydroxide solution and aluminium
powder. Fumes were evolved which turned damp red litmus paper C is potassium nitrate. (KNO3)
blue.

4. Use the following information to identify inorganic chemical D: 4. Blue solution suggests compound of a transition metal

D is in the form of a blue solution. On addition of ammonia solution Blue ppt with ammonia solution ⇒ Cu2+ or Co2+
dropwise to D, a sky blue precipitate is formed. Dissolves to give deep blue solution ⇒ Cu2+
As the ammonia is then added to excess, this precipitate dissolves
leaving a deep blue solution.
No reaction with sodium carbonate ⇒ not acidic (eg not hydrogen
Another sample of B is tested with solid sodium carbonate – there is sulphate)
no observable reaction.
To a different sample of D dilute hydrochloric acid is added, and then White ppt with barium chloride ⇒ sulphate (cannot be hydrogen
barium chloride solution dropwise – a white precipitate forms. sulphate from previous test)

D is copper (II) sulphate (CuSO4)

5. a) Use the following information to suggest possible identities for

5.a)Brick red flame ⇒ calcium
inorganic chemical E:

E produces a brick red flame in a flame test. Gas evolved on addition of acid is carbon dioxide ⇒ carbonate or
On addition of dilute hydrochloric acid to solid E there is hydrogen carbonate
effervescence.
The gas produced is bubbled through lime water, which turns cloudy E is either calcium carbonate, CaCO3 or calcium hydrogen carbonate,
white. Ca(HCO3)2

b) Describe an additional chemical test that could be used to determine b) Add MgSO4 (aq) dropwise to solution.
the identity of E White ppt indicates CO32-, no ppt indicates HCO3-

6. Use the following information to identify inorganic chemical F 6. White solid suggests not a transition metal

F is a white solid. Brown gas is nitrogen dioxide - thermal decomposition of nitrate

On heating, F evolves a brown gas which turns damp blue litmus paper
red. White ppt with sodium carbonate ⇒ cation has insoluble carbonate,
On addition of sodium carbonate solution to a solution of F, a white so not group 1
precipitate is formed.
A flame test produces an apple-green flame Apple-green flame ⇒ barium

F is barium nitrate
2
63. Answering Questions on Identifying Unkown Inorganic Compounds Chem Factsheet

Tests for simple anions

Anion Test Expected Observation
Choride, Cl− To solution add dilute HNO3 then AgNO3 (aq). White ppt of AgCl, soluble in dilute NH3 (aq)
−
Bromide, Br To solution add dilute HNO3 then AgNO3 (aq). Cream ppt of AgBr, soluble in conc. NH3 (aq)
Iodide, I− To solution add dilute HNO3 then AgNO3 (aq). Yellow ppt of AgI, insoluble in conc. NH3 (aq)
Nitrate, NO3− Boil with sodium hydroxide solution and aluminium powder Fumes of ammonia gas
Nitrite, NO2− Add acidified potassium iodide solution Colour of solution turns brown as iodine is liberated
Carbonate, CO32− and Add dilute HCl to solid or solution Effervesence, CO2 produced (turns limewater cloudy white)
hydrogen carbonate, HCO3−
To differentiate between Add MgSO4 (aq) dropwise to solution White ppt indicates CO32-, no ppt indicates HCO3-
CO32− and HCO3−
Sulphate, SO42− and Add dilute HCl then BaCl (aq) to solution. White ppt of BaSO4
hydrogen sulphate HSO4−
To differentiate between Add Na2CO3 to solution Vigorous effervescence of CO2 indicates HSO4-, slight or
SO42− and HSO4− no effervescence indicates SO4-
Sulphite, SO32− Add dilute HCl to solid or solution and warm Pungent SO2 evolved, which turns acidified dichromate
from orange to green

Cation tests using NaOH(aq)

Cation Addition of NaOH (aq) dropwise Addition of excess NaOH (aq)
Ammonium, NH4+ On warming, ammonia gas evolved, turning red litmus paper blue
Chromium, Cr3+ Green ppt Green solution
Manganate, Mn2+ Buff ppt, darkens in air Precipitate does not dissolve
Iron (II), Fe2+ Pale green ppt, browns on surface Precipitate does not dissolve
3+
Iron (III), Fe Red brown ppt Precipitate does not dissolve
Cobalt, Co2+ Blue ppt, turns brown in air Precipitate does not dissolve
Nickel, Ni2+ Pale green ppt Precipitate does not dissolve
Copper, Cu2+ Pale blue ppt Precipitate does not dissolve
Zinc, Zn2+ White ppt Colourless solution

Cation tests using NH3(aq)

Cation Addition of NH3(aq) dropwise Addition of excess NH3 (aq)
Chromium, Cr3+ Green ppt Precipitate does not dissolve
Manganate, Mn2+ Buff ppt, darkens in air Precipitate does not dissolve
Iron (II), Fe2+ Pale green ppt, browns on surface Precipitate does not dissolve
Iron (III), Fe3+ Red brown ppt Precipitate does not dissolve
Cobalt, Co2+ Blue ppt, turns brown in air Precipitate does not dissolve
Nickel, Ni2+ Pale green ppt Blue solution
Copper, Cu2+ Pale blue ppt Deep blue solution
Zinc, Zn2+ White ppt Colourless solution

Flame Tests Nitrates Carbonates

• Group 1 nitrates (except lithium nitrate) • Group 1 carbonates will not decompose on
Cation Expected observation
decompose to give the metal nitrite and heating, except lithium carbonate:
Sodium, Na+ Yellow-orange flame oxygen gas • Group 2 carbonates all decompose (except
Potassium, K+ Lilac flame • Group 2 nitrates (and lithium nitrate) for barium carbonate, which is stable) to
Calcium, Ca 2+
Brick red flame decompose to give the metal oxide, the form the metal oxide and carbon dioxide gas
brown gas nitrogen dioxide and oxygen: • Thermal stability increases down both groups
Barium, Ba2+ Apple green flame • Thermal stability increases down both groups

Tests for gases

Gas Description of gas Test Expected observation
Hydrogen, H2 Colourless, odourless Ignite using a lighted splint ‘Squeaky pop’ sound. Pale blue flame
Oxygen, O2 Colourless, odourless Glowing splint Splint ignites or glows brighter
Carbon dioxide, CO2 Colourless, odourless Bubble through lime water Turns cloudy white
Ammonia, NH3 Colourless, pungent Moist red litmus paper Turns blue
Chlorine, Cl2 Yellow-green, pungent (a) Moist universal indicator paper Turns red then bleached white
(b) Bubble through KBr (aq) Solution turns yellow-orange
Nitrogen dioxide, NO2 Brown, pungent Moist universal indicator paper Turns red
Sulphur dioxide, SO2 Colourless, pungent Moist dichromate paper Turns from orange to green

Acknowledgements: This Factsheet was researched and written by Kieron Heath. Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire, TF1 1NU. ChemistryFactsheets may be copied free of charge by teaching
staff or students, provided that their school is a registered subscriber. No part of these Factsheets may be reproduced, stored in a retrieval system, or transmitted, in any other form or by any other means, without the prior permission
of the publisher. ISSN 1351-5136
3
 Chem Factsheet
www.curriculumpress.co.uk Number 64

Acid Base III: Buffer solutions,

pH Curves and Dibasic Acids
To succeed with this topic you need to understand the concepts of pH, Ka , buffers and pH curves. (Factsheets 25 and 26).
After working through this Factsheet you will:
• understand the link between buffer solutions and the pH curve for a weak acid with a strong base;
• be able to use the pH curve for a weak acid with a strong base to find pKa and Ka for the weak acid involved;
• have met the pH ‘problems’ of H2SO4, a dibasic acid.
Exam Hint : The three main points covered by this Factsheet are
very common examination questions – learn this work thoroughly

Buffer solutions and pH curves

pH curves Buffer solutions
The pH curve for the titration of a weak acid with a strong base has the 1. A buffer solution is one whose pH hardly changes when small
shape shown below: amounts of acid and alkali are added to it.
2. A buffer solution is made by dissolving the salt of a weak acid in the
pH
weak acid itself
14 e.g. sodium ethanoate (CH3COONa) dissolved in ethanoic acid
G H (CH3COOH)
12 F
3. The following mathematical equation is used for buffer
solutions:
10
[acid]
pH = - log10Ka – log10
8 [anion]
E
or
6
D [acid]
B C pH = pKa – log10
4 [anion]
A
2 N.B. ‘p’ = ‘– log10’

We need to look at the link between this pH curve and buffer solutions.
0 10 20 30 40 50
Volume of NaOH added /cm3 Reminder: a buffer solution is a mix of a weak acid (HA) and its salt (A-)
We need to look in more detail at what chemicals are in the solution
mixture at various points on the curve (A-H): Question : Where does this mixture appear on the curve?
A pure weak acid (HA)
Answer: Between points A and E on the curve.
B weak acid (HA) + some of its salt (A−) because of the
neutralisation reaction between the acid and the alkali and The ‘acidic’ part of a pH curve between a weak and a strong base is a
more water because: acid + alkali → salt + water) mixture of the weak acid and its salt i.e. it has the properties of a buffer.
C less weak acid (HA) and more salt (A−)
If, while adding the base, the experiment had been stopped at any point
D even less weak acid (HA) and even more salt (A−) between A and E, the solution could have been used as a buffer solution.
E no weak acid left, the solution contains only the salt
The pH of the buffer solutions could be found by ‘reading’ the
E-F the end-point where one drop of the base (A−) changes the
y-axis at, say, points B, C and D.
solution from acidic to basic (pH 7→11)
F a salt solution + a slight excess of base (NaOH) Note that pH of the buffer is higher, the greater the proportion of salt to
acid.
G+H as an excess of base is added the pH increases to maximum Beyond the point E, no acid is left, only the salt, so the solution would no
value of about pH = 13. longer be a buffer.

1
64. Acid Base III: Buffer solutions, pH Curves and Dibasic Acids Chem Factsheet

We need to move to the equation for a buffer solution. Now the final test of your understanding!

[acid] Question: What is the pH range of the most effective buffer solution?
pH = pKa − log10
[anion] Answer: pH = 5.6 (C) to 6.8 (just below E)

Reason: This is when there is more of the anion, [A−] and less of the
The [acid] is [HA] and the [anion] is [A-].
acid, [HA].
What happens when [HA] = [A-]?
[HA]
log10 = log10 1 = 0 Experimental methods of finding Ka for a weak acid
[A-]
Using the theory covered so far there are two methods to find Ka:
This means the equation becomes
pH = pKa - 0 i.e. Method 1
(a) Pipette 25.00 cm3 of the weak acid into a conical flask
pH = pKa when [HA] = [A−]
(b) Use a pH meter to measure its pH value.

When does [HA] = [A-]? (c) Add 1.00cm3 strong base (NaOH(aq)) from a burette, stir to mix
This happens half-way to the equivalence point. and measure its pH value.
In the example graph,
(d) Continue to add 1.00cm3 of NaOH(aq) and take the pH value
Equivalence point = 25 cm3 NaOH(aq) readings.
so At 12.50cm3 NaOH,
(e) Plot a graph of pH readings against the volume of NaOH(aq)
pH = pKa
added.
This is point C, where the pH is 5.6.
(f) Use the graph to find the equivalence point (end point) in terms
Using the equation, of cm3 of NaOH(aq).

pH = - log10 [H+] (g) Divide the volume by 2.

then pKa = - log10Ka (h) Read off the pH value at end point volume ÷ 2 – this is the pKa
value.

so the use of a calculator will enable us to find Ka. (i) Convert pKa → Ka using the calculator.

Finding the value of Ka for a weak acid from the pH curve Method 2
of a weak acid with a strong base: (a) Pipette 25.00cm3 of the weak acid into a conical flask.

(1) The ‘acid part’ (up to the equivalence point) of the pH curve is (b) Add indicator.
a mixture of HA (weak acid) and its salt (A−),
(c) Titrate with the strong base (NaOH(aq)) until the indicator
(2) A mixture of a weak acid (HA) and its salt (A−) is a buffer solution,
changes colour, record the volume added.
(3) When [HA] = [A−] the mathematical equation for a buffer solution
means pH = pKa (d) Repeat the titration process until concordant titres are achieved.

(4) Reading the pH value from the graph at half the end point value (e) Calculate from the titres the average titre – this will be the end
(cm3) gives you the pKa value. point (equivalence point).
(5) Using a calculator we can change pKa → Ka.
(f) Divide the average titre by 2.
N.B. From the example graph, point A and point E are not buffer
solutions – A has no salt (A−) and E has no acid (HA). (g) Pipette 25.00cm3 of the weak acid into a conical flask.
14
G H (h) Add the average titre volume of NaOH(aq)), divided by 2.
12 F
10 (i) Shake well and using a pH meter, find the pH value – this is the
8 E pKa value.
6
D
4 B C (j) Convert pKa → Ka using a calculator.
A
2

0 10 20 30 40 50

The solution acts as a buffer at pH values of more than 3 (A)

and less than 7 (E).

2
64. Acid Base III: Buffer solutions, pH Curves and Dibasic Acids Chem Factsheet

Practice Questions
The dibasic acid ‘problem’ of H2SO4
1. The following questions are about the pH curve shown below when
H2SO4 is a strong acid.
25.0cm3 of 1.0 mol dm−3 HA(aq) was titrated with 1.0 mol dm−3
Strong acids are defined as ones which fully dissociate in solution, NaOH(aq)

i.e. HCl(aq) → H+(aq) + Cl−(aq) pH

This fact enables us to calculate the pH of a strong acid from its 14

concentration.
12
Q. What is the pH of 0.1 mol dm3 HCl?
10
HCl(aq) → H+(aq) + Cl−(aq)
0.1 0.1 0.1 8
→ +
mol dm-3 mol dm-3 mol dm-3
6
[H+] = 0.1 mol dm-3

pH = - log10 (0.1) = 1.0 4

2
Suppose we take the same approach for H2SO4

H2SO4(aq) → 2H+(aq) + SO42−(aq) 0 10 20 30 40 50

Volume of NaOH added /cm3
0.1 mol dm-3 → 0.2 mol dm−3 + 0.1 moldm−3
Use the pH curve to find
[H+] = 0.2 mol dm-3 (a) the pH of the NaA(aq) solution.
−
pH = log10 (0.2) = 0.14 (b) for the weak acid, HA,
(i) the pKa value
This suggests that H2SO4 is more acidic (pH = 0.14) because it (ii) the Ka value
produces twice the number of H+ ions.
(c) the range of pH values over which the mixture acts as a buffer.
THIS IS NOT TRUE FOR H2SO4!
When measured, the pH of 0.1 mol dm-3 H2SO4 is the same as for (d) the pH of the most efficient buffer solution.
0.1 mol dm-3 HCl.
2. H2SO4 is a strong dibasic acid, whereas HNO3 is a strong monobasic
Why is this? acid. Why are the pHs of these two acids very similar?
As a dibasic acid, sulphuric acid dissociates as shown below:
Answers
Step (1) H2SO4(aq) → H+(aq) + HSO4−(aq)
1. (a) Any value between pH 8 → 11
Step (2) HSO4−(aq) → H+(aq) + SO42−(aq)
(b) (i) 5.8
The key points are that: (ii) 1.58 × 10-6
• the dissociation constant for step (1)
(c) 3.4 – 6.8
is very large - H2SO4 completely dissociates into H+ and HSO4−
• the dissociation constant for step (2) is small (about 0.01) - and
(d) Any value between 5.8 – 7.8
this dissociation is also supressed by the high H+ concentration
produced by step (1)
2. Answers gain credit for the following points:
1) Explanation of dibasic/monobasic acids in terms of the amount of
Result H2SO4 only produces the same amount of ions as HCl
H+/H3O+ ions.
so the pH value is about the same.
2) Explanation of strong acids (complete ionisation)

3) Compares HNO3 (one H+) to H2SO4 (two H+).

4) Links [H+] → pH value.

5) Explains that H2SO4 has complete dissociation for

H2SO4 → H+ + HSO4- but only partial dissociation for
HSO4- → H+ + SO42-
Acknowledgements: This Factsheet was researched and written by Sam
Goodman. Curriculum Press, Bank House, 105 King Street, Wellington,
6) Links the dissociation of acids to pH values i.e. similar because
Shropshire, TF1 1NU. ChemistryFactsheets may be copied free of charge by [H+] similar.
teaching staff or students, provided that their school is a registered subscriber.
No part of these Factsheets may be reproduced, stored in a retrieval system, or
transmitted, in any other form or by any other means, without the prior
permission of the publisher. ISSN 1351-5136
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 Chem Factsheet
www.curriculumpress.co.uk Number 65

Calorimetry Experiments
To succeed in this topic you need to:- The experiments outlined could be used in a school laboratory to collect
• Have a good understanding of AS-level Energetics covered so far in data and thus determine values of ∆H .
Factsheet 08 - Energetics I - Hess's Law;
• be familiar with basic apparatus used in Chemistry. Questions can be met requiring candidates to carry out calculations based
on data from similar experiments. The calculations may involve the use of
After working through this Factsheet you will:- Hess’s Law.
• be familiar with the main types of experiment used in calorimetry at
AS-level; When a reaction is carried out in a calorimeter
• be able to calculate values of enthalpy changes from experimental data. the heat lost/gained the heat gained/lost by the
=
by the reacting system calorimeter and its contents
Experiment 1: Enthalpy changes on displacement and the reactivity
Changes in heat content are calculated using:
series
∆H = mc ∆T where: m = mass
c = specific heat capacity
Introduction
∆T = change in temperature
The relative positions of metals in the reactivity series can be investigated
by adding metals to solutions of salts of other metals, for example
Zn(s) + Cu2+ (aq) → Zn2+ (aq) + Cu(s)
and for the zinc/silver reaction ∆H is –363 kJ mol–1.
This confirms that zinc is ‘above’ copper in the reactivity series. The Experiment 2: Enthalpy change of neutralisation
enthalpy change for this and similar reactions can lead to an illustration
of Hess’s Law. Introduction
Acidic and alkaline solutions mix exothermically. The ionic equation
Method for neutralisation is
• Place 100 cm3 of copper(II) sulphate solution (0.2 mol dm–3) in a
H+(aq) + OH–(aq) → H2O(l)
polystyrene cup (or vacuum flask if available).
• Record the temperature (to the nearest 0.1oC) of the solution every Method
30 seconds for two minutes. • Put 50 cm3 of hydrochloric acid (1.0 mol dm–3) and 50 cm3 of
• At the two minute mark add 2 g (an excess) of zinc powder and stir sodium hydroxide solution (1.0 mol dm–3) into separate measuring
the mixture. cylinders
• Continue recording the temperature for a further five minutes. • Wait for the temperatures of the two solutions to equalise.
• Plot a graph of temperature against time and use the plot to determine • Pour one of the solutions into a polystyrene cup.
the maximum temperature change (∆T). • Add the second solution, stir well and record the maximum
temperature reached.
Calculation
The heat energy exchanged in the experiment is 100 × ∆T × 4.18 joules. The number of joules exchanged can be found by calculation or by the
use of a joulemeter as in experiment 1.
In the reaction 0.02 (= 1/50) mole of copper ions reacted so the heat
exchanged per mole would be 50 × (100 × ∆T × 4.18) joules or Calculation
5 × ∆T × 4.18 kJ. The heat energy exchanged in the experiment is 100 × ∆T × 4.18 joules.
As the reaction is exothermic the value for ∆H (in kJ mol–1) will need As 0.05 (= 1/20) mole of hydrochloric acid has been neutralised the heat
a negative sign. exchanged per mole would be 20 × (100 × ∆T × 4.18) joules or
2 × ∆T × 4.18 kJ.
Alternative Method
Carry out the procedure above to determine the change in temperature. As the reaction is exothermic the value for ∆H (in kJ mol–1) will need
• Then place a further 100 cm3 of copper(II) sulphate solution in the a negative sign.
reaction vessel and insert a low voltage heater connected through a
joulemeter. Extension
• Switch on the current and allow the temperature to rise by the The experiment can be repeated using nitric acid instead of hydrochloric
same number of degrees. acid and potassium hydroxide solution instead of sodium hydroxide
• Record the reading on the joulemeter to determine the heat exchanged solution.
in the experiment and thus calculate a value for ∆H.
In all four possible combinations a similar result should be found as the
Extension ionic equation for each is the same. The standard molar enthalpy change
If similar experiments are carried out to determine the enthalpy changes of neutralisation is –57.6 kJ mol–1. A different, less negative value is
for (say) obtained if a weak acid such as ethanoic acid is used as some heat energy
Cu(s) + 2Ag+(aq) → Cu2+(aq) + 2Ag(s) is used in breaking bonds in the undissociated acid.
and Zn(s) + 2Ag+(aq) → Zn2+(aq) + 2Ag(s)

then Hess’s Law can be illustrated. For the zinc/copper reaction ∆H

is –216 kJ mol–1; for the copper/silver reaction ∆H is –147 kJ mol–1;

1
65. Calorimetry Experiments Chem Factsheet

Experiment 3: Enthalpy of combustion Experiment 4: Finding an enthalpy change that cannot be measured
directly
Introduction
The complete combustion of hydrocarbons, alcohols and other organic
Introduction
compounds containing carbon, hydrogen and oxygen only produces
For a vast number of reactions values of the enthalpy change cannot be
carbon dioxide, water vapour and heat. In school laboratory experiments,
determined directly. However, by using Hess’s Law with values which
results are not very reliable as, apart from heat losses, complete
can be experimentally determined, the missing values can be calculated.
combustion is rarely achieved. The method described is usually restricted
to liquid fuels such as alcohols. Examples include the enthalpy change of reaction which occurs when an
anhydrous salt becomes hydrated.
For more accurate results a bomb calorimeter would be used.
Method
Method • Add 0.1 mol of the anhydrous salt to 100 cm3 of water and determine
• Set up the apparatus filling the calorimeter with water. a value (∆H1) using procedures similar to Experiment 1 above.
• Stir the water in the calorimeter and record the temperature. • Then add 0.1 mol of the hydrated salt to water.
• Fill the spirit lamp with an alcohol and weigh it. • The volume of water used should be less than 100 cm3 to allow for
• Put the lamp in position, light the wick and quickly adjust the air the water contained in the salt.
flow to obtain a steady flame. • A second value (∆H2) can then be calculated.
• Meanwhile stir the water.
• When a temperature rise of about 10oC has been obtained extinguish Calculation
the flame but continue stirring and note the maximum temperature Using Hess’s Law, (∆H1) – (∆H2) will produce a value for the hydration
reached. reaction. Care must be taken over the signs for ∆H in each case.
• Reweigh the lamp as quickly as possible.
• Use an electrical circuit to produce a similar temperature rise and Extension
note the number of joules required. The enthalpy change for the endothermic reaction

Calculation 2KHCO3(s) → K2CO3(s) + H2O(g) + CO2(g)

From the mass of alcohol used (w) and its relative formula mass (M) the
w can be determined by adding appropriate masses of each solid to an
number of moles used can be found.
M excess of hydrochloric acid. Note that 2 mol of potassium
If the number of joules is known, then a value for the molar enthalpy of hydrogencarbonate react to give 1 mol of potassium carbonate. Again a
(number of joules) Hess’s Law triangle or enthalpy level diagram will produce a value for the
combustion can be calculated from
(number of moles) enthalpy change.
Extension
If the experiment is repeated with a number of alcohols it can be shown
that the values of the enthalpies of combustion of successive alcohols
differ by a similar amount. This is because each member of an homologous
series differs from the next by –CH2–. The combustion of this unit
should result in the same release of energy (about 650 kJ mol–1) whatever
the homologous series being investigated.

Practice Questions 4. The enthalpy change for the precipitation of barium carbonate was
1. A student wrote the following account: investigated by mixing barium nitrate solution with sodium carbonate
A piece of zinc weighing 3 g was placed in a glass beaker. 50 cm3 of 0.5 solution. Three experiments were used.
mol dm–3 copper sulphate solution was measured using a measuring
cylinder and added to the beaker. The temperature of the solution was Expt 1 : 10.0 cm3 of barium nitrate solution (1.0 mol dm–3) was
taken before it was added and then every minute afterwards. added to 10.0 cm3 of sodium carbonate solution (1.0 mol dm–3). The
temperature rose by 1.5oC.
The results were:

Time in minutes 0 1 2 3 4 5 Expt 2 : 50.0 cm3 of barium nitrate solution (1.0 mol dm–3) was
added to 50.0 cm3 of sodium carbonate solution (1.0 mol dm–3).
Temperature in oC 22 26 29 27 24 22
Expt 3 : 50.0 cm3 of barium nitrate solution (0.2 mol dm–3) was
Suggest three improvements you would make to the experiment. Give
added to 50.0 cm3 of sodium carbonate solution (0.2 mol dm–3).
reasons for each suggestion.

2. Outline the essential details of an experiment to determine the enthalpy (a) Calculate the temperature rises to be expected in experiments 2
of solution of ammonium nitrate. and 3.
Show how the experimental results would be used to calculate the (b) Which of the experiments should give the most accurate result for
molar enthalpy change. the determination of the temperature change? Give a reason for
3. 2.66 g of anhydrous copper(II) sulphate powder was added to 50.0 your answer.
cm3 of distilled water in a polystyrene cup. The temperature of the (c) Which of the experiments should give the least accurate result for
water rose from 19.6oC to 25.4oC. Calculate the molar enthalpy change the determination of the temperature change? Give a reason for
of solution of anhydrous copper(II) sulphate. You may assume that your answer.
the specific heat capacity of copper(II) sulphate solution is
4.18 Jg–1 K–1 and that there is negligible heat loss to the surroundings.

2
65. Calorimetry Experiments Chem Factsheet

Answers
1. Any three of:
Use powdered zinc – reacts faster so heat losses are reduced
Use a polystyrene cup/vacuum flask – reduces heat loss
Use a burette/pipette – more accurate than a measuring cylinder
Put the solution in the polystyrene cup before the zinc is added – to
enable initial temperature to be checked
Use a thermometer reading to 0.1oC – more accurate temperature change
found
Measure the temperature of the solution for a few minutes before
addition of the solid – gives a better value for the initial temperature
Stir the mixture – helps reduce reaction time
Measure temperatures more frequently during the reaction – produces
a better graph and thus a more accurate figure for the change in
temperature

2. Use a polystyrene cup/vacuum flask of suitable size

Use a burette/pipette to measure 50 cm3 of water and add this to the
polystyrene cup
Weigh accurately 0.05 mol of the powdered solid
Use a thermometer reading to 0.1oC to find the initial temperature
Add the solid, stir the mixture and record the maximum (or minimum)
temperature reached (or note the temperature every 15 seconds)

Determine the change in temperature (∆T) either by simple difference

or graphically
Calculate the heat exchanged using 50 × ∆T × 4.18
As the resulting solution is 1.0 mol dm–3 this calculation gives a
numerical value for the enthalpy of solution. If the reaction is exothermic
a – sign will be needed; if the reaction is endothermic a + sign must be
used.

3. Temperature rise = 25.4 – 19.6 = 5.8 (K). Reaction is exothermic.

Heat exchanged in experiment = 50.0 × 5.8 × 4.18 = 1212.2 J

RFM CuSO4 = 63.6 + 32.0 + (4 × 16.0) = 159.6

1212.2 × 159.6
Heat exchanged per mol of CuSO4 = = 72732 J
2.66
∆H = – 72.7 kJ mol–1

4. (a) 1.5oC 0.3oC

(b) Experiment 2 – large volume, minimises errors
(c) Experiment 3 – temperature change too small

Acknowledgements: This Factsheet was researched and written by Phil Richardson.

Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire, TF1 1NU.
ChemistryFactsheets may be copied free of charge by teaching staff or students, provided
that their school is a registered subscriber. No part of these Factsheets may be reproduced,
stored in a retrieval system, or transmitted, in any other form or by any other means, without
the prior permission of the publisher. ISSN 1351-5136

3
 Chem Factsheet
www.curriculumpress.co.uk Number 66
Maths for Chemists 2
This Factsheet covers logarithms and their use in Chemistry. Powers
• Raising a number to a positive power means multiplying it by itself
What are logarithms?
that number of times - eg 106 = 10 × 10 × 10 × 10 × 10 × 10
Logarithms are closely related to powers, so before continuing, make sure
you know and understand the power facts in the box (right).
• Special cases: any number to the power 1 is the number itself; any
To see how logarithms work, consider the following examples: number to the 0 gives 1 - eg 21 = 2 30 = 1

100 = 102 log10100 = 2 • Negative powers of a number are one over the corresponding postive
0.001 = 10-3 log100.001 = -3 1 1 1
power - eg 10−3 = 3 = =
10 10 × 10 × 10 1000
So when we say "what is log10 1000?", we are asking "What power must
I raise 10 to, to get the answer 1000?" The answer is 3 - so log101000 = 3 • You can also have powers that are decimals - eg 102.156
Although you can have logarithms to different bases, in Chemistry we
will only be looking at logarithms to the base 10 (log10). To save time, we'll • You find powers on your calculator using the button marked xy (or
just write "log" when we mean "log10" yx) - eg to find 102.156, type in 10, then xy , then 2.156
(check - the answer should be 143.2)
Calculating logs
It's easy to work out logs for numbers that are exact powers of 10 and it's When doing work on logarithms in Chemistry, you mainly deal with
worth being able to do so mentally to save time in the exam and guard powers of 10 - so, a few facts about them:
against calculator error. But logs for other numbers have to be worked out
on your calculator. • Positive powers of 10 are easy to recognise - just count the zeroes!
eg 101 = 10 103 = 1000
The button for finding log to the base 10 may be labelled:
LOG LOG10 LG • Negative powers of 10 are easy to recognise as decimals - just count
the decimal places! eg 10-1 = 0.1 10-4 = 0.0001
Note: do NOT use the button labelled ln or loge. This gives you logarithms
to a different base - and hence the wrong answers! • Positive powers are larger than 1; negative powers smaller than 1

Some calculators require you to put the number in first, then press the log Exam Hint: Remembering these points can help you spot a wrong
button - in others, you press the log button first, then the number. Check answer from keying into your calculator wrongly - and hence save
which yours is by finding log100 (the answer should be 2). a few marks!

Finding the number that has a particular log Before moving on to applying logs, check you understand the work so far
There are two ways of doing this on your calculator: by doing these questions. Try not to use your calculator in questions 1
and 3, and in questions 2 and 4, work out mentally the values your answer
• Use the xy (or yx) button to find 10 to the power of the number lies between in order to check your calculation,
eg: logx = 0.123. To find x, enter 10 xy 0.123
1. Find:
a) log 100 b) log 1 c) log 10 d) log 0.1 e) log 0.001
• Use the INV or 2ND or SHIFT button, together with the LOG button
On some calculators you have to press INV LOG first, then the number; 2. Find:
on others you press the number then INV LOG. Check which yours is a) log2 b) log 91 c) log0.61 d) log 0.003 e) log½
by using this method to solve logx = -1.23 (ans 0.0589)
3. Find the number whose log is:
Exam Hint: You should never get a negative number from either of the a) -2 b) 4 c) 1 d) 0 e) 6
above methods. It's impossible to find the log of a negative number - if
you think you have, then you've probably pressed LOG not INV LOG. 4. Find the number whose log is:
a) 0.674 b) 2.18 c) -2.16 d) -0.0521 e) -1.32
If a number has a whole-number log (eg logx = -4 or logy = 3) then you can
find the number without a calculator:
logx = -4 so x = 10-4 = 0.0001 logy = 3 so y = 103 = 1000 e) 0.0479 c) 0.00692 d) 0.887 b) 151 4. a) 4.72

Checking answers e) 1000000 d) 1 c) 10 b) 10000 3. a) 0.001

Once you are confident with logs and can do whole-number examples in
your head, you can use this method to check if your answer is plausible: e) -0.301 d) -2.52 c) -0.215 b) 1.96 2 a) 0.301
If logx = 1.57, since 1.57 is between 1 and 2, x is between 101 and 102
e) -3 d) -1 c) 1 b) 0 1 a) 2
So if, when you found x, it wasn't between 10 and 100 - you'd know there
Answers
was a mistake.

1
66. Maths for Chemists 2 Chem Factsheet

Logarithms and graphs

Sometimes graphs are required for data that cover a very wide range of values – going, for example, from 100 to 100 000. One example of this is
successive ionisation energies for one element.This presents a problem, since if the largest values are to fit on the graph, it will be very hard to plot the
small ones accurately.

Logarithmic scales are used to overcome this problem. Instead of the actual value, the logarithm of the actual value is plotted. This can be done on one
or both axes. This helps because the logarithms will not vary so much in size as the actual data values – eg log 100 = 2 and log100 000 = 5, so it would
be easy to fit both of these on one graph. It is usual to label the axes with the original values instead of their logarithms; this means that the scale is likely
to go up 1, 10, 100, 1000 etc.
Example: logarithmic graph of the successive ionisation energies of sodium. The graph is shown below. Note the values of log(IE) on the axis are
shown only for information here; the y-axis would normally just have IE
Electrons removed Energy required(kJ mol -1) log(energy) values.
1 490 2.69
2 4 560 3.66 IE log(IE)
3 6 940 3.84
1 000 000 6.00
4 9 540 3.98
5 13 499 4.13
6 16 600 4.22 100 000 5.00
7 20 100 4.30
8 25 500 4.41 10 000 4.00
9 28 900 4.46
10 141 000 5.15 1 000 3.00
11 158 700 5.20
100 2.00
We can see from the data that it would be hard to plot all the ionisation
energies accurately, so it's sensible to use a logarithmic scale for them. 0 1 2 3 4 5 6 7 8 9 10 11
There is no need to use one for the other axis, as these are small numbers. electrons removed

Logarithms and calculations on strong acids and bases

You need to be able to use logarithms in work on acids and bases. Example 3
The key definitions involving logs are: Find the pH of a 2 mol dm-3 solution of sodium hydroxide

pH = -log [H+] The key idea here is that as we are dealing with a base, we must use
Note that "p" here is
representing "-log" the two equations relating to pOH.
pOH = -log[OH−] ( = 14 - pH) In addition, we know that sodium hydroxide is a strong base, and so
will be fully dissociated into ions.
We will focus here on the aspects of the calculations involving logarithms;
other Factsheets give further information on more general acid/base problems. pOH = -log[OH−]
= -log2
Example 1 = - 0.301
Find the pH of a 0.1 mol dm-3 solution of hydrochloric acid
pH = 14 - pOH
The key chemistry here is that as hydrochloric acid is a strong acid, it = 14.301
dissociates completely into ions - so [H+] = 0.1

So pH = -log(0.1) Example 4
= - (-1) = 1 A solution of potassium hydroxide has pH 13. Find its concentration

Example 2 Again we use the two equations relating to pOH

A solution of HBr is found to have a pH of 0.5. Find the concentration of
the solution. pOH = 14 - pH
= 14 - 13 = 1
pH = -log[H+]
Now pOH = -log[OH−]
0.5 = -log[H+]
So 1 = -log[OH−]
log[H+] =-0.5
-1 = log[OH−]
[H+] = 10-0.5 = 0.316 mol dm-3
[OH−] = 10-1 = 0.1 mol dm−3
Since again we have a strong acid, this is also the concentration of the
solution. Since we have a strong base, concentration of the solution is 0.1 mol dm-3

Now try these examples. You can assume all acids and bases are strong.

1. Find the pH of a 0.5 mol dm-3 solution of nitric acid 4. pOH = 0 so 1 mol dm-3
3. pOH = -0.477 so pH =14.477
2. Find the concentration of a solution of hydrochloric acid that has pH -0.6
2. 3.98 mol dm-3
3. Find the pH of a 3 mol dm-3 solution of potassium hydroxide 1. 0.301
4. A solution of sodium hydroxide has pH 14. Find its concentration. Answers

2
66. Maths for Chemists 2 Chem Factsheet

Weak acids & bases Buffer Solutions

When weak acids are considered, we must also take into account the A buffer solution is a mixture of a weak acid and its salt (or less commonly,
dissociation constant Ka a weak base and its salt). The pH of a buffer solution changes only very
little if strong acid or base is added to it.
[H+][A−] pKa = -log Ka
Ka for the acid HA =
[HA] There are a variety of examination questions on buffers - see Factsheet 64
- but here we will concentrate on those aspects related to logarithms. The
pKa is often used as a measure of acid strength; unlike pH , it does not key equation for use with buffer solutions is:
depend on the concentration of the solution. [HA]
pH = pKa − log [A−]
Example: hydrofluoric acid has Ka = 6.7 × 10-4. Find pKa
pKa = -log (6.7 × 10-4) = 3.17
Example 1: A buffer solution is made by dissolving 0.1 moles ethanoic
Similarly for bases, we have the base dissociation constant Kb acid and 0.2 moles sodium ethanoate in 1 dm3 distilled water. Find its
pH
[B+][OH−] (Ka for ethanoic acid = 1.78 × 10-5 )
Kb for the base BOH = pKb = -log Kb
[BOH]
The key chemistry here is that we can assume the acid is effectively
undissociated (it would dissociate very little anyway, and dissociation is
Example: ammonia has pKb = 4.74. Find Kb further supressed by the presence of ethanoate ions from the salt). This
4.74 = -logKb means we can assume:
-4.74 = logKb
Kb =1.8 × 10-5
• [CH3COO−] is the original concentration of the salt
• [CH3COOH] is the original concentration of the acid
Exam Hint: A common student error is to treat a pKa (or pKb) value as
if it were Ka (or Kb), and use it directly in the dissociation equation. We have: [CH3COO−] = 0.2 [CH3COOH] = 0.1 pKa = -logKa =4.75
pH = 4.75 - log (0.1/0.2)
pH of weak acids = 4.75 - log0.5
To calculate the pH of a weak acid, you must first calculate [H+]. To do this, = 5.05
you use the acid dissociation expression and the following assumptions: Exam Hint: You may come across the equation for the buffer solution
• [H+] = [A−], so the top of the fraction becomes [H+]2 in slightly different formats. It's best to choose one format and stick to
This is effectively assuming there are no other sources of either ion in it - trying to remember more than one is likely to lead to mistakes.
the solution
The second key fact needed for buffer solutions is:
• [HA] = original concentration of acid
This is assuming an extremely small degree of dissociation - so that the
If [HA] = [A−], then pH = pKa
concentration of undissociated acid is almost the same as the initial
concentration.
Example. Calculate the pH of a 0.5 mol dm-3 solution of ethanoic acid This relationship just comes from the fact that if [HA] = [A−], then
(Ka = 1.78 × 10-5) [HA]/[A−] = 1, and log1 = 0. So if you forget it, you can work it out again
- but it's quicker to be able to remember it in an exam!
Step 1:
[H+][CH3COO−] Example 2: A buffer solution is made by mixing 50cm3 of each of
1.78× 10-5 = [CH3COOH] 0.1 mol dm-3 methanoic acid and 0.1 mol dm-3 potassium methanoate.
[H + 2
] Its pH is 3.74. Find the acid dissociation constant for methanoic acid.
1.78× 10-5 =
0.5 The acid and salt have equal concentrations, so pH = pKa
Step 2: Rearrange the equation
So pKa = 3.74
(1.78 × 10-5) × 0.5 = [H+]2
logKa = -3.74
Step 3: Square root to find [H+] Ka =1.82 × 10-4
[H+] = 1.78 × 10 -5 × 0.5 = 0.00298 Note that if you hadn't noticed that the acid and salt had the same
Step 4: Find pH concentrations, you would have needed to find the concentration of each
pH = -log[H+] = 2.53 (0.05 for each, since the original solutions were diluted by a factor of 2)
and then put the numbers into the equation.
Now try these examples
1. Nitrous acid (HNO2) has pKa =3.35 Now try these examples
a) Find Ka 1. A acidic buffer solution contains equal concentrations of an acid,HA,
b) Find the pH of a 0.5 mol dm-3 solution of nitrous acid and its sodium salt. Its pH is 4.61. Find Ka for HA
2. Methanamine has pKb =3.36 2. A buffer solution is 0.2 mol dm-3 with respect to ethanoic acid and
a) Find Kb 0.3 mol dm-3 with respect to sodium ethanoate. Find its pH
0.1 mole of methanamine is dissolved in 1 dm3 of water. (Ka for ethanoic acid = 1.78 × 10-5 )
b) Assuming the degree of dissociation of methanamine is very low, and
there are no other significant sources of OH−, find [OH−] 3. A buffer solution is 0.3 mol dm-3 with respect to acid HA. It also
c) Find the pH of this solution contains the sodium salt of the acid. The pH of the solution is 6.2
2. c) pH = 14 - pOH. pOH = 2.2 so pH = 11.8 Find the concentration of the sodium salt in the solution
2. b) Same approach as for an acid: [OH−]2/0.1 = Kb This gives [OH−] =6.61 × 10-3 (Ka for HA = 1.1 × 10-7 ).
1. a) 4.47 × 10-4 b) 1.8 2. a) 4.37 × 10-4 So [salt] = [acid]/5.7 = 0.05 mol dm-3
3.First find log([acid]/[salt]) = 0.76 Then find [acid]/[salt] =5.7
Acknowledgements: This Factsheet was researched and written by Cath Brown Curriculum Press, Bank House, 105 King Street, Wellington, TF1 1NU
1. 2.45 × 10-5 2. 4.9
ChemistryFactsheets may be copied free of charge by teaching staff or students, provided that their school is a registered subscriber.
No part of these Factsheets may be reproduced, stored in a retrieval system, or transmitted, in any other form or by any other means, without the prior permission of the publisher. ISSN 1351-5136

3
 Chem Factsheet
www.curriculumpress.co.uk Number 62
Answering Questions on Identifying
Unknown Organic Compounds
Before reading through this Factsheet you should: Information supplied in the question
• Have some practical experience of organic chemistry tests and
Exam Hint: Read the question carefully, assume any information
preparations (Factsheet 60); about the unknown chemical supplied is important and must be
• Have a good understanding of different spectroscopic techniques considered. "Tick off" the information to make sure you have used all
(Factsheets 54, 55 and 56); of it.
• Have a good understanding of AS/A2 organic chemistry;
• Have a good understanding and knowledge of organic functional groups Such problems on identifying unknown organic problems generally begin
and their reactions. by supplying the first ‘clues’. Often this will be information about the
composition:
After working through this Factsheet you will be able to:
• Identify unknown organic chemicals when supplied with the necessary E.g. Compound X contains carbon, hydrogen and oxygen only.
information in a written exam or practical situation.
Sometimes the molecular mass or even the molecular formula is supplied.
The aim of this Factsheet is to build on knowledge of organic chemical
testing and spectroscopic techniques to enable candidates to attempt a Results of Chemical Tests
specific type of question. In a practical exam or assessment, candidates may be given instructions to
carry out simple organic tests, or in a written exam results of such tests
Candidates are often asked to identify an organic compound having been may be described. Inferences must be drawn from these about the unknown
given some information about that compound. Sometimes all of the relevant compound.
information is supplied, and sometimes in practical situations candidates
are given instructions so as the necessary information can be discovered by Exam Hint: Do not treat each piece of information or test result in
chemical testing. isolation. Use all of the knowledge gained about the compound to
build a picture of the unknown structure.

The following table is not a definitive list of chemical tests (see Factsheet 60 for more information) but is included to help candidates make links between
test observations and inferences about unknown organic compounds.

Reagents Positive Test Result Possible Inferences about Unknown Organic Compound
Dry PCl5 solid Steamy white fumes of HCl -OH group present. Could be alcohol or carboxylic acid.

Sodium carbonate or Effervescence, CO2 produced Carboxylic acid.

sodium hydrogen carbonate

2,4-dinitrophenylhydrazine Red-orange crystalline precipitate C=O present. Aldehyde or ketone.

Ammoniacal silver nitrate Silver mirror or grey precipitate Aldehyde.

Fehling's solution Blue solution fades, red precipitate forms Aldehyde.

Iodine and sodium hydroxide Yellow precipitate, antiseptic smell. -COCH3 group or -CHOHCH3 group present.
(or potassium iodide and Triiodomethane – iodoform
sodium chlorate (I))

Acidified potassium dichromate (VI) Colour change orange to green. Oxidation occurs. Could be primary alcohol, secondary alcohol
or aldehyde.
Bromine water Colour change orange/brown to colourless. C=C present.
Sodium hydroxide, acidification White precipitate, soluble in dilute ammonia C-Cl present.
with nitric acid, then addition solution
of silver nitrate solution.
Cream precipitate, soluble in concentrated C-Br present.
ammonia solution.

Yellow precipitate, insoluble in concentrated C-I present.

ammonia solution.
Obviously if test results are negative, negative inferences can be made.E.g. If PCl5 is added to an unknown organic chemical and there is no observable
reaction, the unknown does not contain the –OH group. Similarly, if there is no colour change an addition of acidified potassium dichromate, the substance
will not oxidise - e.g. tertiary alcohol or ketone.
1
62. Answering Questions on Identifying Unknown Organic Compounds Chem Factsheet

Spectroscopic Data Worked Example 2

See Factsheets 54, 55 and 56 for more detail on interpreting mass, IR and Organic compound Y has the molecular formula C5H10O. The IR
simple NMR spectra. In questions involving unknown organic compounds spectrum is supplied:
it is essential that candidates can obtain the following information from
supplied spectra: IR spectrum
• Mass spectra can supply the molecular mass of the unknown compound transmittance /%
– the highest trace reading on the spectrum gives the mass of the 100
‘parent ion’ which is equal to the molecular mass.
• IR spectra supply information about types of bonds present such as 80
O-H and C=O. Use this information to when deducing the structure of
an unknown organic compound.
60

Worked Example 1
Organic compound X contains carbon, hydrogen and oxygen only. 40
Already certain organic chemicals can be ruled out – alkanes, alkenes,
halogenoalkanes or nitrogen containing compounds.
20
Chemical tests on X: C=O stretch
Addition of PCl5 – steamy white acidic fumes. 4000 3500 3000 2500 2000 1500 1000 500
X contains the –OH group, so is likely to be an alcohol or carboxylic wavenumber /cm-1
acid. The presence of a C=O group is confirmed here, so Y is an aldehyde or
ketone. Y cannot be an acid as only one O atom is present, and from the
X is added to acidified potassium dichromate (VI) solution and warmed number of C and H atoms present it can be concluded that there are no
– a colour change of orange to green is observed. further multiple bonds aside from the C=O.
X is oxidised, so cannot be a carboxylic acid, instead must be an alcohol.
Chemical tests on Y:
X is added to iodine and sodium hydroxide and warmed – a yellow Y is warmed with ammoniacal silver nitrate solution – no observable
precipitate with an antiseptic smell is formed. reaction.
X contains the –CHOHCH3 group (note that the previous tests discount Y is not an aldehyde, Y is a ketone. Care must still be taken here as there
the presence of the –COCH3 group!). are still a number of possibilities:
X is a secondary alcohol. e.g. pentan-2-one, pentan-3-one, 2-methylbutanone and so on.

Spectroscopic data: Y is warmed with sodium hydroxide and alkali – no observable reaction.
The mass spectrum of X has a highest peak of m/e=74. The -COCH3 group is not present in Y.
The molecular mass of X is 74. Now this structural information is available, the name and structure of Y
Bringing together all of this information – X is a secondary alcohol of can be deduced.
molecular mass 74, a name and structure can now be assigned to X: Y is pentan-3-one, CH3CH2COCH2CH3
X is butan-2-ol, CH3CH2CHOHCH3

Worked Example 3 Spectroscopic data:

Z is an organic compound containing the elements C, H and O only. Mass spectrum
[43] CH3CO+
Chemical tests on Z: 100
[45] COOH+
Addition of PCl5 – steamy white acidic fumes.
Z contains an –OH group, so is likely to be a carboxylic acid or an 80
alcohol.
relative abundance /%

[60] parent ion

Addition of Z to sodium hydrogen carbonate solution – effervescence, 60
gas produced turns lime water cloudy (carbon dioxide).
Z is a carboxylic acid.
40 [15] CH3+
The molecular mass of Z is that of the parent ion, RMM = 60.
The name and structure of Z, a carboxylic acid of RMM 60, can now be
20
deduced.
Z is ethanoic acid, CH3COOH
0.0
10 20 30 40 50 60 70
m/e

In summary, when attempting a question which requires the identification of an unknown organic compound:
• Use information supplied in the question introduction.
• Use information gained via chemical test results and spectra to build a picture of the chemical.
• Do not just use isolated pieces of information, but combine what you know from the various sources to gradually eliminate possibilities and then
deduce the correct answer.
2
62. Answering Questions on Identifying Unknown Organic Compounds Chem Factsheet

Practice Questions
1. Organic chemical A is a straight chain hydrocarbon.
On addition of bromine water to A there is no observable reaction.
The mass spectrum of A is supplied. Identify A.

mass spectrum
100

80
relative abundance /%

60

40

20

0.0
0 10 20 30 40 50 60

2. Organic chemical B contains the elements C, H and O only, with the carbons all positioned in a straight chain. The mass spectrum of B indicates that
B has a molecular mass of 72.
The following chemical tests were carried out on B.

Chemical test Observations

Addition of PCl5 No observable reaction.

Addition of 2,4-DNP solution Red/orange precipitate.

Addition of ammoniacal silver nitrate solution and warmed Silver mirror formed on inside of test tube.

Identify B

3. C, D and E are all organic chemicals containing C, H and O only. C, D and E all contain 3 C atoms and just one functional group each.
Identify C, D and E from the following test results:

Test C D E

PCl5 No observable reaction Steamy white acidic fumes No observable reaction

2,4-DNP Red/orange precipitate No observable reaction Red/orange precipitate

NaHCO3 solution No observable reaction Effervescence, CO2 No observable reaction

Heat with acidified K2Cr2O7 Colour change orange to green No observable reaction No observable reaction

Warm with I2/NaOH No observable reaction No observable reaction Yellow precipitate with antiseptic smell

E is propanone, CH3COCH3. Acknowledgements: This Factsheet was researched and written by Kieron
D is propanoic acid, CH3CH2COOH. Heath. Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire,
3. C is propanal, CH3CH2CHO. TF1 1NU. ChemistryFactsheets may be copied free of charge by teaching
2. Butanal, CH3CH2CH2CHO. staff or students, provided that their school is a registered subscriber. No part
1. Butane, CH3CH2CH2CH3. of these Factsheets may be reproduced, stored in a retrieval system, or
Answers transmitted, in any other form or by any other means, without the prior
permission of the publisher. ISSN 1351-5136
3
 Chem Factsheet
www.curriculumpress.co.uk Number 63
Answering Questions on Identifying
Unknown Inorganic Compounds
Before reading through this Factsheet you should:
• Be confident in assigning ionic formulae;
• Have gained practical experience of inorganic chemistry tests and preparations. (Factsheet 24);
• Know and understand the AS/A2 content on inorganic chemistry (Factsheets 13, 14, 19, 20, 38, 46, 47).

After working through this Factsheet you will be able to:

• Identify unknown inorganic chemicals when supplied with the necessary information in a written exam or practical situation.
The aim of this Factsheet is to provide candidates with the necessary information and experience to tackle questions involving the identification of
unknown inorganic compounds.

Such questions are commonplace in both written and practical exam situations, and also practical assessments. In practical situations candidates will most
likely be required to carry out simple chemical tests and make observations. In an exam situation the observations may be supplied, or the question may
involve selecting the correct reagents for particular situations.
This Factsheet will provides summaries of the common tests (see tables at the end of the Factsheet) and help in making inferences from the test results.
Strategy
Read the question carefully, assume any information about the unknown chemical supplied is important and must be considered. It is worth "ticking off"
the information to make sure you have used it all.

Unknown inorganic compounds are likely to be ionic - identification is usually achieved through chemical testing for both the anion and cation. Although
some pieces of information can be used in isolation - eg a flame test - be aware that you will often have to make deductions from the results of more than
one test - for example, a white precipitate with acidified barium chloride solution indicates a sulphate or hydrogen sulphate, but you will need to combine
this with a further test (addition of sodium carbonate solution) to distinguish between the two.
Chemical tests are not the only things to provide useful information. You should also note the colour of the compound, and whether it is soluble or not:-
Colour -
• a coloured compound suggests a transition metal,
• most group 1 and 2 compounds are white
Solubility
• alkali metal, ammonium salts and nitrates are soluble
• halides are soluble except for lead, mercury and silver
• sulphates are soluble except for calcium, strontium, barium, silver, mercury and lead
• carbonates and hydroxides are insoluble except for group 1 and ammonium compounds.
These can provide a useful check on the results of chemical tests - if you think you have a solution of copper carbonate, for example, you cannot be right,
as it is insoluble. Likewise, a blue compound is unlikely to be a sodium salt.
The example below indicates how conclusions can be drawn from each piece of information. Further examples are overleaf.

Information given Conclusion drawn

Inorganic compound P is a pale green solid. Suggests P contains transition metal cation

10cm3 of a solution of P was made up in a test tube. P is soluble - not a carbonate or hydroxide (it can't be a group 1 carbonate
or hydroxide)
Sodium hydroxide solution was added to 5cm3 of this solution Green ppt could be Fe2+, Cr3+, Ni2+. Insoluble in excess, so not Cr3+
A pale green precipitate was produced, which became brown on its surface Brown on surface ⇒Fe2+ (brown is from oxidation to Fe3+)
with standing. The precipitate did not dissolve in excess sodium hydroxide.

The mixture from the previous test was warmed. A gas was evolved Gas is ammonia ⇒NH4+ present
which turned damp red litmus paper blue

To the remaining 5cm3 of P, barium chloride solution was added dropwise, White ppt ⇒sulphate or hydrogen sulphate
followed by dilute hydrochloric acid. A white precipitate was observed.

On addition of sodium carbonate solution to this mixture, a very slight Only slight effervescence ⇒Fe2sulphate
effervescence was observed
Compound is ammonium iron (II) sulphate (NH4)2Fe(SO4)2

1
63. Answering Questions on Identifying Unknown Inorganic Compounds Chem Factsheet

Practice Questions Answers

1. Use the following information to identify inorganic chemical A: 1. Yellow-orange flame ⇒ sodium
Flame test: Yellow-orange flame. Silver nitrate test⇒ halide
To 3 cm3 of a solution of A was added 3 cm3 2M HNO3 and 0.1M cream ppt, soluble in conc NH3 ⇒ bromide
AgNO3 dropwise. Note that a cream ppt can be difficult to distinguish from white or
A cream precipitate was produced which would not dissolve in dilute yellow - the solubility in conc ammonia is essential to be certain it is
NH3 (aq), but did dissolve in concentrated NH3 (aq). bromide
A is sodium bromide (NaBr)

2. Use the following information to identify inorganic chemical B: 2. Sodium hydroxide test for cations
No ppt ⇒no cation with insoluble hydroxide present
4 cm3 of a solution of B was made up in a test tube. Sodium hydroxide
Gas given off is ammonia (alkaline gas)
solution was added, and the mixture warmed. A gas was given off
Ammonium ions present
which turned damp red litmus paper blue.
Another sample of B was dissolved in dilute nitric acid, and then Barium chloride test for sulphate or hydrogen sulphate
barium chloride solution was added dropwise. A white precipitate was No effervescence with sodium carbonate ⇒sulphate
observed. Note that if the barium chloride was not acidified, carbonates would
Sodium carbonate was added to a solution of B, and there was no also produce a white ppt
observable reaction.
B is ammonium sulphate (NH4)2SO4)

3. Use the following information to identify inorganic chemical C: 3. Lilac flame ⇒ potassium

Solid C gives a lilac colour in a flame test. Gas evolved is ammonia (from reduction of nitrate ion) ⇒ nitrate
A solution of C is boiled with sodium hydroxide solution and aluminium
powder. Fumes were evolved which turned damp red litmus paper C is potassium nitrate. (KNO3)
blue.

4. Use the following information to identify inorganic chemical D: 4. Blue solution suggests compound of a transition metal

D is in the form of a blue solution. On addition of ammonia solution Blue ppt with ammonia solution ⇒ Cu2+ or Co2+
dropwise to D, a sky blue precipitate is formed. Dissolves to give deep blue solution ⇒ Cu2+
As the ammonia is then added to excess, this precipitate dissolves
leaving a deep blue solution.
No reaction with sodium carbonate ⇒ not acidic (eg not hydrogen
Another sample of B is tested with solid sodium carbonate – there is sulphate)
no observable reaction.
To a different sample of D dilute hydrochloric acid is added, and then White ppt with barium chloride ⇒ sulphate (cannot be hydrogen
barium chloride solution dropwise – a white precipitate forms. sulphate from previous test)

D is copper (II) sulphate (CuSO4)

5. a) Use the following information to suggest possible identities for

5.a)Brick red flame ⇒ calcium
inorganic chemical E:

E produces a brick red flame in a flame test. Gas evolved on addition of acid is carbon dioxide ⇒ carbonate or
On addition of dilute hydrochloric acid to solid E there is hydrogen carbonate
effervescence.
The gas produced is bubbled through lime water, which turns cloudy E is either calcium carbonate, CaCO3 or calcium hydrogen carbonate,
white. Ca(HCO3)2

b) Describe an additional chemical test that could be used to determine b) Add MgSO4 (aq) dropwise to solution.
the identity of E White ppt indicates CO32-, no ppt indicates HCO3-

6. Use the following information to identify inorganic chemical F 6. White solid suggests not a transition metal

F is a white solid. Brown gas is nitrogen dioxide - thermal decomposition of nitrate

On heating, F evolves a brown gas which turns damp blue litmus paper
red. White ppt with sodium carbonate ⇒ cation has insoluble carbonate,
On addition of sodium carbonate solution to a solution of F, a white so not group 1
precipitate is formed.
A flame test produces an apple-green flame Apple-green flame ⇒ barium

F is barium nitrate
2
63. Answering Questions on Identifying Unknown Inorganic Compounds Chem Factsheet

Tests for simple anions

Anion Test Expected Observation
Choride, Cl− To solution add dilute HNO3 then AgNO3 (aq). White ppt of AgCl, soluble in dilute NH3 (aq)
−
Bromide, Br To solution add dilute HNO3 then AgNO3 (aq). Cream ppt of AgBr, soluble in conc. NH3 (aq)
Iodide, I− To solution add dilute HNO3 then AgNO3 (aq). Yellow ppt of AgI, insoluble in conc. NH3 (aq)
Nitrate, NO3− Boil with sodium hydroxide solution and aluminium powder Fumes of ammonia gas
Nitrite, NO2− Add acidified potassium iodide solution Colour of solution turns brown as iodine is liberated
Carbonate, CO32− and Add dilute HCl to solid or solution Effervesence, CO2 produced (turns limewater cloudy white)
hydrogen carbonate, HCO3−
To differentiate between Add MgSO4 (aq) dropwise to solution White ppt indicates CO32-, no ppt indicates HCO3-
CO32− and HCO3−
Sulphate, SO42− and Add dilute HCl then BaCl (aq) to solution. White ppt of BaSO4
hydrogen sulphate HSO4−
To differentiate between Add Na2CO3 to solution Vigorous effervescence of CO2 indicates HSO4-, slight or
SO42− and HSO4− no effervescence indicates SO4-
Sulphite, SO32− Add dilute HCl to solid or solution and warm Pungent SO2 evolved, which turns acidified dichromate
from orange to green

Cation tests using NaOH(aq)

Cation Addition of NaOH (aq) dropwise Addition of excess NaOH (aq)
Ammonium, NH4+ On warming, ammonia gas evolved, turning red litmus paper blue
Chromium, Cr3+ Green ppt Green solution
Manganate, Mn2+ Buff ppt, darkens in air Precipitate does not dissolve
Iron (II), Fe2+ Pale green ppt, browns on surface Precipitate does not dissolve
3+
Iron (III), Fe Red brown ppt Precipitate does not dissolve
Cobalt, Co2+ Blue ppt, turns brown in air Precipitate does not dissolve
Nickel, Ni2+ Pale green ppt Precipitate does not dissolve
Copper, Cu2+ Pale blue ppt Precipitate does not dissolve
Zinc, Zn2+ White ppt Colourless solution

Cation tests using NH3(aq)

Cation Addition of NH3(aq) dropwise Addition of excess NH3 (aq)
Chromium, Cr3+ Green ppt Precipitate does not dissolve
Manganate, Mn2+ Buff ppt, darkens in air Precipitate does not dissolve
Iron (II), Fe2+ Pale green ppt, browns on surface Precipitate does not dissolve
Iron (III), Fe3+ Red brown ppt Precipitate does not dissolve
Cobalt, Co2+ Blue ppt, turns brown in air Precipitate does not dissolve
Nickel, Ni2+ Pale green ppt Blue solution
Copper, Cu2+ Pale blue ppt Deep blue solution
Zinc, Zn2+ White ppt Colourless solution

Flame Tests Nitrates Carbonates

• Group 1 nitrates (except lithium nitrate) • Group 1 carbonates will not decompose on
Cation Expected observation
decompose to give the metal nitrite and heating, except lithium carbonate:
Sodium, Na+ Yellow-orange flame oxygen gas • Group 2 carbonates all decompose (except
Potassium, K+ Lilac flame • Group 2 nitrates (and lithium nitrate) for barium carbonate, which is stable) to
Calcium, Ca 2+
Brick red flame decompose to give the metal oxide, the form the metal oxide and carbon dioxide gas
brown gas nitrogen dioxide and oxygen: • Thermal stability increases down both groups
Barium, Ba2+ Apple green flame • Thermal stability increases down both groups

Tests for gases

Gas Description of gas Test Expected observation
Hydrogen, H2 Colourless, odourless Ignite using a lighted splint ‘Squeaky pop’ sound. Pale blue flame
Oxygen, O2 Colourless, odourless Glowing splint Splint ignites or glows brighter
Carbon dioxide, CO2 Colourless, odourless Bubble through lime water Turns cloudy white
Ammonia, NH3 Colourless, pungent Moist red litmus paper Turns blue
Chlorine, Cl2 Yellow-green, pungent (a) Moist universal indicator paper Turns red then bleached white
(b) Bubble through KBr (aq) Solution turns yellow-orange
Nitrogen dioxide, NO2 Brown, pungent Moist universal indicator paper Turns red
Sulphur dioxide, SO2 Colourless, pungent Moist dichromate paper Turns from orange to green

Acknowledgements: This Factsheet was researched and written by Kieron Heath. Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire, TF1 1NU. ChemistryFactsheets may be copied free of charge by teaching
staff or students, provided that their school is a registered subscriber. No part of these Factsheets may be reproduced, stored in a retrieval system, or transmitted, in any other form or by any other means, without the prior permission
of the publisher. ISSN 1351-5136
3
 Chem Factsheet
www.curriculumpress.co.uk Number 64

Acid Base III: Buffer solutions,

pH Curves and Dibasic Acids
To succeed with this topic you need to understand the concepts of pH, Ka , buffers and pH curves. (Factsheets 25 and 26).
After working through this Factsheet you will:
• understand the link between buffer solutions and the pH curve for a weak acid with a strong base;
• be able to use the pH curve for a weak acid with a strong base to find pKa and Ka for the weak acid involved;
• have met the pH ‘problems’ of H2SO4, a dibasic acid.
Exam Hint : The three main points covered by this Factsheet are
very common examination questions – learn this work thoroughly

Buffer solutions and pH curves

pH curves Buffer solutions
The pH curve for the titration of a weak acid with a strong base has the 1. A buffer solution is one whose pH hardly changes when small
shape shown below: amounts of acid and alkali are added to it.
2. A buffer solution is made by dissolving the salt of a weak acid in the
pH
weak acid itself
14 e.g. sodium ethanoate (CH3COONa) dissolved in ethanoic acid
G H (CH3COOH)
12 F
3. The following mathematical equation is used for buffer
solutions:
10
[acid]
pH = - log10Ka – log10
8 [anion]
E
or
6
D [acid]
B C pH = pKa – log10
4 [anion]
A
2 N.B. ‘p’ = ‘– log10’

We need to look at the link between this pH curve and buffer solutions.
0 10 20 30 40 50
Volume of NaOH added /cm3 Reminder: a buffer solution is a mix of a weak acid (HA) and its salt (A-)
We need to look in more detail at what chemicals are in the solution
mixture at various points on the curve (A-H): Question : Where does this mixture appear on the curve?
A pure weak acid (HA)
Answer: Between points A and E on the curve.
B weak acid (HA) + some of its salt (A−) because of the
neutralisation reaction between the acid and the alkali and The ‘acidic’ part of a pH curve between a weak and a strong base is a
more water because: acid + alkali → salt + water) mixture of the weak acid and its salt i.e. it has the properties of a buffer.
C less weak acid (HA) and more salt (A−)
If, while adding the base, the experiment had been stopped at any point
D even less weak acid (HA) and even more salt (A−) between A and E, the solution could have been used as a buffer solution.
E no weak acid left, the solution contains only the salt
The pH of the buffer solutions could be found by ‘reading’ the
E-F the end-point where one drop of the base (A−) changes the
y-axis at, say, points B, C and D.
solution from acidic to basic (pH 7→11)
F a salt solution + a slight excess of base (NaOH) Note that pH of the buffer is higher, the greater the proportion of salt to
acid.
G+H as an excess of base is added the pH increases to maximum Beyond the point E, no acid is left, only the salt, so the solution would no
value of about pH = 13. longer be a buffer.

1
64. Acid Base III: Buffer solutions, pH Curves and Dibasic Acids Chem Factsheet

We need to move to the equation for a buffer solution. Now the final test of your understanding!

[acid] Question: What is the pH range of the most effective buffer solution?
pH = pKa − log10
[anion] Answer: pH = 5.6 (C) to 6.8 (just below E)

Reason: This is when there is more of the anion, [A−] and less of the
The [acid] is [HA] and the [anion] is [A-].
acid, [HA].
What happens when [HA] = [A-]?
[HA]
log10 = log10 1 = 0 Experimental methods of finding Ka for a weak acid
[A-]
Using the theory covered so far there are two methods to find Ka:
This means the equation becomes
pH = pKa - 0 i.e. Method 1
(a) Pipette 25.00 cm3 of the weak acid into a conical flask
pH = pKa when [HA] = [A−]
(b) Use a pH meter to measure its pH value.

When does [HA] = [A-]? (c) Add 1.00cm3 strong base (NaOH(aq)) from a burette, stir to mix
This happens half-way to the equivalence point. and measure its pH value.
In the example graph,
(d) Continue to add 1.00cm3 of NaOH(aq) and take the pH value
Equivalence point = 25 cm3 NaOH(aq) readings.
so At 12.50cm3 NaOH,
(e) Plot a graph of pH readings against the volume of NaOH(aq)
pH = pKa
added.
This is point C, where the pH is 5.6.
(f) Use the graph to find the equivalence point (end point) in terms
Using the equation, of cm3 of NaOH(aq).

pH = - log10 [H+] (g) Divide the volume by 2.

then pKa = - log10Ka (h) Read off the pH value at end point volume ÷ 2 – this is the pKa
value.

so the use of a calculator will enable us to find Ka. (i) Convert pKa → Ka using the calculator.

Finding the value of Ka for a weak acid from the pH curve Method 2
of a weak acid with a strong base: (a) Pipette 25.00cm3 of the weak acid into a conical flask.

(1) The ‘acid part’ (up to the equivalence point) of the pH curve is (b) Add indicator.
a mixture of HA (weak acid) and its salt (A−),
(c) Titrate with the strong base (NaOH(aq)) until the indicator
(2) A mixture of a weak acid (HA) and its salt (A−) is a buffer solution,
changes colour, record the volume added.
(3) When [HA] = [A−] the mathematical equation for a buffer solution
means pH = pKa (d) Repeat the titration process until concordant titres are achieved.

(4) Reading the pH value from the graph at half the end point value (e) Calculate from the titres the average titre – this will be the end
(cm3) gives you the pKa value. point (equivalence point).
(5) Using a calculator we can change pKa → Ka.
(f) Divide the average titre by 2.
N.B. From the example graph, point A and point E are not buffer
solutions – A has no salt (A−) and E has no acid (HA). (g) Pipette 25.00cm3 of the weak acid into a conical flask.
14
G H (h) Add the average titre volume of NaOH(aq)), divided by 2.
12 F
10 (i) Shake well and using a pH meter, find the pH value – this is the
8 E pKa value.
6
D
4 B C (j) Convert pKa → Ka using a calculator.
A
2

0 10 20 30 40 50

The solution acts as a buffer at pH values of more than 3 (A)

and less than 7 (E).

2
64. Acid Base III: Buffer solutions, pH Curves and Dibasic Acids Chem Factsheet

Practice Questions
The dibasic acid ‘problem’ of H2SO4
1. The following questions are about the pH curve shown below when
H2SO4 is a strong acid.
25.0cm3 of 1.0 mol dm−3 HA(aq) was titrated with 1.0 mol dm−3
Strong acids are defined as ones which fully dissociate in solution, NaOH(aq)

i.e. HCl(aq) → H+(aq) + Cl−(aq) pH

This fact enables us to calculate the pH of a strong acid from its 14

concentration.
12
Q. What is the pH of 0.1 mol dm3 HCl?
10
HCl(aq) → H+(aq) + Cl−(aq)
0.1 0.1 0.1 8
→ +
mol dm-3 mol dm-3 mol dm-3
6
[H+] = 0.1 mol dm-3

pH = - log10 (0.1) = 1.0 4

2
Suppose we take the same approach for H2SO4

H2SO4(aq) → 2H+(aq) + SO42−(aq) 0 10 20 30 40 50

Volume of NaOH added /cm3
0.1 mol dm-3 → 0.2 mol dm−3 + 0.1 moldm−3
Use the pH curve to find
[H+] = 0.2 mol dm-3 (a) the pH of the NaA(aq) solution.
−
pH = log10 (0.2) = 0.14 (b) for the weak acid, HA,
(i) the pKa value
This suggests that H2SO4 is more acidic (pH = 0.14) because it (ii) the Ka value
produces twice the number of H+ ions.
(c) the range of pH values over which the mixture acts as a buffer.
THIS IS NOT TRUE FOR H2SO4!
When measured, the pH of 0.1 mol dm-3 H2SO4 is the same as for (d) the pH of the most efficient buffer solution.
0.1 mol dm-3 HCl.
2. H2SO4 is a strong dibasic acid, whereas HNO3 is a strong monobasic
Why is this? acid. Why are the pHs of these two acids very similar?
As a dibasic acid, sulphuric acid dissociates as shown below:
Answers
Step (1) H2SO4(aq) → H+(aq) + HSO4−(aq)
1. (a) Any value between pH 8 → 11
Step (2) HSO4−(aq) → H+(aq) + SO42−(aq)
(b) (i) 5.8
The key points are that: (ii) 1.58 × 10-6
• the dissociation constant for step (1)
(c) 3.4 – 6.8
is very large - H2SO4 completely dissociates into H+ and HSO4−
• the dissociation constant for step (2) is small (about 0.01) - and
(d) Any value between 5.8 – 7.8
this dissociation is also supressed by the high H+ concentration
produced by step (1)
2. Answers gain credit for the following points:
1) Explanation of dibasic/monobasic acids in terms of the amount of
Result H2SO4 only produces the same amount of ions as HCl
H+/H3O+ ions.
so the pH value is about the same.
2) Explanation of strong acids (complete ionisation)

3) Compares HNO3 (one H+) to H2SO4 (two H+).

4) Links [H+] → pH value.

5) Explains that H2SO4 has complete dissociation for

H2SO4 → H+ + HSO4- but only partial dissociation for
HSO4- → H+ + SO42-
Acknowledgements: This Factsheet was researched and written by Sam
Goodman. Curriculum Press, Bank House, 105 King Street, Wellington,
6) Links the dissociation of acids to pH values i.e. similar because
Shropshire, TF1 1NU. ChemistryFactsheets may be copied free of charge by [H+] similar.
teaching staff or students, provided that their school is a registered subscriber.
No part of these Factsheets may be reproduced, stored in a retrieval system, or
transmitted, in any other form or by any other means, without the prior
permission of the publisher. ISSN 1351-5136
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 Chem Factsheet
www.curriculumpress.co.uk Number 65

Calorimetry Experiments
To succeed in this topic you need to:- The experiments outlined could be used in a school laboratory to collect
• Have a good understanding of AS-level Energetics covered so far in data and thus determine values of ∆H .
Factsheet 08 - Energetics I - Hess's Law;
• be familiar with basic apparatus used in Chemistry. Questions can be met requiring candidates to carry out calculations based
on data from similar experiments. The calculations may involve the use of
After working through this Factsheet you will:- Hess’s Law.
• be familiar with the main types of experiment used in calorimetry at
AS-level; When a reaction is carried out in a calorimeter
• be able to calculate values of enthalpy changes from experimental data. the heat lost/gained the heat gained/lost by the
=
by the reacting system calorimeter and its contents
Experiment 1: Enthalpy changes on displacement and the reactivity
Changes in heat content are calculated using:
series
∆H = mc ∆T where: m = mass
c = specific heat capacity
Introduction
∆T = change in temperature
The relative positions of metals in the reactivity series can be investigated
by adding metals to solutions of salts of other metals, for example
Zn(s) + Cu2+ (aq) → Zn2+ (aq) + Cu(s)
and for the zinc/silver reaction ∆H is –363 kJ mol–1.
This confirms that zinc is ‘above’ copper in the reactivity series. The Experiment 2: Enthalpy change of neutralisation
enthalpy change for this and similar reactions can lead to an illustration
of Hess’s Law. Introduction
Acidic and alkaline solutions mix exothermically. The ionic equation
Method for neutralisation is
• Place 100 cm3 of copper(II) sulphate solution (0.2 mol dm–3) in a
H+(aq) + OH–(aq) → H2O(l)
polystyrene cup (or vacuum flask if available).
• Record the temperature (to the nearest 0.1oC) of the solution every Method
30 seconds for two minutes. • Put 50 cm3 of hydrochloric acid (1.0 mol dm–3) and 50 cm3 of
• At the two minute mark add 2 g (an excess) of zinc powder and stir sodium hydroxide solution (1.0 mol dm–3) into separate measuring
the mixture. cylinders
• Continue recording the temperature for a further five minutes. • Wait for the temperatures of the two solutions to equalise.
• Plot a graph of temperature against time and use the plot to determine • Pour one of the solutions into a polystyrene cup.
the maximum temperature change (∆T). • Add the second solution, stir well and record the maximum
temperature reached.
Calculation
The heat energy exchanged in the experiment is 100 × ∆T × 4.18 joules. The number of joules exchanged can be found by calculation or by the
use of a joulemeter as in experiment 1.
In the reaction 0.02 (= 1/50) mole of copper ions reacted so the heat
exchanged per mole would be 50 × (100 × ∆T × 4.18) joules or Calculation
5 × ∆T × 4.18 kJ. The heat energy exchanged in the experiment is 100 × ∆T × 4.18 joules.
As the reaction is exothermic the value for ∆H (in kJ mol–1) will need As 0.05 (= 1/20) mole of hydrochloric acid has been neutralised the heat
a negative sign. exchanged per mole would be 20 × (100 × ∆T × 4.18) joules or
2 × ∆T × 4.18 kJ.
Alternative Method
Carry out the procedure above to determine the change in temperature. As the reaction is exothermic the value for ∆H (in kJ mol–1) will need
• Then place a further 100 cm3 of copper(II) sulphate solution in the a negative sign.
reaction vessel and insert a low voltage heater connected through a
joulemeter. Extension
• Switch on the current and allow the temperature to rise by the The experiment can be repeated using nitric acid instead of hydrochloric
same number of degrees. acid and potassium hydroxide solution instead of sodium hydroxide
• Record the reading on the joulemeter to determine the heat exchanged solution.
in the experiment and thus calculate a value for ∆H.
In all four possible combinations a similar result should be found as the
Extension ionic equation for each is the same. The standard molar enthalpy change
If similar experiments are carried out to determine the enthalpy changes of neutralisation is –57.6 kJ mol–1. A different, less negative value is
for (say) obtained if a weak acid such as ethanoic acid is used as some heat energy
Cu(s) + 2Ag+(aq) → Cu2+(aq) + 2Ag(s) is used in breaking bonds in the undissociated acid.
and Zn(s) + 2Ag+(aq) → Zn2+(aq) + 2Ag(s)

then Hess’s Law can be illustrated. For the zinc/copper reaction ∆H

is –216 kJ mol–1; for the copper/silver reaction ∆H is –147 kJ mol–1;

1
65. Calorimetry Experiments Chem Factsheet

Experiment 3: Enthalpy of combustion Experiment 4: Finding an enthalpy change that cannot be measured
directly
Introduction
The complete combustion of hydrocarbons, alcohols and other organic
Introduction
compounds containing carbon, hydrogen and oxygen only produces
For a vast number of reactions values of the enthalpy change cannot be
carbon dioxide, water vapour and heat. In school laboratory experiments,
determined directly. However, by using Hess’s Law with values which
results are not very reliable as, apart from heat losses, complete
can be experimentally determined, the missing values can be calculated.
combustion is rarely achieved. The method described is usually restricted
to liquid fuels such as alcohols. Examples include the enthalpy change of reaction which occurs when an
anhydrous salt becomes hydrated.
For more accurate results a bomb calorimeter would be used.
Method
Method • Add 0.1 mol of the anhydrous salt to 100 cm3 of water and determine
• Set up the apparatus filling the calorimeter with water. a value (∆H1) using procedures similar to Experiment 1 above.
• Stir the water in the calorimeter and record the temperature. • Then add 0.1 mol of the hydrated salt to water.
• Fill the spirit lamp with an alcohol and weigh it. • The volume of water used should be less than 100 cm3 to allow for
• Put the lamp in position, light the wick and quickly adjust the air the water contained in the salt.
flow to obtain a steady flame. • A second value (∆H2) can then be calculated.
• Meanwhile stir the water.
• When a temperature rise of about 10oC has been obtained extinguish Calculation
the flame but continue stirring and note the maximum temperature Using Hess’s Law, (∆H1) – (∆H2) will produce a value for the hydration
reached. reaction. Care must be taken over the signs for ∆H in each case.
• Reweigh the lamp as quickly as possible.
• Use an electrical circuit to produce a similar temperature rise and Extension
note the number of joules required. The enthalpy change for the endothermic reaction

Calculation 2KHCO3(s) → K2CO3(s) + H2O(g) + CO2(g)

From the mass of alcohol used (w) and its relative formula mass (M) the
w can be determined by adding appropriate masses of each solid to an
number of moles used can be found.
M excess of hydrochloric acid. Note that 2 mol of potassium
If the number of joules is known, then a value for the molar enthalpy of hydrogencarbonate react to give 1 mol of potassium carbonate. Again a
(number of joules) Hess’s Law triangle or enthalpy level diagram will produce a value for the
combustion can be calculated from
(number of moles) enthalpy change.
Extension
If the experiment is repeated with a number of alcohols it can be shown
that the values of the enthalpies of combustion of successive alcohols
differ by a similar amount. This is because each member of an homologous
series differs from the next by –CH2–. The combustion of this unit
should result in the same release of energy (about 650 kJ mol–1) whatever
the homologous series being investigated.

Practice Questions 4. The enthalpy change for the precipitation of barium carbonate was
1. A student wrote the following account: investigated by mixing barium nitrate solution with sodium carbonate
A piece of zinc weighing 3 g was placed in a glass beaker. 50 cm3 of 0.5 solution. Three experiments were used.
mol dm–3 copper sulphate solution was measured using a measuring
cylinder and added to the beaker. The temperature of the solution was Expt 1 : 10.0 cm3 of barium nitrate solution (1.0 mol dm–3) was
taken before it was added and then every minute afterwards. added to 10.0 cm3 of sodium carbonate solution (1.0 mol dm–3). The
temperature rose by 1.5oC.
The results were:

Time in minutes 0 1 2 3 4 5 Expt 2 : 50.0 cm3 of barium nitrate solution (1.0 mol dm–3) was
added to 50.0 cm3 of sodium carbonate solution (1.0 mol dm–3).
Temperature in oC 22 26 29 27 24 22
Expt 3 : 50.0 cm3 of barium nitrate solution (0.2 mol dm–3) was
Suggest three improvements you would make to the experiment. Give
added to 50.0 cm3 of sodium carbonate solution (0.2 mol dm–3).
reasons for each suggestion.

2. Outline the essential details of an experiment to determine the enthalpy (a) Calculate the temperature rises to be expected in experiments 2
of solution of ammonium nitrate. and 3.
Show how the experimental results would be used to calculate the (b) Which of the experiments should give the most accurate result for
molar enthalpy change. the determination of the temperature change? Give a reason for
3. 2.66 g of anhydrous copper(II) sulphate powder was added to 50.0 your answer.
cm3 of distilled water in a polystyrene cup. The temperature of the (c) Which of the experiments should give the least accurate result for
water rose from 19.6oC to 25.4oC. Calculate the molar enthalpy change the determination of the temperature change? Give a reason for
of solution of anhydrous copper(II) sulphate. You may assume that your answer.
the specific heat capacity of copper(II) sulphate solution is
4.18 Jg–1 K–1 and that there is negligible heat loss to the surroundings.

2
65. Calorimetry Experiments Chem Factsheet

Answers
1. Any three of:
Use powdered zinc – reacts faster so heat losses are reduced
Use a polystyrene cup/vacuum flask – reduces heat loss
Use a burette/pipette – more accurate than a measuring cylinder
Put the solution in the polystyrene cup before the zinc is added – to
enable initial temperature to be checked
Use a thermometer reading to 0.1oC – more accurate temperature change
found
Measure the temperature of the solution for a few minutes before
addition of the solid – gives a better value for the initial temperature
Stir the mixture – helps reduce reaction time
Measure temperatures more frequently during the reaction – produces
a better graph and thus a more accurate figure for the change in
temperature

2. Use a polystyrene cup/vacuum flask of suitable size

Use a burette/pipette to measure 50 cm3 of water and add this to the
polystyrene cup
Weigh accurately 0.05 mol of the powdered solid
Use a thermometer reading to 0.1oC to find the initial temperature
Add the solid, stir the mixture and record the maximum (or minimum)
temperature reached (or note the temperature every 15 seconds)

Determine the change in temperature (∆T) either by simple difference

or graphically
Calculate the heat exchanged using 50 × ∆T × 4.18
As the resulting solution is 1.0 mol dm–3 this calculation gives a
numerical value for the enthalpy of solution. If the reaction is exothermic
a – sign will be needed; if the reaction is endothermic a + sign must be
used.

3. Temperature rise = 25.4 – 19.6 = 5.8 (K). Reaction is exothermic.

Heat exchanged in experiment = 50.0 × 5.8 × 4.18 = 1212.2 J

RFM CuSO4 = 63.6 + 32.0 + (4 × 16.0) = 159.6

1212.2 × 159.6
Heat exchanged per mol of CuSO4 = = 72732 J
2.66
∆H = – 72.7 kJ mol–1

4. (a) 1.5oC 0.3oC

(b) Experiment 2 – large volume, minimises errors
(c) Experiment 3 – temperature change too small

Acknowledgements: This Factsheet was researched and written by Phil Richardson.

Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire, TF1 1NU.
ChemistryFactsheets may be copied free of charge by teaching staff or students, provided
that their school is a registered subscriber. No part of these Factsheets may be reproduced,
stored in a retrieval system, or transmitted, in any other form or by any other means, without
the prior permission of the publisher. ISSN 1351-5136

3
 Chem Factsheet
www.curriculumpress.co.uk Number 66
Maths for Chemists 2
This Factsheet covers logarithms and their use in Chemistry. Powers
• Raising a number to a positive power means multiplying it by itself
What are logarithms?
that number of times - eg 106 = 10 × 10 × 10 × 10 × 10 × 10
Logarithms are closely related to powers, so before continuing, make sure
you know and understand the power facts in the box (right).
• Special cases: any number to the power 1 is the number itself; any
To see how logarithms work, consider the following examples: number to the 0 gives 1 - eg 21 = 2 30 = 1

100 = 102 log10100 = 2 • Negative powers of a number are one over the corresponding postive
0.001 = 10-3 log100.001 = -3 1 1 1
power - eg 10−3 = 3 = =
10 10 × 10 × 10 1000
So when we say "what is log10 1000?", we are asking "What power must
I raise 10 to, to get the answer 1000?" The answer is 3 - so log101000 = 3 • You can also have powers that are decimals - eg 102.156
Although you can have logarithms to different bases, in Chemistry we
will only be looking at logarithms to the base 10 (log10). To save time, we'll • You find powers on your calculator using the button marked xy (or
just write "log" when we mean "log10" yx) - eg to find 102.156, type in 10, then xy , then 2.156
(check - the answer should be 143.2)
Calculating logs
It's easy to work out logs for numbers that are exact powers of 10 and it's When doing work on logarithms in Chemistry, you mainly deal with
worth being able to do so mentally to save time in the exam and guard powers of 10 - so, a few facts about them:
against calculator error. But logs for other numbers have to be worked out
on your calculator. • Positive powers of 10 are easy to recognise - just count the zeroes!
eg 101 = 10 103 = 1000
The button for finding log to the base 10 may be labelled:
LOG LOG10 LG • Negative powers of 10 are easy to recognise as decimals - just count
the decimal places! eg 10-1 = 0.1 10-4 = 0.0001
Note: do NOT use the button labelled ln or loge. This gives you logarithms
to a different base - and hence the wrong answers! • Positive powers are larger than 1; negative powers smaller than 1

Some calculators require you to put the number in first, then press the log Exam Hint: Remembering these points can help you spot a wrong
button - in others, you press the log button first, then the number. Check answer from keying into your calculator wrongly - and hence save
which yours is by finding log100 (the answer should be 2). a few marks!

Finding the number that has a particular log Before moving on to applying logs, check you understand the work so far
There are two ways of doing this on your calculator: by doing these questions. Try not to use your calculator in questions 1
and 3, and in questions 2 and 4, work out mentally the values your answer
• Use the xy (or yx) button to find 10 to the power of the number lies between in order to check your calculation,
eg: logx = 0.123. To find x, enter 10 xy 0.123
1. Find:
a) log 100 b) log 1 c) log 10 d) log 0.1 e) log 0.001
• Use the INV or 2ND or SHIFT button, together with the LOG button
On some calculators you have to press INV LOG first, then the number; 2. Find:
on others you press the number then INV LOG. Check which yours is a) log2 b) log 91 c) log0.61 d) log 0.003 e) log½
by using this method to solve logx = -1.23 (ans 0.0589)
3. Find the number whose log is:
Exam Hint: You should never get a negative number from either of the a) -2 b) 4 c) 1 d) 0 e) 6
above methods. It's impossible to find the log of a negative number - if
you think you have, then you've probably pressed LOG not INV LOG. 4. Find the number whose log is:
a) 0.674 b) 2.18 c) -2.16 d) -0.0521 e) -1.32
If a number has a whole-number log (eg logx = -4 or logy = 3) then you can
find the number without a calculator:
logx = -4 so x = 10-4 = 0.0001 logy = 3 so y = 103 = 1000 e) 0.0479 c) 0.00692 d) 0.887 b) 151 4. a) 4.72

Checking answers e) 1000000 d) 1 c) 10 b) 10000 3. a) 0.001

Once you are confident with logs and can do whole-number examples in
your head, you can use this method to check if your answer is plausible: e) -0.301 d) -2.52 c) -0.215 b) 1.96 2 a) 0.301
If logx = 1.57, since 1.57 is between 1 and 2, x is between 101 and 102
e) -3 d) -1 c) 1 b) 0 1 a) 2
So if, when you found x, it wasn't between 10 and 100 - you'd know there
Answers
was a mistake.

1
66. Maths for Chemists 2 Chem Factsheet

Logarithms and graphs

Sometimes graphs are required for data that cover a very wide range of values – going, for example, from 100 to 100 000. One example of this is
successive ionisation energies for one element.This presents a problem, since if the largest values are to fit on the graph, it will be very hard to plot the
small ones accurately.

Logarithmic scales are used to overcome this problem. Instead of the actual value, the logarithm of the actual value is plotted. This can be done on one
or both axes. This helps because the logarithms will not vary so much in size as the actual data values – eg log 100 = 2 and log100 000 = 5, so it would
be easy to fit both of these on one graph. It is usual to label the axes with the original values instead of their logarithms; this means that the scale is likely
to go up 1, 10, 100, 1000 etc.
Example: logarithmic graph of the successive ionisation energies of sodium. The graph is shown below. Note the values of log(IE) on the axis are
shown only for information here; the y-axis would normally just have IE
Electrons removed Energy required(kJ mol -1) log(energy) values.
1 490 2.69
2 4 560 3.66 IE log(IE)
3 6 940 3.84
1 000 000 6.00
4 9 540 3.98
5 13 499 4.13
6 16 600 4.22 100 000 5.00
7 20 100 4.30
8 25 500 4.41 10 000 4.00
9 28 900 4.46
10 141 000 5.15 1 000 3.00
11 158 700 5.20
100 2.00
We can see from the data that it would be hard to plot all the ionisation
energies accurately, so it's sensible to use a logarithmic scale for them. 0 1 2 3 4 5 6 7 8 9 10 11
There is no need to use one for the other axis, as these are small numbers. electrons removed

Logarithms and calculations on strong acids and bases

You need to be able to use logarithms in work on acids and bases. Example 3
The key definitions involving logs are: Find the pH of a 2 mol dm-3 solution of sodium hydroxide

pH = -log [H+] The key idea here is that as we are dealing with a base, we must use
Note that "p" here is
representing "-log" the two equations relating to pOH.
pOH = -log[OH−] ( = 14 - pH) In addition, we know that sodium hydroxide is a strong base, and so
will be fully dissociated into ions.
We will focus here on the aspects of the calculations involving logarithms;
other Factsheets give further information on more general acid/base problems. pOH = -log[OH−]
= -log2
Example 1 = - 0.301
Find the pH of a 0.1 mol dm-3 solution of hydrochloric acid
pH = 14 - pOH
The key chemistry here is that as hydrochloric acid is a strong acid, it = 14.301
dissociates completely into ions - so [H+] = 0.1

So pH = -log(0.1) Example 4
= - (-1) = 1 A solution of potassium hydroxide has pH 13. Find its concentration

Example 2 Again we use the two equations relating to pOH

A solution of HBr is found to have a pH of 0.5. Find the concentration of
the solution. pOH = 14 - pH
= 14 - 13 = 1
pH = -log[H+]
Now pOH = -log[OH−]
0.5 = -log[H+]
So 1 = -log[OH−]
log[H+] =-0.5
-1 = log[OH−]
[H+] = 10-0.5 = 0.316 mol dm-3
[OH−] = 10-1 = 0.1 mol dm−3
Since again we have a strong acid, this is also the concentration of the
solution. Since we have a strong base, concentration of the solution is 0.1 mol dm-3

Now try these examples. You can assume all acids and bases are strong.

1. Find the pH of a 0.5 mol dm-3 solution of nitric acid 4. pOH = 0 so 1 mol dm-3
3. pOH = -0.477 so pH =14.477
2. Find the concentration of a solution of hydrochloric acid that has pH -0.6
2. 3.98 mol dm-3
3. Find the pH of a 3 mol dm-3 solution of potassium hydroxide 1. 0.301
4. A solution of sodium hydroxide has pH 14. Find its concentration. Answers

2
66. Maths for Chemists 2 Chem Factsheet

Weak acids & bases Buffer Solutions

When weak acids are considered, we must also take into account the A buffer solution is a mixture of a weak acid and its salt (or less commonly,
dissociation constant Ka a weak base and its salt). The pH of a buffer solution changes only very
little if strong acid or base is added to it.
[H+][A−] pKa = -log Ka
Ka for the acid HA =
[HA] There are a variety of examination questions on buffers - see Factsheet 64
- but here we will concentrate on those aspects related to logarithms. The
pKa is often used as a measure of acid strength; unlike pH , it does not key equation for use with buffer solutions is:
depend on the concentration of the solution. [HA]
pH = pKa − log [A−]
Example: hydrofluoric acid has Ka = 6.7 × 10-4. Find pKa
pKa = -log (6.7 × 10-4) = 3.17
Example 1: A buffer solution is made by dissolving 0.1 moles ethanoic
Similarly for bases, we have the base dissociation constant Kb acid and 0.2 moles sodium ethanoate in 1 dm3 distilled water. Find its
pH
[B+][OH−] (Ka for ethanoic acid = 1.78 × 10-5 )
Kb for the base BOH = pKb = -log Kb
[BOH]
The key chemistry here is that we can assume the acid is effectively
undissociated (it would dissociate very little anyway, and dissociation is
Example: ammonia has pKb = 4.74. Find Kb further supressed by the presence of ethanoate ions from the salt). This
4.74 = -logKb means we can assume:
-4.74 = logKb
Kb =1.8 × 10-5
• [CH3COO−] is the original concentration of the salt
• [CH3COOH] is the original concentration of the acid
Exam Hint: A common student error is to treat a pKa (or pKb) value as
if it were Ka (or Kb), and use it directly in the dissociation equation. We have: [CH3COO−] = 0.2 [CH3COOH] = 0.1 pKa = -logKa =4.75
pH = 4.75 - log (0.1/0.2)
pH of weak acids = 4.75 - log0.5
To calculate the pH of a weak acid, you must first calculate [H+]. To do this, = 5.05
you use the acid dissociation expression and the following assumptions: Exam Hint: You may come across the equation for the buffer solution
• [H+] = [A−], so the top of the fraction becomes [H+]2 in slightly different formats. It's best to choose one format and stick to
This is effectively assuming there are no other sources of either ion in it - trying to remember more than one is likely to lead to mistakes.
the solution
The second key fact needed for buffer solutions is:
• [HA] = original concentration of acid
This is assuming an extremely small degree of dissociation - so that the
If [HA] = [A−], then pH = pKa
concentration of undissociated acid is almost the same as the initial
concentration.
Example. Calculate the pH of a 0.5 mol dm-3 solution of ethanoic acid This relationship just comes from the fact that if [HA] = [A−], then
(Ka = 1.78 × 10-5) [HA]/[A−] = 1, and log1 = 0. So if you forget it, you can work it out again
- but it's quicker to be able to remember it in an exam!
Step 1:
[H+][CH3COO−] Example 2: A buffer solution is made by mixing 50cm3 of each of
1.78× 10-5 = [CH3COOH] 0.1 mol dm-3 methanoic acid and 0.1 mol dm-3 potassium methanoate.
[H + 2
] Its pH is 3.74. Find the acid dissociation constant for methanoic acid.
1.78× 10-5 =
0.5 The acid and salt have equal concentrations, so pH = pKa
Step 2: Rearrange the equation
So pKa = 3.74
(1.78 × 10-5) × 0.5 = [H+]2
logKa = -3.74
Step 3: Square root to find [H+] Ka =1.82 × 10-4
[H+] = 1.78 × 10 -5 × 0.5 = 0.00298 Note that if you hadn't noticed that the acid and salt had the same
Step 4: Find pH concentrations, you would have needed to find the concentration of each
pH = -log[H+] = 2.53 (0.05 for each, since the original solutions were diluted by a factor of 2)
and then put the numbers into the equation.
Now try these examples
1. Nitrous acid (HNO2) has pKa =3.35 Now try these examples
a) Find Ka 1. A acidic buffer solution contains equal concentrations of an acid,HA,
b) Find the pH of a 0.5 mol dm-3 solution of nitrous acid and its sodium salt. Its pH is 4.61. Find Ka for HA
2. Methanamine has pKb =3.36 2. A buffer solution is 0.2 mol dm-3 with respect to ethanoic acid and
a) Find Kb 0.3 mol dm-3 with respect to sodium ethanoate. Find its pH
0.1 mole of methanamine is dissolved in 1 dm3 of water. (Ka for ethanoic acid = 1.78 × 10-5 )
b) Assuming the degree of dissociation of methanamine is very low, and
there are no other significant sources of OH−, find [OH−] 3. A buffer solution is 0.3 mol dm-3 with respect to acid HA. It also
c) Find the pH of this solution contains the sodium salt of the acid. The pH of the solution is 6.2
2. c) pH = 14 - pOH. pOH = 2.2 so pH = 11.8 Find the concentration of the sodium salt in the solution
2. b) Same approach as for an acid: [OH−]2/0.1 = Kb This gives [OH−] =6.61 × 10-3 (Ka for HA = 1.1 × 10-7 ).
1. a) 4.47 × 10-4 b) 1.8 2. a) 4.37 × 10-4 So [salt] = [acid]/5.7 = 0.05 mol dm-3
3.First find log([acid]/[salt]) = 0.76 Then find [acid]/[salt] =5.7
Acknowledgements: This Factsheet was researched and written by Cath Brown Curriculum Press, Bank House, 105 King Street, Wellington, TF1 1NU
1. 2.45 × 10-5 2. 4.9
ChemistryFactsheets may be copied free of charge by teaching staff or students, provided that their school is a registered subscriber.
No part of these Factsheets may be reproduced, stored in a retrieval system, or transmitted, in any other form or by any other means, without the prior permission of the publisher. ISSN 1351-5136

3
 Chem Factsheet
www.curriculum-press.co.uk Number 67
Why Students Lose Marks: AS Redox Questions
This Factsheet analyses students’ real answers to exam questions on reduction and oxidation. By the end of this Factsheet, you should be more confident
about:
• What the examiners want
• The kinds of things you are likely to be asked
• Common mistakes and misunderstandings
As you read the students' answers to the questions and the comments, try to work out what the student should have done - using the hints and comments
if necessary - before you read the markscheme.

What do you have to know?

In this type of question, the examiner is trying to assess whether you can:
• recognise examples of redox reactions, oxidising and reducing agents • calculate oxidation numbers usingthe standard rules
• write half-equations for standard redox conversions • write half-equations for new reactions, given appropriate information
• combine half equations

(a) Oxidation used to be defined as ‘combination with oxygen’.

Explain why, even though the definition has now been broadened, it is still generally true to say that combination with oxygen is oxidation.

Because oxygen is an effective oxidising agent - it takes electrons away from other elements easily
.................................................................................................................................................................................................................................
Although this answer is not on the markscheme, 1 mark awarded for the idea that "oxygen takes electrons away from
other elements easily", which demonstrates an understanding of oxidation
............................................................................................................................................................................................................................ [2]

(b) When oxygen reacts with fluorine, converting it into oxygen difluoride, OF2, does the fluorine become oxidised? Explain your answer.
!
No, fluorine always has an oxidation state of -1 in its compounds
.................................................................................................................................................................................................................................
" Although the rule quoted for fluorine is true, a rule is not an explanation - the
student should have referred to fluorine being the most electronegative element - or
............................................................................................................................................................................................................................ [2]
to it being more electronegative than oxygen
Hints and Comments
• Although it's vital to know the rules for assigning oxidation numbers, they are not explanations - you need to understand why fluorine always has
an oxidation number of -1 in compounds, oxygen always -2 except with fluorine or in peroxides/superoxides etc.
• Unless a previous part of the question has asked for a definition of oxidation - or told you it! - there are likely to be marks available for showing
that you understand oxidation is loss of electrons or increase in oxidation number.
Markscheme
(a) Oxygen is a highly electronegative element (1) so the other element generally loses electrons and is oxidised (1)
(b) Fluorine is not oxidised (1) because it is more electronegative than oxygen/ is the most electronegative element (1)

TiO2, known in industry as ‘titanium dioxide’, dissolves in concentrated sulphuric acid to give an orange solution of ‘titanyl sulphate’, TiO2+ SO42-
It also reacts with fused potassium hydroxide to give potassium titanate, (K+)2TiO32-.

(a) Write down the oxidation number of titanium in each of the following : " the working is correct, but the candidate
!correct working and answer !correct working and answer has got into problems with negative numbers

? + 2 x -2 = 0 ?=4
TiO2 ...............................................[1] ?-2 =2 ?=4
2+
TiO ...............................................[1] ? + 3 x -2 = -2 ? = -8
TiO32- ...............................................[1]

(b) Hence state whether each of these conversions involves ‘oxidation’, ‘reduction’ or ‘neither’.
neither -ON doesn't change ON goes down - reduction
TiO2 → TiO2+ ......................................................... [1] TiO2 → TiO32- ......................................................... [1]
!correct working and answer ecf!candidate has drawn conclusions correctly
Hints and Comments using previous incorrect answer
• You generally should put + signs on oxidation numbers where appropriate
• Make sure your answer is plausible - you aren't likely to find oxidation numbers of -8
• It was sensible for the candidate to continue with the question - despite the "weird" answer - as "follow through" marks were awarded

1
67 Why Students Lose Marks: AS Redox Questions Chem Factsheet

Now try marking this student answer before you look at the markscheme and comments

(a) Define disproportionation One element is oxidised and reduced

.......................................................................................................................................................................................

.................................................................................................................................................................................................................................. [2]

(b) Copper(I) compounds (except for complexes) are unstable in aqueous solution and decompose by disproportionation. Suggest what you would
expect to observe when the white soluble salt, copper(I) sulphate, dissolves in water and write a chemical equation for the reaction.
You get copper (II) sulphate and copper
.......................................................................................................................................................................................................................................
Cu2SO4 → CuSO4 + Cu
.......................................................................................................................................................................................................................................

.................................................................................................................................................................................................................................. [3]
what copper (II) sulphate and copper metal looked like.
Note that you did not have to be familiar with copper (I) compounds or properties to answer this question - although you did need to know

and that there is a precipitate of copper metal

copper (I) sulphate only disproportionates when it's in solution, and it's necessary to show the copper (II) sulphate is formed as a solution,
Cu2SO4 → CuSO4 + Cu 0/1 - although the equation is basically correct, state symbols are extremely important here -

colours of solutions/solids/gases, effervescence etc

(b) You get copper (II) sulphate and copper 0/2 -these are not observations - observations refer to what you actually see (or smell!) -

The student clearly understood the term, but lost a mark through not being precise enough in the definition
1/2 - the word "simultaneously" (or "in the same reaction") needed (a) One element is oxidised and reduced
So how did the student score?

Cu2SO4(s) → CuSO4(aq) + Cu(s) (1)

(b) A blue solution (1) and a red / brown precipitate (1)

(a) The simultaneous oxidation and reduction (1) of a single substance / species (1)
Here's the markscheme:

Arsenic is a toxic element and there are many cases of it being used by murderers. It is regularly monitored in European public drinking water
supplies. Modern analytical methods used in water quality assurance begin with complete oxidation of arsenic in the sample, with sodium
persulphate and concentrated sulphuric acid, to form H3AsO4. This is then reduced in two stages; first, using potassium iodide and acid, to form
HAsO2 and, second, using aluminium powder and acid, to form arsenic(III) hydride, AsH3.

Write balanced ionic half-equations for the following reactions.

"" no marks awarded - the candidate has introduced an additional
product - oxygen gas - in an attempt to balance the equation!
H3AsO4 → HAsO2 + H2O + ½O2 The information given about the use of acid has not been included
(i) H3AsO4 to HAsO2 ..................................................................................................................................................................................................................................................................................................................... [2]

2I − → I2 + 2e − ! full marks here - the candidate has recalled this common redox
(ii) Iodide ion to iodine ................................................................................................................................................................................. [1]
half equation correctly, with balanced charges

Hints and Comments

• Examiners may give you questions about substances you're not familiar with, like arsenic. This is to test your understanding of the general
principles and how to apply them - in this sort of question they know you are not relying on memory.
• If you are asked to write half-equations, it's always a good idea to work out the oxidation numbers of the element being reduced or oxidised - that
tells you how many electrons to put in the half-equation - eg if the ON decreases by 5, you need 5 electrons on the left; if it goes up by 3, you need
3 electrons on the right.
• The only substances you should generally be adding to half equations are H+ (if acid conditions are mentioned) and H2O.
• The iodide - iodine conversion is a standard (and easy) one -1you should be able to write the equation down without thinking twice

Markscheme
(i) Calculating oxidation numbers of As in H3AsO4 and HAsO2 as +5 and +3 respectively 1
Correct equation: H3AsO4 + 2H+ + 2e− → HAsO2 + 2H2O 1
(ii) 2I−→ I2 + 2e− One element is oxidised and
1 reduced

2
67 Why Students Lose Marks: AS Redox Questions Chem Factsheet

(a) Write ionic half-equations for the following changes. State symbols may be omitted.

(i) sulphite ions to sulphate ions in acid solution

SO32− + H2O → SO42− + 2H + + 2e − !completely correct equation

..................................................................................................................................................................................................................... [1]

(ii) Manganate(VII) ions to manganese(II) ions in acidic solution.

MnO4− + 8H ++5e − → Mn 2+ + 4H2O !completely correct equation
..................................................................................................................................................................................................................... [1]

(b) Combine the ionic half-equations from above to obtain the complete ionic equation for the redox reaction between manganate(VII) ions and sulphite
ions in acidic solution.
2(SO32− + H2O → SO42− + 2H + ) + 5(MnO4− + 8H ++5e− → Mn 2+ + 4H2O )
..........................................................................................................................................................................................................................
2SO32− + 5MnO4− + 2H2O + 40H + → 2SO42− + 4H + + 5Mn2+ + 20H2O
..........................................................................................................................................................................................................................
2SO32− + 5MnO4− + 36H + → 2SO42− + 5Mn2+ + 18H2O
..................................................................................................................................................................................................................... [3]
""" No marks awarded. The candidate has clearly mis-remembered a method for combining half
equations (the correct approach would be to multiply by the number of electrons in the other half-
equation).
If s/he had included the electrons in the working (rather than assuming they would cancel out ) or
had thought to check the charges balanced at the end, s/he might have realised the mistake.

Hints and Comments

• It makes life simpler in the exam if you make sure you learn the commoner half-equations
• When you are combining half equations, there are two methods you can use - balancing electrons (as mentioned above) or balancing
oxidation number change - in the above equation, the oxidation number of the sulphur increases by 2, while that of the manganese goes down
by 5 - so 5 sulphurs must be oxidised for every 2 manganese that are reduced. Whichever method you choose, however - always make sure
the charges balance at the end
Markscheme
(a) (i) SO32- + H2O → SO42- + 2H + + 2e- (1)
(ii) MnO4- + 8H ++5e- → Mn 2+ + 4H2O (1)
(b) (i)×5 + (ii)×2 (1)
-
2MnO4 + 16H + 5SO +
3
2-
+ 5H2O → 2Mn + 8H2O + 5SO4 + 10H
2+ 2- +
(1)
-
2MnO4 + 6H + 5SO3 + 2-
→ 2Mn + 3H2O + 5SO
2+
4
2-
(1)

Questions
1. (a) Define oxidation and reduction in terms of electrons. [2]
(b) Explain why it is that oxidation and reduction always occur together.
[1]
(1) 2Ti + 6H+ → 2Ti3+ + 3H2
(1) 2H+ + 2e- → H2
2. Calculate the oxidation number of the stated element in each of the
(1) 3. Ti → Ti3+ + 3e−
following species
(i) Mn in MnO42- (ii) N in HNO3
(vi) + 2 (v) + 4 (iv) + 6 (iii) + 2 (ii) + 5 2. (i) + 6
(iii) S in S2O3 2- (iv) Cr in Cr2O72-
(v) V in VO2+ (vi) O in F2O
accepted by another substance, which becomes reduced (1)
(b) When a substance is oxidised it loses electrons; these must be
3. Titanium dissolves in concentrated hydrochloric acid to give
titanium(III) chloride and hydrogen. Construct an ionic equation for (1) Reduction is electron gain
this reaction by writing down two ionic half-equations and then (1) 1. (a) Oxidation is electron loss
combining them. [3] Answers

Acknowledgements:
This Factsheet was researched and written by Cath Brown.
Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire, TF1 1NU.
Chem Factsheets may be copied free of charge by teaching staff or students, provided that their school is a registered subscriber. No part of these
Factsheets may be reproduced, stored in a retrieval system, or transmitted, in any other form or by any other means, without the prior permission of the
publisher. ISSN 1351-5136
3
 Chem Factsheet
www.curriculum-press.co.uk Number 68
Periodic Table: Anomalies of first member of group
Before working through this Factsheet you should: Consequences of high electronegativity
• Be familiar with the general trends across periods and down groups in • Coupled with small size, high electronegativity accentuates nonmetallic
the periodic table; behaviour.
• Be familiar with general properties of Groups 1, 2 and 7. This means that the metallic elements form compounds with appreciable
covalent character, as described above. Some oxides - eg beryllium - are
After working through this Factsheet you will: amphoteric.
• Understand why period 2 elements generally display noticeably
different properties to the other elements in the same group; • Nitrogen, oxygen and fluorine can be involved in hydrogen bonds.
• Be familiar with examples of the atypical properties of lithium, As a consequence, the boiling points of NH3, H2O and HF are higher
beryllium and fluorine; than those of PH3, H2S and HCl, although the general group trend is for
• Understand what is meant by the "diagonal relationship" in the Periodic boiling points of hydrides to increase down the group.
Table.
Why are period 2 elements different? Consequences of lack of d-orbitals
• The atoms are very small in size; • Form a maximum of four bonds.
For example, nitrogen exhibits a maximum valency of 3 (eg ammonia
• The elements are very electronegative;
NH3) but phosphorus can form PCl5. Similarly, sulphur forms SF6, but
• They have no d-orbitals.
no equivalent compound is formed by oxygen.

Consequences of small size • Some reactions which occur for other members of the group cannot
• Lower than expected electron affinity. occur for the first member.
We might have expected high electron affinity for these elements - the This is because some reactions progress via a transition state involving
new electron will be very close to the nucleus. However, because of an additional bond; the lack of availability of d-orbitals in the second
their small size, the extra electron is being put into a region that is energy level means that a mechanism that works for the rest of the
already crowded with electrons - producing a significant amount of group will not work for the first member.
repulsion. For example, carbon tetrachloride (CCl4) is resistant to hydrolysis, but
For example, although the general trend is for electron affinity to the other tetravalent group 4 chlorides will hydrolyse.
decrease down a group, fluorine has a lower electron affinity than
chlorine, and oxygen has a lower electron affinity than sulphur.
Anomalies of lithium
• Increased covalent character for small cations. • Thermal decomposition of carbonates, nitrates and hydroxides to
give the oxide.
This is due to high charge density on the cations - bonds are polarised.
This is due to the high charge density of the lithium ion - combination
with the high charge density oxide ion is favoured.
• Does not form peroxides and superoxides readily due to small size
Li+ Cl − of the ion.
• Some compounds show a degree of covalent character due to
polarising power of the small Li+ ion.
• Relatively low solubility of carbonate, fluoride, hydroxide and
For example lithium chloride dissolves in alcohols, unlike the remainder phosphate due to the high lattice enthalpy.
of group 1 chlorides; beryllium chloride dissolves in diethyl ether,
unlike the remainder of group 2 chlorides. Anomalies of beryllium
• Compounds show appreciable covalent character - eg dissolving
in organic solvents, low melting points, hydrolysed by water. This
Remember: ionic compounds generally dissolve in polar solvents and
is due to its much larger ionisation energy and the much smaller
covalent compounds in non-polar solvents. size of its ions.
• Amphoteric hydroxide.
• Does not form oxide in air at room temperature.
• π-bonds are more efficient between 2p orbitals than 3p (or higher). • Will not react with water and dilute acids.
This is due to the strong overlap because of the small size of the atoms.
Anomalies of fluorine
• Hydrofluoric acid is a weak acid (due to the high H-F bond strength).
• Hydrogen fluoride has a high boiling point (hydrogen bonding).
• The F-F bond strength is very low, because the small size of the
C C Si atom brings the lone pairs close together.
Si
• Forms compounds with all elements except helium, neon and argon.
• Does not form oxy-acids as it is more electronegative than oxygen.
• Only exhibits oxidation state of -1, as it is the most electronegative
element.
• Is such a strong oxidising agent that it must be prepared by
For example carbon forms very many compounds with double or triple electrolysis, rather than chemically.
carbon-carbon bonds, whilst silicon does not. Nitrogen and oxygen • Because of its small size, more fluorine atoms can be packed
exist as diatomic molecules (involving multiple bonds), whilst around a central atom - eg AlF63− is formed, but only AlCl4−.
phosphorus and sulphur exist as P4 and S8 respectively, with no multiple
bonds.
1
68. Periodic Table: Anomalies of first member of group Chem Factsheet

Diagonal Relationships Practice Questions

This refers to the similarities exhibited between the first element of some
groups and the second element of the next group to the right. 1. (a) Explain why the boiling points of hydrogen fluoride and hydrogen
bromide are both higher than that of hydrogen choride
Li Be B C
(b) Explain why hydrofluoric acid is a weak acid
Na Mg Al Si
2. Lithium chloride dissolves in alcohols; sodium chloride does not.
Note: this relationship does not hold for all the groups; the only significant
relationships are the ones illustrated above. (a) Explain the significance of these observations

Why is there a relationship? (b) Account for these observations

Diagonal relationships occur because of the trends in properties down
groups and across periods.The trend in properties across a period is usually 3. (a) Explain why some chemical similarities between beryllium and
opposite to the trend down a group - for example, ionisation energy increases aluminium are to be expected
across a period but decreases down a group, while atomic radius decreases
across a period but increases down a group (Fig 1). (b) State two such similarites

Fig 1. Trends in the periodic table 4. Explain why alkenes are common, but the corresponding silicon
compounds, silenes, are very rare.
Increase in: Decrease in:
• ionisation energy • atomic radius 5. Suggest why lithium fluoride is insoluble
• electronegativity • metallic character
• acidity of oxides 6. Explain why PCl5 exists, but not NCl5

Increase in: bonds.

• atomic radius 6. Nitrogen has no d-orbitals available, and so cannot form more than four
• metallic character
5. Extremely high lattice enthalp due to both anion and cation being small.
Decrease in:
• ionisation energy is very little overlap between the 3p-orbitals
• electronegativity neighbouring 2p-orbitals. The larger size of silicon atoms means there
• acidity of oxides 4. The small size of carbon atoms allows a high degree of overlap between

but not shared with the remainder of group 2)

So, for example, atomic radius decreases from lithium to beryllium, but
they should refer to properties shared by beryllium and aluminium,
increases from beryllium to magnesium. The result is that the atomic radii
which dimerize/polymerize (other acceptable answers are possible-
of lithium and magnesium are similar (1.55×10-10m and 1.6×10-10 m
amphoteric oxides; hydrolysis of salts; electron-deficient chlorides
respectively).
(b) Any two of: appreciable covalent character of compounds;
In particular, the polarising power of the corresponding ions is similar.
This is because the increase in size from one period to the next is offset by electronegativity, atomic radius and polarising power of cations.
the increased charge. below it to the right. These similarites include ionisation energy,
leading to similarites between an element and the element diagonally
Similarities between lithium and magnesium include: period are in the opposite direction to trends down the group,
• on reaction with air, forms oxide, not peroxide or superoxide 3. (a) This is an example of the diagonal relationship. Trends across the
• carbonates thermally decompose, giving the oxide and carbon dioxide
• nitrates thermally decompose, giving the oxide, nitrogen dioxide and character.
oxygen The ionic bond becomes polarised, giving rise to some covalent
(b) The lithium cation is very small with a very high charge density.
Similarities between beryllium and aluminium include
• appreciable covalent character of compounds (eg the chlorides are largely lithiumchloride has appreciable covalent character.
covalent) expected to dissolve in it, but not ionic ones. This suggests that
• formation of electron-deficient covalent chlorides, which tend to 2. (a) Alcohol is an organic solvent. Covalent substances would be
dimerize or polymerize
• amphoteric oxides ionize fully in water
• hydrolysis of salts Since the H-F bond is very strong, hydrogen fluoride does not
Note that lithium and beryllium differ from the remainder of the elements (b) The greater the degree of ionisation in water, the stronger the acid.
in their groups with regard to these properties, as discussed above.
molecular size
Acknowledgements: This Factsheet was researched and written by Cath Brown. increasing strength of the Van der Waals forces, due to increasing
Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire, TF1 bromide is higher than that of hydrogen bromide because of the
1NU. ChemistryFactsheets may be copied free of charge by teaching staff or in HF, which is not present in HCl. The boiling point of hydrogen
students, provided that their school is a registered subscriber. No part of these hydrogen chloride because of the strong hydrogen bonding present
Factsheets may be reproduced, stored in a retrieval system, or transmitted, in 1. (a) The boiling point of hydrogen fluoride is higher than that of
any other form or by any other means, without the prior permission of the Answers
publisher. ISSN 1351-5136

2
 Chem Factsheet
www.curriculum-press.co.uk Number 69
Revision Summary: Trends in the Periodic Table 1
Before working through this Factsheet you should:
• Be familiar with the organisation, layout and information available from the Periodic Table;
• Have studied the AS and A2 work on periodic trends.
After working through this Factsheet you will have revised:
• The layout of the Periodic Table;
• Trends in physical properties and their explanation.
This Factsheet provides a revision summary of periodic table work. If you would like more explanations on any aspect, these can be found in Factsheets
12, 13, 14, 19 and 20. Factsheet 68 also looks at periodic trends in a different context.

Questions on trends in the Periodic Table are popular at AS and A2 level.

Such questions often require two styles of preparation: Properties of an element are a periodic function of their atomic
numbers. Properties repeat regularly, so that elements in the same
• Factual recall – statement of a trend and evidence of it, e.g. the recall of group tend to display similar chemical and physical properties.
particular chemical equations.
• Application and understanding – answers require a description of why
there is a particular trend.
You need to learn the following group names:
First, revision of the Periodic Table itself.
Group Number Group Name
1 Alkali Metals
The elements are placed in order of increasing atomic number.
2 Alkaline Earth Metals
Period: Horizontal row of elements. 7 Halogens
Group: Vertical column of elements. 0 Noble Gases

s, p, d and f blocks
Metals, Metalloids and Non-metals
The Periodic Table is divided up into 4 blocks (s, p, d and f) which show
These can also be shown to be grouped on the Periodic Table:
which is the outer electron sub-shell for the elements in that block.
metalloids non-metals
123456
123456
3 4 5 6 7 0
123456
123456
B 123
C N O F Ne
s p metals 123
Al 123
123456
S i P S Cl Ar
123456
d s Ga123456
123456
Ge As 1234
Se Br Kr
1234
In Sn Sb1234Te I Xe
d T l Pb Bi P o A t Rn

f
f

To categorise the elements into one of these three types, the following
s-block elements: - the metals in group 1 and 2, so called because their
criteria can be used:
outer shell contains s electrons.
e.g. Sodium (Na): Atomic no. 11. Elec. config. 1s22s2 2p63s1
Metals
p-block elements: - the elements from groups 3 to 7, as they have outer • Good conductors of electricity
electrons which are p-electrons. • Form basic oxides (a few form amphoteric oxides)
e.g. Carbon (C): Atomic no. 6. Elec. config. 1s2 2s22p2
Metalloids
d-block elements: - the metals in the block between groups 2 and 3, • Poor conductors of electricity (except graphite)
known as the transition metals. d-block elements have incomplete • Form amphoteric oxides
d-sub shells. Non-metals
e.g. Titanium (Ti): Atomic no. 22. Elec. config. 1s22s2 2p63s23p64s23d2 • Virtually non-conductors of electricity (insulators)
• Form acidic oxides
f-block elements: - a block of elements within the transition metals, so
called because electrons are being added into the f-subshell in these Note: You may find differences between textbooks on which elements are
elements. e.g. Cerium (Ce) Atomic no. 58. classified as "metalloids" and which as "non-metals". Do not worry
Elec. config. 1s22s2 2p63s23p64s23d104s65s24d105p66s24f2 about this - the key point is understanding the characteristics.

1
69. Revision Summary: Trends in the Periodic Table 1 Chem Factsheet
Trends in physical properties - Period 3
Group 1 2 3 4 5 6 7 0 Notes
Element sodium magnesium aluminium silicon phosphorus sulphur chlorine argon
Symbol Na Mg Al Si P S Cl Ar
All metals have metallic structure - this leads to good conductance.
Giant Giant Silicon has a (covalently bonded) diamond structure.
Molecular Atomic Chlorine and the other halogens all exist as diatomic molecules; phosphorus and sulphur are
Structure Metallic Covalent
simple molecular, but not diatomic. All noble gases are monatomic
Metallic character generally decreases across a period; this is associated with the decrease in
Metalloid/ ionisation energy (so less likely to form positive ions) and increase in electronegativity/electron
Character Metallic Non - Metallic
Non-metal affinity (more likely to attract electrons)
Melting point is determined by structure - for metals, generally the more valence electrons, the
stronger the metallic bonding and the higher the melting point. Giant covalent structures always
Melting Point General increase General decrease produce high melting points. For simple molecular structures, melting point is determined by the
strength of van der Waals forces, which depend on molecular size
General increase Associated with metal/metalloid/non-metal character - within the metals, the higher the number of
Conductance General decrease valence electrons available, the higher the conductivity
Note this just refers to forming the M+ ion, not the commonest ion formed. It is always endothermic
The effective nuclear charge increases across a period - since electrons are being added to the same
shell, so there is comparatively less shielding. This makes it harder to remove an electron.
First Ionization Energy General increase Note the exceptions due to half-shell stability, full-sub-shell stability and p electrons being easier to
remove than s-electrons - the 1st IE for aluminium is less than for magnesium, and for sulphur less
than for phosphorus
Again, this decreases due to increasing effective nuclear charge - electrons are held more tightly by
Atomic Radius General decrease the nucleus
This refers to the commonest ion formed - eg Na+, S2− etc
Not Not For positive ions, the higher the charge, the smaller the ion, since the remaining electrons are
Ionic Radius applicable applicable pulled closer to the nucleus.
General decrease General decrease For negative ions, the higher the charge, the larger the ions, since the nucleus is having to retain
more additional electrons
Silicon and argon do not form ions
Ionic Radius compared Not Not Positive ions are always smaller than the neutral atom, and negative ions larger, since the fewer the
Smaller Larger
to Atomic Radius applicable applicable electrons, the closer they are pulled to the nucleus
Measures the ability to attract electrons within a bond.
Not Increases due to increasing effective nuclear charge.
Electronegativity General increase applicable Bond type is determined by the difference in electronegativity, and it also helps explain the transition
from metallic to non-metallic character
Measures the ability to attract an electron - always exothermic
First Electron Affinity Not
General increase Increases due to the increase in effective nuclear charge. Elements with high electron affinity are
applicable more likely to form negative ions. Note that this is not a uniform increase - atoms with full sub-shell
or half sub-shell stability have a lower electron affinity than would be expected.
2
69. Revision Summary: Trends in the Periodic Table 1 Chem Factsheet

Group trends
The table below shows general trends that apply throughout all groups of the periodic table; other trends are specific to particular groups.

General Trends
ionic 1 st electron Notes
atomic 1 st ionisation Electronegativity
radius radius energy affinity • Atomic and ionic radius increase because of increasing number of shells of electrons
• First ionisation energy increases because the electron being removed is further from
the nucleus and the increased shielding due to inner shells
Decreases

Decrease
Increases
Increases

General
Electronegativity and electron affinity decrease due to the increased shielding.

Decrease
General
• There are some anomalies in the decreasing trend for electronegativity -eg Group 4
• There are also anomalies in the decreasing trend for electron affinity - fluorine, for
example, has a lower first electron affinity than chlorine, due to repulsion from the
electrons already in place.

Group 1 and 2 Trends

Group 7 trends
Members of groups 1 and 2 are all metals They are silver in colour and
Members of group 7 are all non-metals and have low melting and boiling
tarnish in air. Mant of their characteristic trends in their physical properties
points
can be explained by the fact that they show weak metallic bonding.
Notes Notes
melting boiling density melting boiling
The melting point decreases down the The melting and boiling points here are determined
point point point point
group because in the metallic bond, the by the strength of the Van der Waals forces.
number of delocalised electrons remains All the halogens form diatomic molecules, so as
the same and the charge on each metal
Decreases

Decreases

the group is descended, the molecules get larger.

Increases

Increases

Increases
cation stays the same, but the ionic radius This produces larger Van der Waals forces, and
increases so the attraction between the hence increased melting and boiling points
delocalised electrons and the metal cations
decreases.
The density increases because the atomic
mass increases faster than the size of the
atom.

Waals forces; these increase, due to increase in molecular size.

In group 7, melting point is determined by the strength of the Van der
Practice Questions
1. State and explain how the following properties vary for the elements increases, producing decreased attraction between the cations and electrons
of Period 3 (Na – Ar). the number of delocalised electrons remain constant, the ionic radius
bonding. This decreases, because although the charge on the cation and
(a) Atomic radius. (b) Melting point. (c) First ionisation energy.
5. In groups 1 and 2, melting point is determined by strength of metallic
2. (a) Explain why the ionic radius of bromine is larger than its atomic
radius. and increased shielding.
(b) Explain why the ionic radius of Al3+ is smaller than that of Na+
(b) Decreases, due to increased distance of electron from nuclues
4. (a) Increases, due to increasing number of shells of electrons
3. Electrical conductivity is measured in units called siemens per metre,
S m-1. Values for the elements in Period 3 are given in the table below.
movement of electrons
(c) Covalent bonding. Electrical conductivity is low, so very limited
Hence there are more free / delocalised / mobile electrons
Element Electrical conductivity / 108 S m-1 (b) Number of outer shell electrons increases from 1 to 2 to 3
Na 0.218 move under an applied p.d. throughout the entire metal
Mg 0.224 3. (a) They have metallic bonding, so electrons are delocalised and can
Al 0.382
Si 10-10 particle
P
Hence the electrons in Al3+ are more tightly held, making it a smaller
10-17 greater nuclear charge.
S 10-23 (b) Al3+ and Na+ have the same number of electrons, but Al3+ has a
Cl − the particle.
Ar − This causes electron repulsion to increase, increasing the size of
2. (a) Bromine forms Br- ion, involving the addition of an electron.
(a) Explain why the electrical conductivity of sodium, magnesium and
aluminium is relatively high.
Increasing nuclear charge.
(b) Why does electrical conductivity increase from Na to Mg to Al? (c) Increases across period.
bonding, P – Ar held by much weaker Van der Waals forces.
(c) The electrical conductivity of boron is 10-12 (in units of 108 S m-1) Na – Si increasing metallic bond strength, Si very strong covalent
Use this value to state and explain the type of bonding present in (b) Increase Na – Si, then decrease P – Ar.
boron quantum shell.
Increasing nuclear charge, whilst electrons being added into the same
4. State and explain how the following properties vary going down a 1. (a) Decreases across the period.
group of the Periodic Table Answers
(a) Atomic radius. (b) First ionisation energy. Acknowledgements: This Factsheet was researched and written by Kieron Heath. Curriculum Press, Bank
House, 105 King Street, Wellington, Shropshire, TF1 1NU. ChemistryFactsheets may be copied free of charge
5. In groups 1 and 2 of the Periodic Table, melting points decrease down by teaching staff or students, provided that their school is a registered subscriber. No part of these Factsheets
may be reproduced, stored in a retrieval system, or transmitted, in any other form or by any other means, without
the group, but in group 7, they increase. Explain this difference. the prior permission of the publisher. ISSN 1351-5136

3
 Chem Factsheet
www.curriculum-press.co.uk Number 70
Revision Summary: Trends in the Periodic Table 2
Before working through this Factsheet you should:
• Be familiar with the organisation, layout and information available from the Periodic Table;
• Be familiar with the trends in properties such as atomic radius, ionisation energy etc (covered in Factsheet 68).
After working through this Factsheet you will have revised:
• Trends in the chemical properties of Period 3 and Groups 1, 2 and 7, together with their explanations.
Note that the chemical reactions depend on the trends on physical properties (Factsheet 69) so you should revise these first before attempting to learn
the material covered here.

Reactions of Period 3 elements with oxygen, chlorine and water

Element Reaction with oxygen Reaction with water Reaction with chlorine
Sodium Burns to form mixture of peroxide and oxide Reacts very vigorously to form the hydroxide Reacts vigorously
2Na + O 2 → Na2O2 and 4Na + O2 → 2Na2O 2Na + 2H2O→ 2NaOH + H2 2Na + Cl2→ 2NaCl

Magnesium Burns in air Reacts with steam to form the oxide Reacts readily
2Mg + O2 → 2MgO (or hydroxide with excess steam) Mg + Cl 2→ MgCl2
Mg + H 2O→ MgO + H2
Mg + 2H 2O→ Mg(OH)2 + H2

Aluminium Does not normally react readily with air, Reacts with steam to form the oxide Reacts readily
due to surface layer of oxide. Burns in oxygen . 2Al + 3H2O(g) → Al2O3 + 3H2 2Al +3Cl2→ 2 AlCl3
4Al + 3O2 → 2Al2O3

Silicon Thin oxide coating prevents reaction with air No reaction Reacts vigorously
unless very high temperatures used. Si + 2Cl2→ SiCl4
Si + O2 → SiO2

Phosphorus White phosphorus spontaenously ignites in air, No reaction Reacts vigorously

P4 + 5O2 → P4O10 2P + 3Cl 2→ 2PCl3

Sulphur Burns in air . No reaction Reacts on heating

S8 + 8O2 → 8SO3 S8 + 4Cl2→ 4S2Cl 2

Chlorine Does not react with oxygen Reacts with water to form chlorate (I) ions N/A
(although oxides do exist) Cl2(g) + H2O(l) ¾ OCl−(aq) + 2H+(aq) + Cl−(aq)

Argon No reaction No reaction No reaction

Oxides - key points Reactions with water - key points Chlorides - key points
The enthalpy of formation of the oxides is usually When metals react, the products are basic. As with oxygen, we see a
negative, so the oxides are generally very stable. Most non-metals do not react, but those that decline in stability going across
This is due to the high electronegativity of oxygen. do form acidic products. the period; again, this is due to
the decreasing electronegativity
Moving across the period, electronegativity increases difference. Likewise, the
- so the electronegativity difference with oxygen bonding becomes increasingly
decreases. This results in reduced stability and covalent.
increasing covalent character.

We also see a change from basic to acidic oxides.

Exam Hint: You need to be able to quote both the reactions and the balanced equations for them. Many of the equations and products are easy
to remember; concentrate on learning the "unusual" ones, such as S2Cl2

1
70. Revision Summary: Trends in the Periodic Table 2 Chem Factsheet

Aside from the reactions of the period 3 elements themselves, you also need to know the characteristics and trends in the reactions of their oxides and
chlorides. The following tables give summaries of these reactions.
Period 3 oxides
Oxide Structure/Bonding Acidic/Basic character Reaction with water
sodium oxide Na2O giant ionic basic Reacts to form a strong alkali
Na2O(s) + H2O(l) → 2NaOH(aq)
magnesium oxide MgO giant ionic, basic, but less so than Na2O Reacts to form a weak alkali
polarised MgO(s) + H2O(l) → Mg(OH)2(aq)
aluminium oxide Al2O3 ionic, some amphoteric - reacts with No reaction
covalent character both H+ and OH− ions
Al2O3(s) + 6H+(aq) → 2Al3+(aq) + 3H2O(1)
Al2O3(s) + 2OH−(aq) + 3H2O(1) → 2Al(OH)4−(aq)
silicon(IV) oxide SiO2 giant covalent acidic - reacts with OH− ions No reaction
SiO2(s) + 2OH−(aq) → SiO32−(aq) + H2O(l)
phosphorus(V) oxide P4O10 molecular acidic Reacts to form phosphoric (V) acid
covalent solid P4O10(s) + 6H2O(l) → H3PO4(aq)
sulphur(IV) oxide (or dioxide) SO2 molecular acidic React to form sulphuric (IV)
sulphur(VI) oxide (or trioxide) SO3 covalent gas and sulphuric (VI) acids:
SO2(g) + H2O(l) → H2SO3(aq)
SO3(g) + H2O(l) → H2SO4(aq)
chlorine oxide(Cl2O) molecular acidic Reacts to form hypochlorous acid
covalent gas Cl2O(g) + H2O(l) → 2HOCl(aq)

Period 3 chlorides

Chloride Structure/ Bonding Reaction with water

sodium chloride NaCl Giant ionic Dissolves to give a neutral solution
magnesium chloride MgCl2 Giant ionic Dissolves to give a weakly acid solution
aluminium chloride AlCl3 When anhydrous, covalent solid Anhydrous form reacts to produce hydrochloric acid
which exists as dimers Al2Cl6 AlCl3(s) + 3H2O(l) → Al(OH)3(s) + 3HCl(aq)

The hydrated form is an ionic solid Hydrated form is hydrolysed in water, forming acidic solution
[Al(H2O)6]3+(aq) + H2O(l) → Al[(H2O)5(OH)]2+(aq) + H3O+(aq)
silicon chloride SiCl4 molecular covalent liquid Reacts to produce hydrochloric acid
SiCl4(1) + 2H2O(1) → SiO2(s) + 4HCl(aq)
phosphorus chlorides molecular covalent liquid Reacts to form phosphoric and hydrochloric acids
PCl3 and PCl5 PCl3(1) + 3H2O(1) → H3PO4(aq) + 3HCl(aq)
sulphur chlorides molecular covalent liquid Reacts to form hydrochloric acid
S2Cl2, SCl2 and SCl4 2S2Cl2(1) + 2H2O(1) → 3S(s) + SO2(aq) + 4HCl(aq)

Practice questions on trends across the period

1. One of the period 3 elements forms an amphoteric oxide. Use equations Cl2O(g) + H2O(l) → 2HOCl(aq)
to illustrate the amphoteric nature of the compound. P4O10(s) + 6H2O(l)→ H3PO4(aq)
SO3(g) + H2O(l) → H2SO4(aq)
2. Explain why the heat evolved in the formation of the period 3 chlorides SO2(g) + H2O(l) → H2SO3(aq)
decreases as we move across the period. (b) Oxide: SO2, SO2, P4O10 or Cl2O Nature: Acidic

3. If an oxide of an element can react with water, it will form either a MgO(s)+H2O(l)→Mg(OH)2(aq)
hydroxide or an oxyacid depending on the nature of the element Na2O(s)+H2O(l)→2NaOH(aq)
concerned. Using examples from period 3, (a) Oxide: Na2O / MgO Nature: Basic 3

(a) Give an example of an oxide which forms a hydroxide with water the heat released on formation decreases.
and state the nature of the oxide. Write a balanced chemical equation across the period, bonds formed become more covalent in character and
for the reaction which occurs. electronegative chlorine, releasing a great deal of energy. As we move
2. s-block metals are very electropositive, so form strong ionic bonds with
(b) Give an example of an oxide which forms an oxyacid with water
As an acid: Al2O3 (s) + 2OH− (aq) + 3H2O (l) → 2Al(OH)4− (aq)
and state the nature of the oxide. Write a balanced chemical equation
As a base: Al2O3 (s) + 6H+ (aq) → 2Al3+ (aq) + 3H2O (l)
for the reaction which occurs.
1. Aluminium oxide is amphoteric.
Answers
2
70. Revision Summary: Trends in the Periodic Table 2 Chem Factsheet

Trends within groups of the Periodic Table

Elements within the same group on the Periodic Table tend to show similar chemical and physical properties due to similarities in electronic configuration.
Groups 1 and 2
Members of groups 1 and 2 are all metals. The trends in groups 1 and 2 are generally similar.
Notes
Reactivity thermal stability thermal stability
The reactivity increases down the group due to the decrease in 1st ionisation energy - which is due to the
of nitrates of carbonates
increasing distance of the outer electrons from the nucleus, and the increased shielding.

There are two ways of looking at the thermal stability - arguments are given for carbonates, but nitrates
Increases

Increases

work the same way. First note that the carbonates decompose to give the oxide and carbon dioxide.

Increases
1. Lattice enthalpy. The comparative sizes of the lattice enthalpy for the carbonate and oxide
indicate how much energy must be supplied to force the carbonate to decompose.
Both lattice enthalpies decrease down the group due to the increasing size of the metal ions - and so the
increasing distance between the positive and negative ions. However, the percentage decrease in the
Exam Hints: oxide lattice enthalpy is greater. This is because the oxide ion is small, so the increasing size of the metal
1. Check whether your specification requires ions has a large % impact on the distance between ions: the carbonate ion is much bigger, so the
you to know the explanations for the trends, proportional impact of the metal ions is much less.
or just what they are. 2. Polarising ability. The carbonate ion has a system of delocalised electrons. In an ionic compound,
2. When quoting trends, you need to be able to it tends to be polarised so that the oxygen adjacent to the cation acquires a greater share of the negative
quote appropriate examples - for example, what charge. This tendency makes it easier for the carbon and other two oxygens to break away on heating
evidence is there that reactivity increases down to form carbon dioxide. The smaller cations at the top of the groups have a greater polarising ability,
Group 1 ? because of their greater charge density - so it requires less heat to decompose their carbonates.

Group 2 Only Trends

• Solubility of hydroxides increases as group is descended. • Solubility of sulphates decreases as group is descended.
Both of these trends are due to the changes in lattice enthalpy and hydration enthalpy as the group is descended.
The lattice enthalpy falls going down the group - the distance between cations and anions increase as the cations become larger. The hydration enthalpy also
falls - the water molecules are less strongly attracted to the larger ions. So the issue is which of them falls faster - if the lattice enthalpy falls faster, then
dissolving becomes more exothermic and compounds become more soluble, whereas if the hydration enthalpy falls faster, dissolving becomes more
endothermic and solubility decreases.
As explained above, the percentage decrease in lattice enthalpy is greater if the anion is small, since the size of the cation then contributes more significantly
to the distance between the ions. Hydroxide ions are smaller than sulphate ions - so the lattice enthalpy for hydroxides decreases faster than that for
sulphates. For hydroxides, the lattice enthalpy decreases faster than the hydration enthalpy - they become soluble. For sulphates, the hydration enthalpy
decreases faster than the lattice enthalpy - they become less soluble.

Products of reactions of Group 1 and 2 metals

The table shows the reactions of groups 1 and 2 with oxygen, water and chlorine.

Element Products of reaction with:

Oxygen Water Chlorine

Li Li2O LiOH + H2 LiCl
Na Na2, NaO2 NaOH + H2 NaCl
K K2O, K2O2, KO2 KOH + H2 KCl
Rb Rb2O, Rb2O2, RBO2 RbOH + H2 RbCl
Cs Cs2O, Cs2O2, CsO2 CsOH + H2 CsCl

Be BeO No reaction BeCl2

Mg MgO Mg(OH)2 + H2 MgCl2
Ca CaO Ca(OH)2 + H2 CaCl2
Sr SrO Sr(OH)2 + H2 SrCl2
Ba BaO Ba(OH)2 + H2 BaCl2

Points to note
• Group 1 generally form oxides, peroxides and superoxides; however lithium forms only the oxide and sodium only the oxide and peroxide. This is
due to the relatively small size of lithium and sodium cations
• Beryllium is anomalous in its lack of reaction with water
• Beryllium chloride is covalent and polymerise via dative bonds

3
70. Revision Summary: Trends in the Periodic Table 2 Chem Factsheet

Group 7 trends
Group 7, the halogens, are the most reactive group of non-metals. They are strong oxidising agents as they require only one electron to gain the electronic
configuration of noble gases
Notes
solubility reactivity oxidising acidity Fluorine is the most reactive - and the strongest oxidising agent - because of its high electronegativity.
ability of HX When the halogens act as oxidising agents, they are attracting an electron; as the atoms increase in size,
this becomes less exothermic as the electron is at an increasing distance from the nucleus, with increased
shielding - hence they become less effective oxidising agents. (Though note that the first electron affinity
Decreases

Decreases
for fluorine is actually smaller than that of chlorine)
Decreases

Increases
The increasing acidity of the hydrogen halides is due to the decreasing bond strength (the H - X bond
becomes longer as we go down the group). Note that HF is a weak acid, unlike HCl, HBr and HI.

Practice questions on group trends

1. State and explain the trend in reactivity as group 2 is descended. (c) Higher
2. (a) Under what conditions does water react rapidly with magnesium? (b) Bubble through limewater - the limewater goes cloudy
Write a balanced chemical equation for the reaction, giving the
states of matter for all reactants and products. 6. (a) MgCO3(s) → MgO(s) + CO2(g)
(b) State the conditions and write a similar chemical equation for the (d) Fluorine is a more powerful oxidising agent than chlorine (1)
reaction of barium powder with water.
Fluorine with water: Redox / oxidation-reduction
(c) State and explain two ways in which the reactions in a) and b) (c) Chlorine with water: Disproportionation
differ from each other.
(b) 2F2(aq) + 2H2O(l) → 4HF(aq) + O2(g)
3. (a) State the trend in thermal stability of nitrates within group 2.
shifting the position of equilibrium to the left hand side
(b) Write an equation for the thermal decomposition of calcium nitrate the system responds to counteract the increased [H+] by
(iii) The odour of chlorine increases. By Le Chatelier’s principle
4. State the trends in solubility of group 2 hydroxides and sulphates
and very volatile (½)
5. (a) (i) Chlorine appears to dissolve in water to form a solution completion. So free chlorine is present, which is yellow-green
commonly called ‘chlorine water’. Write a balanced chemical (ii) A dynamic equilibrium exists / reaction does not proceed to
equation for this reversible reaction.
5. (a) (i) Cl (aq) + H2O(l) ¾ HCl(aq) + HOCl(aq)
(ii) Explain why the solution is yellowish-green in colour and
smells of chlorine. less soluble down the group
4. hydroxides become more soluble down the group; sulphates become
(iii) Using the chemical equation from a) (i) above, predict the
effect on the odour of chlorine water when acid is added to it. (b) 2Ca(NO3)2 → 2CaO + 4NO2 + O2
3. (a) Increases
(b) Fluorine, by contrast, reacts violently with water. White, steamy
fumes are produced together with another gas, which will rekindle Mg(OH)2 decomposes into MgO (1)
a glowing splint. Write a balanced chemical equation for this
hydroxide. At the high temperature needed for Mg to react,
reaction.
Reaction with Mg gives the oxide / reaction with Ba gives the

(c) What type of chemical reaction occurs in each case? standard electrode potential of Ba is of greater magnitude
temperature. Ba is a stronger reducing agent than Mg / the
(d) What conclusion can you draw concerning the relative oxidising (c) Reaction with Ba is easier / more rapid / occurs at a lower
powers of chlorine and fluorine?
Ba(s) + 2H2O(l) → Ba(OH)2(aq) + H2(g)
6. (a) Write a balanced chemical equation, including state symbols, for (b) Add barium to cold water in a large trough
the reactions that occurs on heating magnesium carbonate with a .
Bunsen burner. Mg(s) + H2O(g) → MgO(s) + H2(g)
2. (a) Pass steam over heated magnesium
(b) How would you test for the presence of one of the products of
the thermal decomposition of magnesium carbonate? nucleus and outer shell electrons, and increased shielding.
energies decrease down group as there is increased distance between
(c) Magnesium carbonate undergoes thermal decomposition rapidly Due to reactions involving the loss of electrons (oxidation) and ionisation
at around 700 oC. Would the thermal decomposition of barium 1. Elements become more reactive as group 2 is descended
carbonate require a higher or lower temperature? Answers

Acknowledgements: This Factsheet was researched and written by Kieron Heath. Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire, TF1 1NU. ChemistryFactsheets may
be copied free of charge by teaching staff or students, provided that their school is a registered subscriber. No part of these Factsheets may be reproduced, stored in a retrieval system, or
transmitted, in any other form or by any other means, without the prior permission of the publisher. ISSN 1351-5136

4
 Chem Factsheet
www.curriculum-press.co.uk Number 71

Revision Summary: Electronegativity,

Ionisation Energies & Electron Affinities
Before reading through this Factsheet you should: A chemist named Pauling assigned electronegativities to elements on an
• Have a good understanding of atomic structure; arbitrary scale from 0 to 4. The following is a list of some such values:
• Have a good appreciation of how the Periodic Table is arranged.
Fig 2. Pauling electronegativities
After working through this Factsheet you will be able to:
• Define electronegativity, ionisation energies and electron affinities; Value 0.9 1.0 1.2 1.5 1.5 1.8 2.0 2.1
• Explain electronegativity, ionisation energies and electron affinities in
Element Na Li Mg Al Be Si B H
terms of electron movement;
• Recall trends in electronegativity, ionisation energies and electron
Value 2.1 2.5 2.5 3.0 3.0 3.5 4.0
affinities within the Periodic table.
Element P C S Cl N O F
This Factsheet is written as a revision aid, the main objective being to
ensure that there are no misconceptions or confusion about electronegativity,
ionisation energies and electron affinities. This list simply helps chemists to quantify the power an atom has to
attract bond pair electrons.
Electronegativity
Electronegativity can be used to classify the bond type between particles:

Definition: The electronegativity of an atom is the ability of its Ionic bonds: Occur between two particles which differ greatly in
nucleus to attract electrons in a bond pair. electronegativity - commonly bonds between metals and non-metals.

The bond pair of electrons are drawn close to the more electronegative
A very electronegative nucleus has the ability to strongly attract bonding particle forming a negative anion, and also a positive cation.
electrons, whilst a nucleus which is not very electronegative (is
electropositive) does not attract bonding electrons strongly. Covalent bonds: Occur between two particles which do not differ
significantly in electronegativity - commonly bonds between two non-
Trends in the electronegativity in the Periodic Table are shown clearly in
metals. The bond pair electrons are shared between the two neutral atoms.
this diagram, and need to be remembered:
Pauling estimated the percentage of ionic character of a bond in a binary
Fig 1. Electronegativity trends
molecule from the difference in electronegativity of the two atoms in a
increasing along each period bond.

H Fig 3. Estimated % ionic character

Li Be B C N O F
Difference in EN 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
Na S Cl
increasing up each group % ionic character 1.0 4.0 9.0 15 22 30 39 47
K Br
Rb I Difference in EN 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2
% ionic character 55 63 70 76 82 86 89 92

Electronegativity increases: Note that the greater the difference in electronegativity between the two
• Across each period. particles, the more ionic the bond between them.
• Up each group. Ionic, covalent and intermediate bonding are discussed in detail in Factsheet 5.

This makes fluorine the most electronegative atom. Examples:

Electronegativity increases across a period because the effective nuclear
• Carbon has an EN of 2.5 and hydrogen has an EN of 2.1. So the C - H
charge of the atoms increases, hence increasing the electron-attracting power. bond has a very small percentage ionic character - 4% only.

Electronegativity decreases down each group because the number of quantum • Aluminium has an EN of 1.5 and chlorine has an EN of 3.0. So we
shells of electrons increases, increasing the shielding effect around the would expect aluminium chloride to be just over 40% ionic
nucleus, hence decreasing the electron-attracting power.
NB: You do not have to remember actual electronegativity figures or the
percentages in the above table!
1
71. Revision Summary: Electronegativity, Ionisation Energies & Electron Affinities Chem Factsheet

Fig 4. EN difference and bonding Whilst there is a general increase in IE across a period, this is not a smooth
trend – as shown in fig 5.
electron distribution
EN Difference
Fig 5. First ionisation energies for the elements of period 2
pure
covalent 0 Ne
filling of 2p
sub-shell
F

first ionisation energy

polar bond- N pairing of
some ionic δ+ S+ S- δ- small
2p electrons
filling of 2s C
character Be O
sub-shell
2p sub-shell half-fills
ionic, but polarised, B
so some covalent + _ large
Li
character
atomic number

pure ionic - _ very

spherical ions + large As the graph shows, the first ionisation energy decreases from Be to B and
from N to O. A similar phenomenon occurs between groups 2 to 3 and 5 to
6 in the other periods. This can be explained by the existence of sub shells:
Ionisation Energy • group 2 elements have full subshell stability, hence are more difficult
If an atom is supplied with enough energy, it will lose an electron. Additional to ionise than group 3 elements.
supplies of energy may cause the loss of a second electron, then a third, • group 5 elements have half subshell stability, hence are more difficult
and so on. to ionise than group 6 elements.
If a neutral atom loses an electron, it becomes a positive ion (a cation).
Electronic Structure from Ionisation Energies
Examining successive ionisation energies for an element gives us an insight
Definition into the electronic structure of that element.
First ionisation energy – the energy required to remove 1 mole of
electrons from 1 mole of gaseous atoms. Fig 6. Successive ionisation energies for sodium
X(g) → X+(g) + e−
1000000 these 2 electrons are in the n=1 shell,
closest to the nucleus. These
Second ionisation energy – the energy required to remove 1 mole of experience very strong attractive
electrons from 1 mole of gaseous 1+ charged cations. 100000 forces from the nucleus.

X (g) → X (g) + e
+ 2+ −
ionisation energy / kJ mol-1

10000

these 8 electrons are in the n=2 shell,

Trends in ionisation energies in the Periodic Table
1000 between the n=1 and n=3 shells.
These electrons experience strong
• Ionisation energies decrease down a group. attractive forces from the nucleus
• Ionisation energies generally increase across a period. 100
this electron is in the n=3 shell,
furthest from the nucleus. This
10 electron experiences comparatively
Going down a group, we are adding more electron shells. So in each weak attractive forces from the
successive period, the outer electrons are: nucleus.
0
• Further away from the nucleus
• More shielded from the nucleus by the inner electrons
Accordingly, ionisation energies decrease down a group. The pattern shows us that sodium has 11 electrons arranged in three
quantum shells, or energy levels. The first electron is relatively easy to
Moving across a period the nuclear charge increases, but we are adding remove as:
electrons in the same shell, so they add little to the shielding. This means
• It exists further from the nucleus
that the outer shell electrons are attracted increasingly strongly to the
• The electrons orbiting closer to the nucleus shield the outer electron
nucleus – thus more energy is required to remove them. So generally we
from the positive centre so attractive forces are comparatively weak.
would expect ionisation energy to increase across the period.
The next 8 electrons have similar ionisation energies (as they are all a
Exam Hint: - Many candidates lose marks by: similar distance from the nucleus) but do get successively more difficult to
• when explaining the group trends, not referring to shielding, remove as the relative positive charge within the ion is increasing.
• when explaining trends across the period, just referring to The last 2 electrons are very difficult to remove as they exist very close to
"increased nuclear charge" without explaining why it is not the unshielded nucleus.
counterbalanced by increasing numbers of electrons

2
71. Revision Summary: Electronegativity, Ionisation Energies & Electron Affinities Chem Factsheet

Electron Affinities Practice Questions

It is possible to add electrons to an atom, forming a negative anion. The 1. Explain the term ‘electronegativity’.
energy change associated with this is the electron affinity.
2. (a) Use the data below to plot a graph of ‘electronegativity difference’
Definition
(y-axis) against ‘% ionic character’ (x-axis).
First electron affinity – the energy change when 1 mole of electrons is
added to 1 mole of gaseous atoms. Difference in EN 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
O(g) + e− → O−(g) ∆Hê = -141 kJmol− 1 % ionic character 1.0 4.0 9.0 15 22 30 39 47
EA1

Second electron affinity – the energy required to add 1 mole of electrons

to 1 mole of gaseous 1- charged anions. Difference in EN 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2

O (g) + e → O (g)
− − 2−
∆Hê = +798 kJmol − 1 % ionic character 55 63 70 76 82 86 89 92
EA2
(b) Use the data below to calculate the electronegativity difference
between the following bonded elements:
The first EA is always exothermic (energy is released) because the electron
goes into a vacancy in the outer energy level. This is ‘bond-making’ so
Value 0.9 1.0 1.2 1.5 1.5 1.8 2.0 2.1
energy is released.
Element Na Li Mg Al Be Si B H
However, this creates a 1- charged anion, so to add a second electron
requires energy to overcome the repulsion (-ve to –ve) between the electron Value 2.1 2.5 2.5 3.0 3.0 3.5 4.0
and the anion. Consequently the second EA is always endothermic (energy
is absorbed). Element P C S Cl N O F

Trends in Electron Affinities in the Periodic Table

Bond EN difference Bond EN difference
Electron Affinity LiF HO
• Increases across a period (to group 7)
NO BeCl
• Decreases down a group.
CO NaF
PO SCl
Electron affinity follows the same trends as electronegativity for similar
reasons. (c) Use the graph to estimate the ionic character, and then place in
order of increasing ionic character, the above bonds.
As we move across a period there is increased effective nuclear charge, so
an additional electron would be more strongly bound to the nucleus and
3. Define the fourth ionisation energy of an element.
more stable, releasing more energy on the formation of this bond. Note
that this is not a uniform increase - full sub-shell stability and half sub-shell
4. Use the idea of ionisation energies to explain why group 2 metals are
stability result in a lower than expected first electron affinity in groups 2
less reactive than group 1 metals.
and 5.
As we move down a group, the available site for an additional electron 5. Define the fourth electron affinity of an element.
would be further away from the positive nucleus, in a position where there
is greater electron shielding from the nucleus. Hence there is a weaker force 6. State whether the fourth electron affinity of an element is likely to be
of attraction between the additional electron and the nucleus, so EA is less. exothermic or endothermic.

overcoming this repulsion will require energy.

6. The fourth electron affinity is likely to be endothermic, as it involves adding a negatively charged electron to a negatively charged 3- anion, and
O3-(g) + e− → O4−(g)
Fourth electron affinity – the energy required to add 1 mole of electrons to 1 mole of gaseous 3- charged anions. 5.
1 metals.
electrons (hence 2 ionsation energies required) whereas group1 form stable 1+ cations. Hence activation energies are lower for reactions of the group
would be required for group 2 metals to remove electrons than group 1. Also group 2 metals form stable 2+ cations, involving the donation of 2
4. When metals react the donate electrons (reducing agents). Ionisation energy increases across a period (from group 1 to group 2) meaning more energy
X3+(g) → X4+(g) + e−
3. Fourth ionisation energy – the energy required to remove 1 mole of electrons from 1 mole of gaseous 3+ charged cations.
(c) Order: NO, SCl, CO, HO, PO, BeCl, LiF, NaCl.
SCl 0.5
2. (b) LiF 3.0; HO 1.4; NO 0.5; BeCl 1.5; CO 1.0; NaF 3.1; PO 1.4;
1. The electronegativity of an atom is the ability of its nucleus to attract electrons in a bond pair.
Answers

Acknowledgements: This Factsheet was researched and written by Kieron Heath. Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire, TF1
1NU. ChemistryFactsheets may be copied free of charge by teaching staff or students, provided that their school is a registered subscriber. No part of these
Factsheets may be reproduced, stored in a retrieval system, or transmitted, in any other form or by any other means, without the prior permission of the
publisher. ISSN 1351-5136
3
 Chem Factsheet
www.curriculum-press.co.uk Number 72
Graphical Techniques
The AS/A2 Specifications state:
Students should be able to:
• plot two variables from experimental or other data;
• understand that y = mx + c represents a linear relationship;
• determine the slope and intercept of a linear graph;
• draw and use the slope of a tangent to a curve as a measure of rate of change (A2 only).
This Factsheet will review the methods and knowledge needed for students to achieve these objectives.

1. Plot two variables from experimental or other data The scale should be linear - i.e. the scale goes up in equal units (like 20, 40,
This clearly refers to plotting a graph: the key elements in doing this 60 etc). (The only exception to this is in logarithmic graphs, which you
correctly are: may encounter for ionisation energy etc, but will not be required to plot.)
• correct allocation of variables to axes
You do not have to:
• appropriate choice of scale
• use the same scale on each axis (most of the time you won't be able to!)
• accurate plotting
• start the scale at 0, unless you want to show proportionality (i.e. that
• correct drawing of line or curve your line or curve passes through (0, 0)) or need to find the y-intercept
(in which case, you only have to start the scale on the x-axis at 0)
Allocating variables to axes It is often advantageous not to start a scale at 0 - for example, if you were
The independent variable goes on the x (horizontal) axis, the dependent plotting the values 1050, 2040, 2890 and 3250, you would have no points
variable on the y (vertical) axis. This means that what you put on the y-axis between 0 and 1000, with the rest of your points comparatively cramped
must depend on what you put on the x-axis. up. If you started the scale at 1000 instead, you could use a larger scale,
hence spreading the points out more.
For example, you could say that rate of reaction depends on concentration
of a particular reactant - so that tells you that you put rate on the y-axis
Accurate plotting
and concentration on the x-axis. Similarly, if you are recording the pH
Most of the points to be considered here are obvious, but many students
change during a titration, since pH depends on volume of alkali (or acid)
lose marks from sloppy work!
added, pH is on the y-axis and volume on the x-axis
• use a pencil not a pen so you can erase mistakes
Similarly, you could say that concentration depends on time - but not that • use a sharp hard pencil
time depends on concentration. So concentration would go on the y-axis • make sure you put your dot (or the centre of your cross) exactly on the
and time on the x-axis
appropriate point
Exam Hint: In any graph involving time, time goes on the x-axis • take the time to read your scale carefully - work out how many units
each small square is worth.
You may also encounter graphs where one of the variables is not something • you probably cannot plot much more accurately than half a small
you actually measure; these include square - but nor should you plot less accurately than this!
• graphs of ionisation energy, electron affinity, melting point etc for
different elements or corresponding compounds across a period or Correct drawing of line or curve
down a group There are three cases to consider
• graphs of successive ionisation energies for an element Graphs where it is inappropriate to join the points up in any way.
In cases like this, the non-measured variable (eg the names of the elements These include any where points half way between the ones plotted are
or compounds, or the ionisation energy number (1st, 2nd 3rd etc) always go meaningless - for example, there is no element half way between lithium
on the horizontal axis; this also coincides with the earlier rule, since the and beryllium, and no ionisation energy half way between the 1st and the
melting point depends on the element, not vice versa. 2nd. (Warning - you will often see these graphs with lines joining the points
in textbooks and on the internet! But that doesn't mean it is correct!)
Note - we always refer to a graph of y against x - eg rate against concentration
means that rate is on the y-axis, and concentration on the x-axis. Graphs where you should draw a best straight line
Obviously these need to look at least approximately like a straight line!
Choosing a scale You must also consider the underlying chemistry - you might expect a
You should always ensure you use at least half of the graph paper in both graph of rate of reaction against concentration to possibly be a straight line
directions - if you don't, your graph is too small and will be hard to read for a first order reaction, but you should be surprised to have a titration
(and may lose you marks!) curve looking linear. Note that the "best" straight line is not necessarily
the one going through the most points; you should aim to have roughly the
The scale you use must be easy to use - for example, 5 units to one large same number of points above the line and below the line. If you have one
square of graph paper is easy, but 3 units to one large square is not, because obviously strange result, ignore it when drawing the line.
you'd be using 31/3 small squares to one unit!

1
72. Graphical Techniques Chem Factsheet

Graphs where you should draw a curve of best fit Extrapolating

As for straight lines, you must make sure that the graph looks like a curve! Extrapolating refers to extending your graph to make predictions, or cross
Ensure you are familiar with the types of curve you are likely to get (see the axes and other lines. Before doing this, you must ask yourself - is it
Fig 1 below). Make sure your curve is smooth - it's easier to do this if you valid? Extrapolating assumes that the trend shown by the graph continues
draw from the inside (concave) side of the curve. It does not have to go before the first measurement and/or after the last measurement. In many
through every single point. Do not "join the dots" using a ruler. cases this is fine - but be aware:
• Many curves look like straight lines if you just consider a limited range
In some cases - for example when determining enthalpy changes of data - so your "linear" data may in fact be part of a curve. Use your
experimentally - you will have two sets of points - "before" and "after". theoretical knowledge to judge whether there's any possibility of this.
The two sets need to be treated individually for drawing lines or curves.
• There are cases where the trend can definitely not be continued - one
Fig 1. Some common curves example is the effect of enzymes at different temperatures, where too
high temperatures cause the enzymes to stop working altogether
First order reaction; concentration of reactant against time
• Make sure you have enough data to see what the trend really is - for
example, if you used just the first part of a concentration against time
curve in a rates experiment, you would not see that the rate slowed
concentration

down, and any extrapolation would probably be wrong.

2. Understand that y = mx + c represents a linear relationship/

Determine the slope and intercept of a linear graph
time This means that you must be able to:
• recognise the equation of a straight line graph (without seeing the
Second order reaction; concentration of reactant against time
graph)
(superficially similar to 1st order graph, but does not fall away so
quickly, and does not have constant half-life property) • understand how the slope (gradient) and intercept of a straight-line
graph relate to its equation
• be able to determine the slope and intercept - and hence the equation -
of a straight line from its graph
concentration

As stated above, the equation of a straight line is of the form

whatever variable goes the gradient - how

on the vertical axis steep the line is
time
the y-intercept - where it
y = mx + c crosses the vertical axis.
NB The curves for concentration of product against time are these
shapes turned upside down. whatever variable goes
on the horizontal axis
Any equation that can be rearranged into this form will also be the equation
Second order reaction; rate against concentration of reactant of a straight line - for example, 2y − x = 6 can be rearranged into the form
y = ½ x + 3 (so m = ½ and c = 3).

The strategy for rearranging is:

First get the y-axis variable on its own by adding or subtracting as necessary.
rate

Then divide both sides of the equation by any numbers in front of the
y-axis variable. (A later Factsheet will concentrate on rearranging equations).

Exam Hint: Any equation just involving x, y and numbers, without the
concentration x's and y's being multiplied together or raised to any powers, will be
the equation of a straight line
Acid-alkali titration curve
One example you will certainly meet is
rate = k[A] where [A} is the concentration of a reactant.
Here, our two variables are rate (y-axis) and [A] (x-axis). The gradient is k
(it's the number in front of the variable on the x-axis) and the y-intercept is
pH zero - there is no number added to or subtracted from the "k[A]" on the
right hand side of the equation. An intercept of zero means that the straight
line passes through the origin - this means we have direct proportionality.
rate (mol dm-3 s-1)

volume of alkali
[A] (mol dm-3)
2
72. Graphical Techniques Chem Factsheet

Another example you may encounter is if you plot concentration of reactant Draw and use the slope of a tangent to a curve as a measure of rate
against time for a zero-order reaction. This gives a line with a slope of -k of change
(where k is the rate constant) and y-intercept equal to the initial concentration This means that you must be able to:
of the reactant.
• understand what a tangent is
• be able to draw a tangent accurately
[A]\(mol dm-3)

• be able to find the slope of a tangent and understand what it means

A tangent to a curve is used to find its gradient at a particular point. It is

a straight line which must just touch the curve at the specified point. The
t (s) diagram below shows the tangent to the curve at the point (2, 4)

To determine the intercept from the graph: 25

• make sure your scale on the x-axis starts at 0
• continue your line back to the y-axis
• write down the point at which the line crosses the y-axis - this is the 20
intercept

To determine the slope (gradient) from the graph:

• draw a triangle on the line - make it as large as possible but make sure
15
you are clear where its sides are on the scale (try to use "easy" numbers
if you can)
• using your scale, work out the height and base of your triangle
• work out height ÷ base 10
• make sure you have the right sign:
! lines with positive gradient slope upwards
! lines with negative gradient slope downwards
5
• put in the units -it's the units from the y-axis divided by the units from
the x-axis

Exam Hint:- even though you may be quite happy calculating the
gradient without drawing a triangle, doing so means you are showing 0 1 2 3 4 5
your working - which can be useful if you make a numerical slip.

Worked Example. The graph below shows how the concentration varied The gradient of the tangent is 16− 0 = 4 - so that tells us the gradient of
with time in the course of a reaction. thecurve at the point (2, 4) is 4. 5 − 1
(a) State the order of the reaction
(b) Find the value of k. Accuracy is very important when drawing tangents – use as fine a pencil as
possible for both the original curve and the tangent, and spend some time
0.14 ensuring the tangent is just touching the curve, rather than missing it
altogether or crossing it twice.

0.12 As always when finding a gradient, make your "triangle" as large as possible;
this minimises the effects of any errors.
concentration (mol dm-3)

0.10
In chemistry, you are most likely to need to draw tangents in rates
experiments to determine the rate at a given time (or times) from a
0.08 concentration-time graph. The units of the gradient will be, in this case,
0.10 concentration/time (i.e. mol dm-3s-1).
0.06
If you have to draw several tangents in order to plot a rate against
concentration graph, then make your life simpler by plotting them at "easy"
0.04 values of concentration (eg 0.1 rather than 0.076). You should always
80 draw them at regular intervals.
0.02
Exam Hint: Do not erase your tangents after you have drawn them and
calculated the gradient - they are an essential part of your working.
0 10 20 30 40 50 60 70 80
time (seconds) Acknowledgements: This Factsheet was researched and written by Cath Brown..
Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire, TF1
(a) the reaction is zero order (concentration against time a straight line) 1NU. ChemistryFactsheets may be copied free of charge by teaching staff or
(b) gradient = -0.10÷ 80 = -0.00125. So k = 0.00125 mol dm-3 s-1 students, provided that their school is a registered subscriber. No part of these
Factsheets may be reproduced, stored in a retrieval system, or transmitted, in
Exam Hint: One of the commonest mistakes when calculating a any other form or by any other means, without the prior permission of the
gradient is "counting squares" rather than using the scale. publisher. ISSN 1351-5136

3
 Chem Factsheet
www.curriculum-press.co.uk Number 73

Reaction Mechanisms - Revision Summary

Before working through this factsheet you should:
• Have a good understanding of electronegativity and bond polarity; Free radical substitution
• Have a good knowledge of bond fission; Involves the formation of free radicals from a molecule in the initiation
• Have read Factsheets 40 (reaction mechanisms) and 52 (reactions of stage.
functional groups – a summary). Cl2 → 2Cl.

After working through this factsheet you will: This is followed by propagation which involves two reactions, both of
• Have been shown the relationship between bond polarity and bond which involve a free radical colliding with a molecule to give another
breaking; free radical and molecule.
• Have been given an explanation of which substances react by which Cl. + CH 4 → HCl + CH 3.
mechanism; CH . + Cl
3 2
→ CH Cl + Cl. 3

• Be able to suggest a mechanism for an unknown reaction. Radical Molecule Molecule Radical

Two free radicals collide to form a molecule in the termination stage.

Substitution Reactions
CH3. + Cl. → CH3Cl
Substitution reactions involve bond breaking, then bond forming.
2CH3. → C2H 6
CH3CH2Cl + NaOH → CH3CH2OH + NaCl 2 Radicals 1 Molecule

A C-Cl bond breaks, then a C-OH bond forms. The instigator is the chlorine radical; the type of reaction is substitution.
The mechanism is free radical substitution.
Breaking a covalent bond can happen in two ways:
1. Homolytic fission where each fragment retains one of the bonding
electrons and free radicals are formed. Nucleophilic substitution
In thermal cracking Polar bonds in halogenoalkanes and alcohols produce Cδ+.
CH3(CH2)10−(CH2)8CH3 → CH3(CH2)10. +CH3(CH2)8.
δ+ δ− δ+ δ−
2. Heterolytic fission where one fragment retains both bonding electrons. C X C OH
Positive and negative ions are formed.
C11H23−C9H19 → C11H23+ + C9H19−
(X is a halogen atom)

The type of fission depends on bond polarity. Cδ+ is susceptible to attack from a nucleophile which approaches this
electron-deficient site. The bond breaks heterolytically and the lone
Non-polar bonds are present in diatomic molecular elements (eg the pair of electrons on the nucleophile forms a new bond.
Cl-Cl bond in Cl2) and symmetrical molecules (eg the C-H bonds in
alkanes). δ+ δ−

• There is an equal sharing of electrons between atoms. C X C OH + :X−

lone pair of polar bond breaks
• On breaking, there is no tendency for the two electrons to go with electrons heterolytically
one atom rather than the other provided for
bonding
• free radicals are formed by homolytic fission. : OH −
nucleophile
Polar bonds are formed between atoms of different electronegativities.
The instigator is OH-, the nucleophile. The type of reaction is
• One atom attracts the bonding pair of electrons more than the other.
substitution. The mechanism is nucleophilic substitution.
• On breaking, ions are formed by heterolytic fission.
Note: that when X or OH is attached directly to a benzene ring,
The term used to define a reaction mechanism indicates
nucleophilic substitution does not take place. The bonds are too strong.
1. the type of reaction, and
2. the instigator of the reaction.

Reactant Bond Broken Nucleophile Bond Formed Products

:OH −
C−OH alcohol
halogenalkane C−X :NH3 C−NH2 amine
:CN− C−CN nitrile

alcohol C−OH :X− C−X halogenoalkane

1
73. Reaction Mechanisms - Revision Summary Chem Factsheet

Electrophilic substitution

The π-bonding in benzene involving delocalised electrons above and Electrophile Bond Formed Product
below the benzene ring means that this negative charge density repels
+
nucleophiles but attracts electrophiles (electron-deficient species). NO 2 NO 2 nitrobenzene
nitryl cation -
electophile an alkylbenzene
+ R+ R
NO 2 H NO 2 NO 2 (alkyl) (e.g. methylbenzene)
electrons from
benzene ring
+ + H+ RCO+ R a ketone
C
(acyl)
C-H bond breaks benzene has
O
heterolytically regained the
giving electrons delocalised +
back to ring electrons and
Br Br Bromobenzene
stability

CH 3 CH 3 CH2Cl CH2OH
O 2N NO 2 O 2N NO 2 O2N NO 2
A B C

NO 2 NO 2 NO 2
Reaction Bond broken Bond formed Substitution mechanism

A C−H of benzene C−NO 2 electrophilic

B C−H of methyl group C−Cl free radical

C C−Cl (polar bond) C−OH nucleophilic

Addition Reactions
In an addition reaction, two molecules add together to give one molecule.
In aldehydes and ketones, the carbonyl group, C=O is polar.
In alkenes, the π-bonding of the C=C bond involves negative charge
density above and below the bond. This repels the nucleophile but
δ+
attracts the electrophile. :Br− C susceptible to attack from a nucleophile
+
H 2C CH2 CH 3CH2 CH3CH2Br O δ−
the more electronegative element
electron carbocation
movement H δ+ polar intermediate
molecule
to Hδ+(the δ− δ+
electrophile) Br C :CN− C CN C CN
bond breaking cyanide ion
:O −
hetrolytically O δ− (from HCN) OH
+
lone pair of electrons provided for H
The instigator is the electrophile, Hδ+ of H−Br. It is an addition reaction. bonding with electron-deficient Cδ+ (from HCN) a hydroxynitrile
The mechanism is electrophilic addition.

=CH2
Addition to RCH= The nucleophile, CN- is the instigator. It attacks the Cδ+ of the C=O. It
Molecule added Electrophile Product(s) is an addition reaction. The mechanism is nucleophilic addition.

δ+ δ− Added Nucleophile Product(s)

Br2 Br Br RCHBrCH2Br
a dihalogenoalkane
δ+ δ− HCN :CN− C CN
HBr H Br RCHBrCH2 + RCH2CH2Br
(major) (minor) from HCN OH
a hydroxynitrile
halogenoalkanes
+
H 2O H RCH(OH)CH3 + RCH2CH2OH 2H atoms :H− C OH
(major) (minor) from NaBH4 H
alcohols an alcohol

2
73. Reaction Mechanisms - Revision Summary Chem Factsheet

Elimination Reactions

In an elimination reaction, one molecule becomes two molecules. It is the In alcohols, water is eliminated across adjacent carbon atoms. This is
opposite of addition. dehydration.

In halogenoalkanes, hydrogen halide is eliminated across adjacent carbon 1 2 3

atoms. This is dehydrohalogenation. CH3CH(OH)CH3 CH3CH=CH2 + H2O
propan-2-ol propene
Elimination of HBr across carbons 1 and 2
2 1 H H H
CH3CH2CH2Br CH3CH=CH2 + HBr +
1- bromopropane propene CH3CH C H CH3CH C H CH3CH C H + H2O

H H H
H H :OH O+
deprotonation
protonation
CH3CH=CH2 + :Br− H+ H H
CH3 C C Br elimination
this bond breaks (conc. H2SO4) CH3CH=CH 2 + H+
heterolytically of water
H H
H+ (conc. H2SO4) is a
the bonding pair of
CATALYST
:OH− electrons becomes
part of the C=C

behaves as a base extracting a proton, H+

CH3CH2CH2CH(OH)CH3
1
pentan-2-ol
2 3 4 5
CH3CHClCH2CH2CH3
2-chloropentane
2 1 2 3
CH3CH2CH2CH=CH2 CH3CH=CHCH2CH3
1 2 2 3
pent-1-ene pent-2-ene
CH2=CHCH2CH2CH3 CH3CH=CHCH2CH3 elimination of H 2 O across elimination of H2O across
pent-1-ene pent-2-ene carbons 1 and 2 carbons 2 and 3
elimination of HCl across elimination of HCl across
carbons 1 and 2 carbons 2 and 3 Both products are formed
Both products are formed

Note that both these reaction mechanisms are described simply as elimination. No indication is needed as to the instigator of the reaction.

Exam Hint: Do not be put off by the complexity of an organic molecule. Organic chemistry is the chemistry of functional groups. In order
to identify a mechanism:
1. Identify the difference between reactant and product,
2. Decide whether substitution, addition or elimination has taken place,
3. Identify the instigator – free radical, electrophile or nucleophile (not elimination),
4. Now you can describe the mechanism.

Summary
YES ELECTROPHILIC

Is the substitution
SUBSTITUTION directly into the
YES
benzene ring? Is the bond
YES NUCLEOPHILIC
broken polar?
NO

Does the change involve a Is the bond broken YES

bond breaking and a new FREE RADICAL
non- polar?
bond forming?

NO Is it across C=C? YES

YES ELECTROPHILIC
Have atoms been added across ADDITION
an unsaturated bond?
Is it across a polar YES
NUCLEOPHILIC
NO YES bond e.g. C=O?
Has a molecule been lost
ELIMINATION
across adjacent C atoms

3
73. Reaction Mechanisms - Revision Summary Chem Factsheet

Questions
1. Identify the mechanisms, A to F, in the following reaction sequence:

CH 2CH3 CH 2CH3 CH2CH2Cl

O 2N NO 2 O 2N NO 2
A B

NO 2 NO 2
C

CH 2CH 2OH
O 2N NO 2

NO 2 E

CH=CH2
CH2CHO
O 2N NO 2
O2N NO 2

NO 2
NO 2

D F

CHBrCH2Br
CH2CH(OH)CN
O 2N NO 2
O 2N NO 2

NO 2
NO 2

2. Which one of the following products is formed when but-2-enal, CH3CH=CHCHO reacts with NaBH4 (H-)?
a) CH3CH2CH2CHO b) CH3CH=CHCH2OH c) CH3CH2CH2CH2OH

The answer is b), CH3CH=CHCH2OH

Addition across C=C does not take place.
C=C has negative charge density which repels the nucleophile, H−.
Two H atoms add across the C=O to give the alcohol.

O C
δ− δ+
2. H- is a nucleophile. It attacks the electron deficient Cδ+ of C=O.

F is electrophilic addition. (Br2 is added to C=C)

E is elimination. (H2O is removed forming C=C)
D is nucleophilic addition. (HCN is added across polar C=O) Acknowledgements: This Factsheet was researched and written by Derek
C is nucleophilic substitution. (Polar C-Cl breaks, C-OH forms). Swain. Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire,
B is free radical substitution. (Non-polar C-H breaks, C-Cl forms) TF1 1NU. ChemistryFactsheets may be copied free of charge by teaching
staff or students, provided that their school is a registered subscriber. No part
1. A is electrophilic substitution. (C-H of benzene breaks, C-NO2 forms).
of these Factsheets may be reproduced, stored in a retrieval system, or
Answers transmitted, in any other form or by any other means, without the prior
permission of the publisher. ISSN 1351-5136

4
 Chem Factsheet
www.curriculum-press.co.uk Number 74

Ammonia and the Haber Process

Before working through this Factsheet you should: Exam Hint:
• Have a good knowledge of the properties of ammonia required at GCSE • Examiners like well drawn sketches with appropriate labels and
level. annotation to illustrate a response. Remember, a picture paints a
• Have a good knowledge and understanding of the principles of gaseous thousand words!
equilibria (described in Factsheet 9). • When illustrating hydrogen bonding show a) the lone pair on the
• Have some understanding of hydrogen bonding, acids and bases, nitrogen atom of one molecule, b) the bond polarity of a N−H bond
oxidation numbers, nucleophiles and ligands. of a neighbouring molecule, clearing labelling the Hδ+ and c) a
• Understand Le Chatelier’s Principle and its application to gaseous dotted line from N: to Hδ+, clearly labelled ‘hydrogen bond’
equilibria.
After working through this Factsheet you will: Chemical properties
• Understand why ammonia has an abnormal boiling point. 1. It is a base
• Know and understand the chemical properties of ammonia. Ammonia gas is extremely soluble in water. It dissolves in water to give
• Be able to understand the Haber process and its economic factors. an alkali.
• Realise the importance of ammonia and its uses. +H +

Properties of ammonia NH3(g) + H2O(l) ¾ NH4+(aq) + OH−(aq)

A study of the properties of ammonia covers a vast spectrum of chemistry Base Acid an Alkali
– inorganic, organic and physical. −H+
Its formula is NH3 and its bonding involves a nitrogen atom linked by single A test for ammonia gas is that it turns moist red litmus paper blue.
covalent bonds to three hydrogen atoms.
It reacts with acids to form ammonium salts.
H +H +
H N Lone Pair
NH3(g) + HCl(g) ¾ NH4+Cl−(s)
H
Base Acid −H + Dense white fumes
There are three bonding pairs and one lone pair on the central nitrogen
atom, giving the molecule a trigonal pyramidal shape. • Ammonia accepts a proton to form the ammonium ion.
• Hydrogen chloride donates a proton and forms the chloride ion.
N • This is an acid-base reaction.
Bonding pair-lone pair repulsion greater
1070 than bonding pair-bonding pair repulsion Note that the ammonium ion contains a dative covalent or co-ordinate
H H
H bond, indicated by an arrow from the lone pair on nitrogen (the donor) to
hydrogen (the acceptor).
Most of the properties of ammonia are due to the lone pair of electrons on
the nitrogen atom. + H +
H
Physical properties H N H H N H
The boiling point of ammonia is abnormally high compared with other
group 5 hydrides. H H
300 both electrons from N atom

250 2. It is a nucleophile
b.p. (K) In organic chemistry, an ethanolic solution of ammonia will react with a
200 halogenoalkane to form an amine.

150 electron-deficient site

δ+ +
100 CH 3CH 2 Br CH3CH2NH3 + Br− CH3CH2NH2 + H+
NH 3 PH 3 AsH 3 SbH3 :ΝΗ ethylamine
3
nucleophile
This is due to hydrogen bonding between N: on one NH3 molecule and
Hδ+ neighbouring NH3 molecule.
H -Br has been substituted with –NH2. This is nucleophilic substitution.
δ-
H N H N
H H
hydrogen bond
H

1
74. Ammonia and the Haber Process Chem Factsheet

3. It is a ligand Exam Hint: When drawing the shape of an octahedral complex ion
The lone pair of electrons on the nitrogen atom of ammonia is donated to you must indicate it three-dimensionally by showing bonds going
an empty orbital of a central transition metal cation. into and coming out of the plane of the paper. Failing that, show the
square planar middle and/or label at least two 90° bond angles – one

all bond angles are 90o

NH 3 3+ NH 3 3+ must show a vertical and the other a ‘square planar’ bond angle.
H 3N NH3 H3N NH3 NH3
90o
Cr Cr
H3N
H3N NH3
NH 3
H 3N NH 3 Cr 90o
NH 3 NH 3
H 3N NH3
The hexaamminechromium(III)ion octahedral
NH3
The bond between Cr3+ and NH3 is dative covalent or coordinate.

4. It is used to test for transition metal ions

An aqueous solution of ammonia is added to an aqueous solution containing the metal ion.

Transition metal ion tests

Appearance [Fe(H2O)6]2+(aq) [Fe(H2O)6]3+(aq) [Cu(H2O)6]2+(aq) [Cr(H2O)6]3+(aq) [Co(H2O)6]2+(aq)

No NH3(aq) added green solution yellow solution blue solution red-blue solution pink solution

A little NH3(aq) added green precipitate brown precipitate blue precipitate green precipitate blue precipitate

Excess NH3(aq) added precipitate stays precipitate stays deep blue solution purple solution pale brown solution

In all cases, addition of a little NH3(aq) results in the formation of an insoluble hydroxide.
−2H+

[Cu(H2O)6]2+(aq) + 2NH3(aq) → [Cu(H2O)4(OH)2](s) + 2NH4+(aq)

little
+2H+

The ammonia acts as a base and accepts a proton, H+ from a water molecule. This is an acid-base reaction.
Addition of excess NH3(aq) causes the precipitate to dissolve.

[Cu(H2O)4(OH)2](s) + 2NH4+(aq) + 2NH3(aq) → [Cu(H2O)2(NH3)4]2+(aq) + 2H2O(l)

excess
Adding equations 1 and 2 together gives the overall equation.

[Cu(H2O)6]2+(aq) + 4NH3(aq) → [Cu(H2O)2(NH3)4]2+(aq) + 4H2O(l)

This is ligand substitution where four water molecules have been substituted with four ammonia molecules.

5. It is a reducing agent. Exam Hint:

Ammonia reacts with hot, black copper (II) oxide to form salmon pink What to look for when deciding the type of reaction ammonia is involved
copper metal. in:
• NH3 gains H+ and forms NH4+ - acid-base.
heat • The nitrogen atom changes from –3 in ammonia to a higher
3CuO(s) + 2NH3(g) 3Cu(s) + N2(g) + 3H2O(g) oxidation number – redox.
Oxidation • NH3 replaces another ligand in a complex ion – ligand substitution.
+2 −3 0 0
numbers • A halogen atom of an organic molecule is replaced by ammonia
forming –NH2, an amine – nucleophilic substitution.
Copper is reduced from +2 to 0. Nitrogen is oxidised from –3 to 0. This
is a redox reaction.

2
74. Ammonia and the Haber Process Chem Factsheet

Manufacture of ammonia
In Industry, ammonia is produced by the direct combination of its elements, • The reaction is reversible and both reactants and product are in the
nitrogen and hydrogen in the Haber process. This process is very gaseous state.
important. Plants need nitrogen for growth. Approximately 4/5ths of air • The equilibrium is dynamic; the rates of forward and backward reactions
is nitrogen but the gas is extremely unreactive. In the Haber process, are the same.
nitrogen is converted into ammonia which is then used to make fertilisers. • The equilibrium position can be changed to produce a higher yield of
These can be added to soil, plants can gain the nitrogen they need and the product.
yield of crops is increased.
Le Chatelier’s principle indicates the ideal conditions of
For the process to be successful, the following factors need to be considered: temperature and pressure to produce this yield.
• The yield of ammonia.
When a system is at equilibrium and a change in conditions occurs, the
• Costs (raw materials and operating conditions).
equilibrium will shift in such a way as to counteract the change.
• Reaction rate.
• Safety.
When a boxer throws a punch at an opponent’s chin, his opponent can
• Pollution.
either a) move his chin towards the punch, b) move his chin away from the
punch or c) simply not move at all and take it on the chin! Of course, he
will move away. He will minimise the effect of the punch.

Change in condition Shift in equilibrium Reason for shift Effect on rate Reason for rate change

Increase in temperature In endothermic direction To absorb the extra heat Increases Collision rate increases
and more collisions
exceed Ea

Increase in pressure To smaller numbers of To decrease gas pressure Increases Molecules closer
moles together with greater
chance of collision

Note that gaseous equilibria take place in sealed vessels and gas pressure is exerted on the walls of the vessel. The higher the number of moles of gas,
the higher the pressure.

In the Haber process

N2(g) + 3H2(g) ¾ 2NH3(g) , ∆H -ve

1 mole 3 moles 2 moles (exothermic) Yield of NH3 Costs Safety Reaction rate

4 moles Temperature High ✗ ✗ ✗ ✓

The graphs below indicate that low temperature and high pressure are Low ✓ ✓ ✓ ✗
needed to obtain a high yield of ammonia.
Pressure High ✓ ✗ ✗ ✓

Low ✗ ✓ ✓ ✗
yield

yield

Compromise temperature and pressure is necessary.

A catalyst is also needed in order to speed up the reaction at the low
temperature required for a reasonable yield of ammonia. It does not
affect the yield of ammonia but speeds up the attainment of equilibrium.

The optimum conditions for the process are 450°C, 200 atmospheres
pressure temperature pressure and iron catalyst. Nitrogen and hydrogen are mixed in the
(temperature constant) (pressure constant) ratio 1:3 by volume.

Application of Le Chatelier’s principle will explain why.

• The reaction is exothermic from left to right. Increase in temperature As far as costs are concerned
will cause the equilibrium to shift to the left, in the endothermic direction • The raw materials for the process are air (from which nitrogen is
in order to absorb the extra heat. Less ammonia is formed. extracted), natural gas and steam (from which hydrogen is obtained
• There are four moles of reactants and two moles of product. Increase by reaction). They are all naturally occurring.
in pressure will cause the system to reduce its pressure by shifting • Using optimum conditions, the yield of ammonia is only 15% but
to the right where there are fewer moles. More ammonia is formed. ammonia is condensed out of the final gaseous mixture and unreacted
But nitrogen and hydrogen gases are recycled.
• Low temperatures give a slow reaction rate. • The iron catalyst ensures the product is obtained quickly and heating
• High pressures are expensive to achieve and maintain and dangerous costs are at a minimum.
– there is a greater risk of explosion and ammonia is a toxic gas. • The optimum pressure ensures a reasonable yield at a reasonable cost.

3
74. Ammonia and the Haber Process Chem Factsheet

Uses of ammonia Ammonia, with a boiling point of -33°C can be easily liquefied by
application of pressure. It has been used as a refrigerant but not extensively
A refrigerant manufacture of nowadays. Its place has been taken by CFCs which unlike ammonia are
nitric acid odourless and not toxic.

manufacture of Exam Hint: If a question concerns the economics of the Haber process,
Ammonia the following table should help your responses:
explosives (TNT)
Economical Not economical

production of High yield High temperature

fertilisers Fast reaction rate High pressure
manufacture of fibres, e.g. Naturally occuring raw materials High transport costs
Continuous process
nylon (a polyamide) (recycling)

Nitric acid is made using the Ostwald process

Pt + Rh catalyst
Questions
4NH3(g) + 5O2(g) o
4NO2(g) + 6H2O(g) 1 1. From the following equations, A to E, involving ammonia, indicate the
-3 900 C +2 type of reaction taking place. Explain your decisions.
from Haber process air

on cooling A 2NH3 + H2SO4 → (NH4)2SO4

the gaseous 2NO(g) + O2(g) 2NO2(g) 2 B 4NH3 + 5O2 ¾ 4NO + 6H2O
mixture +2 air +4 C [Co(H2O)6]2+ + 6NH3 ¾ [Co(NH3)6]2+ + 6H2O
D NH3 + CH3Cl → CH3NH2 + HCl
4NO2(g) + O2(g) + 2H2O(l) 4HNO3(l) 3 E [Fe(H2O)6]3+ + NH3 ¾ [Fe(H2O)5(OH)]2+ + NH4+
+4 Run down +5
2. The following equation represents the industrial manufacture of
a tower
ammonia from its elements by the Haber process:
• Reaction 1 is a gaseous equilibrium. It is exothermic from left to N2(g) + 3H2(g) ¾ 2NH3(g)
right, hence the relatively low compromise temperature of 900°C to (a) The yield of ammonia decreases as temperature increases.
increase the yield of NO(g) and the presence of a catalyst to speed up (i) What does this tell you about the enthalpy change in this
the reaction rate. With 9 moles of reactants and 10 moles of products, gaseous equilibrium? Explain your answer.
pressure has little effect on equilibrium position. (ii) What effect will increasing the pressure have on the yield of
• Platinum is a heterogeneous catalyst that can be poisoned by the ammonia? Explain your response.
presence of arsenic-containing impurities, preventing the effective
adsorption of gas molecules onto the catalyst surface. The slower (b) Why does the use of iron as a catalyst make the process more
reaction rate has adverse cost implications. viable economically? Give one other factor of this process which
also contributes to reduced costs.
• Oxygen gas is involved at each stage of the process, therefore excess
air is required from the start.
Unreacted nitrogen and hydrogen gases are recycled.
Note that each stage involves a redox reaction as shown by the increase in The raw materials are naturally occurring.
oxidation number of nitrogen from –3 to +2 in stage 1, +2 to +4 in stage 2 Reduced costs – any one of:
and +4 to +5 in stage 3. ammonia, resulting in increased profits.
cost of heat energy. The lower temperature means a greater yield of
• Care must be taken at stages 2 and 3 because should NO2(g) escape
enables the reaction to proceed at a lower temperature, saving on
into the atmosphere, it will react with oxygen and water vapour to (b) The catalyst speeds up the reaction, saving time and money. It
form acid rain.
number of moles, ie to the right.
• Natural fertilisers, such as farmyard manure, are uneconomical to moles of products. The equilibrium shifts in the direction of least
transport long distances due to their bulk and cannot completely replace mixture. There are four moles of gaseous reactants and two
the nutrients removed from soil by crops. Artificial inorganic fertilisers equilibrium will shift so as to reduce the pressure of the gaseous
are increasingly being used to supplement if not replace them. (ii) Increasing pressure increases the yield of ammonia. The
therefore, is exothermic from left to right.
• Ammonium salts such as ammonium sulphate and ammonium nitrate endothermic direction, to absorb the extra heat. The reaction,
are manufactured as nitrogen-containing fertilisers. 2. (a) (i) Higher temperature shifts the equilibrium to the left, in the

→ (NH4)2SO4
OH -).
2NH3 + H2SO4 E – Acid-base. NH3 gains H+ to form NH4+. (A H2O ligand loses H+ to form
sulphuric acid ammonium sulphate bond, substituting –Cl with –NH2, the amine.
D – Nucleophilic substitution. :NH 3 attacks the Cd+ of the polar C-Cl
NH3 + HNO3 → NH4NO3 by NH3 to form the ammine complex ion.
nitric acid ammonium nitrate C – Ligand substitution. The H2O ligand in the aqua complex is substituted
(O decreases oxidation number from 0 in O2 to –2 in NO).
B – Redox. N of NH3 increases oxidation number from –3 to +2 in NO.
Often fertiliser plants are found on the same site as ammonia and nitric (or
form SO42- ).
sulphuric) acid plants to save on transport costs. 1. A – Acid-base. NH3 gains a proton/H+ to form NH4+. (H2SO4 loses 2H+ to
NH4NO3 has a higher nitrogen content than (NH4)2SO4 and is, therefore a Answers
more efficient fertiliser but the leaching of nitrates through the soil into
Acknowledgements: This Factsheet was researched and written by Derek Swain. Curriculum Press, Bank
rivers causes eutrophication and the death of fish-life. Controlled quantities House, 105 King Street, Wellington, Shropshire, TF1 1NU. ChemistryFactsheets may be copied free of charge
of nitrate fertilisers need to be added and not when rain is forecast. by teaching staff or students, provided that their school is a registered subscriber. No part of these Factsheets
may be reproduced, stored in a retrieval system, or transmitted, in any other form or by any other means, without
the prior permission of the publisher. ISSN 1351-5136

4
 Chem Factsheet
www.curriculum-press.co.uk Number 75

The Chemistry of Chromium

To succeed in this topic you need to understand: The +6 state
• the basics of transition metals (covered in Factsheet 28); This is described as an ‘oxidising state’ because most species (i.e. molecules
• the reactions of transition metal ions with hydroxides and ammonia and ions) of chromium in this state have a tendency to become reduced to
(covered in Factsheet 46); more stable chromium(III) species, usually the Cr3+ ion. The Cr2O72- ion is
• the principles of oxidation and reduction (covered in Factsheet 11). particularly important: in acidic solution (dilute H2SO4 is usually used), its
orange solution is reduced to a green solution of Cr3+(aq):
After working through this Factsheet you will:
• know the oxidation states of chromium; Cr2O72-(aq) + 14H+(aq) + 6e- → 2Cr3+(aq) + 7H2O(l)
• know that the +3 state is stable, while +6 is an oxidising state and +2 Reducing agents which can be oxidised by dichromates(VI) include Fe2+
is a reducing state; salts (to Fe3+ salts), sulphites (to sulphates) and ethanol (to ethanal).
• understand the relationships between the principal compounds of
chromium; Remember - Not all chromium(VI) species are oxidants. (A reaction
• know the acid-base character of the oxides; will occur only if a mechanism is available.) In particular, the
• understand the reactions of Cr3+(aq) with OH-(aq), NH3(aq) and CO32-(aq); chromate(VI) ion, CrO42-, is not an oxidant.
• understand how to access the +6 oxidation state;
• know the interconversion of chromium(VI) compounds. The +2 state
This is a reducing state - a remarkably powerful one.

The element Practical 1 - The action of air on Cr2+

Chromium (atomic number = 24) is the fourth member of the first series of Prepare a chromium(II) compound in the absence of air by boiling a
d-block transition elements. solution of potassium dichromate(VI) with zinc and dilute hydrochloric
acid in a conical flask fitted with a bunsen valve (Fig 1).
• Its electronic configuration is 1s2, 2s2, 2p6, 3s2, 3p6, 3d5, 4s1. This
arrangement, in which each of the 3d orbitals is singly occupied, is Fig 1. A conical flask fitted with a bunsen valve
more stable than the alternative [Ar] 3d4, 4s2.
• It is a hard metal with a bluish tinge, familiar as chromium plating on glass rod as a stopper
furniture and the trim of classic cars. The melting point is very high
(1890 oC). rubber tubing with a slit
rubber bung
Exam Hint - Although chromium itself is not in A-level specifications,
its aqueous chemistry is a popular topic. glass tubing

Oxidation states

The oxidation states of chromium are +2, +3 and +6, of which

only +3 is stable.

Principal compounds and ions are as follows.

• CrII The chromium(II) ion, Cr2+. Its electronic configuration is 1s2, 2s2, The solution changes colour from orange to green and then to sky blue as
2p6, 3s2, 3p6, 3d4. chromium is reduced from +6 to +3 and then to +2. Afterwards, remove
the bunsen valve and shake the flask. The solution immediately changes
• CrIII Chromium(III) oxide, Cr2O3, chromium(III) hydroxide, Cr(OH)3, from blue to green as oxygen from the air oxidises chromium(II) to
the chromium(III) ion, Cr3+, and various complex ions such as the chromium(III).
hydrated chromium(III) ion, [Cr(H2O)6]3+.
The electronic configuration of the Cr3+ ion is 1s2, 2s2, 2p6, 3s2, 3p6,
3d3. Remember - The most stable oxidation state of chromium is +3.
Remember - Whenever ions are formed from atoms of transition
elements, it is always the outer 4s electrons that are lost first. Redox chart
On the redox chart of chromium (p2), the principal compounds and ions
have been arranged in order of oxidation number.
• CrVI Chromium(VI) oxide, CrO3, the chromate(VI) ion, CrO42-, and the • Any movement up the chart represents an oxidation process, for which
dichromate(VI) ion, Cr2O72-. an oxidising agent is required.
Exam Hint - Never say that a chromate(VI) or a dichromate(VI) • Movement down the chart corresponds to reduction. For this, a reducing
contains Cr6+ because this symbolises a non-existent ion. The agent is needed, such as Zn and HCl(aq) in Practical 1.
correct abbreviation for chromium(VI), i.e. chromium in the +6 • Movement across the chart is neither oxidation nor reduction, and is
oxidation state, is CrVI. achieved with reagents such as water, dilute acids, NaOH(aq), NH3(aq)
or Na2CO3(aq).
1
Chem Factsheet

OXIDATION OUTLINE CHEMISTRY OF CHROMIUM

NO. OF Cr
+6 CrO3 H2CrO4 *CrO 2−− Acid
Cr 2O72−−
4
OXIDISING Alkali
Dark red-brown solid Chromic(VI) acid Chromate(VI) ion Dichromate(VI) ion
STATE
Soluble in water Yellow Orange
Acidic
Oxidation with Reducing agents
Na2O2 or PbO2 e.g. Fe2+ salts
in alkaline solution or Zn + dilute HCl(aq)
[Cr(OH) (H O) ]− ¾ [Cr(OH) (H2O)2]2−− ¾ [Cr(OH)6]3−−
4 2 2 5
q)
H(a Chromate(III) ions Green solution
+3 NaO
Heat
STABLE Cr2O3 Cr(OH)3 Lim
STATE NaO ited
Green solid Chromium(III) Hydroxide o H(a
r N q)
Insoluble or N H3 (aq) [Cr(H2O)6]3+ + Η2Ο ¾ [Cr(OH)(H2O)5]2++ + H3O+

2
Green ppt
Amphoteric Amphoteric a2 CO
3(aq) Purple Green
Conc. NH3(aq) Green solution
[Cr(NH3)6]3+ AIR (O2) Zn + HCl(aq) NO AIR
Violet
+2 CrO
75. The Chemistry of Chromium

REDUCING Black solid

[Cr(H2O)6]2+
STATE Insoluble Blue solution
Basic
REDUCTION
OXIDATION
* CrO42−− is not an oxidant
75. The Chemistry of Chromium Chem Factsheet

Oxides
Chromium forms three oxides.
• Chromium(II) oxide, CrO, a little known basic oxide.
• Chromium(III) oxide, Cr2O3, which is amphoteric, dissolving in acids to give chromium(III) salts and in alkalis to give chromates(III).
• Chromium(VI) oxide, CrO3, which is acidic, dissolving in water to give chromic(VI) acid, H2CrO4, and in alkalis to give chromates(VI).

Chromium(III) hydroxide, Cr(OH)3, like the oxide, is amphoteric. The The acidity of oxides increases with oxygen content.
nature of a hydroxide is usually the same as that of the corresponding (Some people say that acidity increases with oxidation number.)
oxide.

Aqueous chemistry of chromium(III)

Hydrated chromium(III) ion Practical 4 - Reverse changes
[Cr(H2O)6]3+, named systematically as the hexaaquachromium(III) ion, is Add a dilute acid to a chromate(III) solution. Chromium(III) hydroxide
purple, but gives a turquoise coloured acidic solution. is precipitated at first, and then dissolves in excess acid to give a bluish-
green solution of a chromium(III) salt.
Practical 2 - Hydrolysis of chromium(III) salts H+(aq) ions from the acid react with OH-(aq) ions (to give H2O) so that
Dissolve in water a purple chromium(III) salt, such as chrome alum, and the various equilibria are disturbed to the left hand side.
test the solution with pH paper. Note the change in colour and the pH
of the solution.
Practical 5 - Cr(III) salts with NH3(aq)
The hydrated chromium(III) ion can donate a proton from one of its
Add dilute NH 3(aq) dropwise, with shaking, to a solution of a
coordinated water molecules to a molecule of solvent water:
chromium(III) salt. As with NaOH(aq), a grey-green precipitate of
[Cr(H2O)6]3+ + H2O(l) ¾ [Cr(OH)(H2O)5]2+(aq) + H3O+(aq) hydrated chromium(III) hydroxide is formed in an acid-base reaction:
An equilibrium is established containing both [Cr(H2O)6]3+, which is [Cr(OH)(H2O)5]2+(aq) + 2NH3(aq) ¾ [Cr(OH)3(H2O)3](s) + 2NH4+(aq)
purple, and [Cr(OH)(H2O)5]2+, which is green. Consequently, the solution
Now add concentrated NH3(aq). Although the precipitate is insoluble in
is bluish-green. It is also acidic, because H3O+(aq) ions (“hydrogen
dilute NH3(aq), it will partially dissolve in the concentrated reagent in a
ions”) are formed, and the concentration of these is greater than that of
ligand substitution reaction to give a violet solution containing the
OH-(aq) ions.
hexaamminechromium(III) ion:
The reaction is known as an acid-base reaction or deprotonation [Cr(OH)3(H2O)3](s) + 6NH3(aq) ¾ [Cr(NH3)6]3+(aq) + 3OH-(aq) + 3H2O(l)
because [Cr(H2O)6]3+ behaves as an acid (proton donor) and H2O as
a base (proton acceptor).
Other molecules or ions, notably OH-, NH3 and CO32- can also react
as bases with [Cr(H2O)6]3+, but these species are stronger bases Practical 6 - Cr(III) salts with CO32-(aq)
than H2O and further deprotonation can occur. Add Na2CO3(aq), with shaking, to a solution of a chromium(III) salt.
Notice the formation of a grey-green precipitate of hydrated chromium(III)
hydroxide, accompanied by effervescence. Collect the gas evolved in a
squeezed out teat pipette and bubble it through limewater.
Practical 3 - Cr(III) salts with OH-(aq) Again, there is an acid-base reaction but, when CO32- ions accept protons,
Add dilute NaOH(aq) dropwise, with shaking, to a solution of a carbonic acid is not formed because of its instability. Instead, its
chromium(III) salt. A grey-green precipitate of hydrated chromium(III) decomposition products, carbon dioxide and water, are produced.
hydroxide is formed at first. This dissolves in excess NaOH(aq) to give
a grass-green solution of a chromate(III). [Cr(OH)(H2O)5]2+(aq) + CO32-(aq) → [Cr(OH)3(H2O)3](s) + H2O(l) + CO2(g)

Exam Hint - Do not confuse a green chromate(III) with a yellow The addition of NaOH(aq), NH3(aq) or Na2CO3(aq) to an
chromate(VI). aqueous solution of a chromium(III) salt gives an identical grey-
green precipitate of hydrated chromium(III) hydroxide. In all cases,
Chromium(III) hydroxide is formed in an acid-base reaction in which an acid-base (deprotonation) reaction occurs, in which the hydrated
three water molecules coordinated to Cr3+ each lose a proton. This can be chromium(III) ion acts as an acid on the Brønsted-Lowry theory, i.e.
represented by the equation: a proton donor.
[Cr(OH)(H2O)5]2+(aq) + 2OH-(aq) ¾ [Cr(OH)3(H2O)3](s) + 2H2O(l)
Now add excess Na 2CO 3(aq) to the precipitate of chromium(III)
or hydroxide. For two reasons it will not dissolve.
[Cr(H2O)6]3+(aq) + 3OH-(aq) ¾ [Cr(OH)3(H2O)3](s) + 3H2O(l) • CO32- is a weaker base than OH-, so a chromate(III) ion cannot be
The dissolving of chromium(III) hydroxide in excess NaOH(aq) occurs formed.
by a continuation of the same process: • CO32-, unlike NH3, is not a ligand, so there can be no ligand substitution
reaction.
[Cr(OH)3(H2O)3](s) + OH-(aq) ¾ [Cr(OH)4(H2O)2]-(aq) + H2O(l)
Remember - With Na2CO3(aq), M2+ ions form precipitates of metal
[Cr(OH)4(H2O)2]-(aq) + OH-(aq) ¾ [Cr(OH)5(H2O)]2-(aq) + H2O(l) carbonates, MCO3, while M3+ ions give metal hydroxides, M(OH)3,
[Cr(OH)5(H2O)]2-(aq) + OH-(aq) ¾ [Cr(OH)6]3-(aq) + H2O(l) plus CO2. Whatever the precipitate, it will never dissolve in excess
reagent.
An equilibrium is established in which the dominant ion is
[Cr(OH)4(H2O)2]- at low concentrations of OH-, and [Cr(OH)6]3- at high
concentrations.

3
75. The Chemistry of Chromium Chem Factsheet

Aqueous chemistry of chromium(VI) Interconversion of Cr(VI) compounds

Access to the +6 state
In general, it is difficult to oxidise Cr(III) compounds to Cr(VI) ones for Practical 8 - Preparation of sodium dichromate(VI)
two reasons. Acidify the solution of sodium chromate(VI) prepared in Practical 7.
• Most species containing Cr(VI) have a strong tendency to become reduced Notice the colour change from yellow to orange.
back to the Cr(III) state. However, the CrO42- ion is not an oxidant, so
this provides an obvious point of entry to the +6 oxidation level. 2CrO42-(aq) + 2H+(aq) → Cr2O72-(aq) + H2O(l)
• Most oxidising agents operate only in acidic solution and, under these
conditions, the CrO42- ion is converted to Cr2O72-. Now make the solution alkaline again and see the colour revert to
yellow.
Oxidising agents which function in alkaline conditions and
which are powerful enough to convert chromate(III) ions to Cr2O72-(aq) + 2OH-(aq) → 2CrO42-(aq) + H2O(l)
chromate(VI) ions include sodium peroxide, hydrogen peroxide and
lead(IV) oxide. Remember - Chromates(VI) are yellow but dichromates(VI) are
orange.

Practical 7 - Preparation of sodium chromate(VI) Potassium dichromate(VI) is made by adding KCl(aq) to Na2Cr2O7(aq)
Pour a solution of a chromium(III) salt into a beaker and add NaOH(aq) and crystallising the solution. Adding KOH to K2Cr2O7 will give
with stirring until the initial precipitate of Cr(OH)3 dissolves. Add K2CrO4.
Na2O2(s), stir and warm until the green solution changes colour to yellow.
Boil the solution to decompose excess Na2O2, then cool it and allow
Na2CrO4 to crystallise out. Answers
1 Add zinc (or other suitable metal) and boil. The Cr2O72- solution
2Cr (aq) + 3O2 (aq) + 4OH (aq) → 2CrO (aq) + 2H2O(l)
3+ 2- -
4
2-
changes colour to green and stays green. The VO2+ solution changes
colour to green and then to blue (see Factsheet 46).
Practice Questions
1 Acidified solutions containing the dichromate(VI) ion, Cr2O72-, and the 2 (a) Ammonium dichromate(VI), (NH4)2Cr2O7
dioxovanadium(V)ion, VO2+, are both orange and can both act as oxidising (b) Chromium(III) oxide, Cr2O3
agents. Suggest a chemical means of distinguishing between them. Choose (c) C is green/blue-green/turquoise.
one test only, and describe what you would expect to see with each It contains [Cr(H2O)6]3+ (also [Cr(OH)(H2O)5]2+).
solution. D is green.
2 When crystals of an orange solid A were heated they decomposed It contains [Cr(OH)4(H2O)2]-, [Cr(OH)5(H2O)]2- and [Cr(OH)6]3-.
exothermically, leaving a green solid B which dissolved in nitric acid to (d) Cr2O72-(aq) + 2OH-(aq) → 2CrO42-(aq) + H2O(l)
give a solution C and also in concentrated sodium hydroxide solution (e) NH4+(aq) + OH-(aq) → NH3(g) + H2O(l)
to give a solution D. When sodium hydroxide solution was added to A, 3 (a) From orange to dark green
it formed a yellow solution of E and gave off a pungent gas F which (b) Fe → Fe3+ + 3e- × 2 add
turned moist red litmus paper blue. Cr2O72- + 14H+ + 6e- → 2Cr3+ + 7H2O
(a) Write down the name and formula of A. ⇒ 2Fe + Cr2O72- + 14H+ → 2Fe3+ + 2Cr3+ + 7H2O
(b) Identify B. (c) Hydrogen
(c) State the colours of solutions C and D and write down the formulae (d) Some of the electrons lost by Fe as it dissolves are transferred to
of their chromium containing ions. hydrogen ions from the acid: 2H+(aq) + 2e- → H2(g)
(d) Write an ionic equation for the formation of E.
(e) Write an ionic equation for the formation of F. 4 Only free Cl- ions will react with AgNO3(aq): not Cl- ions which are
3 When iron wire was added to an acidified solution of potassium coordinated to the central Cr3+ ion.
dichromate(VI), the wire dissolved, the solution changed colour, and Weigh out equal masses of the three isomers, dissolve each in water,
an odourless, neutral gas was evolved. acidify with dilute HNO3 and add excess AgNO3(aq). Filter off the
(a) What colour change was observed? precipitated AgCl, wash, dry and weigh.The masses will be in the ratio
(b) Construct an ionic equation for the overall reaction between iron 3:2:1.
and dichromate(VI) ions. (You may omit state symbols.) 3d 4s
(c) What gas was evolved? 5 (a) 2+
Cr [Ar]
(d) In terms of electron transfer, how do you account for the formation
of this gas?
4 There are three isomers of chromium(III) chloride-6-water, with the Cr3+ [Ar]
following formulae:
[Cr(H2O)6]Cl3 [CrCl(H2O)5]Cl2.H2O [CrCl2(H2O)4]Cl.2H2O (b) 3d sub-shell electrons are split by ligands into two sets of d-
Suggest a chemical method for distinguishing between them. orbitals. There are three orbitals in the lower energy set and two in
the higher energy set. Cr3+ can have all its 3d electrons in the lower
5 (a) Using half-arrows to represent electrons, complete the following set, but Cr2+ must have at least one 3d electron in the upper set.
electronic configurations of the Cr2+ and Cr3+ ions.
3d 4s Acknowledgements: This Factsheet was researched and written by John
Cr2+ [Ar] Brockington. Curriculum Press, Bank House, 105 King Street, Wellington,
Shropshire, TF1 1NU. ChemistryFactsheets may be copied free of charge by
teaching staff or students, provided that their school is a registered subscriber.
Cr3+ [Ar] No part of these Factsheets may be reproduced, stored in a retrieval system, or
transmitted, in any other form or by any other means, without the prior
(b) Suggest why Cr2+ ions are readily oxidised to Cr3+ ions. permission of the publisher. ISSN 1351-5136
4
 Chem Factsheet
www.curriculum-press.co.uk Number 76

Polymers
To succeed in this topic you need to:
Addition Polymer Structure Repeating Monomer
• Be able to recall the features of polymers as represented in this
Unit Structure
Factsheet.
• Have a thorough knowledge of the importance of polymers. H H H H ethene
• Be able to manipulate structural formulae to show monomer, poly(ethene) H H
polymer and repeating units ‘polythene’ C C C C
C C
H H n H H H H
After working through this Factsheet, you will:
• Have revised the chemistry relating to polymers that is required poly(chloroethene) chloroethene
for AS and A2 chemistry modules. H Cl H Cl
‘PVC’ H Cl
• Have a reference paper with you as you start to work through C C C C C C
questions about polymers. H H
H H n H H
Please check your specification carefully to see which areas of polymer H CH 3 propene
poly(propene) H CH3
chemistry you need to study. H CH 3
‘polypropylene’ C C C C C C
What are polymers? H H n H H H H
Polymers are very large, covalently bonded molecules that are made up of
repeating units. Many polymers are synthetic but a great many are natural phenylethene
H H H H H
poly(phenylethene) H
substances. Avoid using words like ‘plastic’ in your answers when you
‘polystyrene’ C C C C C C
actually mean ‘synthetic polymers’. The word ‘plastic’ describes a
H
property of many polymers as well as other substances, which, when a H n H
force is applied to them, alter their shape - like ‘plasticine’ or uncooked
pastry. tetrafluoroethene
poly(tetrafluoroethene) F F F F
‘P.T.F.E’ F F
Addition polymers C C C C
Teflon®
The simplest way that polymers are formed is by a process called addition C C
F F n F F
polymerization. All addition polymers are based on the structure of ethene. F F
In such reactions, the double bond between the carbon atoms becomes a
single bond. In most cases this is a free radical reaction in which a free Please note that many polymers go by more than one name - for instance,
radical initiates the reaction which is then propagated, ending in a the IUPAC (International Union of Pure and Applied Chemistry) give
termination step (see Factsheet 16 Organic Chemistry II Reactions 1). official names for poly(ethene), poly(propene) etc., but they also have
Free radical reactions are difficult to control and need extreme conditions of common names like ‘polythene’ and ‘polystyrene‘. In exam answers, use
pressure and temperature. Catalysts involving transition metals may enable the correct chemical name for any compound that you are discussing. If
a more controllable reaction to take place. In the case of poly(ethene) the you mention a polymer and can only think of its common name, use
catalyst used is the Ziegler-Natta catalyst (which uses titanium chloride speech marks to show that you recognise that this is not the chemical
in a system with triethylaluminium). name. Sometimes polymers are referred to by trade names like Teflon®; if
you use these names, use a ‘®’ symbol to show that you recognise this.
H H H H H H
H H
C C → C C C C C C Exam Hint: you are sometimes asked to draw polymer structures -
n H H do this in the way shown above using brackets, and making sure
H H H H H H n
that lines representing bonds extend through them. The letter ‘n’
many monomer molecules one polymer molecule indicates that this unit is repeated for an unstated number of times.

(n is a very large number, usually from 100 to 10,000)

The following table gives the names and structures of common addition
polymers. As you can see, there is a pattern of structure, all based on the
ethene model - unsaturated molecules polymerise to form saturated
molecules.

1
76. Polymers Chem Factsheet

Monomers are saturated molecules, the C=C bonds making them very
Often an examination question will ask:
reactive. The polymers, however, contain all C−C bonds in the chain and
• Given the structure of the monomer, show the structure of the
are, therefore, very unreactive. This inertness contributes to many of
repeating unit (or the structure of the polymer formed from it).
their uses but gives rise to environmental problems. They are non-biode-
1. Rewite the structure of the monomer replacing the C=C with C−C
gradable - disposal is difficult
2. Draw two extra single bonds, one on each C atom

extra single bond (brackets cutting bonds) Condensation polymers

Many polymers seem to have a more complex structure than addition
H CH3 H CH3 H CH 3 polymers and these are usually prepared by adding two molecules via a
e.g. C C → C C condensation reaction.
C C or
H H
H H H H n The two monomer molecules both have two functional groups. They react
propene
poly(propene) alternately, eliminating a simple molecule, to give a polymer chain.
single bond
Polyamides
Monomer Repeating Polymer One molecule is a diamine
Unit e.g. H2N(CH2)6NH2, hexane-1,6-diamine
Note that if the question asks for a structure showing two repeating The other molecule is a dicarboxylic acid.
units e.g. HOOC(CH2)4COOH, hexanedioic acid.
H CH 3 H CH3 (Note that a diacyl chloride or a dimethyl ester can be used instead).
C C C C
H H H H OH H Cl H OCH 3 H
• Given the structural formula of the polymer, draw the structural C N C N C N
formula of the monomer from which it has been formed H H H
Procedure is the reverse of the above: O O O
Rewrite the structure of the polymer with: (carboxylic acid) (acyl chloride) (methyl ester)
1. A C=C in the place of C−C H2O eliminated HCl eliminated CH3OH eliminated
2. Eliminate the single bonds extending from the two carbon atoms
3. Eliminate the brackets and the 'n' NH
double bond The 'molecules' are linked by −CONH− or C
e.g. H Cl H Cl O
C C → C C an amide bond, or peptide link
H H n H H HO OH H H HO OH H H
poly(chloroethene) Chloroethene C(CH2)4C N(CH2)6N C(CH2)4C N(CH2)6N
Polymer Monomer H H
O O H O O H
• Circle a repeating unit of the following polymer structure:
H H H H H H H H
C C C C C C C C
C(CH2)4CNH(CH2)6NHC(CH2)4CNH(CH2)6NH
H H H
O O O O
contains 2 carbon atoms of the chain
6 C atoms 6 C atoms Nylon - 6,6

The geometry of polymer chains

With addition polymers it is possible to have different arrangements of Repeating unit: CO(CH2)4CONH(CH2)6NH
groups within the chain. Using poly(propene) as an example (CH3 is
the 'substituent group').
The formula of the polymer is CO(CH2)4CONH(CH2)6NH
Isotactic form H CH 3 H CH 3 H CH 3 H CH3 n
C C C C C C C C
H H H H H H H H Condensation polymerisation can take place using amino acids.
OH
All the methyl (CH3) groups are above the plane of the molecule. Amino acids have two different functional groups, C and NH 2
CH 3 H CH3 H in the one molecule.
H H H H
O
Syndiotactic form OH H OH
C C C C C C C C H
H H H N(CH2)5C N(CH2)5C
CH3 H H H CH3
H O H O
The methyl groups alternate above and below the plane of the molecule.

H CH3 H H H CH 3 H CH 3
Atactic form
C C C C C C C C NH(CH2)5CONH(CH2)5CO
Nylon - 6
H H H CH 3 H H H H
The methyl groups are randomly situated along the chain.
n H2N(CH 2) 5COOH NH(CH2)5CO + nH2O
Note that these forms exist with the larger substituent groups. If the n
substituent group is very small then full rotation about the C−C bond 6- aminohexanoic acid
can occur.

2
76. Polymers Chem Factsheet

Polyesters
As with polyamides one molecule is a dicarboxylic acid, diacyl chloride or Exam Hint : An examination question may give you the structures of
dimethyl ester. The other molecule is a diol. the two monomer molecules in a condensation polymerisation reaction
and ask you to draw the structure of a dimer.
Benzene-1,4-dicarboxylic acid and ethane-1,2-diol react together to form • Draw the structures side by side with the functional groups adjacent
terylene. Water is the simple molecule eliminated. • Eliminate the simple molecule between them
• The other functional groups do not change.
HO OH
eliminated
C C HO CH 2CH2 OH HO OH H
e.g. C C N(CH2)4NH2
O O
H
O O
stays the same stays the same
C C OCH 2CH 2O The repeating unit

O O
HO C CONH(CH2)4NH2
O
C O the dimer
is the ester linkage
O

Altering polymers Natural polymers

One way to classify synthetic polymers is by looking at the effect that Natural polymers include substances like rubber, oils, cotton, leather, paper,
heat has on them. Polymers which can have their shape altered by heating silk and hair. Often these polymers have a complex structure but are made
(and thus can be re-melted and reshaped), are called thermoplastic or up of proteins, carbohydrates, lipids or, in the case of rubber, an addition
sometimes thermosoftening polymers. Other polymers cannot be re- polymer. These natural polymers have not been fully replaced by synthetic
melted and have to be moulded in manufacture; these are called ones and the properties of materials like leather and cotton have proved
thermosetting plastics. The property that makes thermosetting plastics difficult to copy.
so resistant to heat is usually the presence of covalently bonded cross-
links between the polymer strands.
Carbohydrates
Thermoplastic polymers may be forced into moulds under pressure - All carbohydrates are produced as a result of photosynthesis
injection molding, or can be forced through small holes, which process is
called extrusion. 6CO2(g) + 6H2O(l) → C6H12O(s) + 6O2(g)
Carbohydrates form polymers by a condensation reaction involving the
Synthetic polymers in the environment elimination of water. For instance, in the diagram below a molecule of
Many synthetic polymers are very long-lasting and will exist in the fructose links to a molecule of glucose with the elimination of one water
environment for perhaps thousands of years. Generally speaking, polymers molecule.
break down much faster in sunlight, so substances on the surface do not
take more than seven to ten years for their structure to start to disintegrate. G F
OH HO
The problem of synthetic polymer disposal is partially overcome by
recycling. The difficulty with this is that many products are made from a G O F + H2O
mixture of polymers, making them difficult and expensive to recycle. For
instance, a bottle may be made of PVC with a poly(propene) cap, a
poly(ethene) wad and a paper label. In a different example, but with more detail, we can see that if two
glucose molecules join together, water is eliminated. In this way, long
Another solution being used for poly(ethene) is to add small amounts of polymers of carbohydrate molecules such as starch are built up.
starch when the material is being moulded. This has the effect of the
individual polymer fibres becoming separated in the environment, with the
product eventually breaking down. H O H H O OH
HO OH HO H
50 years ago carrier bags were made of brown paper. Children's toys were
made from wood or metal! There was little plastic to be seen! Then came α glucose β glucose
the polymer revolution!
H O H H O OH
+ H2O
HO O H

3
76. Polymers Chem Factsheet

Uses of synthetic polymers

Synthetic polymer Uses Advantages and disadvantages

High density poly(ethene) Milk bottles, buckets, kitchen containers, crates and packing material. Very strong and easily coloured. Can be
recycled with ease. Very long-lasting in
the environment.

Low density poly(ethene) Plastic bags, sheeting, electrical cable insulation, poly-tunnels Can be made transparent or opaque.
(greenhouses). Flexible and easy to manipulate. Can be
recycled with ease. Very long-lasting in
the environment.

‘PVC’ Cable insulation, window frames, cling film. Is used in a rigid ‘unplasticised form
‘uPVC’ or flexible ‘plasticised’ form.
Very resistant in the environment.
Combustion may release toxic gases
into the environment.

Polyamide ‘nylon’ Clothing ropes and parachutes. Can form very strong fibres, which are
long-lasting under extreme conditions.

Polystyrene Insulation, packing materials, flowerpots. Can be used either in its expanded form
or compressed. Very difficult to
dispose of.

‘PTFE’ ‘Stick-proof’ tools and cookwear, coating for clothing. The unreactivity of this compound
makes it very useful, non-toxic and
almost indestructible.

Proteins Hydrolysis
Amino acids build up into polymers by forming peptide links. Never The natural polymers given above are all condensation polymers, formed
refer to a peptide link as a ‘peptide bond’; by the removal of water molecules. Under certain conditions (usually
The general structure of an amino acid is: acidic or by the use of an enzyme), the water can be replaced and the
polymer broken down into its monomer units again. This is called
R
hydrolysis.
They are α-amino acids where the −NH2 HO H HO H HO
H C NH 3 group is on carbon 2 e.g. the protein H R1 R2 R3
COOH illustrated above:
N CHC N CHC N CHC
Different amino acid monomers join via the elimination of water H O H O H O
molecules. R1 R2 R3
H OH H OH H OH
NCHC NCHC NCHC H2NCHCOOH + H2NCHCOOH + H2NCHCOOH
H H O H O R1 R2 R3
O
The separate amino acids
R1 R2 R3
Synthetic condensation polymers are also susceptible to hydrolysis to
HNCHCONHCHCONHCHCO give the original monomers. This means that they are biodegradeable
and do not create a disposal problem.

Hydrogen bonding Useful websites

Proteins and synthetic polyamides have hydrogen bonding between the You may find it helpful to visit these websites as part of your exam
polymer chains. The bonding is between the N−H of one chain with the preparation for polymer chemistry.
C=O of another. www.chemsoc.org/networks/learnnet/index.htm
N H O C www.environment.allinfoabout.com
www.chemsoc.org/networks/learnNet/green.chem.htm
hydrogen bond

Despite individual hydrogen bonds being weak, the accumulative effect

along the full lengths of the polymer chains gives an enhanced attraction.
Kevlar, a polyamide of benzene1,4-dicarboxylic acid and benzene-1,4-
diamine, due to this hydrogen bonding between chains is stronger than
steel and is used as replacement steel cord in tyres and bullet proof
vests.

4
76. Polymers Chem Factsheet

Practise Questions Answers

1. Perspex is a polymer with the following structure 1. (a)
H CH 3 CH 3 H
H CH 3 H CH3 H CH 3 H CH 3
C C C C
C C C C C C C C or
H COOCH3 COOCH3 H
H COOCH3 H COOCH3 H COOCH3 H COOCH3

(a) Circle the repeating unit

(b)
H CH 3
(b) Draw the structural formula of the monomer
C C
(c) Which type of polymerisation has taken place in its formation?
H COOCH3
(d) Why is this polymer non-biodegradeable?
(c) Addition
2. Kevlar is a synthetic polyamide formed from the two molecules
HO OH (d) The C−C bonds in the polymer chain are unreactive/ inert
C C H 2N NH 2
and 2. (a) HO
O O C C N NH 2
benzene-1,4-dicarboxylic acid benzene-1,4-diamine
O O H
(a) Draw the structural formula of the dimer formed when the two (b) Condensation
molecules react.
(c) (i) Hydrogen bonding between the polymer chains
(b) What type of polymerisation occurs?
(ii) The amide bond / peptide link can be hydrolysed.
(c) Why is Kelvar:
(i) so strong

(ii) biodegradeable?

Acknowledgements: This Factsheet was researched and written by Ray Lovegrove. Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire,
TF1 1NU. ChemistryFactsheets may be copied free of charge by teaching staff or students, provided that their school is a registered subscriber. No part of these
Factsheets may be reproduced, stored in a retrieval system, or transmitted, in any other form or by any other means, without the prior permission of the
publisher. ISSN 1351-5136

5
 Chem Factsheet
www.curriculum-press.co.uk Number 77

The Importance of Hydrogen Bonding

To succeed in this topic you need to: The Water Molecule
• Be able to recall the features of hydrogen bonding as represented in this The distribution of charges on a water molecule is important for showing
Factsheet. how hydrogen bonds are formed. The hydrogen atoms have their electrons
• Have a thorough knowledge of the importance of hydrogen bonding. involved in covalent bonds with oxygen. This leaves the hydrogen nuclei
• Be able to decide between which molecules hydrogen bonding will exposed and gives a small positive area of charge to this area of the molecule
occur, and draw them in diagrams. (δ+). The oxygen atom of the water molecule has all of the electrons in the
• Have read factsheets and revised electronegativity and hydrogen bonding molecule gathered around it, giving this part of the molecule a small negative
After working through this Factsheet, you will: charge (δ-).
• Have revised the chemistry relating to hydrogen bonds that are required
δ+ δ+
for AS and A2 chemistry modules including option modules.
• Have a reference paper with you as you start to work through questions H H
about hydrogen bonding. O

..
..
Electronegativity
Electronegativity is a measure of how good atoms are at attracting electrons. δ-
The value given to any element is just an index, a way of comparing it with
other elements. Electronegativity values have no units. You are not required In diagrams hydrogen bonds are usually drawn as dashed lines - - - - - . In
to remember electronegativity values but it is a good idea to learn that the exam questions candidates are often asked to draw in the hydrogen bonds
bottom left hand side of the periodic table has the lowest electronegativity between molecules
and the top right hand side (excluding group VIII) has the highest. If a
covalent bond is formed between two atoms of differing electronegativity, The structure of ice
the electrons are unevenly distributed and the bond is described as polar. A As water gets colder the molecules lose kinetic energy and the random
bond between two atoms of similar electronegativity is not going to have movement of particles gives way to the more regular structure of ice. In
areas of charge and the bond is non-polar. In the diagram below all the this structure oxygen atoms are held in position by two hydrogen bonds
bonds are polar except the H−P bond. and two covalent bonds. The hydrogen bonds keep the molecules further
apart than in the liquid state. This accounts for the fact that ice is less dense
δ + H- - - - - - - -x- -N δ- than water. Snow flakes have a structure based on a six pointed star which
δ+ = small amount of positive charge relates to the position of the hydrogen bonds.
δ + H- - - - - - - - x -O δ-
δ- =small amount of negative charge
δ + H - - - - - - - - -x-F δ- H H
x = theoretical position of pair of
electrons H- - - - - -x - - - - - -P H
O
O
Hydrogen bonds are intermolecular forces that occur when hydrogen H
is covalently bonded to another atom with a high electronegativity H H
H
value. In practise, H-bonds occur when hydrogen is bonded to oxygen,
O O
fluorine or nitrogen atoms. Oxygen in a molecule where it is only joined to H H H
carbon ( C=O ) form hydrogen bonds with hydrogen that is joined to
oxygen in another molecule (O-H). O

The strength of Hydrogen Bonds

Hydogen bonding is an example of an intermolecular force which can be Importance of hydrogen bonding in water
defined as weak attraction between molecules caused by weak electrostatic Physical properties
charge. You do not have to give a value for the strength of hydrogen bonds in
exam answers but remember that hydrogen bonds are stronger than Van der The fact that hydrogen bonds form between water molecules accounts for
Waals forces but nowhere near the strenghth of a typical covalent bond a large number of the unusual physical properties of water;
(between 5 and 10% the strength)
• Water is a liquid at room temperature. If we look at hydrogen sulphide
Hydrogen bonds are formed when propanone (which has no hydrogen H2S, we see that it is closely related to water with the oxygen being
bonds) is added to water in a test tube. This is an exothermic reaction and replaced by the next element down the group - sulphur. H2S is a gas at
you can feel the heat given off as the two liquids mix together and the room temperature and we would expect water to be a gas as well. H-
hydrogen bonds are formed. bonds are present in H2O but not in H2S.
H
H • Liquids generally contract in volume as the temperature decreases. In
H C
H Propanone
the case of water however, it starts to expand at 4oC. This is because
H C C the H-bonds prevent the water molecules from coming close together.
O As water molecules lose kinetic energy, the H-bonds form and a lattice
H
H H starts to emerge. This accounts for the fact that ice is less dense than
O Water water and therefore floats on the water surface.

1
77. The Importance of Hydrogen Bonding Chem Factsheet

• On the surface of water, a large number of charged areas (δ+ and δ-) on
molecules are exposed. This gives water a charged surface and gives Biological importance of hydrogen bonding
rise to surface tension, which behaves like a ‘skin’. As life is based on water, and proteins contain N—H bonds it is not too
surprising that hydrogen bonding is of great biological importance;
• The charged areas on water molecules makes them adhere to other • Many organisms use the surface tension of water to live on the
charged surfaces; this accounts for the ‘wetting’ properties of water surface of ponds and lakes (caddis fly lavae and water boatmen).
• Plants move water through the xylem in their stems relying on
• The small areas of charge on water molecules are responsible for the capillary action as part of the cohesion-tension process.
attraction between the water and the container it is in. This leads to the
• Water living animals survive freezing conditions as ice floats on
meniscus when water is placed in glass and to capillary action in
water leaving liquid water below this ice.
which water is drawn up through fine tubes.
• DNA builds its double helix structure on hydrogen bonding between
• Ice skating works because the high pressure applied by the blade of the the bases on the DNA strands.
skate crushes the hydrogen bonds and turns the ice back to water. This
• The secondary and tertiary structures of many proteins has hydrogen
water provides a lubricant for the skater to move upon.
bonds as one of its components. Hydrogen bonding between the
peptide links in a protein cause the chains to fold or twist in a
regular manner . The precise shape due to folding of its chains is
critical for insulin to act in the way it does. Enzymes are proteins
and they also require these highly specific shapes in order to catalyse
Hydrogen bonding in organic chemistry the biological changes needed for life to exist and continue.

Alchols, carboxylic acids and amimes:

These types of organic molecule exhibit hydrogen bonding due to their functional groups.

Functional CH3CH 2CH2CH 3 CH3 CH2 CH 2NH2 CH 3CH2CH 2OH CH3COOH

group
Mr 58 59 60 60
Alcohols −OH
b.p. (K) 273 321 371 414
Carboxylic C −OH
Intermolecular Van der Waal's Hydrogen bonding Hydrogen bonding Hydrogen bonding
acids O forces forces
Amines −NH 2
The higher than expected boiling points are due to the stronger hydrogen bonding compared with the Van der Waal's
forces present in alkanes with similar Mr value

O O H Dimerization is the name given to the situation where two carboxylic acid molecules form a pair
H H of hydrogen bonds. On a cold day it is this hydrogen bonding that causes ethanoic acid to become
C C H ‘glacial’ - solid like ice (glacial ethanoic acid).
H C C
H H
H O O These organic molecules have two 'enols', e.g. alcohols

non-polar polar
In smaller molecules the hydrophilic end dominates and they are readily soluble in water. As the
hydrocarbon chain functional
molecule increases in size, the hydrocarbon chain becomes longer. The hydrophobic end starts to
OH dominate and the solubility in water decreases
hydrophobic hydrophilic
(water hating) (water loving)

Acid amides e.g. O Acids amides are soluble in water and form crystalline solids due to extensive hydrogen bonds.
H 3C C
NH 2

Cis-trans isomers e.g

The difference in physical properties in cis-trans isomers is due to the ease in which
H hydrogen bonds are formed. The trans example given is able to form two hydrogen bonds
O H with its neighbouring molecules the cis form of this molecule would tend to form internal
H H
hydrogen bonds and would have a lower melting and boiling point.
C C C C
H O O O
H H H
Trans Cis

2
77. The Importance of Hydrogen Bonding Chem Factsheet

The hydrides of fluorine oxygen and nitrogen have abnormally high melting and boiling points.

Hydrides of group 6 Hydrides of group 5 and 7

abnormally high due to stronger
hydrogen bonding Group 7 Group 5
H2O Hydride HF HCl HBr HI NH3 PH3 ASH3 SbH3
boiling point (K)

H 2Te
b.p (K) 293 188 206 238 240 185 218 256

H2Se
H 2S

Increase in b.p (bigger molecules - stronger

Van der Waal's forces between them)

Practice Questions
Explain why:
(a) Ammonia (NH3) has a higher boiling point than phosphine (PH3)

(b) Ethanoic acid (CH3COOH) is more soluble in water than butanoic acid (CH3CH2CH2COOH)

(c) Ice floats on water

(d) Hydogen bonding in enzymes is essential for them to speed up biological processes in the body

Answers
(a) Hydrogen bonding occurs between HN3 molecules but not between PH3 molecules. Hydrogen bonding is stronger than Van der Waal's forces,
needing more heat energy to separate the molecules.

(b) The hydrophilic OH is dominant in CH COOH

3
C

The longer hydrophobic hydrocarbon chain of CH3CH2CH2COOH is more dominant therefore its solubility is lower.

(c) Hydrogen bonds form as water molecules come closer together. The molecules are kept further apart than they were in liquid water. The
density decreases, therefore the ice floats.

(d) Hydrogen bonding between the protein chains in enzymes cause folding and the formation of a precise shape which is essential for the enzyme
to act as a biological catalyst.

Find out more

The following website has more information about hydrogen bonding which may help you prepare for your exam.
www.chemsoc.org/networks/learnnet/index.htm

Acknowledgements: This Factsheet was researched and written by Ray Lovegrove. Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire,
TF1 1NU. ChemistryFactsheets may be copied free of charge by teaching staff or students, provided that their school is a registered subscriber. No part of these
Factsheets may be reproduced, stored in a retrieval system, or transmitted, in any other form or by any other means, without the prior permission of the
publisher. ISSN 1351-5136
3
 Chem Factsheet
www.curriculum-press.co.uk Number 78

Recognising, Constructing &

Interpreting Redox Reactions
Before working through this Factsheet you should:
• Understand oxidation and reduction and know how to find the oxidation There are a variety of redox reactions to be found at AS/A2, in particular:
numbers of elements present in a substance or ion ( Factsheet 11); • Displacement of H2(g) from water and acids by elements of groups 1
• Understand oxidation and reduction in terms of both change in oxidation and 2.
numbers and electron transfer. • Change in oxidation states of group 7 elements
Cl2 Cl- ClO- ClO3-
After working through this Factsheet you should:
Oxidation number: 0 -1 +1 +5
· Recognise, given the equation, whether or not a reaction is redox;
· Be able to construct an overall redox equation using redox half-equations; • Change in oxidation states of transition metal ions, eg vanadium:
· Given an overall redox equation, be able to write the two half-equations
VO2+ VO2+ V3+ V2+
showing both oxidation and reduction;
Oxidation number: +5 +4 +3 +2
· Be able to identify both the oxidising and reducing agents from a redox
equation.
Constructing redox reactions
Given sufficient information about reactants and products it is possible to
Be aware that oxidation numbers and oxidation states are one and
construct redox reactions using redox half-equations.
the same. If your exam board uses the term ‘oxidation state’ substitute
that term for ‘oxidation number’ throughout this Factsheet.
1. Write the reactants and products given in the question as an equation.

2. Using oxidation numbers identify those elements involved in oxidation

Remember and reduction.

Oxidation Reduction 3. Balance these elements only in the equation.

Oxidation number Increases Decreases 4. Work out the two half-equations involving electrons lost and gained
Electrons Lost Gained 5. Multiply one (or both) the half equations by a number to balance
electrons lost and gained.

6. Add the two half-equations together.

Recognising a redox reaction
The simplest way to recognise a redox reaction is to identify the oxidation
At step 4, there may be other elements present in the equation that are not
numbers of all the elements involved in the reaction. Going from reactants
changing oxidation state – usually hydrogen or oxygen. These may be
to products, if one element increases in oxidation number and another
unbalanced - eg oxygen only on one side. The table below shows how to
decreases the reaction is redox. If none of the elements change in oxidation
deal with this
number the reaction is not.
Problem Solution Example
Zn + H2SO4 → ZnSO4 + H2
0 +1 +2 0 ! Too many Add H+ H2S → S + 2H+
hydrogen on left on right
KOH
+1 -2 +1
+ HNO3
+1 +5 -2
→ KNO3
+1 +5 -2
+ H2O
+1 -2
" Too many oxygen Add H+ on left, MnO4− + 8H+ → Mn2+ + 4H2O
on left H2O on right
5Fe2+
+2
+ MnO4− + 8H+ → 5Fe3+ + Mn2+ + 4H2O
+7 +3 +2 +1 -2
! Too many oxygen Add H+ on right, SO2 + 2H2O → SO42− + 4H+
on right H2O on left
Pb(NO3)2 + 2KI → 2KNO3 + PbI2 "
+2 +5 -2 +1 -1 +1 +5 -2 +2 -1
Once you have dealt with the hydrogen and oxygen in step 4, you need to
add the appropriate number of electrons to the half equations. You use the
5I− + IO3− + 6H+ →
-1 +5
3I2 + 3H2O
0 +1 -2
! principle that the charges must balance - for example, if your total charge is
+8 on the left hand side and +3 on the right hand side, then you need to add
5 electrons (5e−) to the left hand side, to make the charges equal.
2CrO42− + 2H+ ¾
+6 -2 +1
Cr2O72+ + H2O
+6 -2 +1 -2
" Exam Hint: - The overall equation must NOT have electrons in it - they
are cancelled out in stages 5 and 6.

1
78. Recognising, Constructing & Interpreting Redox Reactions Chem Factsheet

1. Fe3+(aq) reacts with I−(aq) to give Fe2+(aq) and I2(s). Obtaining oxidation and reduction half-equations from the overall
3+
1. Fe (aq) + I (aq) → Fe (aq) + I2(s)
− 2+ equation
2. +3 -1 +2 0 Using oxidation numbers, identify the two elements that are oxidised and
3. Fe3+(aq) + 2I−(aq) → Fe2+(aq) + I2(s) reduced.
(Iodine balanced) Take each one in turn and construct the half-equation by
4. Fe3+(aq) + e− → Fe2+(aq) 1 1. writing the appropriate species on each side of the equation,
2I (aq) → I2(s) + 2e−
−
2 2. balancing that element in the equation,
(No O or H atoms involved; electrons added to balance charges) 3. adding or removing oxygen/hydrogen as previously described, balancing
5. Equation 1 × 2 (to balance electrons lost and gained) the equation and finally
6. 2Fe3+(aq) + 2I−(aq) → 2Fe2+(aq) + I2(s) 4. balancing the charges on each side of the equation by adding electrons
to reactants or products.
Fe3+(aq) is reduced to Fe2+(aq); I-(aq) is oxidised to I2(s).
1. 5Fe2+ + MnO4− + 8H+ → 5Fe3+ + Mn2+ + 4H2O
+2 +7 +3 +2
2. Bromide ion, Br− reacts with concentrated sulphuric acid, H2SO4
to give bromine, Br2 and sulphur dioxide, SO2. 1. Fe → Fe
2+ 3+ MnO4 → Mn2+
−

2. Fe balanced Mn is balanced
1. H2SO4 Br− → Br2 + SO2
+
3. No O or H atoms MnO4− + 8H+ → Mn2+ + 4H2O
2. +6 -1 0 +4
3. H2SO4 + 2Br− → Br2 + SO2 4. Fe2+ → Fe3+ + e− (+7) (+2)
MnO4− + 8H+ + 5e− → Mn2+ + 4H2O
(Br balanced)
4. 2Br− → Br2 + 2e− 1
H2SO4 + 2H+ → SO2 + 2H2O (to deal with oxygens) 2. 2VO2+ + 3Zn + 8H+ → 2V2+ + 3Zn2+ + 4H2O
+5 0 +2 +2
H2SO4 + 2H+ + 2e- → SO2 + 2H2O 2
(electrons added to balance charges) 1. Zn → Zn2+ VO2+ → V2+
5. Electrons lost and gained are balanced 2. Zn balanced V is balanced
6. 2Br− + H2SO4 + 2H+ → Br2 + SO2 + 2H2O 3. No O or H atoms VO2+ + 4H+ → V2+ + 4H2O
(+5) (+2)
H2SO4 is reduced to SO2; Br- is oxidised to Br2. 4. Zn → Zn2+ + 2e− VO2+ + 4H+ + 3e− → V2+ + 4H2O

Exam Hint: - A common error is to try to balance charges too early.

3. Sulphur dioxide, SO2 reacts with acidified dichromate(VI) ions, This has to be done after H+ etc are included - i.e. at the last stage.
Cr2O72- to give sulphate ions, SO42- and chromium(III) ions, Cr3+.
Disproportionation reactions
1. SO2 +Cr2O72− → SO42− + Cr3+
During a disproportionation reaction the same element is both oxidised
2. +4 +6 +6 +3
and reduced.
3. SO2 + Cr2O72− → SO42− + 2Cr3+
For example, in the reaction between Cl2 and cold, dilute alkali, eg NaOH(aq),
(to balance Cr)
the chlorine disproportionates.
4. SO2 + 2H2O → SO42− + 4H+ (to balance oxygen)
SO2 + 2H2O → SO42− + 4H+ + 2e− 1
Cl2 + 2NaOH → NaCl + NaClO + H2O
(to balance charges)
0 -1 +1
Cr2O72− + 14H+ → 2Cr3+ + 7H2O (to balance oxygen) Cl2 is both reduced to Cl− (Cl2 + 2e− → 2Cl−)
and oxidised to ClO− (Cl2 + 4OH− → 2ClO− + 2H2O + 2e−).
Cr2O72− + 14H+ +6e− → 2Cr3+ + 7H2O 2
(6+) At a higher temperature, with concentrated alkali, the ClO− (chlorate(I)
(12+) ion) further disproportionates to give Cl− and ClO3− (chlorate(III)) ions:
5. Equation 1 × 3 (to balance electrons lost and gained) [ClO− + 2H+ + 2e− → Cl− + H2O] ×2 ——— reduction
6. 3SO2 + 6H2O + Cr2O72− + 14H+ → 3SO42− +12H+ + 2Cr3++ 7H2O ClO− + 2H2O → ClO3− + 4H+ + 4e- ——— oxidation
- Cancelling H+ and H2O: 3ClO− → 2Cl− + ClO3− ——— overall redox equation
3SO2 + 2H+ + Cr2O72− → 3SO42− + H2O + 2Cr3+
Copper(I) chloride is stable when dry. In aqueous solution, however, the
2- 3+ 2-
copper(I) ion is unstable and disproportionates into Cu2+(aq) and Cu(s).
Cr2O is reduced to Cr ; SO2 is oxidised to SO4 . −
7 2CuCl + aq → Cu2+(aq) + 2Cl (aq) + Cu(s)
+1 +2 0
Cu+ + e− → Cu ——— reduction
Cu+ → Cu2+ + e− ——— oxidation

Oxidising and reducing agents

oxidation
Many students get confused about which is which. One way to think of it
is that a cleaning agent does not clean itself, it cleans the article to which Cl2 + 2Br− → 2Cl− + Br2
it is applied. In the process it does itself become dirty! 0 -1 -1 0
reduction
An oxidising agent causes the other reactant to be oxidised. It is itself
reduced. or Cl2 + 2e− → 2Cl− reduction

In terms of electrons, oxidation involves electron loss. The oxidising agent 2Br− → Br2 + 2e− oxidation
receives those electrons and is therefore reduced. The converse is true of
Cl2 is the oxidising agent; Br-is the reducing agent.
the reducing agent.
2
78. Recognising, Constructing & Interpreting Redox Reactions Chem Factsheet

Exam Hint: - When describing redox reactions some candidates Answers

use the oxidation state of the element rather than the actual formula 1. A (Cl changes oxidation number from 0 to –1, Br- from –1 to 0).
of the reactant. E.g. in the following equation B (Cu from +2 to 0, N from –3 to 0).
-1 C (N from +5 to +4, O from –2 to 0 in O2)
E (S from +7 to +6, I from –1 to 0).
Cu + 4HNO3 → Cu2+ + 4NO2 + 2H2O G (Na from 0 to +1, Cl from 0 to –1)
0 +5 +2 +4
H (Mg from 0 to +2, Zn from 2+ to 0)
HNO3 is the oxidising agent, not N5+ - There is no such ion!
The redox half-equation is
2. (a) A Cl2: (Cl decreases oxidation number from 0 to –1 and is
reduced).
HNO3 + H+ + e- → NO2 + H2O B SO2 (S from +4 to 0)
(+5) (+4)
and not N5+ + e- → N4+
C HNO3 (N from +5 to +4 in NO2).
D MnO4− (Mn from +7 to +2).
Questions E H2O2 (O from –1 to –2). [Note that the oxidation number of
1. Which of the following equations are redox reactions? O in H2O2 is –1, not –2. If it was –2, H would be +2 which
A Br2 + 2I− → I2 + 2Br− is not possible because a H atom only has one electron and
B 3CuO + 2NH3 → 3Cu + N2 + 3H2O cannot form H2+].
C 2Pb(NO3)2 → 2PbO + 4NO2 + O2
D 2[Fe(H2O)6]3+ + 3CO32− → 2[Fe(OH)3(H2O)3] + 3CO2 + 3H2O (b) A Ca (increases oxidation number from 0 to +2 and is oxidised).
E Na2S2O8 + 2NaI → I2 + 2Na2SO4 B I− (I from –1 to 0).
F 2NaHCO3 → Na2CO3 + H2O + CO2 C Cu (from 0 to +2).
G 2Na + Cl2 → 2NaCl D SO32− (S from +4 to +6).
H Mg + Zn2+ → Mg2+ + Zn E Zn (from 0 to +2).
I K2CO3 + 2HCl → 2KCl + H2O + CO2
J Ag+(aq) + I-(aq) → AgI(s) 3. (a) [Fe2+ → Fe3+ + e− ] × 6 OXIDATION
Cr2O72− + 14H+ + 6e− → 2Cr3+ + 7H2O REDUCTION
2. (a) Identify the oxidising agent in each of the following equations:
A 3Cl2 + 2Fe → 2FeCl3 6Fe2+ + Cr2O72− + 14H+ → 6Fe3+ + 2Cr3+ + 7H2O
B 2H2S + SO2 → 3S + 2H2O Cr2O72- (acidified) is the oxidising agent. It receives electrons from
C Cu + 4HNO3 → Cu(NO3)2 + 2H2O + 2NO2 Fe2+ and is reduced.
D 5H2O2 + 2MnO4− + 6H+ → 2Mn2+ + 5O2 + 8H2O
E H2O2 + H2S → S + 2H2O (b) I2 + 2e− → 2I− REDUCTION
(b) Identify the reducing agent in each of the following equations: 2S2O32− → S4O62− + 2e− OXIDATION
A Ca + 2H2O → Ca(OH)2 + H2 I2 + 2S2O32− → 2I− + S4O62−
B Cl2 + 2I− → 2Cl- + I2
C Cu + 2H2SO4 → CuSO4 + SO2 + 2H2O S2O32− is the reducing agent. It gives electrons to I2 and is oxidised.
D 3SO32− + Cr2O72− + 8H+ → 3SO42− + 2Cr3+ + 4H2O
E 2VO2+ + Zn + 4H+ → 2V3+ + Zn2+ + 2H2O 4. (a) 2I− → I2 + 2e− OXIDATION
H2O2 + 2H+ + 2e− → 2H2O REDUCTION
3. (a) Fe2+ is changed into Fe3+ by reaction with acidified Cr2O72− which
becomes Cr3+. Using redox ½-equations construct the overall redox (b) 2I− → I2 + 2e− OXIDATION
equation for this reaction. Which species is the oxidising agent? 2IO3− + 12H+ + 10e− → I2 + 6H2O
Give a reason for your answer.
(b) During the course of a redox reaction between iodine, I2 and the 5 (a) A disproportionation reaction is one in which the same element is
thiosulphate ion, S2O32−, the products formed are the iodide, I− and both oxidised and reduced.
tetrathionate, S4O62− ions. Using redox ½-equations, construct the (b) Manganese is both oxidised and reduced:
overall equation for the reaction. Identify the reducing agent, giving MnO42− → MnO4− + e− OXIDATION
reasons for your decision. +6 +7
4. From the two equations given below, construct and identify the two MnO42− + 4H+ + 2e- → MnO2 + 2H2O REDUCTION
redox ½-equations: +6 +4
(a) 2I− + H2O2 + 2 H+ → I2 + 2 H2O
(b) I− + IO3− + 6H+ → I2 + 3H2O

5. The manganate(VI) ion in acid solution undergoes a disproportionation

reaction as follows:
3MnO42−(aq) + 4H+(aq) → 2MnO4- + MnO2(s) + 2H2O(l)
(a) What is a disproportionation reaction?
(b) Show, using both oxidation numbers and ½-equations, that this is
an example of such a reaction.

Acknowledgements: This Factsheet was researched and written by Derek Swain. Curriculum Press, Bank House, 105 King Street, Wellington,
Shropshire, TF1 1NU. ChemistryFactsheets may be copied free of charge by teaching staff or students, provided that their school is a registered
subscriber. No part of these Factsheets may be reproduced, stored in a retrieval system, or transmitted, in any other form or by any other means, without
the prior permission of the publisher. ISSN 1351-5136

3
 Chem Factsheet
www.curriculum-press.co.uk Number 79
Catalysts
Before working through this Factsheet you should After working through this Factsheet you will
• Know the effect of change in conditions on rate of reaction; • Know that there are two types of catalyst, homogeneous and
• Know the significance of a reaction’s activation energy; heterogeneous;
• Know that a catalyst changes the rate of a chemical reaction but • Be able to recall examples of both types of catalysis;
remains chemically unchanged at the end; • Understand how catalysts affect reaction rate;
• Familiariseyourself with reaction profiles and Maxwell-Boltzman • Understand why transition elements make good catalysts;
distribution curves, (covered in Factsheet 10 - Kinetics 1 – Rates of • Know that enzymes are biological catalysts.
Reaction);
• Understand the atomic structure of transition elements and their general
properties (Factsheet 38).

The catalyst has caused an increase in reaction rate because

• For reactant particles to react and change into products they must • there is an increase in concentration of reactants at the catalyst surface
collide. enabling a greater chance of particle collision.
• Not all collisions result in chemical change. • there will be more collisions between molecules with favourable
• There is a minimum energy on collision that must be achieved or orientation and less energy is needed to break the weakened bonds,
exceeded for products to form. encouraging chemical reaction. The activation energy of the reaction
• This minimum energy is known as the activation energy (Ea) for has been lowered.
that reaction.
• A catalyst lowers the activation energy of the reaction, therefore Factors which affect the effectiveness of a heterogeneous catalyst
more collisions result in product formation. • The smaller the particle size of the catalyst, the more surface area
available for adsorption of reactant particles and the more effective the
Exam Hint: If a question asks for an explanation of how a catalyst catalyst. (Finely divided Raney Nickel is used in the manufacture of
works remember that it does not increase the energy, or rate of margarine).
collision, of reactant particles. It lowers the activation energy of • Adsorption onto the catalyst surface must be good but neither too
the reaction itself. weak nor too strong.
Too strong and the product particles cannot easily leave, blocking
Catalysts are widely used in the chemical industry, as they active sites for adsorption of other reactant molecules.
• speed up chemical reactions, and time costs money! Too weak and reactant bonds are hardly weakened. The activation
• are not used up in the reaction. Reactants cost money also! energy, and hence the reaction rate, is little changed.
Note however that some reactions may be too fast, even explosive.
Ideal adsorption Adsorption too strong Adsorption too weak
Negative catalysts (inhibitors) are added to slow down such reactions.
For example, an organic compound, acetanilide is added to stored hydrogen Nickel, platinum, Tungsten Silver
peroxide to slow down its decomposition into oxygen and water. palladium
Heterogeneous catalysis
• Catalyst poisons adversely affect the effectiveness of a catalyst. The
A heterogeneous catalyst is in a different phase (physical state)
offending molecules adsorb more strongly onto the catalyst surface
to the reactants. The most common examples involve gaseous reactants
than reactant molecules. The catalyst becomes inactive.
and a solid catalyst.

Process Catalyst Poison

The speeding up of the reaction takes place on the catalyst surface.
Adsorption (which is absorption on a surface) of reactant molecules onto Haber Process Iron Carbon monoxide
active sites on the catalyst surface causes a weakening of the bonds Contact Process Platinum Arsenic containing
within the molecules. Bonds break, new bonds form and the product substances
molecule(s) are desorbed and leave the catalyst surface. e.g. Catalytic Catalytic converter Platinum, rhodium Lead
hydrogenation of ethene. and palladium
Catalytic cracking Zeolite catalyst Carbon (soot)
Ni Catalyst
CH2 CH2(g) + H2(g) C2H6(g) (an aluminosilicate)
heat
ethene ethane Production of H2(g) Nickel Sulphur containing
new bonds formed for Haber Process compounds
H H (CH4(g) + H2O(g))
H H H H
H C C H
CH2 CH 2 weaker bonds
H H • Addition of a catalyst promoter improves the effectiveness of the
catalyst. Sodium hydroxide can be added to iron in the Haber Process.
H H CH2 CH 2 H H
The optimum temperature for the process can now be reduced by as
catalyst
much as 100K.
surface

1
79. Catalysts Chem Factsheet

Catalytic converters
In a catalytic converter in the exhaust system of a motor vehicle, harmful carbon monoxide and oxides of nitrogen are converted into nitrogen and
carbon dioxide. 2CO(g) + 2NO(g) → 2CO2(g) + N2(g)
The catalyst consists of platinum, palladium and rhodium. These are very expensive. To save on costs, they are thinly spread on a cheap ceramic
material. (A technique often used in industry for economic reasons). The support medium is like a honeycomb in structure thus giving maximum surface
area available for catalysis to take place. Catalytic converters are approximately 90% efficient.

Process Reaction Product Catalyst

Manufacture of margarine Vegetable oils(l), H2(g) Margarine Nickel

Haber process N2(g), H2(g) NH3(g) Iron

Contact process SO2(g), O2(g) SO3(g) Vanadium(V)oxide

Manufacture of nitric acid NH3(g), O2(g) NO(g) Platinum

Catalytic cracking High b.p alkanes (big molcules) Low b.p alkanes and alkenes Zeolite catalyst

Catalytic reforming and isomerisation Straight chain alkanes Branched chain alkanes Platinum

[Three of the above examples are reversible reactions. The presence of a catalyst does not affect the position of equilibrium (Kc is not affected) but
if does speed up the attainment of that equilibrium].

Transition elements Note that

All the catalysts indicated in the above table are transition elements or • Fe3+(aq) is also a catalyst for the reaction.
their compounds. They are used widely as heterogeneous catalysts. • Adding equations 1 and 2 gives the overall equation for the reaction.
Transition elements in the first transition series, for example, have both S2O82−(aq) + 2I−(aq) → 2SO42− + I2(aq)
3d and 4s electrons and orbitals available at the catalyst surface, which • The catalyst does not appear in the overall equation.
can form weak bonds with reactant molecules. e.g. Nickel • All the reactions are redox reactions.
Ni 1s2 2s2 2p6 3s2 3p6 3d8 4s2 • The catalyst has provided an alternative route with a lower activation
28
energy.
[Ar]
The reaction profile for a typical reaction involving two stages is
available for weak bonding

Homogeneous catalysis Ea
No catalyst
A homogeneous catalyst and the reactants are in the same
physical state.
Reactants Ecat
Enthalpy

Most examples are in aqueous solution and involve hydrated ions. Here,
the catalyst does take part in the reaction. An intermediate is formed
Intermediate present
which is then converted back to the catalyst.

For example, the reaction between peroxodisulphate ions [S2O82-(aq)] and Products
iodide ions [I-(aq)] is very slow. Both ions are negatively charged and
repel each other.
Reaction path
The reaction is catalysed by the addition of Fe2+(aq).
The Fe2+(aq) reacts with S2O82-(aq) to give SO42-(aq), a reaction product, Transition metal ions, because of their ability to change oxidation
and Fe3+(aq), the intermediate ion. state, are used in redox reactions involving homogeneous catalysis.

S2O82−(aq) + 2Fe2+(aq) → 2SO42−(aq) + 2Fe3+(aq) 1 The redox reaction between acidified manganate(VII) ions and ethanedioate
+7 +2 +6 +3 ions is an example of autocatalysis.
reduction oxidation 2MnO4−(aq) + 6H+(aq) + 5C2O42−(aq) → 2Mn2+(aq) + 10CO2(g) + 8H2O(l)
The reacting ions are oppositely charged and reaction rate is consequently
faster. Both MnO4−(aq) and C2O42−(aq) are negatively charged and repel.
A product of the reaction, Mn2+(aq) now speeds it up.
The Fe3+(aq) now reacts with the other reactant ion, I-(aq) to give the
second product, I2(aq) and the Fe2+(aq) catalyst back again. 4Mn2+(aq) + MnO4−(aq) + 8H+(aq) → 5Mn3+(aq) + 4H2O(l)
2Mn3+(aq) + C2O42−(aq) → 2CO2 + 2Mn2+(aq)
2I−(aq) + 2Fe3+(aq) → I2(aq) + 2Fe2+(aq) 2 Mn2+(aq) is the autocatalyst. Mn3+(aq) is the intermediate ion.
-1 +3 0 +2 When a little C2O42-(aq) is added to purple MnO4-(aq) decolourisation is
slow at first but as the product Mn2+(aq) concentration increases,
oxidation reduction
decolourisation is fast.

2
79. Catalysts Chem Factsheet

Quite a number of reactions are acid-catalysed. Enzymes are biological catalysts. They speed up chemical reactions in
the body. They are complex protein molecules which have highly specific
Reaction Product Catalyst molecular shapes. Their active sites match exactly the structure of the
reactant molecule. The two structures have an exact fit.
Alcohol + halide ion Halogenalkane Conc H2SO4
Biological washing powders contain enzymes to assist in the cleaning
Alcohol + Carboxylic acid Ester Conc. H2SO4 process. The enzymes break down blood, food and fats. They enable
(esterification) washing to take place more quickly and at low temperature. High
temperatures cause the enzymes to denature and lose their specific shape.
Dehydration of alcohols Alkene Conc. phosphoric acid They become non-effective. They have also been known to cause allergies
and asthma.
In the dehydration of alcohols Like other catalysts, enzymes lower the activation energy of a reaction
H H H
+
H
+
Activation energy (kJmol−1)
CH 3CH2 . . → CH 3CH2
O O → H C C H → CH2 CH2 + H+ Reaction No Pt Enzyme
H catalyst catalyst catalyst
H
H+
2H2O2(aq) → 2H2O(l) + O2(g) +79 +49 +23
1. H+ ions from the acid protonate the oxygen of the hydroxyl group, -OH.
2. A water molecule leaves, enhancing the reactive site C+. Practice Questions
3. A double carbon-carbon bond forms to give the alkene. H+, the 1. (a) What features of the catalysts in a catalytic converter present in
catalyst, is regenerated. the exhaust system of a motor vehicle make it more efficient and
The acid catalyst has enhanced the reactive site. less expensive?
(b) The converter changes NO(g) and CO(g) into N2(g) and CO2(g).
(i) Write an equation for this conversion.
The reaction between iodine and propanone (CH3COCH3) has the overall (ii) Explain how this conversion occurs at the catalyst surface.
reaction
2. In the following reaction mechanism
CH3COCH3(aq) + I2(aq) → CH3COCH2I(aq) + HI(aq) Cu2+(aq) + V3+(aq) → Cu+(aq) + V4+(aq)
The reaction is acid-catalysed. Cu+(aq) + Fe3+(aq) → Cu2+(aq) + Fe2+(aq)
Experiments show that the rate of reaction = k[CH3COCH3][H+] (a) Construct the overall equation.
The reaction is first order with respect to propanone. (b) Name the catalyst.
(c) Which is the intermediate ion?
It is also first order with respect to H+(aq) even though H+(aq) does not (d) What type of catalysis is represented here? How do you know?
appear in the overall equation. (e) How does the catalyst increase the reaction rate?
(f) Sketch a reaction profile which illustrates a typical two stage
It is zero order with respect to iodine even though iodine does appear
mechanism involving a catalyst.
in the overall equation. (Factsheet 43 – Orders of Reaction).
Reaction path
This information about the kinetics of the reaction is extremely useful in
the determination of its mechanism - the rate equation indicates that the
rate determining step involves the reaction between 1 mole of propanone Products
and 1 mole of H+(aq).
Enthalpy
Even though H+(aq) is not apparent from the overall equation, it is Intermediate present
involved in the reaction mechanism.
Ecat Reactants
An example of homogeneous catalysis where reactants and catalyst are
in the gaseous phase is illustrated in the destruction of the ozone layer No catalyst
by CFC emission. Ea

In the presence of uv-light, chlorofluorocarbon molecules are decomposed

to give chlorine free radicals. (f)
u-v energy/Ea.
CCl3F CCl2F. + Cl.
light Allows an alternative pathway which requires a lower activation (e)
The chlorine radical is the catalyst. The ClO· is the intermediate Homogeneous. Catalyst in same physical state/phase as reactants. (d)
radical. Cu+(aq). (c)
Cl. + O3 → O2 + ClO. Cu2+(aq). (b)

ClO. + O. → O2 + Cl.
V3+(aq) + Fe3+(aq) → V4+(aq) + Fe2+(aq) 2. (a)
catalyst surface.
The following reaction sequence now takes place are formed and the product molecules are desorbed/leave the
Bonds in the reactant molecules are weakened. Product bonds
(ii) NO and CO molecules are adsorbed onto the catalyst surface.
Acknowledgements: This Factsheet was researched and written by Derek Swain. Curriculum
Press, Bank House, 105 King Street, Wellington, Shropshire, TF1 1NU. ChemistryFactsheets
(b) (i) 2NO(g) + 2CO(g) → N2(g) + 2CO2(g)
may be copied free of charge by teaching staff or students, provided that their school is a honeycomb structure (to increase surface area available).
registered subscriber. No part of these Factsheets may be reproduced, stored in a retrieval
system, or transmitted, in any other form or by any other means, without the prior permission 1. (a) They are thinly coated onto a cheap, inert ceramic material in a
of the publisher. ISSN 1351-5136 Answers

3
 Chem Factsheet
www.curriculum-press.co.uk Number 80

The Extraction of Aluminium

To succeed in this topic you need to: The Extraction of Aluminium
· Understand and learn the relevant equations;
Raw materials
· Understand the principles in electrolysis;
The aluminium ore mined for the production of aluminium is called bauxite.
· Be able to write balanced half equations.
Bauxite rock contains the following compounds:
After working through this Factsheet you will:
· Know the physical and chemical processes involved in extracting Chemical name Formula Description
aluminium;
Hydrated aluminium oxide Al2O3.2H2O Source of aluminium
· Recognise that these processes occur on an industrial scale;
· Have experience in using this knowledge in exam style questions. Silicon (IV) oxide SiO2 Acidic impurity

Aluminium is the most abundant metal in the Earth’s crust, and is of Iron (III) oxide Fe 2O 3 Basic impurity
tremendous importance. The properties of the metal make it very useful.
The first stage in the extraction of aluminium is to mine the bauxite, and
Some important properties of aluminium: then to produce pure aluminium oxide.
• Shiny surface when polished
• Low density metal Candidates require an understanding of these purification processes; exam
• Malleable question often focus on how the amphoteric nature of aluminium oxide is
• Good electrical conductor utilised (see Factsheet 19).
• Good thermal conductor, with ability to act as thermal insulator also, The ground bauxite is crushed and heated under pressure a concentrated
as polished surface reflects infra-red radiation solution of sodium hydroxide.
• Resistant to corrosion due to formation of self protecting formation
of oxide layer on surface Learn these equations!
New uses for aluminium are being discovered all the time, here are just a few. The amphoteric aluminium oxide reacts and dissolves in the alkali:
Al2O3(s) + 2NaOH(aq) → 2NaAlO2(aq) + H2O(l)
Use of aluminium Reasons for use
The acidic silicon (IV) oxide reacts and dissolves in the alkali:
Overhead power cables Good electrical conductor, low density
Food and drinks packaging Resistant to corrosion, affordable SiO2(s) + 2NaOH(aq) → Na2SiO3(aq) + H2O(l)

Transport manufacture Low density, resistant to corrosion

The basic iron (III) oxide does not react with the alkali, so is precipitated
Saucepans and cooking foil Good thermal conductor, resistant to
and can be filtered out.
corrosion, low density
Carbon dioxide gas, which is acidic, is then blown through the remaining
Blankets for athletes and Shiny surface reflects radiated heat so
solution. The sodium aluminate reacts and a precipitate of aluminium
premature babies acts as insulator
hydroxide is formed, whilst the sodium silicate remains in solution.
Reflective coating on glass in Shiny surface, resistant to corrosion,
The aluminium hydroxide precipitate is filtered off, washed and heated,
cameras and car headlights malleable
forming the desired product, purified anhydrous aluminium oxide, sometimes
known as alumina (Fig 1).
As aluminium is such a useful and abundant metal, millions of tonnes are
produced annually. Because of the importance of the extraction of
aluminium, it is frequently examined in AS and A2 papers.

Fig 1. Extraction of aluminium

Sodium silicate
remains in solution

ground bauxite Precipitate of

crushed under pressure Sodium aluminate solution Add CO2(g) aluminium hydroxide
bauxite with a concentrated Sodium silicate solution
NaOH(aq)

Remove iron(III)oxide
precipitate

Anhydrous aluminium filter, wash

oxide (Alumina) and heat

1
80. The Extraction of Aluminium Chem Factsheet

Extraction using Electrolysis Exam Hint: Several questions on past exam papers have concerned
Before 1886 aluminium was extracted from its compounds by displacement, the anodes in this process. Be very clear in your explanation and
and since aluminium is itself quite a reactive metal, a very reactive metal use the equations where appropriate.
such as sodium had to be used. This made the extraction of aluminium, and
hence the cost of the metal, very expensive.
Cost
The Hall-Heroult process of extraction, which involves electrolysis, lowered The extraction of aluminium is an expensive process due to the high
the costs and has allowed aluminium to be manufactured on an industrial temperatures and electrical energy required, so the recycling of aluminium
scale. makes economic sense. The low melting point of aluminium (660oC)
makes it easy to separate from other metals, and relatively cheap to melt
The industrial plants themselves tend to be located at the coast, so the down and re-use.
purified aluminium oxide can be shipped in, and near to an adequate supply
of affordable electricity. Practice Questions
The Electrolyte 1. Name the rock which is mined as aluminium ore.
Pure aluminium oxide has a melting point of 2040oC, making it unsuitable 2. Explain why aluminium and alloys of aluminium are used in the
as an electrolyte. Not only would this temperature be very expensive to manufacture of aircraft.
maintain, but also the handling of a liquid at this temperature would be
difficult. 3. Explain why pure aluminium oxide is not used as the electrolyte in the
extraction of aluminium.
Consequently a solvent must be used. The solvent is molten cryolite,
4. Write balanced half equations to show the reactions which occur at the
sodium hexafluoroaluminate, Na3AlF6, which dissolves the aluminium oxide
electrodes in the extraction of aluminium.
whilst having a much lower melting point.
5. State the biggest cost to the manufacturer in the production of
The electrolyte contains:
aluminium.
Name Formula Quantity Purpose 6. What are the anode and cathode made from in the electrolytic cell used
Aluminium oxide Al 2O 3 10% Source of aluminium in the manufacture of aluminium?

Cryolite Na3AlF6 80% Solvent 7. Give reasons why aluminium is recycled.

Calcium fluoride CaF2 10% Lower melting temperature 8. Why must the anodes be periodically replaced during the electrolysis?
of mixture 9. What would happen if the power supply to the electrolytic cell were
to be stopped for more than a couple of hours?
The electrolyte mixture is melted and maintained above its melting point at
around 900oC by a current of 100 000 amps. 9. The contents of the cell would solidify.

Fig 2. Electrolytic cell for aluminium extraction carbon dioxide gas.

8. The carbon anode burns in the oxygen produced at the anode producing
porous crust of solid electrolyte
Carbon lining
cathode adjustable carbon anodes to produce electricity required.
processes compared to manufacture, especially if fossil fuel used
_ + + + + · Less pollutants and greenhouse gases produced during recycling
syphon · Preserve reserves of aluminium ore
· Less waste in environment
· Cheaper to recycle than to manufacture
7. From:
6. Carbon graphite.
5. Electricity.
anode 2O2− → O2(g) + 4e−
molten electrolyte cathode Al3+ + 3e− → Al(l) 4.
molten aluminium allows electrolysis to occur at a lower temperature, around 900oC.
Instead the aluminium oxide is dissolved in molten cryolite which
electrolyte (expensive to maintain high temps and difficult to handle).
3. Melting point of aluminium oxide is too high to produce molten
At the cathode, aluminium ions are reduced: Al3+ + 3e− → Al(l)
aluminium is not strong enough.
The aluminium (mp 660oC) is a liquid at the working temperature, so can of aluminium tend to be used for the structure of aircraft as pure
be siphoned off and cast into blocks for sale and use. 2. Aluminium has a low density and is resistant to corrosion. NB Alloys

2O2− → O2(g) + 4e−

1. Bauxite
At the anode, oxygen ions are oxidised:
Answers
The carbon graphite anodes must be replaced every month as at the high
temperatures in the cell they react with the oxygen gas formed, producing
carbon dioxide gas, hence the anodes themselves are gradually burning Acknowledgements: This Factsheet was researched and written by Kieron
away. Heath. Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire,
TF1 1NU. ChemistryFactsheets may be copied free of charge by teaching
C(s) + O2(g) → CO2(g) staff or students, provided that their school is a registered subscriber. No part
of these Factsheets may be reproduced, stored in a retrieval system, or
This is why the carbon anodes are ‘adjustable’. transmitted, in any other form or by any other means, without the prior
Any remaining carbon is recycled as new anodes are produced. permission of the publisher. ISSN 1351-5136

2
 Chem Factsheet
www.curriculum-press.co.uk Number 81
UV and Visible Spectroscopy
Typical absorptions for simple isolated functional groups:
To succeed in this topic you need to:
• Be familiar with the other spectroscopic techniques (outlined in
Chromophore Absorption wavelength λmax (nm)
Factsheets 54, 55 and 61);
• Be able to name and recognise organic molecules. Nitrile 160

After working through this Factsheet you will: Alkyne 170

• Have a basic understanding of how a UV-Visible spectrometer Alkene 175
works;
• Know how UV-Visible spectra can assist analytical chemists; Alcohol 180
• Be able to recognise UV-Visible spectra;
Ether 180
• Be able to assign peaks on a UV-Visible spectrum if given the
necessary data; Ketone 180
• Recognise conjugated systems within molecules; 280
• Be aware of the effect of conjugation on UV-Visible spectra.
Aldehyde 190
Ultraviolet-visible spectroscopy is a useful tool for the analytical chemist 290
when presented with an unknown organic compound. As with IR spectra, Amine 190
there is little for the A2 level candidate to fear as at this level only a basic
understanding and interpretation of spectra is required. Acid 205
Ester 205
All organic molecules absorb radiation in the IR region of the electromagnetic
spectrum (Factsheet 54). Because different bonds absorb different Amide 210
wavelengths of IR, the spectra are used to characterise molecules. Thiol 210

The operation and workings of a UV-Visible spectrometer are similar to Nitro 271
those of the IR spectrometer. The key difference, of course, is that it is UV Azo 340
and visible light that is passed through the sample and not IR radiation.
The generated absorption spectra have the following appearance:
Fig 1. UV spectrometer Fig 2. Butene

beam
sample
splitter
light source cell
λmax = 176 nm
2.5
εmax = 1200
wavelenghts spectrum lg ε 2
reference computer recorder H2C=CH.CH 2CH3
selector
cell
1.5

The useful UV region is from around 200 to 400 nm wavelength, and the 1
visible light region is from around 400 to 750 nm wavelength.
150 160 170 180 190
This high energy radiation has the ability to cause electronic transitions in wavelength/nm
certain bonds.

unoccupied The spectrum is shown as the strength of absorption, as lg ε, on the

electron Energy y-axis against the wavelength, λ, in nm. The spectra tend to show broad
orbitals absorbed as peaks, with chemists looking for the maxima of these peaks to identify
electron is the wavelength at maximum absorption, λmax, and the corresponding value
electrons promoted of lg ε, from which ε is calculated.
uv/vis in ground to a higher
radiation state level For the above example, the spectrum indicates the presence of a C=C
group due to the absorption peak being present at 176 nm. Other
spectroscopic techniques such as mass spectrometry would help to
Electrons in different environments absorb UV-Visible radiation of different identify the alkene as but-1-ene.
wavelengths, so a characteristic absorption spectrum can be generated.
The absorbing groups are called chromophores.

1
81. UV and Visible Spectroscopy Chem Factsheet

As each compound has its own unique UV-Visible absorption spectrum, Consequently UV-Visible spectroscopy can be used to help assign where
like a fingerprint, analytical chemists can compare the spectrum of an double bonds may be occurring in a carbon chain.
unknown compound with many others on a vast database and hence
identify the unknown chemical. Key points for success at A-level:
• Be able to recognise UV-Visible spectra.
It should be pointed out that due to the nature of the UV-Visible spectra, the • Use supplied data to assign peaks.
broad quite featureless peaks which can often engulf one another if more than • Be able to recognise conjugated and isolated systems.
one chromophore is present, are not as useful as IR or NMR in terms of • Be aware of the effect of conjugation on a spectrum.
identifying molecular structure. UV-Visible spectroscopy is most useful for
identifying π-electron systems. Because the π electrons are less strongly
held in their ground state orbitals than σ electrons, π electrons absorb light Practice Questions
intensely – producing clear, characteristic absorption peaks. 1. Do the following molecules contain conjugated systems?

The most common use of UV-Visible spectroscopy is in the detection of (a) CH2=CHCH=CHCH=CHCH3
multiple carbon-carbon bonds and detecting whether or not they are part
(b)
of a conjugated system.
(c) octa-1,4-diene
A conjugated system of double bonds is where a carbon chain has double
bonds alternating with single bonds. CH3
(d) H
Examples of conjugated alkenes:
Buta-1,3-diene CH2=CH-CH=CH2 O
Hexa-1,3,5-triene CH2=CH-CH=CH-CH=CH2 2. Using IR and mass spectrometry chemists identified an unknown
compound as a pentadiene, C5H8, but were unable to assign the positions
Contrast these structures with the following isolated systems (where
of the double bonds within the molecule.
there is not conjugation).
What structural information can be gained from the UV-Visible spectrum
Pent-1-ene CH2=CH-CH2-CH 2-CH3
of the compound shown below?
Hexa-1,4-diene CH2=CH-CH2-CH=CH-CH3
Conjugation does not just occur in simple alkenes, there is conjugation in
the following molecules also:
H 4.0
C C C O
H λmax = 176 nm
H H lg ε
εmax = 16 600
3.6

β- carotene (from carrots)

3.2
Conjugation has a marked effect on the UV-Visible spectrum of a compound.
If conjugation is present in a molecule, the absorption peaks are:
• Shifted to a longer wavelength 160 170 180 190
• Significantly larger, more intense peaks wavelength/nm
The following trace contrasts the absorption spectra of but-1-ene, with an Hint: Use the data table showing typical absorptions for isolated
isolated C=C, and buta-1,3-diene, a conjugated system Fig 3.. functional groups.
CH 2=CH-CH2-CH=CH2
Fig 3. Absorption spectra The compound is likely therefore be pent-1,4-diene.
are isolated.
5.0 the pentadiene does not contain a conjugated system, the double bonds
lg ε peak appears close to this value. A conclusion can then be made that
4.5
double bond is at λ = 175 nm. In the illustrated spectrum, the absorption
4.0 double bond. The expected position for the absorption peak for a C=C
But-1,3-diene 2. Penta-1,4-diene contains just one type of functional group, the C=C
3.5
(d) yes
3.0 (c) no
(b) yes
2.5 1. (a) yes
2.0 But-1-ene
Answers.

1.5
Acknowledgements: This Factsheet was researched and written by Kieron Heath. Curriculum
Press, Bank House, 105 King Street, Wellington, Shropshire, TF1 1NU. ChemistryFactsheets
1 may be copied free of charge by teaching staff or students, provided that their school is a
registered subscriber. No part of these Factsheets may be reproduced, stored in a retrieval
150 160 170 180 190 200 210 220 230 system, or transmitted, in any other form or by any other means, without the prior permission
wavelength/nm of the publisher. ISSN 1351-5136

2
 Chem Factsheet
www.curriculum-press.co.uk Number 82
Why Students Lose Marks: AS Energetics
This Factsheet analyses students’ answers to AS exam questions on Energetics. By the end of this Factsheet, you should be more confident about:
• What the examiners want
• The kinds of things you are likely to be asked
• Common mistakes and misunderstandings
As you read the students' answers to the questions and the comments, try to work out what the student should have done - using the hints and comments
if necessary - before you read the markscheme. NB: this Factsheet is not intended to teach you energetics for the first time - this is covered in Factsheets
8 and 65.
What do you have to know?
In this type of question, the examiner is trying to assess whether you can:
• understand and explain what is meant by the various enthalpy changes;
• recall definitions accurately and precisely;
• understand and apply Hess's law;
• calculate ∆Hê directly from experimental results, and understand why the value may be different to theoretical results,
For some examination boards, you will also have to
• draw enthalpy level diagrams and reaction profiles.
In any question involving calculation, there are likely to be marks available for showing a clear method. If you have to use one answer in the next part
of the question, there are likely to be "error carried forward" marks available - so you are only penalised once for a wrong answer. Also note that you may
be asked to use other skills such as writing balanced equations and simple moles calculations.

(a) Define standard enthalpy of formation

The enthalpy change when a compound is formed from its elements

.................................................................................................................................................................................................................................. [3]
!"! The student understands what the term means, and gains 1 mark for "formed from its elements". S/he should have realised that this
was not enough for 3 marks - there is no real attempt to be precise in giving the definition - how much of the compound is formed?
what state are the elements in? what conditions are used?

The table below gives some data on enthalpies of formation

Substance O2(g) CO2(g) H2O (l) C2H6(g)

∆Hêf /kJmol-1 0 -394 -286 -85

(b) Why is the enthalpy of formation of oxygen gas zero?

Because it is an element " Correct - an element in its standard state always has zero enthalpy of formation. Although the
.................................................................................................................................................................................................................................. [1]
mark was awarded, the candidate should really have referred to "standard state" as well - for
example, the enthalpy of formation of gaseous carbon would not be zero.

(c) Use the data from the table to calculate the enthalpy change for the following reaction:

2C2H6(g) + 7 O2(g) → 4CO2(g) + 6H2O (l)

!!! The calculations of Σ∆Hêf for products and reactants were correct, but the correct
∆Hêf (reactants) = 2 × -85 = -170
.......................................................................................................................................................................................................................................
equation to calculate ∆Hê is ∆Hê = Σ∆Hêf (products) - Σ∆Hêf (reactants)
∆Hêf (products) = 4 × -394 + 6 × -286 = -3292 The student would have lost two of the three marks for using this the wrong way round
.......................................................................................................................................................................................................................................
(and hence getting the wrong sign for ∆Hê).
The final mark is lost for incorrect units - it is kJ mol-1, not kJmol.
∆Hê = -170 − -3292 = 3122 kJ mol
.................................................................................................................................................................................................................................. [3]
! This equation and value refer to 2 moles of ethane, not 1.
3122 If the student had halved his/her incorrect answer to (c),
(d) Hence write down the standard enthalpy of combustion of ethane ................................................................................................................... [1]
this mark would have been awarded as a "follow through".
However, the student should have realised at this stage
that the sign of their answer could not be correct - the
enthalpy of combustion of a fuel like ethane must be negative.
Markscheme
(a) the enthalpy change when one mole of a compound (1) is formed from its constituent elements (1) in their standard state (1) under standard conditions
(b) because it is an element (1)
(c) ∆Hê = Σ∆Hêf (products) - Σ∆Hêf (reactants) (or enthalpy cycle) (1)
4 × -394 + 6 × -286 − 2 × -85 (1 - also award first mark if this is seen)
=-3122 kJ mol-1 (1)
Max 1 mark for incorrect sign. Penalise incorrect units; ignore no units

1
82 Why Students Lose Marks: AS Energetics Chem Factsheet

(a) State Hess's Law

energy change in a reaction only depends on the initial and final states, not the route taken
.................................................................................................................................................................................................................................. [2]
!" The student has the general idea, but has made one crucial mistake - you must refer to "enthalpy change" or "heat energy change" rather
than "energy change".

Sucrose (C12H22O11) reacts with oxygen to form carbon dioxide and water
C12H22O11 (s) + 12 O2(g) → 12CO2(g) + 11H2O (l)

(b) Write a balanced chemical equation to represent the formation of 1 mole of sucrose from its constituent elements in their standard states
12C + 11H2 + 5½O2 → C12H22O11 "! This is the correct equation, correctly balanced - but state symbols were needed
.................................................................................................................................................................................................................................. [2]
to indicate that the elements were in their standard states.
Note that "follow through" marks would have been awarded in part (c) if an incorrect
equation had been produced here.

(c) Use the enthalpy of combustion data given below to determine the enthalpy of formation of sucrose

Substance C(s) H2(g) C12H 22O 11 (s)

∆Hêc / kJmol-1 -393.5 -285.8 -4098

∆Ηêf
12C + 11H2 + 5½O2 C12H22O11

"!! The first mark is awarded for the correctly drawn enthalpy cycle.
12 ∆Hêc(C) + 11∆Hêc(H2) ∆Hêc(C12H22O11)
Unfortunately the remaining two marks are lost due to the
mistake in writing "−4098" rather than "− -4098" as is required,
as we are going against the direction of the arrow. This could
just be an arithmetic slip, but it could also indicate a lack of
12CO2 + 11H2O understanding of how to use the enthalpy cycle.
The implausibly large negative value of ∆Hêf should have
∆Ηêf = 12 (-393.5) + 11(-285.8) -4098 = -11963.8 kJmol-1 alerted the student to the fact there was something wrong
.................................................................................................................................................................................................................................. [3]
Markscheme
(a) the enthalpy change (1) for a reaction is independent of the route taken (1) (or depends only on initial and final state)
(b) 12C(s) + 11H2(g) + 5½O2(g) → C12H22O11 (s) (1) correct formulae and balanced (1) correct state symbols
(c) ∆H = Σ∆Hêc(reactants) - Σ∆Hêc (products) (1) (or enthalpy cycle)
∆H = 12 × -393.5 + 11 × -285.8 - -4098 (1 - also award first mark if this is seen)
-1
= -3767.8 kJmol (1)
Positive answer scores 2 marks; if other incorrect answer given, correct signs and multipliers score 2 marks.

A student added 30cm3 of sodium hydroxide to 30 cm3 of hydrochloric acid in a polystyrene cup. The concentration of each solution was 2 mol dm-3.
The temperature rose by 6.3o C.

(a) Calculate the enthalpy change for this reaction. (The final solution has a specific heat capacity of 4.18 J g–1K–1 and a density of 1.00 g cm–3 .)
"! The calculation is correct (although the units - joules - were not given). However, the sign
∆H ê= mc∆T = 60 ×4.18 × 6.3 = 1580 is incorrect - since the reaction is exothemic, the enthalpy change is negative
......................................................................................................................................................................................................................................... [2]

(b) Calculate the molar enthalpy change for this reaction

""! The calculation is largely correct, and no marks are deducted for carrying forward
moles of NaOH = 0.03 × 2 = 0.06 the sign error from part (a). However, the units given in the final answer are incorrect
.............................................................................................................................................................................................................................................
- since the answer in (a) was given in joules, this answer is also in joules.
molar enthalpy change = 1580 ÷0.06 = 26333 kJmol-1 To convert to kJ, it should be divided by 1000.
......................................................................................................................................................................................................................................... [3]

(c) Explain why this is likely to be less than the theoretical value given in data books
" Correct. This is a common question; the other possible answer in many cases is that the
Some heat will be lost from the cup reaction may not have completed.
........................................................................................................................................................................................................................................ [1]
Markscheme
(a) ∆Hê = - 60 × 4.2 × 6.3 = -1580 J (or -1.580 kJ) (1 - value 1 - sign)
(b) Moles of NaOH or HCl = 0.03 × 2 = 0.06 (1)
Molar enthalpy change = answer to (a)/ 0.06 (1 ecf) = -26.33 kJ mol-1 (1 ecf - penalise incorrect units)
(c) Heat loss (1)

2
82 Why Students Lose Marks: AS Energetics Chem Factsheet

(a) Explain the term mean bond enthalpy

"! Since the question says "Explain", it is necessary to say that the actual energy
the average energy required to break a covalent bond required varies between compounds, and hence an average is used
......................................................................................................................................................................................................................................... [2]

(b) (i) Use the data given below to find the enthalpy change for the reaction NH3(g) → N(g) + 3H(g)

Data: ½H2(g) → H(g) ∆Hê = + 218 kJmol-1

½N2 (g) → N(g) ∆Hê = + 473 kJmol-1
∆Hf (NH3) = -46 kJmol-1
∆Hê
NH3 (g) N(g) + 3H(g)
"!"! First mark awarded for correct species in
the cycle. However, the arrow for ∆Hêf of
ammonia is in the wrong direction, losing the
second mark for the cycle. The first mark for
∆Hêf(NH3) 473 + 3 ×218 calculation is given for the correct multipliers
(473 + 3 × 218) but the final mark is not
awarded, as it should be +46 not -46

½N2 (g) + 1½H2 (g)

∆Hê = -46 + 473 + 3 ×218 = 1081 kJ mol-1

......................................................................................................................................................................................................................................... [4]

(ii) Deduce a value for the mean bond enthalpy of an N - H bond in ammonia
1081 ÷3 = 360 kJ mol-1 " Mark awarded (error carried forward)
......................................................................................................................................................................................................................................... [1]

(c) The mean bond enthalpy for the N - H bond given in data books is 391 kJmol-1. Comment on this.
! This is never a sensible answer! The key point is that the bond enthalpy has slightly
There are errors in the calculations different values in different compounds - the data book figure is a mean across all
......................................................................................................................................................................................................................................... [1]
compounds containing N - H bonds - so it is surprising if it is exactly the same as
the answer obtained
Markscheme
(a) The energy required to break a specific covalent bond (1) varies between compounds, so an average is used (1)
(b) (i) Enthalpy cycle (or equivalent) with correct species (1)
Entire cycle correct (1)
∆Hê = 46 + 473 + 3×218 (1)
= 1173 kJ mol-1 (1)
(ii) 1173/3 = 391 kJmol-1 (1 ecf)
(c) Would expect it to be slightly different from the calculated value for the bond in ammonia, as it is an average across all compounds (1)
(allow reasonable comment explaining difference if (b) (ii) is incorrect)

Practice Question Markscheme

(a) What is the meaning of the term enthalpy change? [2] (e) Difference due to heat loss in experiment (1)
= 910 kJmol-1(1)
(b) (i) Define the standard enthalpy of combustion [3]
Standard enthalpy of combustion = 7.14/0.00783 (1)
(ii) Write an equation corresponding to the standard enthalpy of
Moles of ethanol = 0.36/46 = 0.00783 (1)
combustion of ethanol (C2H5OH) [2]
(d) ∆Hê = mc∆T = 100 × 4.2 × 17 (1) = 7140J = 7.14 kJ
(c) Using the mean bond enthalpy data below, calculate a value for the ∆Hê = 4719 - 5998 = -1279 kJmol-1 (1)
enthalpy of combustion of ethanol [4] Bonds formed: 4(805) + 6(463) (1)
Bond Mean bond enthalpy Bonds broken: 348 + 5(412) + 360 + 463 + 3(496) (1)
C−H +412 kJmol-1 (c) ∆Hê = Σ bonds broken - Σ bonds formed (1)
C−C +348kJmol-1 (1 correct balanced equation, 1 state symbols)
C=O +805kJmol-1 (ii) C2H5OH(l) + 3O2(g) → 2CO2(g) + 3H2O(l)
O=O +496kJmol-1 burnt in oxygen (1) under standard conditions (1)
O−H +463kJmol-1 (b) (i) the enthalpy change when one mole of a compound (1) is completely
C−O +360kJmol-1 (a) heat energy change (1) measured at constant pressure (1)
(d) In an experiment, the combustion of 0.36 grammes of ethanol produced
a temperature rise of 17oC in 100cm3 of water. Use these data to calculate Acknowledgements: This Factsheet was researched and written by Cath Brown. Curriculum
Press, Bank House, 105 King Street, Wellington, Shropshire, TF1 1NU. ChemistryFactsheets
a value for the standard enthalpy of combustion of ethanol [4] may be copied free of charge by teaching staff or students, provided that their school is a
(density of water=1gcm-3. Specific heat capacity of water = 4.2 Jg-1K-1) registered subscriber. No part of these Factsheets may be reproduced, stored in a retrieval
(e) Comment on the difference between your two calculated values system, or transmitted, in any other form or by any other means, without the prior permission
of the publisher. ISSN 1351-5136

3
 Chem Factsheet
www.curriculum-press.co.uk Number 83
The Chemistry of Copper
To succeed in this topic you need to understand:
Oxidation states
• the basics of transition metals (covered in Factsheet 28);
• the reactions of transition metal ions with hydroxides and ammonia
The oxidation states of copper are +1 and +2.
(covered in Factsheet 46);
• the principles of oxidation and reduction (covered in Factsheet 11).

After working through this Factsheet you will: Principal compounds and ions are as follows.
• know that copper will not liberate hydrogen from dilute acids but is • CuI The copper(I) ion, Cu+, copper(I) oxide, Cu2O, copper(I)
attacked by oxidising acids; chloride, CuCl, and various complex ions such as [CuCl2]−. There
• know that the oxidation states of copper are +1 and +2; is no hydroxide.
• understand the action of water on copper(I) salts;
• understand the relationships between the principal compounds of copper; • The electronic configuration of the Cu+ ion is
• understand the chemistry of both copper(I) oxide and copper(II) oxide; 1s2, 2s2, 2p6, 3s2, 3p6, 3d10.
• understand the aqueous chemistry of Cu2+(aq);
• know the preparation of copper(I) chloride and its reaction with • CuII Copper(II) oxide, CuO, copper(II) hydroxide, Cu(OH)2, the
concentrated hydrochloric acid. copper(II) ion, Cu2+, and various complex ions such as the hydrated
copper(II) ion, [Cu(H2O)6]2+.
The element
• The electronic configuration of the Cu2+ ion is
Copper (atomic number = 29) is the last member of the first series of 1s2, 2s2, 2p6, 3s2, 3p6, 3d9.
d-block transition elements.(Remember that zinc is not a transition
element.)

Its electronic configuration is 1s2, 2s2, 2p6, 3s2, 3p6, 3d10, 4s1. This Stability of oxidation states
arrangement, in which all five 3d orbitals are fully occupied, is more Although CuI and Cu II are of comparable stability, the Cu+ ion
stable than the alternative [Ar] 3d9, 4s2. disproportionates in aqueous solution.
Copper is a brownish red metal with a high density (8.92 g cm−3). It has
O N Cu2+(aq)
a high thermal conductivity (hence its use in saucepans) and a high electrical ATI
conductivity (hence its use in electrical wiring). XID
Cu+(aq) WATER O
RED
Exam Hint - Do not say that copper is used for electricity cables, UC
TIO
because this implies that it is used for overhead power lines. It is too N Cu(s)
heavy and expensive for this purpose. Aluminium is used instead.
Copper(I) sulphate, for example, an off-white solid, dissolves in water to
give a blue solution of copper(II) sulphate and a reddish brown precipitate
Copper is a relatively unreactive metal but is attacked by oxidising acids,
of copper.
notably nitric acid and concentrated sulphuric acid.
Exam Hint - Disproportionation should be defined as the
simultaneous oxidation and reduction of a single species or a
Practical 1 - The action of nitric acid on copper single substance.
Heat a piece of copper foil in a boiling tube with dilute nitric acid. The
copper dissolves to give a blue solution of copper(II) nitrate and brown The copper(I) state is particularly stable in three circumstances.
fumes of nitrogen dioxide. Caution! These fumes are toxic. • At high temperatures. Some copper(II) compounds decompose on
Copper atoms are oxidised to Cu2+ ions: at the same time, NO3- ions are heating into the corresponding copper(I) compounds, e.g.
reduced to molecules of NO which, with O2 from the air, become oxidised
2CuCl2(s) → 2CuCl(s) + Cl2(g)
to molecules of NO2.
• In insoluble compounds, e.g. Cu2O and CuCl.
Practical 2 - The action of hydrochloric acid on copper • In complex ions, e.g. [CuCl2]- and [Cu(NH3)2]+.
Heat a piece of copper foil in a boiling tube with dilute hydrochloric acid.
Notice that there is no apparent reaction. Redox chart
On the redox chart of copper (p 2), the principal compounds and ions
have been arranged in order of oxidation number.
Copper lies below hydrogen in the electrochemical series • Any movement up the chart represents an oxidation process, for
and will not liberate hydrogen from dilute acids. which an oxidising agent is required.
• Movement down the chart corresponds to reduction. For this, a
reducing agent is needed.
• Movement across the chart is neither oxidation nor reduction, and is
achieved with reagents such as dilute acids, NaOH(aq), NH3(aq) or
Na2CO3(aq).
1
Chem Factsheet

OXIDATION OUTLINE CHEMISTRY OF COPPER

NO. OF Cu
Heat
Conc. HCl NaOH(aq) or Excess NH3(aq)
+2 CuO [CuCl4]2−− H2O
[Cu(H2O)6]2++ Cu(OH)2 [Cu(NH3)4(H2O)2]2++
Black Solid Yellow Solution Blue Solution Limited NH3(aq) Acid Blue Precipitate Deep Blue Solution
Insoluble, Basic
Conc.
NaOH(aq)
Cu or Na2CO3(aq) KI(aq)
SO2 Air (O2)
CuCO 3
CuI + I 2
[Cu(OH)4]2−−
Blue-Green White Brown Blue Solution
Precipitate Precipitate Solution
Cl − Cl − Conc. HCl CuCl
+1
[CuCl4]3−− [CuCl3]2−− [CuCl2]− White Solid Conc. HCl Cu 2O NH3(aq) [Cu(NH3)2]+
H2O H 2O H2O Red-Brown Solid

2
Insoluble Insoluble Colourless
Dark Greeny - Brown Solution Solution
Dil. H2SO4 Dil. HNO3
H ,Co CuSO + Cu 4
Cu(NO ) + Cu3 2
2 r CO Blue Red - Brown Blue HNO3
Solution Precipitate Solution
Cu Cu(NO3)2 + NO
0
83. The Chemistry of Copper

O2
HCl(aq) or
Dil. HNO3
Dil. H SO
2 4
NO 2
REDUCTION
No Reaction Cu(NO3)2 + NO Brown
OXIDATION

Blue Air (O2) Gas

Solution
NO 2
Brown
Gas
83. The Chemistry of Copper Chem Factsheet

Oxides
Copper forms two oxides, both of which are basic. Copper(II) oxide, CuO
Copper(II) oxide is a black solid that can be prepared by heating
Cu(OH)2, CuCO3 or Cu(NO3)2. It is insoluble in water but dissolves in
dilute acids to give solutions of CuII salts.
Copper(I) oxide, Cu2O
This compound is prepared by reducing copper(II) salts in alkaline
solution.
Practical 8 - Preparation of CuSO4.5H2O
Pour dil. H2SO4 into a beaker, heat it, and add CuO with stirring until no
Practical 3 - Preparation of copper(I) oxide more will dissolve. Filter off the excess CuO. Transfer the filtrate to an
Pour into a boiling tube roughly equal volumes of Fehling’s solution A evaporating basin, place it on a tripod and gauze, and boil the solution
(copper(II) sulphate) and Fehling’s solution B (an alkaline solution of until crystals show signs of forming. Turn out the heat and allow the
potassium sodium tartrate) and mix. Then add a few drops of ethanal solution to cool and crystallise. Filter off the crystals, wash them with
and boil cautiously. The dark blue colour of the solution fades to give a a little deionised water, and dry.
reddish brown precipitate of copper(I) oxide.
A redox reaction occurs in which ethanal is oxidised to a salt of ethanoic
Exam Hint - ‘Crystallisation’ is different from ‘evaporation to
acid while CuII, in the form of a complex tartrate, is reduced to CuI which dryness’. The latter is not recommended because:
appears as Cu2O. • it gives poorly formed crystals;
• there may not be enough water left to act as water of crystallisation,
Remember - This reaction is used in organic chemistry to distinguish resulting in the formation of anhydrous copper(II) sulphate;
between aldehydes and ketones. Ketones will not reduce Fehling’s • impurities leave solution with the CuSO4.5H2O contaminating it.
solution because, unlike aldehydes, they are resistant to oxidation.

Copper(I) oxide is a reddish brown solid which is insoluble in water but Aqueous chemistry of copper(II)
soluble in acids.
[Cu(H 2 O) 6 ] 2+(aq) takes part in acid-base reactions
(deprotonation) with OH-(aq) and NH3(aq), ligand substitution with Cl−
Copper(I) oxide reacts with dilute sulphuric acid, dilute (aq), precipitation with CO32−(aq), and oxidation-reduction with I−(aq).
nitric acid and concentrated hydrochloric acid, but the products
are not copper(I) sulphate, copper(I) nitrate and copper(I) chloride.
Copper(I) sulphate and copper(I) nitrate disproportionate in water
(see above), while copper(I) chloride dissolves in conc. HCl(aq) to Practical 9 - CuII salts with OH-(aq)
give complex ions. Add dilute NaOH(aq) dropwise, with shaking, to a solution of a
copper(II) salt. A gelatinous pale blue precipitate of hydrated copper(II)
hydroxide is formed. Two protons are transferred from molecules of
coordinated water to hydroxide ions:

Practical 4 - Cu2O with dilute H2SO4 +2H+

Add Cu2O to dilute sulphuric acid in a test tube and warm gently. A
blue solution of copper(II) sulphate is formed. The reddish brown [Cu(H2O)6]2+(aq) + 2OH-(aq) → [Cu(OH)2(H2O)4](s) + 2H2O(l)
solid appears to remain unaltered, but in fact changes from Cu2O to Cu.
-2H+
Practical 5 - Cu2O with dilute HNO3
Add Cu2O to dilute nitric acid in a test tube. On warming, the Cu2O Exam Hint - Do not show this as a precipitation reaction. All transition
dissolves to give a clear blue solution of CuSO4 plus brown fumes of metal ions, and Al3+, react with OH-(aq) and NH3(aq) in acid-base
NO2. Caution! These fumes are toxic. From Practical 4, a red-brown (deprotonation) reactions.
deposit of Cu might be anticipated, but Practical 1 shows that Cu
dissolves in dil. HNO3.
Divide the precipitate of copper(II) hydroxide into two portions. To
one portion add concentrated NaOH(aq) and notice that it dissolves to
Practical 6 - Cu2O with concentrated HCl(aq) give a blue solution containing the tetrahydroxocuprate(II) ion:
Add conc. HCl(aq) to a little Cu2O and heat to obtain a dark greenish
brown solution containing various chloro-complex ions of copper(I) (p 4). [Cu(OH)2(H2O)4](s) + 2OH-(aq) → [Cu(OH)4]2-(aq) + 4H2O(l)

Copper(I) oxide is also attacked by concentrated aqueous ammonia Remember - Although CuO is basic, Cu(OH)2 is amphoteric.
because the NH3 molecule is a ligand and can coordinate to the Cu+ ion.

Heat the other portion of Cu(OH)2 and see how the colour changes from
Practical 7 - Cu2O with concentrated NH3(aq) blue to black as the hydroxide decomposes into the oxide:
Add conc. NH3(aq) to a little Cu2O in a test tube, warm gently, shake
carefully, and allow to stand. The solution above the unreacted Cu2O [Cu(OH)2(H2O)4](s) → CuO(s) + 5H2O(l)
will be blue. The diamminecopper(I) ion, [Cu(NH3)2]+, is formed, but
O2 from the air oxidises this to the dark blue copper(II) complex, Remember - Nearly all metal hydroxides decompose into the
[Cu(NH3 )4(H2 O)2] 2+. corresponding oxides on heating. The only ones which are stable to
heat are those of the alkali metals.

3
83. The Chemistry of Copper Chem Factsheet

Practical 10 - CuII salts with NH3(aq)

Add dilute NH3(aq) dropwise, with shaking, to a solution of a copper(II) salt. A gelatinous blue precipitate of hydrated copper(II) hydroxide is
formed at first in an acid-base reaction:

[Cu(H2O)6]2+(aq) + 2NH3(aq) → [Cu(OH)2(H2O)4](s) + 2NH4+(aq)

Now add excess dil. NH3(aq). The precipitate dissolves in a ligand substitution reaction to give a deep blue solution containing the
tetraamminediaquacopper(II) ion:

[Cu(OH)2(H2O)4](s) + 4NH3(aq) → [Cu(NH3)4(H2O)2]2+(aq) + 2OH-(aq) + 2H2O(l)

Add ethanol to this solution to obtain a deposit of tiny crystals of [Cu(NH3)4]SO4.H2O which can be filtered off and dried at room temperature.

Exam Hint - The [Cu(NH3)4(H2O)2]2+ ion has a distorted octahedral shape. NH3 molecules surround the Cu2+ ion in a square planar arrangement,
with H2O molecules above and below this plane but relatively far from Cu2+. Never describe this ion as ‘square planar’ because this description
ignores the H2O molecules.

Practical 11 - CuII salts with Cl−(aq) Copper(I) chloride, CuCl

Add concentrated HCl(aq) dropwise, with shaking, to a solution of a
copper(II) salt. The solution changes colour from blue to green and
then to yellow as a ligand substitution reaction occurs to form the • Copper(I) chloride is prepared by reducing [CuCl4] 2- with Cu or
tetrachlorocuprate(II) ion: SO2.
• It dissolves in conc. HCl(aq) to give a series of chloro-complexes.
[Cu(H2O)6]2+(aq) + 4Cl−(aq) ¾ [CuCl4]2-(aq) + 6H2O(l)
Blue Yellow
Practical 14 - Preparation of copper(I) chloride
The reaction is reversible. Add water to the [CuCl4]2- solution and To CuSO4(aq) in a boiling tube, add conc. HCl(aq) until the solution
notice that the colour changes back to green and then to blue. turns yellow. This produces [CuCl4]2-. Add a few pieces of copper
foil and boil for a few minutes until the solution changes colour to a
dark greenish brown. [CuCl4]2- becomes reduced to chloro-complexes
Practical 12 - CuII salts with CO32-(aq) of copper(I), e.g.
Add Na2CO3(aq) dropwise, with shaking, to a solution of a copper(II)
salt until the reagent is eventually present in excess. Blue-green [CuCl4]2-(aq) + Cu(s) → 2[CuCl2]-(aq)
copper(II) carbonate, which does not dissolve in excess Na2CO3(aq), is
formed in a precipitation reaction: Now pour the contents of the tube into cold water in a beaker. This
decomposes the chloro-complexes (see below) to give a white
Cu2+(aq) + CO32-(aq) → CuCO3(s)
precipitate of CuCl that can be filtered off, washed and dried.

Remember
• With Na2CO3(aq), all M2+(aq) ions give a precipitate of the metal
Practical 15 - CuCl with conc. HCl(aq)
carbonate, MCO3. M3+(aq) ions, in contrast, give a precipitate
Add conc. HCl(aq) to CuCl and shake. The white solid dissolves to give
of the metal hydroxide, M(OH)3, plus effervescence due to CO2(g).
a dark greenish brown solution containing three complex ions of copper(I)
• Precipitates formed with Na2CO3(aq) never dissolve in excess
in equilibrium with one another.
reagent.
Cl− Cl− Cl−
CuCl [CuCl2]- [CuCl3]2- [CuCl4]3-
H 2O H2 O H 2O

Practical 13 - CuII salts with I-(aq) At high concentrations of Cl- the dominant ion is [CuCl4]3-.
Add KI(aq) to a solution of a copper(II) salt, shake and allow to stand. At low concentrations of Cl- equilibrium is disturbed to the left hand
A white precipitate of copper(I) iodide settles underneath a brown side. Add water to the dark brown solution and see the reprecipitation
solution of iodine. A redox reaction occurs in which Cu2+ oxidises I− to of CuCl.
I2, and is itself reduced to Cu+:
Exam Hint - Do not confuse the tetrachloro-complexes of
2Cu2+(aq) + 4I−(aq) → 2CuI(s) + I2(aq) copper(I) and copper(II). They have different charges and
different colours.
Remember Cu I: [CuCl4 ]3- Dark greenish brown
• The product is copper(I) iodide; not copper(II) iodide. Cu II: [CuCl4 ]2- Yellow
• Copper(II) iodide does not exist. If it did, it would decompose
into copper(I) iodide and iodine by electron transfer from anion
to cation:

Cu++ I− I− → Cu+ I− + I (2I → I2)

• The same applies to any other salt (e.g. iron(III) iodide) consisting
of a cation that is easily reduced and an anion that is easily
oxidised.

4
83. The Chemistry of Copper Chem Factsheet

Questions
1 Devise a simple test, not requiring laboratory reagents, for distinguishing between solutions containing [CuCl4]2- and [CuCl4]3- ions. State what you
would observe in each case.

2 This question concerns the following ions: [Cu(H2O)6]2+ and [CuCl4]2-

A B
(a) Name A and B.
(b) State the colours of A and B.

(c) State the shapes of A and B.

(d) Explain the difference in coordination numbers.

3 U, V and W are three dark coloured solids, insoluble in water. They all dissolve in dilute nitric acid to give a blue solution of compound X. At the same
time U and W evolve brown fumes but V does not do so. With concentrated hydrochloric acid, U does not dissolve, but V dissolves to give a green
solution Y and W dissolves to to give a greenish brown solution Z.

(a) Identify U, V and W.

(b) Name the blue compound X.

(c) Write a balanced equation, with state symbols, for V dissolving in dilute nitric acid.

(d) Write down the formulae of all copper containing ions in solutions Y and Z.

4 Suggest why, when copper(I) chloride is shaken with water, the aqueous extract is green.

5 Explain why copper(II) sulphate-5-water is coloured, although copper(I) sulphate and anhydrous copper(II) sulphate are both colourless.

occupied. If there are no vacancies in the upper set, promotion cannot occur.
Anhydrous CuSO4 contains simple Cu2+ ions (no ligands), so there is no splitting of the d-orbitals. The Cu+ ion in Cu2SO4 has all its 3d orbitals fully
and therefore appears coloured. [Cu(H2O)4]2+ in CuSO4.5H2O absorbs the red and yellow frequencies but transmits blue and green.
frequencies of white light can be absorbed in promoting electrons from the lower to the upper set. Transmitted light is deficient in these frequencies
3d electrons are split by ligands into two sets of d-orbitals. There are three orbitals in the lower energy set and two in the upper set. Certain 5

[CuCl4]2- (yellow). O2 from the air assists the oxidation of CuI to CuII.
CuCl dissolves slightly to give a solution containing Cu+ and Cl-. Cu+ disproportionates giving [Cu(H2O)6]2+ (blue) which, with Cl-, gives some 4

Y contains [Cu(H2O)6]2+ and [CuCl4]2-. Z contains [CuCl2]-, [CuCl3]2- and [CuCl4]2-. (d)
CuO(s) + 2HNO3(aq) → Cu(NO3)2(aq) + H2O(l) (c)
Copper(II) nitrate (b)
U = Cu V = CuO W = Cu2O (a) 3

The Cl- ion is a larger ligand than the H2O molecule and fewer of them can be packed around the small Cu2+ cation. (d)
A is octahedral/distorted octahedral. B is tetrahedral. (c)
A is blue. B is yellow. (b)
A = hexaaquacopper(II) B = tetrachlorocuprate(II) (a) 2

Add water. Solution of [CuCl4]2- changes colour to green and then blue. Solution of [CuCl4]3- gives a white precipitate. 1
Answers

Acknowledgements: This Factsheet was researched and written by John Brockington. Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire,
TF1 1NU. ChemistryFactsheets may be copied free of charge by teaching staff or students, provided that their school is a registered subscriber. No part of these
Factsheets may be reproduced, stored in a retrieval system, or transmitted, in any other form or by any other means, without the prior permission of the
publisher. ISSN 1351-5136

5
 Chem Factsheet
www.curriculum-press.co.uk
Cl——Cl → 2Cl⋅

Number 84
Free Radical Subsitution & Polymerisation
To succeed in this topic you need to: Initiation
• understand the nature of the covalent bond ( Factsheet 5);
• know the reactions of alkanes (Factsheet 16); During initiation, free radicals are formed from molecules
• understand the principle of addition polymerisation (Factsheet 18). by the homolytic fission (homolysis) of a single covalent bond.

After working through this Factsheet you will: When a covalent bond between two atoms undergoes homolytic fission,
• know that free radical substitution occurs in three stages; it is broken symmetrically so that each of the bond pair of electrons goes
• know that free radicals are formed at the initiation stage by homolytic to one of the atoms so as to give a pair of free radicals.
fission;
• know that there are two reactions at the propagation stage, each of which Definition Homolytic fission is the breaking of a covalent
requires a free radical; bond so as to produce two fragments that are the same as each other
• know that termination occurs by the coupling of free radicals; in the sense that they are both free radicals.
• understand the mechanism of free radical polymerisation.
In the chlorination of methane, chlorine molecules break homolytically to
Free radical substitution reactions are shown by alkanes, e.g. give chlorine free radicals:
methane, and alkylaromatic hydrocarbons, e.g. methylbenzene.
Cl——Cl → 2Cl⋅

A well known example is the chlorination of methane in the presence of In this equation, the movement of a single electron is symbolised by a
ultraviolet light: curly half-arrow. It must start from the origin of the electron and point
towards its final location.
CH4(g) + Cl2(g) → CH3Cl(g) + HCl
Exam Hint - Take care not to use a curly arrow with a full arrowhead
Remember - ‘Substitution’ means ‘replacement’. A substitution reaction because this symbolises the movement of a pair of electrons.
should be defined as one in which an atom or group of atoms belonging
to the substrate (the molecule which is being attacked) is replaced by Notes on homolytic fission
another atom or group from the reagent. • The two fragments produced may not be identical. The splitting of
the iodine chloridemolecule into an iodine free radical and a chlorine
free radical is still an example of homolytic fission:
In a free radical substitution, the reagent provides an attacking species called
a free radical.
I——Cl → I⋅ + Cl⋅
Definition A free radical is an atom or group of atoms with an • The weakest bond is always broken preferentially. In the chlorination of
unpaired electron. methane, the Cl-Cl bond, with a bond dissociation enthalpy of 242 kJ
mol-1, breaks in preference to the C-H bond (∆Hêdiss = 435 kJ mol-1).
An example is the chlorine free radical, supplied by the reagent Cl2 (chlorine
gas) when it is heated to high temperatures or exposed to ultraviolet light. Propagation
This is just a chlorine atom. The electronic configuration 1s2, 2s2, 2p6, 3s2,
3p5 shows that there is an odd number of 3p electrons, so one of them must There are two reactions at the propagation stage.
be unpaired. The symbol for a chlorine free radical is Cl⋅, where the superscript • In each of these, one free radical is consumed while another is
dot symbolises the unpaired electron. formed.
• Each consumes a molecule of initial reactant and liberates a
Remember - A chlorine atom and a chlorine free radical are one and the molecule of end product.
same thing. We refer to a chlorine free radical, Cl⋅, when we want to
emphasise the unpaired electron. In the chlorination of methane, propagation proceeds as follows.
Reaction 1 Cl⋅ + CH4 → CH3⋅ + HCl
Other examples of free radicals include the methyl free radical, CH3⋅, and the Reaction 2 CH3⋅ + Cl2 → CH3Cl + Cl⋅
ethyl free radical, CH3CH2⋅.
As for initiation, where alternative reactions are possible, energy
Every free radical substitution reaction proceeds in three stages. requirements dictate what occurs. In the chlorination of methane, the
• Initiation following propagation reaction satisfies the basic principles:
• Propagation Cl⋅ + CH4 → CH3Cl + H⋅
• Termination
Nevertheless, it does not occur because it is energetically unfavourable.
ultraviolet light provides sufficient energy to break Cl-Cl but not C-H
Remember - Hydrogen free radicals are uncommon reaction
intermediates because a large amount of energy is needed to form
them, i.e break a C-H bond.

1
84. Free Radical Subsitution & Polymerisation Chem Factsheet

Termination
C6H5CH3 + Cl2 → C6H5CH2Cl + HCl
Termination occurs by coupling, i.e. the joining together of C6H5CH2Cl + Cl2 → C6H5CHCl2 + HCl
pairs of free radicals to give molecules.
C6H5CHCl2 + Cl2 → C6H5CCl3 + HCl
Chlorination can be stopped at the end of either intermediate step, with a
For the CH4 + Cl2 reaction, there are three possibilities: good yield of C6H5CH2Cl or C6H5CHCl2, when the observed increase in
2Cl⋅ → Cl2 mass corresponds to that which is calculated.

2CH3⋅ → CH3CH3 Exam Hint- There are two common sorts of questions on free radical
ethane subsitution
CH3⋅ + Cl⋅ → CH3Cl • You may be asked to write mechanistic equations for a given
reaction, generally for 3 marks. If so, give the equation for initiation,
chloromethane (first substitution product) both equations for propagation, and one of the equations for
Notes on coupling termination.
• Alternatively, you may be asked to explain the mechanism of a
• Coupling is the opposite of homolytic fission. particular reaction, typically for about 5 marks. In this case, you
• Coupling takes place from the start, but becomes dominant in the later must include mechanistic equations (as before) and, to score
stages of the reaction when the concentration of reactants has fallen to additional marks, say that the reaction is a free radical substitution,
a low level. name the three stages, and include the terms ‘homolytic fission’
• Although some chloromethane is formed by coupling, most of it is and ‘coupling’ where appropriate.
produced at the propagation stage.
Free radical polymerisation
Exam Hint - Examiners may focus on the formation of ethane at the
Alkenic compounds (i.e. those whose molecules contain a C=C bond) can
termination stage. You can be asked to explain why, when methane is
undergo addition polymerisation to give high polymers. In the presence of
chlorinated, the product always contains a trace of ethane. Alternatively,
organic peroxide catalysts, polymerisation occurs by a mechanism very
you can be asked about evidence for a free radical mechanism, in
similar to that of free radical substitution.
which case you should quote the formation of ethane which could
happen only by the coupling of two CH3⋅ free radicals.
Free radical polymerisation takes place by a three stage
mechanism.
• Initiation
Further chlorination of methane
• Propagation
When a mixture of methane and chlorine is exposed to ultraviolet light, four
• Termination
reactions occur simultaneously:

A CH4 + Cl2 → CH3Cl + HCl The polymerisation of ethene to give poly(ethene) is a simple example.
B CH3Cl + Cl2 → CH2Cl2 + HCl nCH2=CH2 → —CH2-CH2—n

C CH2Cl2 + Cl2 → CHCl3 + HCl Initiation

Free radicals (R⋅) are formed from the catalyst by homolytic fission. (Details
D CHCl3 + Cl2 → CCl4 + HCl
are not needed.)
Consequently, the product is always a mixture of chloromethane,
dichloromethane, trichloromethane and tetrachloromethane, although with Propagation
a limited amount of chlorine it is predominantly chloromethane and with a An infinite number of reactions can occur, in each of which a free radical
large excess of chlorine it is mainly tetrachloromethane. combines with a molecule of monomer to give a larger free radical. The first
of these reactions involves the free radical from the catalyst:
The reason is that, as soon as chloromethane starts to accumulate, reaction
B commences. As soon as dichloromethane accumulates, reaction C begins. R⋅ + CH2 CH2 → R-CH2-CH2⋅
And so on.
The π-bond of the alkene is broken homolytically. One electron joins the
unpaired electron of the free radical to form a new covalent bond, while the
Remember - The chlorination of methane does not occur in clearly
other remains (unpaired) on the terminal carbon atom.
defined steps and is said to be ‘non-stepwise’.
In the next reaction, this new free radical behaves in a similar way:

This is easily explained in mechanistic terms. R-CH2-CH2⋅ + CH2 CH2 → R-CH2-CH2-CH2-CH2⋅

The process can be repeated indefinitely to give very long chain free radicals.
Chlorine free radicals produced at the propagation stage
(Reaction 2) can do two things. Termination
• React with some more CH4 to give more CH3Cl. Any two free radicals may couple so as to give a molecule of polymer, e.g.
• React with CH3Cl by a similar mechanism to give CH2Cl2,
dichloromethane R-CH2-CH2⋅ + CH2-CH2-R → R-CH2-CH2-CH2-CH2-R
⋅

Propagation steps: Cl⋅ + CH3Cl → CH2Cl⋅ + HCl Polymers are therefore formed with varying chain lenghts.
CH2Cl + Cl2 → CH2Cl2 + Cl
⋅ ⋅
Remember
• Although every propagation reaction consumes one free radical and
generates another, it does not give a molecule of the final product.
Some free radical substitutions are stepwise, e.g. the chlorination of
• The product, i.e. the polymer, is formed only at the termination stage.
methylbenzene in ultraviolet light.
2
 3
publisher. ISSN 1351-5136
Factsheets may be reproduced, stored in a retrieval system, or transmitted, in any other form or by any other means, without the prior permission of the
TF1 1NU. ChemistryFactsheets may be copied free of charge by teaching staff or students, provided that their school is a registered subscriber. No part of these
Acknowledgements: This Factsheet was researched and written by John Brockington. Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire,
Answers
1 Initiation Cl2 → 2Cl⋅
Propagation Cl⋅ + C6H5CH3 → C6H5CH2⋅ + HCl
C6H5CH2⋅ + Cl2 → C6H5CH2Cl + Cl⋅
Termination 2Cl⋅ → Cl2
2C6H5CH2⋅ → C6H5CH2CH2C6H5
C6H5CH2⋅ + Cl⋅ → C6H5CH2Cl
2 For two reasons. First, the chlorination of methane is exothermic. Therefore, when the reaction starts, heat is evolved and the consequent rise of
temperature increases the rate of reaction. Second, many chlorine free radicals are released simultaneously, each of which can react with a molecule
of methane. As a result, a lot of energy is released all at once.
3 (a) In any chemical reaction, energy is needed to break bonds but is released when bonds are formed. Energy changes are therefore as follows.
Equation 1 +412 -431 = -19 kJ mol-1
Equation 2 +412 -338 = +74 kJ mol-1
Because the reaction shown by Equation 1 is exothermic (while that for Equation 2 is endothermic) it is energetically favoured.
(b) If Equation 1 were correct, the product would contain traces of butane, formed by coupling of CH3CH2⋅ radicals. If Equation 2 were correct, it
would contain traces of hydrogen, formed by the coupling of H⋅ radicals.
4 Propagation
R⋅ + CH=CH2 → R-CH-CH2⋅
 
CH3 CH3
R-CH-CH2⋅ + CH=CH2 → R-CH-CH2-CH-CH2⋅
   
CH3 CH3 CH3 CH3
Termination
2R-CH-CH2-CH-CH2⋅ → R-CH-CH2-CH-CH2-CH2-CH-CH2-CH-R
     
CH3 CH3 CH3 CH3 CH3 CH3
5 Termination reactions can take place at any time. Some occur before free radicals have had a chance to grow, to give short polymer chains of low Mr.
However, some free radicals survive long enough to accept a great many monomer molecules and, when they eventually couple together, the result
is a long chain polymer of high Mr. The product is always a mixture of low and high polymers with a range of Mr values.
Explain, by referring to the mechanism of their formation, why addition polymers are assigned an average relative molecular mass. 5
Write equations for propagation and termination reactions when propene is polymerised in the presence of a catalyst that provides free radicals, R⋅. 4
(b) Explain how your prediction could be confirmed by analysis of the final product.
C-H = 412 C-Cl = 338 H-Cl = 431
(a) Use the following bond dissociation enthalpies (all in kJ mol-1) to predict which of these equations is likely to be correct.
Equation 2 Cl⋅ + CH3CH3 → H⋅ + CH3CH2Cl
Equation 1 Cl⋅ + CH3CH3 → CH3CH2⋅ + HCl
In the propagation stage of the chlorination of ethane there are two possible first reactions, as shown by Equations 1 and 2. 3
Suggest why an explosion occurs when methane is chlorinated in high intensity ultraviolet light. 2
Write mechanistic equations for the conversion of methylbenzene to (chloromethyl)benzene. 1
Questions
Chem Factsheet 84. Free Radical Subsitution & Polymerisation
 Chem Factsheet
www.curriculum-press.co.uk Number 85
Salt Hydrolysis
To succeed in this topic you need to understand:
• bonding (covered in Factsheet 5); Remember
• the Brønsted-Lowry theory of acids and bases (covered in Factsheet • δ− represents a small amount of negative charge which is unspecified
25); but less than the charge on an electron. (Conversely for δ+.)
• the pH scale of acidity and alkalinity (covered in Factsheet 25); • The molecule as a whole is electrically neutral.
• complex ion formation (covered in Factsheet 38).
Negatively charged oxygen atoms are attracted to cations, and positively
After working through this Factsheet you will: charged hydrogen atoms to anions (Fig 1). There are approximately six
• know that there are two ways in which ions can become hydrated; water molecules in the primary (i.e. first) hydration shell.
• understand why salts derived from a weak acid and a strong base are
alkaline in solution; Fig 1. The dissolving of an ionic compound A+ B- in water
• understand why salts derived from a strong acid and a weak base are
acidic in solution;
• understand why salts derived from a strong acid and a strong base are B− B−
neutral in solution; A+
A + B− A + B − A + A + B− A + B− A +
• understand why salts derived from a weak acid and a weak base are ¾ ¾ A +
B−
approximately neutral in solution. B − A + B − A + B− B− A + B− A + B−
B−
Hydration of ions B− A+
Before you can understand the topic of salt hydrolysis, you need to know A+ B− (s) A+ B− (s)
Dry solid Wet solid A+
about the hydration of ions in aqueous solution.
H H A+(aq) B−(aq)
represents a water molecule Aqueous solution
Remember - Hydration is defined as ‘combination with water’. O

Anions, such as CO32−, Cl−, SO42− and NO3−, are hydrated by ion-dipole
When a salt dissolves in water, it dissociates, i.e. its ions break away from attraction only. The same applies to all cations of the s-block elements,
their regular arrangement in the crystal and become free to move about in the except for Be2+.
water. For a salt An+ Bn-, this is represented by the equation:
2. For all other cations, notably Al3+ and cations of the transition
elements, ion-dipole attraction is reinforced by coordination, i.e. the
AB(s) + aq ¾ An+(aq) + Bn-(aq)
formation of coordinate bonds (dative covalent bonds) between H2O
molecules and the cation. The reason is that these cations are relatively
The equation is written with two half-arrows because the change is reversible.
small and have a charge of at least 2+. They therefore have a high
The reverse change, i.e. the joining together of ions from solution to give the
surface charge density, i.e. high density of positive charge on the
crystalline solid, occurs during crystallisation.
surface. (Some people say that they have a high charge:radius ratio.)
Exam Hint - Do not refer to dissociation in this context as ‘ionisation’.
Exam Hint - The term ‘surface charge density’ refers only to ions.
Ionisation means, literally, ‘ion formation’, but all that happens here
Never apply it to atoms or molecules, because such particles are
is the separation of ions which are already present in the crystal.
uncharged and cannot possibly have a charge density.

Ions exist in solution, not as simple ions, but as hydrated ions, i.e. surrounded Any cation with a high surface charge density attracts a lone pair of
by shells of water molecules: hence the symbols An+(aq) and Bn-(aq) in the electrons from the outer shell of the oxygen atom of a water molecule so
above equation. strongly that the lone pair can be donated from one to the other so that a
coordinate bond is formed.
Why do ions become hdrated?
There are two causes. Remember - A coordinate bond is a special kind of covalent bond, in
which both electrons of the bond originate from one atom. Once
1. Common to all ions is an effect known as ion-dipole attraction. The
formed, a coordinate bond is identical with a covalent bond.
water molecule is a dipole; literally, one with two electrical poles. Because
oxygen is more electronegative than hydrogen, the electron pair of each
Generally, as for Al3+, six H2O molecules are coordinated to a cation so
O-H bond is drawn towards the oxygen atom. Consequently, it acquires
that an octahedral complex is formed.
a slight negative charge, while each hydrogen atom has a slight positive
charge: H2O
δ+ δ+ The hydrated Al3+ ion
H H H2O OH2
.. δ− δ− .. Al3+
O
H2O OH2
H2O
1
85 Salt Hydrolysis Chem Factsheet

Because cations that are hydrated by coordination are complex ions, they Practical 1 - Hydrolysis of sodium ethanoate
can be given formulae and names on the IUPAC system: indeed, to Dissolve a few crystals of sodium ethanoate in water at room
understand the chemistry of salt hydrolysis, this is vital. The hydrated temperature and measure the pH of the solution with a pH meter, pH
aluminium ion, for example, often represented by the symbol Al3+(aq), has paper or universal indicator.
the formula [Al(H 2 O) 6 ] 3+ and is named systematically as the
hexaaquaaluminium(III) ion. Note In all Practicals in the Factsheet it is advisable to use freshly
deionised water or, failing that, freshly drawn tap water. Water that
An important difference betwween ions that are hydrated by has been standing is likely to be slightly acidic due to the absorption of
ion-dipole attraction only, and those where the attraction is reinforced CO2 from the air.
by coordination, is that the latter are acids on the Brønsted-Lowry
theory, i.e. they are proton donors. Sodium ethanoate dissociates in solution:

The high surface charge density on the cation causes the electrons of the CH3COONa(s) + aq ¾ CH3COO−(aq) + Na+(aq)
metal-oxygen bond to be drawn towards the metal. This in turn increases
polarisation of the O-H bonds (Fig 2). CH3COOH is a weak acid (proton donor); therefore its anion, CH3COO−
, is a strong conjugate base (proton acceptor). This causes ethanoate ions
Fig 2. Electron shifts in a complex aqua-cation to accept protons from water molecules:
δ+ δ+
H H CH3COO-(aq) + H2O(l) ¾ CH3COOH(aq) + OH−(aq)
δ−

O Consequently, [OH−] > [H3O+], i.e. the solution is alkaline.

Ignore Na+(aq). This cation is hydrated by ion-dipole attraction only and
is neither an acid nor a base.
M n+
Remember - Opposites go together.
• A strong acid is related to a weak conjugate base, e.g. HCl & Cl−.
• A weak acid is related to a strong conjugate base, e.g. CH3COOH
This causes weakening of the O-H bonds. You can argue that H atoms & CH3COO-.
become more like protons and hence more easily lost as protons in the • A strong base is related to a weak conjugate acid, e.g. OH− & H2O.
presence of a base, i.e. a proton acceptor. • A weak base is related to a strong conjugate acid, e.g. NH3 & NH4+.
Remember - On the Brønsted-Lowry theory:
• an acid is a species (molecule or ion) that can donate protons.
• a base is a species that can accept protons. Practical 2 - Hydrolysis of sodium carbonate and sodium
• neutralisation is a process of proton transfer from acid to base. hydrogencarbonate
• every acid is related to a conjugate base, i.e. the species formed Dissolve small amounts of sodium carbonate and sodium
from it by loss of a proton. For most acids, this is the anion produced hydrogencarbonate separately in water. Measure the pH value of each
on ionisation. solution and try to account for the difference.
• every base is related to a conjugate acid, i.e. the species formed
from it by gain of a proton. Sodium carbonate dissociates:
Na2CO3(s) + aq ¾ 2Na+(aq) + CO32−(aq)

Salt hydrolysis The carbonate ion is the conjugate base of an extremely weak acid (carbonic
acid). It strongly attracts protons from H2O molecules to give a solution
Salt hydrolysis is essentially the reverse of neutralisation. with a pH of ~12:

CO32−(aq) + H2O(l) ¾ HCO3−(aq) + OH−(aq)

Neutralisation
Acid + Base → Salt + Water In contrast, the hydrogencarbonate ion, with its single negative charge, has
a lower surface charge density than the carbonate ion and is a considerably
Salt hydrolysis
weaker base. It exerts a feeble attraction for protons and the pH of the
Salt + Water → Acid + Base solution only reaches ~8.5.

or Salt + Water → Acid + Basic salt Exam Hint - Beware of questions in which you are asked how, in the
laboratory, you would distinguish between Na2CO3 and NaHCO3.If
you are allowed to use any test, measuring the pH values of their
Both acids and bases can be classed as strong or weak, depending upon solutions provides a good answer. If, however, you are asked for a
their degree of dissociation in water. Salts can therefore be divided into chemical test, this will not do. For such a question you’d need to
four broad categories. suggest a reagent such as magnesium sulphate solution. This would
give a white precipitate of MgCO3 with CO32-(aq), but no precipitate
Salts derived from a weak acid and a strong base with HCO3-(aq) because magnesium hydrogencarbonate is soluble in
Such salts undergo partial hydrolysis to give an alkaline solution. An water.
example is sodium ethanoate, which is derived from ethanoic acid (a weak
acid) and sodium hydroxide (a strong base).

2
85 Salt Hydrolysis Chem Factsheet

Salts derived from a strong acid and a weak base Practical 5 - Hydrolysis of iron(II) chloride and iron(III) chloride
All such salts undergo partial hydrolysis to give an acidic solution. However, Dissolve small amounts of iron(II) chloride and iron(III) chloride
for study purposes, you must distinguish between two kinds of weak separately in water. Measure the pH of each solution and try to
bases. account for the difference.

• Weak covalent bases, e.g. ammonia and amines. Despite being very Both salts dissociate in solution to give hexaaquacations:
soluble in water, such compounds give a low concentration of OH−
FeCl2(s) + 6H2O(l) ¾ [Fe(H2O)6]2+(aq) + 2Cl−(aq)
ions in solution because of a low degree of ionisation:
FeCl3(s) + 6H2O(l) ¾ [Fe(H2O)6]3+(aq) + 3Cl−(aq)
NH3(aq) + H2O(l) × NH4+(aq) + OH−(aq)
Like [Al(H2O)6]3+, both hydrated cations are acidic, e.g.
• Weak ionic bases, e.g. aluminium hydroxide and transition metal
[Fe(H2O)6]2+(aq) + H2O(l) ¾ [Fe(OH)(H2O)5]+(aq) + H3O+(aq)
hydroxides. Like ammonia and the amines, these compounds give a
low concentration of OH- ions in solution but for a very different Compared with Fe2+, however, Fe3+ has a greater charge and a smaller
reason, namely their low solubility in water. radius. It therefore has a higher surface charge density than Fe2+ and causes
more polarisation of the O-H bonds of coordinated H2O molecules. Proton
Salts derived from a strong acid and a weak covalent base transfer to solvent H2O molecules can therefore occur more readily and the
An example is ammonium chloride, which is derived from hydrochloric solution has a lower pH.
acid (a strong acid) and ammonia (a weak base).
Salts derived from a strong acid and a strong base
Such salts do not undergo hydrolysis and their solutions are neutral. An
Practical 3 - Hydrolysis of ammonium chloride
example is sodium chloride, derived from hydrochloric acid and sodium
Dissolve a few crystals of ammonium chloride in water and measure
hydroxide.
the pH of the solution.
Practical 6 - Non-hydrolysis of sodium chloride
Ammonium chloride dissociates in solution:
Dissolve a little sodium chloride in water and measure the pH of the
solution.
NH4Cl(s) + aq ¾ NH4+(aq) + Cl−(aq)
Sodium chloride dissociates:
NH3 is a weak base; therefore its related cation, NH4+, is a strong conjugate
acid which can donate a proton to a water molecule: NaCl(s) + aq ¾ Na+(aq) + Cl-(aq)

NH4+(aq) + H2O(l) ¾ NH3(aq) + H3O+(aq) However, Na+(aq) is not an acid; neither is Cl-(aq) a base. There is therefore
no proton transfer of any kind, i.e. no chemical reaction, and the pH of the
Consequently, [H3O+] > [OH−], i.e. the solution is acidic. solution is that of pure water (7.0).
Ignore Cl-(aq). This is the conjugate base of an extremely strong acid (HCl) Salts derived from a weak acid and a weak base
and is therefore an extremely weak base. Again, for study purposes, you need to distinguish between weak covalent
bases and weak ionic bases.
Remember - For all practical purposes, HCl, HBr, HI, H2SO4 and
HNO3 are almost completely dissociated in aqueous solution. Salts derived from a weak acid and a weak covalent base
Such salts undergo extensive hydrolysis to give an approximately neutral
solution. An example is ammonium ethanoate, derived from ethanoic acid
Salts derived from a strong acid and a weak ionic base and ammonia.
An example is aluminium chloride, which is derived from hydrochloric acid
and aluminium hydroxide. Practical 7 - Hydrolysis of ammonium ethanoate
Dissolve a little ammonium ethanoate in water and measure the pH of
Practical 4 Hydrolysis of aluminium chloride the solution.
Dissolve in water a few crystals of aluminium chloride-6-water and
Ammonium ethanoate dissociates:
measure the pH of the solution.
CH3COONH4(s) + aq ¾ CH3COO-(aq) + NH4+(aq)
The salt dissociates in solution:
CH3COO-(aq) is a base and accepts protons:
AlCl3.6H2O(s) + aq ¾ [Al(H2O)6] (aq) + 3Cl (aq)
3+ -
CH3COO-(aq) + H2O(l) ¾ CH3COOH(aq) + OH-(aq)

As explained on p 2, the hydrated aluminium ion is an acid on the Brønsted- This change by itself would make the solution alkaline; but it is not the only
Lowry theory. One of its coordinated water molecules ionises into H+ and reaction. NH4+(aq) is an acid and donates protons:
OH-. OH- stays where it is, i.e. bonded to aluminium, but H+ (a proton) is NH4+(aq) + H2O(l) ¾ NH3(aq) + H3O+(aq)
donated to a molecule of solvent water:
This change tends to make the solution acidic. The two effects virtually
[Al(H2O)6]3+(aq) + H2O(l) ¾ [Al(OH)(H2O)5]2+(aq) + H3O+(aq) cancel each other out, with the result that [H3O+] ≈ [OH-], i.e. the solution
is approximately neutral.
Consequently, [H3O+] > [OH-], i.e. the solution is acidic.
Salts derived from a weak acid and a weak ionic base
Again, Cl-(aq) should be disregarded for the reason given above.
An example would be aluminium carbonate, derived from carbonic acid and
aluminium hydroxide. Such salts are completely hydrolysed in the presence
Exam Hint - When writing the formulae of complex ions containing
of water and, for this reason, are often said to be ‘non-existent’.*
different sorts of ligands, ionic ligands (e.g. OH-) should be written
before molecular ligands, (e.g. H2O). * This statement is debatable. Aluminium oxide is known to absorb carbon
dioxide. Is aluminium carbonate formed? Possibly. But it is certain that such
salts cannot exist in the presence of water.
3
85 Salt Hydrolysis Chem Factsheet

Remember
• Salt derived from a weak acid and a strong base
The base is dominant and the solution is alkaline (pH > 7.0)
• Salt derived from a strong acid and a weak base
The acid is dominant and the solution is acidic (pH < 7.0)
• Salt derived from a strong acid and a strong base
Neither acid nor base is dominant and the solution is neutral (pH = 7.0)
• Salt derived from a weak acid and a weak base
Neither acid nor base is dominant and the solution is more or less neutral (pH ≈ 7.0)

NOTE Although these rules of thumb are useful, they must never be used in an examination to explain salt hydrolysis.

Questions
1 Explain why the hydrated beryllium ion, unlike other cations of the s-block elements, is a complex ion.

2 State whether you would expect each of the following salts to be acidic, alkaline or neutral in aqueous solution.

(a) CuSO4 (b) NaNO3 (c) KBr (d) ZnCl2 (e) (NH4)2SO4 (f) C6H5NH3+ Cl− (g) Li2CO3

3 Unlike many other salts derived from a weak acid and a weak base, ammonium carbonate gives an alkaline solution. Explain this.

4 Unlike many other salts derived from a strong acid and a strong base, sodium hydrogensulphate gives a strongly acidic solution. Explain this.

5 “Aluminium chloride dissociates in solution to give aluminium ions and chloride ions:

AlCl3 ¾ Al3+ + 3Cl− .....................................................................................(1)

Water ionises to a small extent into hydrogen ions and hydroxide ions:

H2O ¾ H+ + OH− .......................................................................................(2)

Oppositely charged ions attract one another. H+ and Cl- cannot join up to give molecules of HCl because HCl is a very strong acid and completely
dissociated in solution, but Al3+and OH- ions can join together to give solid aluminium hydroxide:

Al3+ + 3OH− → Al(OH)3 ..........................................................................(3)

This disturbs Equilibrium (2) to the right, so that more water ionises to replace the lost OH- ions. In this way the solution contains many more
hydrogen ions than hydroxide ions and is strongly acidic.”
This extract from an old textbook contains one serious error of fact and one serious error of theory. What are they?

acid NH4+, and Reaction 2 occurs to a greater extent than Reaction 1.

acid. Hence the conjugate base CO32− is stronger than than the conjugate
but a hydrated complex ion, [Al(H2O)6]3+. Although ammonia is a weak base, carbonic acid is an extremely weak
Error of theory The aluminium ion in solution is not a simple ion, Al3+,
stand.) CO32-(aq) + H2O(l) ¾ HCO3−(aq) + OH−(aq) (Reaction 2)
hydroxide is formed over a period of time if thesolution is allowed to and the latter is a base:
insoluble aluminium hydroxide. (Note A small amount of aluminium NH4+(aq) + H2O(l) ¾ NH3(aq) + H3O+(aq) (Reaction 1)
transparent). It is not cloudy, as it would be if it contained particles of in solution. The former is an acid:
Error of fact A solution of aluminium chloride is completely clear (i.e. 5 Ammonium carbonate dissociates to give NH4+(aq) and CO32−(aq) ions 3
acid. (g) Alkaline
The process is identical to the second stage in the ionisation of sulphuric (a) Acidic (b) Neutral (c) Neutral (d) Acidic (e) Acidic (f) Acidic 2
HSO4-(aq) + H2O(l) ¾ SO42−(aq) + H3O+(aq) so that coordinate bonds are formed.
hydrogen atom, it can function as an acid: pairs of electrons from the oxygen atoms of surrounding water molecules
acid, and is therefore an extremely weak base. However, because of its therefore has the highest surface charge density and can attract lone
ions in solution. HSO4− is the conjugate base of H2SO4, a very strong left to right across the Periodic Table and also up the groups.) Be2+
Sodium hydrogensulphate dissociates to give Na+(aq) and HSO4-(aq) 4 Be2+ is the smallest of the s-block cations. (Ionic radii decrease from 1
Answers

Acknowledgements: This Factsheet was researched and written by John Brockington. Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire,
TF1 1NU. ChemistryFactsheets may be copied free of charge by teaching staff or students, provided that their school is a registered subscriber. No part of these
Factsheets may be reproduced, stored in a retrieval system, or transmitted, in any other form or by any other means, without the prior permission of the
publisher. ISSN 1351-5136
4
 Chem Factsheet
www.curriculum-press.co.uk Number 86
Deprotonation (Acid-Base Reactions)
To succeed in this topic you need to understand: Table 1 shows the precipitates that are formed with limited amounts of
• the Brønsted-Lowry theory of acids and bases (Factsheet 25); NaOH(aq).
• the basics of transition elements and complex ions (Factsheet 28);
• salt hydrolysis (Factsheet 85). Table 1 - Some insoluble metal hydroxides
Cation Formula of precipitate Colour
After working through this Factsheet you will:
3+
•· have a more extensive knowledge of deprotonation reactions (Factsheet Al (aq) Al(OH)3 White
46); Cr3+(aq) Cr(OH)3 Grey-green
• be able to describe what is observed when solutions containing each of Fe2+(aq) Fe(OH)2 Green*
the following cations:
Al3+, Cr3+, Fe2+, Fe3+, Co2+, Ni2+, Cu2+ Fe3+(aq) Fe(OH)3 Brown
2+
is reacted with each of the following reagents: Co (aq) Co(OH)2 Blue
NaOH(aq) Ni2+(aq) Ni(OH)2 Green
NH3(aq) 2+
Na2CO3(aq) Cu (aq) Cu(OH)2 Blue
• understand the chemistry of each reaction in terms of deprotonation,
ligand substitution or precipitation.
* On standing, this precipitate changes colour, first to bottle-green and
Exam Hint - You may be asked to describe what you would observe then to brown, because of aerial oxidation.
when any of the three reagents is added to a solution containing any of
these cations, and then explain the chemistry. In all cases deprotonation occurs.Protons are transferred
To describe observations accurately, it is important that you have successively from coordinated water molecules to hydroxide ions.
either carried out the tests yourself or seen them demonstrated by a This gives, initially, hydroxo-complex ions in solution, and finally
teacher. molecules of solid, hydrated metal hydroxides.

What exactly is a deprotonation reaction? Ionic equations can be written for each stage, e.g.
• M2+ and M3+ cations exist in solution as aqua-complexes; [M(H2O)6]2+
or [M(H2O)6]3+. [Al(H2O)6]3+(aq) + OH−(aq) ¾ [Al(OH)(H2O)5]2+(aq) + H2O(l) ............(1)
• Nearly all such cations form precipitates of metal hydroxides when
[Al(OH)(H2O)5]2+(aq) + OH−(aq) ¾ [Al(OH)2(H2O)4]+(aq) + H2O(l) ....(2)
treated with OH-(aq), NH3(aq) or CO32-(aq). (M2+(aq) with CO32-(aq) is
an exception.) [Al(OH)2(H2O)4]+(aq) + OH−(aq) ¾ [Al(OH)3(H2O)3](s) + H2O(l).....(3)
• In these reactions the hydrated metal cation loses one or more protons to
the reagent. For this reason, they are termed deprotonation reactions. Remember - When writing the formulae of complex ions with two
• The hydrated metal cation behaves as an acid on the Brønsted-Lowry sorts of ligands, anionic ligands (e.g. OH-) are put before molecular
theory, i.e. a proton donor. OH-, NH3 or CO32- behaves as a base, i.e. ligands (e.g. H2O).
proton acceptor.
• Consequently, the changes can also be referred to as acid-base reactions. Bearing in mind that aluminium salts are extensively hydrolysed in solution
(Factsheet 85), the first of these equations can be written as follows:
Cations with dilute NaOH(aq)
[Al(H2O)6]3+(aq) + H2O(l) ¾ [Al(OH)(H2O)5]2+(aq) + H3O+(aq)
Practical 1 - Metal salt solutions with dilute NaOH(aq)
Carry out the following experiment on each of the cations Al3+, Cr3+, For examination purposes, an overall equation is generally sufficient:
Fe2+, Fe3+, Co2+, Ni2+ and Cu2+.
• Pour into a test tube, to a depth of about 2 cm, a salt solution [Al(H2O)6]3+(aq) + 3OH-(aq) ¾ [Al(OH)3(H2O)3](s) + 3H2O(l)
containing the cation under investigation.

• Add dilute aqueous sodium hydroxide dropwise, with shaking, until Exam Hint - Do not write:
a precipitate is formed.
Al3+(aq) + 3OH-(aq) → Al(OH)3(s)
• Record the colour of this precipitate.

• Continue to add the reagent, with further shaking, until it is eventually Equations of this sort represent precipitation reactions, i.e. those
brought about by an attraction between oppositely charged ions in
present in excess. solution. For the formation of insoluble metal hydroxides, this is
• Record whether or not the precipitate dissolves and, if so, what quite simply wrong.
colour solution is formed.

1
86. Deprotonation (Acid-Base Reactions) Chem Factsheet

With excess NaOH(aq) Cations with dilute NH3(aq)

Practical 1 shows that precipitates formed with dilute NaOH(aq) may
dissolve in excess reagent. Practical 3 - Metal salt solutions with dilute NH3(aq)
Repeat Practical 1 with the same salts as before, but with dilute
aqueous ammonia instead of NaOH(aq).
For a metal oxide or hydroxide to dissolve in alkali, it must be
amphoteric, i.e. it must have both basic and acidic character.
Practical 3 shows that, with a limited amount of reagent, precipitates are
The only metal hydroxides from Table 1 which dissolve in excess dilute
formed which, in all cases, appear similar to those formed with dilute
NaOH(aq) are Al(OH)3 and Cr(OH)3.
NaOH(aq).
Note - Some other hydroxides, notably Fe(OH)2, Fe(OH)3, Co(OH)2
and Cu(OH)2, will dissolve in concentrated NaOH(aq). With a limited amount of dilute NH3(aq), hydrated cations
behave exactly as they do with NaOH(aq). The same precipitates
(Table 1) are formed.
Aluminium hydroxide dissolves in excess dilute NaOH(aq) to give a
colourless solution of sodium diaquatetrahydroxoaluminate(III), commonly Again, deprotonation (acid-base) reactions occur, the only difference being
called ‘sodium aluminate’. The reaction is a deprotonation that follows that the base is the NH3 molecule instead of the OH- ion, e.g.
logically from Reactions (1), (2) and (3):
[Al(H2O)6]3+(aq) + 3NH3(aq) ¾ [Al(OH)3(H2O)3](s) + 3NH4+(aq)
[Al(OH)3(H2O)3](s) + OH−(aq) ¾ [Al(OH)4(H2O)2]−(aq) + H2O(l) ..........(4)
With excess NH3(aq)
Fig. 1 The diaquatetrahydroxoaluminate(III) ion Some metal hydroxides dissolve in excess dilute NH3; some do not. Those
which dissolve are not the same as those that dissolve in dilute
- NaOH(aq).
H 2O
HO OH Metal hydroxides which dissolve in aqueous ammonia do
Al so, not because NH3 is a base (it is a much weaker base than OH-), but
because it is a ligand, which can coordinate to cations to give soluble
HO OH ammonia complexes called ammines.
H 2O

Ammine formation is largely restricted to d-block elements towards the

right of the Periodic Table. On progressing from left to right across the first
Exam Hint - Do not confuse complex aluminates with simple series of d-block elements, cations become smaller and the density of
aluminates. Complex aluminates, such as Na[Al(OH)4(H2O)2, exist positive charge on their surfaces (‘surface charge density’) becomes greater.
in solution only. On evaporation of the solution, water is lost: first,
They therefore exert a stronger attraction for NH3 molecules, and ammines
solvent water, then coordinated water, and finally H2O between OH
groups. This leaves a solid residue of the simple salt, NaAlO2. are formed more readily.

Exam Hint - Do not confuse ammines with amines.

Ammines are complex ions or salts formed by the coordination of
If aluminium hydroxide is treated with concentrated NaOH(aq), ammonia to cations of d-block elements.
deprotonation goes to completion: Amines are organic derivatives of ammonia.

[Al(OH)3(H2O)3](s) + 3OH−(aq) ¾ [Al(OH)6]3−(aq) + 3H2O(l)

For practical purposes, there is a cut-off line between iron and cobalt:
Chromium(III) hydroxide is more susceptible than aluminium hydroxide
to attack by NaOH(aq), and gives a green solution containing an equilibrium Sc Ti V Cr* Mn Fe Co Ni Cu Zn
mixture of [Cr(OH)4(H2O)2]-, [Cr(OH)5(H2O)]2− and [Cr(OH)6]3− even Hydroxides dissolve in dilute
Hydroxides are insoluble in dilute NH3(aq).
with dilute NaOH(aq). NH3(aq).
Ammines are not formed. Ammines are formed.
Exam Hint - Do not confuse green chromate(III) solutions with the
more common yellow solutions of chromate(VI) ions, CrO42-
* Cr(OH)3 is partially soluble in concentrated NH3(aq) to give a violet
solution containing the complex ion [Cr(NH3)6]3+.
Reverse changes
Table 2 shows the formulae and colours of the ammines that are formed.
All the above reactions are reversible (notice the two half-
arrows in the equations) and can be reversed by adding an acid. Table 2 - Some common ammines
H+(aq) ions from the acid remove OH-(aq) ions (H+ + OH− = H2O)
and hence disturb the equilibria to the left hand side. Eventually, the Cation Formula Colour
original hydrated cation is reformed.
Co2+ [Co(NH3)6]2+ Pale red-brown
2+ 2+
Ni [Ni(NH3)6] Blue
Practical 2 - Reversing the changes Cu2+ [Cu(NH3)4(H2O)2]2+ Dark blue
Add excess NaOH(aq) to a solution of an aluminium salt and then add 2+ 2+
a dilute acid, dropwise with shaking, to the resultant aluminate(III) Zn [Zn(NH3)4] Colourless
solution. Notice the formation of a white precipitate of aluminium
hydroxide, which dissolves in excess acid.
Repeat the experiment with a solution of a chromium(III) salt.

2
86. Deprotonation (Acid-Base Reactions) Chem Factsheet

Ammines are formed by ligand substitution; not deprotonation. The

reactions can be represented by the following type of equation: Practical 5 - Metal salts solutions with Na2CO3(aq)
Repeat Practical 1 with the same salts as before, but with sodium
[Co(OH)2(H2O)4](s) + 6NH3(aq) → [Co(NH3)6]2+(aq) + 2OH−(aq) + 4H2O(l) carbonate solution instead of sodium hydroxide. If there is effervescence,
collect the gas in a squeezed-out teat pipette and bubble it slowly
Exam Hint - You are more likely to be asked for an equation for the through a small amount of limewater in an ignition tube.
overall change, e.g.
Practical 5 shows that, in all cases, precipitates are formed, but the
[Co(H2O)6]2+(aq) + 6NH3(aq) → [Co(NH3)6]2+(aq) + 6H2O(l) observations (Table 3) are quite different from those with both NaOH(aq)
and NH3(aq).

The ammines of cobalt and copper need more detailed study.

Table 3 - Cations with Na2CO3(aq)
Cobalt
The pale red-brown solution of hexaamminecobalt(II) ions darkens on Cation Observation(s) Product(s)
standing because of aerial oxidation: Al3+(aq) White precipitate + effervescence Al(OH)3 + CO2
2+
[Co(NH3)6] (aq) → [Co(NH3)6] (aq) 3+
+ e − 3+
Cr (aq) Grey-green precipitate + effervescence Cr(OH)3 + CO2
Pale red-brown solution Dark brown solution Fe2+(aq) Pale green precipitate* FeCO3
3+
Fe (aq) Brown precipitate + effervescence Fe(OH)3 + CO2
Copper
2+
The hexaamminecopper(II) ion, [Cu(NH3)6] , is formed only with liquid Co2+(aq) Blue precipitate CoCO3
2+
ammonia. The common ammine is [Cu(NH3)4(H2O)2]2+; Fig. 2. Ni (aq) Green precipitate NiCO3
Cu2+(aq) Blue precipitate CuCO3
Fig. 2 The tetraamminediaquacopper(II) ion
* On standing, this precipitate changes colour, first to bottle-green and
2+ then to brown, because of aerial oxidation.
H2O
H3N NH 3 A glance at Table 3 shows that what happens with Na2CO3 depends on
whether the cation is of the kind M2+ or M3+.
Cu
M2+ cations form metal carbonates.
H 3N NH 3
M3+ cations form metal hydroxides + carbon dioxide.
H 2O

M2+(aq)
Metal carbonates are formed in precipitation reactions; not deprotonation.
Exam Hint - Do not describe the [Cu(NH3)4(H2O)2]2+ ion as ‘square
planar’. It is true that the four NH3 molecules lie at the corners of a
The general equation is:
square with Cu2+ at the centre, but the H2O molecules, above and M2+(aq) + CO32-(aq) → MCO3(s)
below the plane but relatively distant from it, should not be ignored.
The ion therefore has a distorted octahedral structure. M3+(aq)
These ions are more acidic than M2+(aq) ions (Factsheet 85) and, with
CO32- ions, undergo deprotonation reactions. The simplest general equations
Practical 4 - you can write to show the formation of both a metal hydroxide and carbon
Preparation of tetraammine copper(II) sulphate-1-water dioxide are as follows:
Add aqueous ammonia, until in excess, to an aqueous solution of
copper(II) sulphate.Then add ethanol to precipitate [M(H2O)6]3+(aq) + H2O(l) ¾ [M(OH)(H2O)5]2+(aq) + H3O+(aq)
[Cu(NH3)4]SO4.H2O, filter off the crystals and allow them to dry at
room temperature. [M(OH)(H2O)5]2+(aq) + CO32-(aq) → [M(OH)3(H2O)3](s) + H2O(l) + CO2(g)

Afterwards, leave the crystals exposed to the atmosphere for a few Remember - With Na2CO3(aq):
days and note any change in their appearance. Try to explain this. M2+ ions undergo precipitation reactions.
M3+ ions undergo deprotonation.
Cations with Na2CO3(aq)

Exam Hint - Reactions of cations with Na2CO3(aq) may not be in With excess Na2CO3(aq)
your specification. If in doubt, check with your teacher. Practical 5 should have shown that, in all cases, no further changes occur.

Precipitates formed with Na2CO3(aq) never dissolve in excess

reagent.

3
86. Deprotonation (Acid-Base Reactions) Chem Factsheet

Questions
1 Given NaOH(aq), but no other reagents, describe how you could distinguish between solutions of chromium(III) sulphate, iron(II) sulphate and
nickel sulphate.

2 Solutions of sodium carbonate are strongly alkaline because of salt hydrolysis, i.e. [OH-(aq)] > [H+(aq)]. Why, therefore, is it wrong to represent
the reaction between sodium carbonate and a solution of an aluminium salt by the equation:

Al3+(aq) + 3OH-(aq) → Al(OH)3(s) ?

3 Vanadium(III) salts dissolve in water to give green solutions containing the ion [V(H2O)6]3+(aq). Describe what you would expect to observe when
each of the following reagents is added, until in excess, to a solution of a vanadium(III) salt.Write balanced ionic equations for all the reactions you
describe.

(a) Dilute NaOH(aq)

(b) Dilute NH3(aq)

4 Suggest two reasons why precipitates of metal hydroxides, formed by adding Na2CO3(aq) to aqueous solutions of M3+ salts, never dissolve in excess
reagent.

cannot be formed.
CO32− is a weaker base than OH−, so further deprotonation cannot occur. Also, CO32−, unlike NH3, is not a ligand, so complexes similar to ammines 4

[V(H2O)6]3+(aq) + 3NH3(aq) ¾ [V(OH)3(H2O)3](s) + 3NH4+(aq)

(b) Green precipitate, insoluble in excess dilute NH3(aq):

[V(H2O)6]3+(aq) + 3OH−(aq) ¾ [V(OH)3(H2O)3](s) + 3H2O(l)

(a) Green precipitate, insoluble in excess dilute NaOH(aq): 3

The equation should show not only the formation of a precipitate of aluminium hydroxide but also the evolution of carbon dioxide. 2

NiSO4 gives a green precipitate which is insoluble in excess reagent and which does not change colour on standing.

FeSO4 gives a green precipitate, insoluble in excess reagent, which turns brown on standing in air.

Cr2(SO4)3 gives a green precipitate which dissolves in excess NaOH(aq) to give a green solution. 1
Answers

Acknowledgements: This Factsheet was researched and written by John Brockington. Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire,
TF1 1NU. ChemistryFactsheets may be copied free of charge by teaching staff or students, provided that their school is a registered subscriber. No part of these
Factsheets may be reproduced, stored in a retrieval system, or transmitted, in any other form or by any other means, without the prior permission of the
publisher. ISSN 1351-5136

4
 Chem Factsheet
www.curriculum-press.co.uk Number 87

σ - and π - Bonds and the

Structure of Benzene
To succeed in this topic you need to understand: A great deal of heat is evolved as the two atoms combine together, showing
• atomic structure (Factsheet 1); that a hydrogen molecule is more stable than two separate hydrogen
• bonding (Factsheet 5). atoms. It has lower enthalpy value. Stability results from the high electron
• calculation of enthalpy changes using average bond energies (Factsheet 8) density that exists between the two nuclei (Fig.2).
After working through this Factsheet you will: Fig. 2 The region of a hydrogen molecule where there is a high
• understand the difference between σ- and π-covalent bonds;
probability of locating the two electrons is between the two nuclei
• know that the carbon-carbon double bond in alkenes comprises a σ- and
a π-bond;
• know that the benzene ring contains six identical carbon-carbon bonds;
• understand the nature of these bonds;
• know that the π-bond electrons in benzene are delocalised;
• know that delocalisation leads to enhanced stability;
• be able to calculate the stabilisation energy of benzene.

Single covalent bonds

A covalent bond is formed when a pair of electrons, one from each atom, is
shared between them. Both electrons must originally be in singly occupied
atomic orbitals. The two hydrogen atoms are strongly bonded together
because:
Remember - An atomic orbital (AO) is a three-dimensional region of • the shared pair of electrons reduces repulsion between the two
space around the nucleus of an atom where there is a high probability of nuclei;
finding an electron. An atomic orbital may be: • the positive nucleus of each atom is attracted to the neagtive
charge density betwen them..
• vacant, i.e. empty, symbolised
• singly occupied, i.e. containing one electron, symbolised σ- and π- bonds
s-Orbitals are spherically symmetrical about an atomic nucleus and there
• fully occupied, i.e. containing a pair of electrons with opposite spin,
is only one way in which they can overlap. p-Orbitals, however, are
symbolised
dumb-bell shaped, and overlap could conceivably occur in two ways
(Fig. 3).
When the atoms approach each other, their singly occupied orbitals overlap
and interact to give a molecular orbital (MO) which surrounds both nuclei Fig. 3 Possible modes of overlap of p-orbitals
and holds both electrons. Fig. 1 shows the fomation of a σ-molecular orbital
or σ-bond (pronounced ‘sigma bond’) between two hydrogen atoms.

Fig. 1. Formation of the H-H bond

(a) Head-on overlap of p-orbitals, leading to a σ-bond (σ-MO)

1s 1 1s 1 1s 1 1s 1 σ1s1 (b) Sideways overlap of p-orbitals, leading to a π-bond (π-MO)
(a) (b) (c)
Wherever possible - and this applies to molecules such as
(a) The approach of two hydrogen atoms possessing s-orbital electrons F2 and Cl2 - there is head-on approach of p-orbitals because this
with opposite spins leads to a greater degree of overlap and hence greater stability.
(b) Overlap of atomic orbitals
(c) The resultant molecular orbital
The formation of a F2 or Cl2 molecule is therefore represented by Fig.
3(a). Notice that the shape of a σ-bond, like that of the σ-bond in the H2
molecule, stems from the fact that electron density is greatest between
the two atomic nuclei. The overlapping lobes of the AOs are thus
increased in size, while the outer lobes are correspondingly decreased.
1
87. σ - and π - Bonds and the Structure of Benzene Chem Factsheet

Double covalent bonds Fig. 6 The π

π-MO in the ethene molecule
In certain circumstances p-orbitals can only overlap in a sideways manner,
to give relatively weak π-bonds. This is what happens in the formation of
the ethene molecule, CH2=CH2. H H
H H
Formation of the σ -framework of ethene
Carbon in its ground state (i.e. most stable electronic state) has the
configuration: 1s2, 2s2, 2p2
Remember - Both electrons of the π-bond exist in both lobes. Do not
This means that the atom has two unpaired electrons:
make the mistake of thinking that each electron is restricted to one lobe.
1s 2p
Ground state
The strength of any covalent bond depends on the degree of overlap of
atomic orbitals as the molecular orbital is formed. Because, in ethene, there
This in turn would lead to a covalency of 2, i.e. the ability to form two
is little sideways overlap of π-orbitals, the p-bond is relatively weak.
covalent bonds. However, if energy is available, one of the 2s electrons can
be promoted to a vacant 2p orbital:
Remember
• Although the carbon-carbon double bond is printed C=C, the two
1s 2p covalent bonds are different from each other. One is a σ-bond and
Excited state the other, which exists above and below the plane of the σ-
framework, is a π-bond.
In this excited state carbon has four unpaired electrons, corresponding to • The π-bond is much weaker than the σ-bond. This is the one
its well known covalency of 4. In forming ethene, two carbon atoms each that is broken during addition reactions.
use their 2s and two of their 2p electrons to give the σ-framework of the
molecule (Fig.4), so-called because all the bonds are σ-bonds.
The C-C single bond in alkanes is very difficult to break because of the
strength of the σ-bond. The electron density is between the atoms.
Fig. 4 σ-Framework of the ethene molecule The π-bond present in the C=C double bond in alkenes is
• weak
H H • gives negative charge density above and below the C-C σ-bond which
120o
attracts electrophiles.
In addition reactions of alkenes, the strong σ-bond in the molecule is not
120o C C broken, e.g.
CH2=CH2 + H2 → CH3−CH3
double bond single bond
H H (σ and π-bonds) (σ -bond only)

Bonding in benzene
Exam Hint - There is no need to study the formation of the σ- Benzene has the molecular formula C6H6. August Kekulé (1865) proposed
framework in detail, but you do need to know that it is trigonal planar a structural formula in which the six carbon atoms were linked together in
with bond angles of 120o about each carbon atom. a regular, planar hexagon (the ‘benzene ring’) by alternate double and single
bonds (Fig. 7).
Formation of the π-bond in ethene Fig. 7 The Kekulé formula of benzene
After forming the σ-framework, each carbon atom has an unpaired 2p
electron ‘left over’. These electrons occupy orbitals which lie perpendicular H
to the plane of the σ-framework, and which are sufficiently close together
to overlap slightly in a sideways manner both above and below the plane H C
H
(Fig. 5). C C
abbreviated or
Fig. 5 Sideways overlap of 2pz AOs in the ethene molecule C C to
H H
C

H
H H
H H
Although Kekulé’s formula was accepted for many years, evidence
accumulated showing that it was not entirely correct. Measurements of
bond lengths were particularly damning:
σ bond
Length/nm
C-C single bond 0.154
Overlapping leads to interaction, and the result is a π-bond which holds C-C double bond 0.134
both the electrons. It consists of two lobes, one above and the other below C-C bond in benzene 0.139
the plane, each with a shape that is derived from those of the contributing All C-C bonds in benzene were found to have a length of 0.139 nm. This
AOs (Fig. 6). suggested that they had an identical character, between that of a single
bond and that of a double bond. The Kekulé theory was eventually replaced
by the molecular orbital theory, according to which the benzene molecule
contains σ- and π-bonding, similar to that in ethene.

2
87. σ - and π - Bonds and the Structure of Benzene Chem Factsheet

Formation of the s-framework of benzene

In forming the σ-framework (Fig. 8), each carbon atom, as in ethene, uses Because of the symmetry of the σ-framework, the π-orbitals
its 2s and two of its unpaired 2p electrons. (As for ethene, details are not cannot overlap in pairs to give alternate double and single bonds.
required by current A-level specifications.)
Consequently, the old symbol for benzene,
Fig. 8 σ-Framework of the benzene molecule
has been replaced by a new one, , in which the circle represents
the π- bond.
H H

C C Delocalisation of π-electrons

H C C H
120o • If the benzene molecule had three separate π-bonds, as implied by
the Kekulé formula, the π-electrons would be localised, i.e. confined
120o C C to the three regions between the doubly bonded carbon atoms.
• Because there is a single π-bond extending all around the molecule,
H H the π-electrons are delocalised, i.e. not restricted to certain localities
but dispersed among all six carbon atoms.

Formation of the π-bond in benzene

All six carbon atoms have their remaining singly occupied 2p orbitals lying Delocalisation energy
perpendicular to the plane of the σ-framework. They are close enough Delocalisation of electrical charge always leads to an increase in stability.
together to overlap uniformly all around the ring (Fig. 9). In the case of a metal sphere, if electrons were to be concentrated at one
point on its surface, they would repel one another and immediately become
Fig. 9 Uniform overlap of six 2pz AOs, perpendicular to the plane of uniformly distributed over the entire surface to give a more stable
the benzene σ-framework arrangement.

Benzene, because of its delocalised π-bond, is more stable

than it would be if it had three localised π-bonds between alternate
pairs of carbon atoms.

A question often asked in examinations is this: how much more stable is

benzene as a result of delocalisation? A figure can be calculated from
enthalpies of hydrogenation or combustion.

Calculation of delocalisation energy from enthalpies of

hydrogenation
The molar enthalpy of hydrogenation of cyclohexene, a six-membered
Interaction gives a π-bond holding the six electrons.* It consists of two ring compound with one localised π-bond, is -119.6 kJ mol-1:
lobes, one above and one below the σ-framework. As always, the shape of
the molecular orbital is derived from the shapes of the contributing atomic (g) + H2(g) → (l); ∆H = -119.6 kJ mol-1
orbitals (Fig. 10).
Cyclohexene Cyclohexane
* Strictly, this is wrong: no orbital can hold more than two electrons. In
fact, three π-molecular orbitals are formed, of different shapes and with Consequently, if benzene were a cyclic compound with three localised
two electrons in each, but at A-level it is assumed that all six electrons π-bonds, its molar enthalpy of hydrogenation would be 3(-119.6)
occupy the π-orbital shown here. = -358.8 kJ mol-1:

Fig. 10 The π- molecular orbital in the benzene molecule (g) + 3H2(g) → (l); ∆H = -358.8 kJ mol-1

Actual benzene has one delocalised π-bond and the experimental value
of its molar enthalpy of hydrogenation is -208.4 kJ mol-1:

(g) + 3H2(g) → (l); ∆H = -208.4 kJ mol-1

The difference between these values, 150.4 kJ mol-1, is known as the

delocalisation energy or stabilisation energy of benzene.

Because of the delocalisation of its π-electrons, benzene is at

a lower energy level than it would otherwise be to the extent of
150.4 kJ mol-1.

3
87. σ - and π - Bonds and the Structure of Benzene Chem Factsheet

Fig. 11 will help you to understand this. Practice Questions

1 (a) What atomic orbitals contribute to the covalent bond of the HF
Fig. 11 Enthalpy diagram to show the delocalisation energy of molecule?
benzene (b) Draw a diagram to show the mode of overlap of these atomic
orbitals.
(c) Is the resulting molecular orbital a σ-bond or a π-bond?
Benzene
2 Why is the double bond in ethene not twice as strong as the single bond
150.4 kJ mol−1
in ethane?
delocalisation
Benzene energy
3 Briefly explain why ethene is more reactive than ethane, even though
the carbon-carbon bond is stronger.
enthalpy

- 358.8 - 208.8
kJ mol−1 kJ mol−1 4 Why does HBr react with ethene but not with benzene?
Cyclohexane
5 The molar enthalpy of combustion of benzene is -4866 kJ mol-1. Use
this information and the following average bond enthalpies (all in kJ
mol-1) to estimate the delocalisation energy of benzene.
C-C = 348; C=C = 612; C-H = 412; C=O = 743; O=O = 496;
O-H = 463.
Delocalisation is not confined to benzene, but occurs in all conjugated [C6H6 + 7½O2 → 6CO2 + 3H2O]
compounds, i.e. those with alternating double and single bonds. An example
is buta-1,3-diene:
1 2 3 4
CH2=CH-CH=CH2

While double bonding is most marked between C1 and C2, and between C3
and C4, the bond between C2 and C3 also has a certain amount of double
bond character as a result of delocalisation.

∴ delocalisation energy = 5094 - 4866 = 228 kJ mol-1

Overall ∆H, i.e. enthalpy of combustion of ‘Kekulé benzene’, = +6600 - 11694 = -5094 kJ mol-1.
+6600 kJ mol-1 Total =
Total = -11694 kJ mol-1 +3720 7½ O=O 7½(+496) =
6 O-H 6(-643) = -2778 +1836 3 C=C 3(+612) =
12 C=O 12(-743) = -8916 +1044 3 C-C 3(+348) =
∆H for bond formation ∆H for bond breaking
+ 7½O2 → 6CO2 + 3H2O
5 Answer should be based on the combustion of ‘Kekulé benzene’:
strongly attracted.
delocalised, so that the electron density between any two adjoining carbon atoms is lower than it is in ethene. Electrophilic reagents are therefore less
HBr is an electrophilic (electron seeking) reagent, which is strongly attracted to the π-bond electrons of ethene. In benzene, the π-electrons are 4
internuclear axis, are more susceptible to electrophilic attack.
In most reactions of ethene only the π-bond is broken. This is weaker than the σ-bond in ethane, and the electrons, since they lie beyond the 3

below the internuclear axis, making less contribution to the reduction of internuclear repulsion / so that the bond is weaker.
The double bond comprises a σ-bond and a π-bond, whereas a single bond consists of a σ-bond only. Electrons in a π-bond are located above and 2

(c) σ-bond.
Note. Diagram must show end-on overlap of the p-oribtal

(b)
1 (a) 1s orbital of hydrogen and a singly occupied 2p orbital of fluorine.
Answers

Acknowledgements: This Factsheet was researched and written by John Brockington. Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire,
TF1 1NU. ChemistryFactsheets may be copied free of charge by teaching staff or students, provided that their school is a registered subscriber. No part of these
Factsheets may be reproduced, stored in a retrieval system, or transmitted, in any other form or by any other means, without the prior permission of the
publisher. ISSN 1351-5136

4
 Chem Factsheet
www.curriculum-press.co.uk Number 88
Disproportionation
To succeed in this topic you need to: Fig 1. helps you to understand these basic principles.
• understand oxidation numbers (covered in Factsheet 11),
Fig. 1 Reaction between an oxidant (A) and a reductant (B)
• be familiar with redox charts (examples are included in Factsheets
75 and 83,
• understand standard electrode potentials and electrochemical cells Electron transfer
A B
(covered in Factsheet 37).
Oxidant Reductant
After working through this Factsheet you will:
• have revised the basic principles of oxidation and reduction;
• know that disproportionation is a special kind of redox involving A causes the oxidation of B B causes the reduction of A
essentially one substance only; by removing electrons from it. by giving electrons to it.
• be able to predict disproportionation products from inspection of In doing so, A accepts electrons, In doing so, B loses electrons,
redox charts; i.e. it is reduced. i.e. it is oxidised.
• be familiar with common examples of disproportionation;
• have revised the principles of electrochemical cells; What is the difference between disproportionation and redox?
• be able to predict, from standard electrode potentials, the feasibility
of disproportionation reactions; Disproportionation is a kind of redox reaction involving one
• understand the difference between disproportionation and substance only. Part of it behaves as an oxidising agent and part as a
reproportionation. reducing agent.
A disproportionation reaction is a special kind of redox reaction. To
understand this topic, you must therefore begin by making sure you know That part of the substance which acts as an oxidising agent becomes
the basic ideas of oxidation and reduction. reduced, while the part which acts as a reducing agent becomes
oxidised. This leads to the accepted definition of disproportionation.
Remember - Principles of oxidation and reduction
• Oxidation is a chemical change involving the loss of electrons, e.g. Disproportionation is defined as the simultaneous oxidation
and reduction of a single substance*.
Na → Na +
+ e −

* Chemists often talk about the disproportionation of ions (such as

• Reduction is a chemical change involving the gain of electrons, e.g. Cu+ or ClO−) in aqueous solution. For this reason, disproportionation
Cl + e− → Cl− can also be defined as the simultaneous oxidation and reduction of a
single species.
• Oxidation and reduction must occur together. Whenever a chemical
species (i.e. atom, molecule or ion) is oxidised, the electrons it loses
are accepted by another species, which thus becomes reduced. Prediction of products
Redox charts of elements, in which the principal molecules or ions are
shown in order of oxidation number, are very useful in predicting the
A chemical reaction in which one species is oxidised while another is
products of disproportionation reactions.
simultaneously reduced is known as an oxidation-reduction or redox reaction.
Again make sure you know the basic principles. Species at the top of a redox chart cannot undergo disproportionation
because they cannot be oxidised; neither can species at the bottom because
Remember - Principles of redox reactions they cannot be reduced. Between these extremes, many elements have
• Every reaction of this sort is a combination of two half-reactions, i.e. species which could, in principle, undergo disproportionation.
the oxidation of one species and the reduction of another.
Use of redox charts in predicting disproportionation products.
• Most reactions involve essentially two substances, namely an oxidising
• Locate the reacting molecule or ion on the redox chart.
agent and a reducing agent.
• Look upwards to identify the oxidation product.
• Another substance (water, an acid or an alkali) may also be needed • Look downwards to identify the reduction product.
for the reaction to occur. • Do not assume there will always be one move upwards (an increase
of 1 in oxidation number) and one move downwards (a decrease
• The oxidising agent provides an oxidant, i.e. a species which brings
of 1 in oxidation number)
about oxidation. Often, as in the case of Cl2, an ‘oxidising agent’ and
• Movement up or down the chart ceases when a stable oxidation
an ‘oxidant’ are one and the same thing.
level is reached.
• The reducing agent provides a reductant, i.e. a species which brings
about reduction. Often, as in the case of Zn, a ‘reducing agent’ and a If the change in oxidation number (ON) is the same in both directions, the
‘reductant’ are one and the same thing. product ions or molecules will be formed in a 1:1 ratio; otherwise the
• During a redox reaction, electrons are transferred from the reductant ratio will be different.
to the oxidant.
In all cases, the number of electrons lost on forming the
• Because the reductant loses electrons, it becomes oxidised as the oxidation product is equal to the number of electrons gained on
reaction occurs. Conversely, because the oxidant gains electrons, it forming the reduction product.
becomes reduced.
Here are some well known examples to illustrate these principles.
1
88. Disproportionation Chem Factsheet

Halogens with alkalis

When chlorine is passed into cold, aqueous sodium hydroxide, it disproportionates to give a solution of sodium chloride, NaCl, and sodium chlorate(I),
NaClO. The redox chart of chlorine (Fig. 2) helps to explain this.

Fig 2. Disproportionation of Cl2 and ClO− shown on the redox chart of chlorine

Oxidation number
of Cl

+7 HClO4 ClO4-
Chloric(VII) acid Chlorate(VII) ion

+5 HClO3 ClO3-
Chloric(V) acid Chlorate(V) ion

OXIDATION
+3 HClO2 ClO2- (Four electrons lost)
Chloric(III) acid Chlorate(III) ion
(Unstable) (Unstable)

O R
X
+1 HClO ClO- Heat
E Chloric(I) acid Chlorate(I) ion
I D N
D U A TIO lost)
ID n
A C OX tro
e lec REDUCTION
T OH− ne
T 0 Cl2 (O (Two electrons gained)
I I (On R
O e e EDUC
O lect
ron TION
N N gai
−1 HCl ned
) Cl-
Hydrogen chloride
Chloride ion

Reduction can lead only to Cl− ions, but what about oxidation? Upward Remember - Vertical movements on redox charts stop at stable oxidation
movement could conceivably give ClO−, ClO2−, ClO3− or ClO4− ions, so levels.
why is the product ClO−? The answer is that ClO- ions are formed first
and, because they are stable at room temperature, they stay as they are.
On going from ClO− to Cl− the ON of Cl changes by -2, corresponding to a
On oxidising Cl2 to ClO−, the ON of chlorine changes by +1, corresponding two electron gain. From ClO− to ClO3− it changes by +4, corresponding to
to a one electron loss. Reduction of Cl2 to Cl− changes it by -1, corresponding a four electron loss. Consequently, in the equation, ClO3− and Cl− ions
to a one electron gain. Because the number of electrons lost on oxidation is appear in a 1:2 ratio:
equal to the number gained on reduction, ClO− and Cl− ions are formed in a
1:1 ratio: 3ClO−(aq) → ClO3−(aq) + 2Cl−(aq) (2)
Cl2(g) + 2OH (aq) → ClO (aq) + Cl (aq) + H2O(l)
− − −
(1)
To obtain the overall ionic equation for the reaction between Cl2 and OH−
Bromine and iodine behave in a similar manner to chlorine. Other alkalis at temperatures > 70 oC, multiply Equation (1) × 3 and add to Equation (2):
(e.g. KOH) behave like NaOH.
3Cl2(g) + 6OH−(aq) → ClO3−(aq) + 5Cl−(aq) + 3H2O(l)
Thermal decomposition
Many thermal decomposition reactions involve disproportionation. If
chlorine is passed into hot aqueous sodium hydroxide, the products are Exam Hint - Not all thermal decompositions are disproportionation
reactions. For example, in the decomposition of calcium carbonate
sodium chloride and sodium chlorate(V), NaClO3, because the ClO− ion
the oxidation numbers of all the elements remain unchanged:
which is formed at first is unstable at temperatures above 70 oC and CaCO3(s) → CaO(s) + CO2(g)
undergoes disproportionation.
• Reduction of ClO− cannot give chlorine, because Cl2 and OH− would ON of Ca +2 +2
immediately react together, but continues down the chart to give Cl−. ON of C +4 +4
• Oxidation of ClO− does not stop at the unstable ClO2− ion but proceeds ON of O -2 -2 -2
further to the more stable ClO3− ion at the +5 oxidation level.

2
88. Disproportionation Chem Factsheet

Non-metal oxides with water To use Eê values to predict whether a proposed disproportionation reaction
Most non-metal oxides are acid anhydrides, i.e. acids without water. They will actually occur, you need to imagine that the reaction is taking place in
dissolve in water to give acids and, although reactions occur, there is no an electrochemical cell. You must therefore be familiar with the construction
change in the ON of the non-metal, e.g. and operation of such cells.

SO3(s) + H2O(l) → H2SO4(aq) Remember - Principles of electrochemical cells

ON of S +6 +6 • A cell is a device for carrying out a redox reaction in such a way that
energy is released as electrical energy rather than heat.
P4O10(s) + 6H2O(l) → 4H3PO4(aq) • The two half-reactions (i.e. oxidation and reduction) are carried out
ON of P +5 +5 in separate half-cells connected by a salt bridge.
• Each half-cell is a system comprising an oxidant and related reductant.
However, a few non-metal oxides react with water to give a mixture of two It may consist of a metal dipping into a solution containing its ions
acids and are thus described as mixed anhydrides. A well known example (e.g. Zn(s) in contact with Zn2+(aq)), or it may comprise a ‘redox
is nitrogen dioxide, which dissolves in water to give a mixture of nitrous electrode’ consisting of Pt immersed in a solution containing a mixture
acid and nitric acid. Here, the ON of the principal element (N) is of ions (or molecules) in an oxidised state and related ions (or
simultaneously increased and decreased, so the reaction is a molecules) in the reduced state.
disproportionation: • As a result of the redox reaction, the metal of one half-cell becomes
+vely charged while that of the other half-cell becomes −vely charged.
2NO2(g) + H2O(l) → HNO2(aq) + HNO3(aq) The half-cells are therefore referred to, respectively, as the +ve and
ON of N +4 +3 +5 −ve poles of the cell.
• The system with the more +ve Eê value is always the +ve pole of the
Ions in aqueous solution cell.
Copper(I) sulphate (an uncommon compound) is a white solid. On • Reduction occurs at the +ve pole of a cell and oxidation at the −ve
dissolving it in water you’d expect to see a colourless solution, but what pole.
actually appears is a blue solution of ordinary copper(II) sulphate and a
red-brown precipitate of metallic copper. Copper(I) ions in solution always The maximum potential difference (i.e. voltage) that a cell can develop is
undergo disproportionation: known as its electromotive force (e.m.f.) or cell potential, symbol Ecell. For
cells in general it is the difference between the potentials of its electrodes
ON of Cu under conditions of zero current flow:
+2 N Cu2+
OXIDAT IO Ecell = E+ − E−
+1 Cu+
0 REDUCTIO Cu For a cell consisting of two standard electrodes (all that is relevant to A-
N
level), its standard cell potential is given by Equation (3):
The equation for the reaction is:
Eêcell = Eê+ − Eê− (3)
Cu2SO4(s) + aq → CuSO4(aq) + Cu(s)
where Eê+ and Eê- refer to the standard electrode potentials (Eê values) of
the systems at the +ve and -ve poles respectively.
Exam Hint - Although silver is immediately below copper in the Periodic
Table, Ag+ ions do not behave in the same way as Cu+ ions. If you are Bearing in mind that reduction occurs at the +ve pole and oxidation at the
asked to explain this, you must base your argument on Eê values - see -ve one, Equation (3) can be rewritten:
below.
Eêcell = Eêreduction − Eêoxidation (4)
Feasibility of disproportionation where Eêreduction and Eêoxidation refer to the standard electrode potentials (Eê
Although redox charts suggest the possibility of disproportionation values) of the systems in the half cells where reduction and oxidation
reactions and help you to predict the identity of the products, they will respectively are occurring.
not tell you whether such reactions take place. In reality, only a tiny
number of possible disproportionations actually occur. To find out the Remember - Equation (4) spells REDOX:
feasibility of a disproportionation reaction, you must use standard electrode Eêcell = EêREDuction − EêOXidation
potentials.

A standard electrode potential (symbol Eê) is a property of a redox system, This is the equation that you need to answer questions on disproportionation.
i.e. a solution containing equal concentrations (1 mol dm-3) of an oxidant Imagine that the proposed reaction is taking place in an electrochemical
and chemically related reductant, such as Fe3+(aq) and Fe2+(aq). It is defined cell, with oxidation in one half-cell and reduction in the other. Calculate the
as the potential that develops on a piece of platinum dipped into the e.m.f. of the cell by applying Equation (4) and see whether the value is +ve
system at a temperature of 298 K, referred to a standard hydrogen electrode or −ve.
assumed to have a potential of 0.00 V.
Significance of the result
Eê values of systems provide a useful measure of their oxidising or reducing • If Eêcell is negative, disproportionation will not occur. (It is
powers. impossible to have a cell with a −ve e.m.f.)
• If Eêcell is positive, disproportionation will occur.
Remember - Significance of Eê values • If Eêcell is positive, but with a value < ~0.3 V, the reaction will not
• The more +ve an Eê value, the more strongly oxidising is the system. proceed to completion. (A dynamic equilibrium is established.)
• Negative Eê values indicate reducing systems: the more −ve the
value, the greater the reducing power.
• A system will oxidise any other system with a less +ve (or more −ve)
Eê value.

3
88. Disproportionation Chem Factsheet

Example Reproportionation
Eê/V This is essentially the opposite of disproportionation.
Cu+(aq) + e− ¾ Cu(s) +0.52
Cu2+(aq) + e− ¾ Cu+(aq) +0.15 Reproportionation occurs when two species containing the
same element in different oxidation states react together to give a
Does the copper(I) ion disproportionate in aqueous solution under standard single species in which the element is present in a third, intermediate
conditions? oxidation state.
Answer The proposed reaction is:
For example, when ammonium nitrate is heated, the ammonium ion is
2Cu+(aq) → Cu2+(aq) + Cu(s) oxidised, the nitrate ion is reduced, and all nitrogen finishes up as
Oxidation dinitrogen monoxide:
Reduction NH4+ NO3−(s) → N2O(g) + 2H2O(l)
ON of N -3 +5 +1
Eê cell = Eêreduction - Eêoxidation
= +0.52 - (+0.15) = +0.37 V Dinitrogen monoxide is formed from both NH4+ and NO3- ions because,
as in ordinary disproportionation, the number of electrons lost on
The value is positive and > 0.3 V, so this disproportionation will go to oxidation must be equal to the number gained on reduction. Oxidation
completion. of NH4+ to N2O corresponds to a four electron loss (ON increase from
-3 to +1), and the gain of four electrons by NO3- takes the ON down
Exam Hint - Never change the sign of an Eê value! from +5 to +1, again producing N2O.
It is conventional, as in the above example, to quote an Eê value
alongside the system to which it relates, written in the form of an ionic
half-equation for a reduction process (i.e. with the oxidised species
on the LHS). As a result, students may argue that if Eê is, say, +x V for (c) NH4+(aq) + NO2-(aq) → N2(g) + 2H2O(l)
a reduction process, it must be -x V for the reverse change, i.e. the gain.
oxidation process. Reduction of NO2- to N2 decreases ON by 3; hence a three-electron
THIS IS WRONG! Eê values do not refer to reactions but to systems, loss.
and their quoted values and signs should be substituted unchanged (b) Oxidation of NH4+ to N2 increases ON by 3; hence a three-electron
into Equation (4). (a) N 2 6
LHS.
Practice questions RHS, but in alkaline solution the excess of OH- ions disturbs it to the
1 Most nitrates decompose on heating to give the metal oxide together solution OH− ions are removed and equilibrium is disturbed to the
with nitrogen dioxide and oxygen, e.g. The very low e.m.f. shows that the reaction is reversible. In acidic
2Mg(NO3)2(s) → 2MgO(s) + 4NO2(g) + O2(g) Eêcell = +0.60 - (+0.56) = +0.04 V
By considering the oxidation numbers of the elements involved, show Reduction
that this reaction is a disproportionation. Oxidation
2 Explain, using oxidation numbers, whether or not each of the following 3MnO42−(aq) + 2H2O(l) → 2MnO4−(aq) + MnO2(s) + 4OH−(aq)
thermal decomposition reactions involves disproportionation. positive e.m.f.
(a) 2KClO3(s) → 2KCl(s) + 3O2(g) 5 Disproportionation of the manganate(VI) ion is possible, as shown by
(b) 2NaHCO3(s) → Na2CO3(s) + H2O(g) + CO2(g) Because the value is negative, this disproportionation will not occur.
(c) NH4Cl(s) → NH3(g) + HCl(g) ∴ Eêcell = +0.80 − (+1.98) = -1.18 V
(d) 2H2O2(aq) → 2H2O(l) + O2(g) Eêcell = Eêreduction − Eêoxidation
3 Chlorine dioxide, ClO2, is a mixed anhydride. Use the redox chart of
Reduction
chlorine (p. 2) to predict the acids that it will form with water, and
Oxidation
write an equation for the reaction.
2Ag+(aq) → Ag2+(aq) + Ag(s)
The proposed reaction is: 4
4 Use the following data to predict whether or not the silver(I) ion
disproportionates in aqueous solution under standard conditions. 2ClO2(g) + H2O(l) → HClO3(aq) + HClO2(aq)
Eê/V reduction.
Ag+(aq) + e− ¾ Ag(s) +0.80 ClO2 forms chloric(V) acid by oxidation and chloric(III) acid by 3
Ag2+(aq) + e− ¾ Ag+(aq) +1.98
(d) Yes. ON of O changes from -1 in H2O2 to -2 in H2O and 0 in O2.
5 Use the following standard electrode potentials to explain why, under (N = -3, H = +1 and Cl = -1 in both reactants and products.)
acidic conditions, potassium manganate(VI) dissolves in water to form (c) No. ON of all elements remain constant.
a purple solution and a brown precipitate, but under alkaline conditions products.)
it just gives a green solution. (Na = +1, H = +1, C = +4 and O = -2 in both reactants and
Eê/V (b) No. ON of all elements remain constant.
MnO42−(aq) + 2H2O(l) + 2e− ¾ MnO2(s) + 4OH−(aq) +0.60 2. (a) Yes. ON of Cl falls, from +5 to -1; that of O increases from -2 to 0.
MnO4−(aq) + e− ¾ MnO42-(aq) +0.56 disproportionation occurs.
6 When a mixed solution of ammonium chloride and sodium nitrite is The changes in ON show that N is reduced and O is oxidised, i.e.
boiled, reproportionation occurs between ammonium ions and nitrite ON of O -2 (-2) (-2) 0
ions so that a new nitrogen-containing species is formed. ON of N +5 +4
(a) What species is this? 1. 2Mg(NO3)2 → 2MgO + 4NO2 + O2
(b) Use changes in oxidation number to justify your answer to (a). Answers
(c) Write an equation for the reaction. ____________________________________________________________________________
Acknowledgements: This Factsheet was researched and written by John Brockington. Curriculum Press, Bank
House, 105 King Street, Wellington, Shropshire, TF1 1NU. ISSN 1351-5136
4
www.curriculum-press.co.uk
Chem Factsheet Number 89
The Chemistry of Aluminium
To succeed in this topic you need to understand: In an examination, you could be awarded marks for the following details.
• the principles of oxidation and reduction (covered in Factsheet 11); • Cryolite is used as a flux, i.e. a substance that allows aluminium oxide
• salt hydrolysis (covered in Factsheet 85); to be obtained in the molten state at a temperature well below its
• deprotonation (covered in Factsheet 88). melting point of 2045 oC.
After working through this Factsheet you will: Exam Hint - Do not say: ‘It lowers the m.p. of Al2O3’, because Al2O3
• know to have revised the extraction of aluminium; (like all solids) has a fixed melting point. Better to say that a
• know how and why aluminium is recycled; mixture of Al2O3 and cryolite has a lower m.p. than Al2O3 alone.
• understand its amphoteric behaviour;
• understand why some of its compounds are covalent;
• know the principal reactions of aluminium; • The cathode is the graphite cell lining.
• understand its aqueous chemistry; • Several carbon rods are used as anodes.
• know the chemistry of its principal compounds.
• The voltage is very low (about 6 V) but the current is enormous
Aluminium (atomic number = 13) is the most abundant metal in the Earth’s (about 100 000 A).
crust. It is the second element of Group 3 of the Periodic Table, although its
• The electrode reactions are:
chemistry has much in common with that of beryllium at the head of Group 2.
Cathode Al3+ + 3e− → Al
Anode 2O2− → O2 + 4e−
Remember - The head element of a group of the Periodic Table often
resembles the second element of the one to the right of it. The similarities • The anodes burn away in the liberated O2 and have to be replaced
are known as diagonal relationships. periodically. Heat from the burning anodes helps to keep the
electrolyte molten.
Aluminium is a p-block element (i.e. one formed by the filling of p-orbitals) • Fresh bauxite is added from time to time.
and has the electronic configuration 1s2, 2s2, 2p6, 3s2, 3p1. It forms only one
stable ion, Al3+, by the loss of all three outer shell electrons. • Conditions are adjusted so as to minimise decomposition of cryolite.

Occurrence Exam Hint - If you’re asked about the siting of an aluminium

The only commercial ore is bauxite, Al2O3.2H2O, found mainly in Jamaica. smelter, remember that the most important requirement is a plentiful
The main impurities are SiO2 and Fe2O3 which gives it a red brown colour. supply of relatively cheap electricity, usually from a near-by
Before aluminium is extracted by electrolysis, the Fe2O3 must be removed, hydroelectric or nuclear power station. Another consideration is
otherwise the product is an Al/Fe alloy with poor resistance to corrosion. proximity to a port, for importing bauxite.
The purification of bauxite is described in Factsheet 80.
Recycling of aluminium
Extraction Scrap aluminium (especially from drinks cans) is cut up and melted
Aluminium is a very reactive metal near the top of the electrochemical series. down, after any steel has been removed with a magnet. Recycling has
A lot of energy is released when it is converted into its oxide: a similar four advantages:
amount of energy is therefore needed to reconvert the oxide to the metal. • It requires far less energy than electrolysing bauxite.
That is why Al2O3 cannot be reduced by carbon: not enough energy is • It conserves limited reserves of bauxite.
available as C is converted to CO. Electrolytic reduction has to be used • Tipping in landfill sites is reduced.
instead, because this allows unlimited energy to be supplied. Even so, a huge • Unlike the electrolysis of bauxite, it does not produce carbon dioxide
amount of electricity is needed. - a greenhouse gas.

Purified Al2O3 is dissolved in molten cryolite, Na3[AlF6], at ~900 oC and Exam Hint - Do not simply say that ‘Recycling of aluminium is
electrolysed in a cast iron cell with a graphite lining (Fig. 1). cheaper’ without explaining why.

Fig. 1 The cell for the extraction of aluminium Uses of aluminium

• For the manufacture of aircraft, because of its low density and
resistance to corrosion.
Carbon anode
• For overhead power transmission cables, because of its high electrical
+ conductivity and low density.
Molten aluminium syphoned off

- • For saucepans, because of its high thermal conductivity and resistance

Cast iron tank to corrosion.
with graphite
• For foil and drinks cans, because of its malleability and resistance to
lining as cathode
corrosion.
Electrolyte of Corrosion resistance is due to a very thin protective film of oxide that
molten Al2O3 immediately forms on the surface whenever aluminium is exposed to the
and cryolite at air. Unlike rust (on iron), this does not flake off. The thickness of the
800 - 950 0C oxide layer, and hence the resistance to corrosion, can be increased
Molten aluminium
electrolytically. So-called anodised aluminium is used for making window
frames.
1
89.The Chemistry of Aluminium Chem Factsheet

Chemical properties Covalent compounds

Aluminium is described as a ‘weak metal’. This does not mean that it is Most binary compounds of aluminium, i.e. those derived from aluminium
mechanically weak (even though it does have a low tensile strength) but and one other element, are covalent. There are two reasons for this.
that it has some of the characteristics of non-metals. • The large amount of energy needed to convert an aluminium atom to an
Al3+ ion (Table 1). The formation of covalent compounds rather than
Aluminium is a weak metal because: ionic ones is therefore favoured.
• its oxide and hydroxide are amphoteric, i.e. they have both basic
and acidic character; Table 1 Energy required to convert gaseous metal atoms to ions
• it is chemically attacked by alkalis, e.g. NaOH(aq); Change Energy/kJ mol-1
• some of its compounds are covalent.
Na(g) → Na+(g) 494
Mg(g) → Mg2+(g) 2186
Al(g) → Al3+(g) 5137
Amphoteric character
Aluminium oxide and aluminium hydroxide dissolve in both acids and However, binary compounds which contain anions of high surface
alkalis: charge density are ionic. A notable example is Al2O3. Such compounds
ACIDS Aluminium(III) salts have a lattice energy which is high enough to give a stable ionic structure,
Al2O3 or Al(OH)3 i.e. the energy released when gaseous ions join together to give the
ALKALIS Aluminates(III) crystal lattice more than compensates for the energy required to form
the ions.
Aluminates, i.e. salts with aluminium in the anion, are also produced when • Anions, unless they are particularly small, are polarisable, i.e. their
aluminium dissolves in alkalis. Few other metals behave in this way. electron clouds are not rigidly held by their nuclei and can be distorted
by Al3+, a cation of high surface charge density with exceptional
Remember - Well known weak metals are: Al, Zn, Cr, Sn, Pb, Be. polarising power. Consequently, the bond pair of electrons ceases to
be located at the anion (as in NaCl) but occupies a position between
the two nuclei: the essential condition for covalency.
So why aluminium? The key to amphoteric behaviour lies in the very high
charge density on the surface of the aluminium ion. Remember - According to Fajans’ rules, ionic bonding in a compound
A+ B- tends towards covalency when:
Fig. 2 To illustrate the high surface charge density on the Al3+ ion • A+ is small;
+ • the charge on A+ is high;
+ • B- is large.

Na Mg + Al Reactions with non-metals

+
Aluminium reacts with most non-metals on heating to give binary
+ + compounds with names ending in -ide, e.g. aluminium oxide, Al2O3;
metallic aluminium chloride, AlCl3; aluminium sulphide, Al2S3.
radius/ 0.186 0.160 0.143 Reactions with acids
nm Aluminium dissolves readily in hydrochloric acid to give a solution of
aluminium chloride plus hydrogen. On crystallising the solution,
Al3+ is a tiny ion (Fig 2) with three positive charges distributed over its AlCl3.6H2O is obtained. Anhydrous aluminium chloride is prepared by
small surface area. Consequently, whenever Al3+ is in the presence of OH- using hydrogen chloride gas (see below).
ions, lone pairs of electrons in the outer shell of the O atoms are attracted
Exam Hint - Anhydrous aluminium chloride cannot be prepared by
so strongly that coordinate (or dative covalent) bonds are formed and a
heating crystals of AlCl3.6H2O. Thermal decomposition leads to the
complex ion is produced. Figure 3 shows the hydroxo-complex obtained formation of Al2O3, HCl & H2O.
by dissolving Al, Al2O3 or Al(OH)3 in aqueous sodium hydroxide.
There is no reaction with dilute sulphuric acid, because of the protective
Fig. 3 The diaquatetrahydroxoaluminate(III) ion oxide film on the surface, but with concentrated sulphuric acid oxidation-
reduction occurs to give Al 2(SO4)3 + SO2. With nitric acid, of any
H 2O - concentration, aluminium is rendered passive, i.e. inert. HNO3, a powerful
oxidising agent, increases the thickness of the surface oxide film.
HO OH
Reaction with alkalis
Al
Aluminium dissolves readily in dilute aqueous sodium hydroxide.
HO OH
Practical 1 - The action of NaOH(aq) on aluminium
H 2O Cautiously warm a piece of aluminium foil with dilute NaOH(aq) in a
boiling tube. Test the gas evolved with a lighted spill.

‘Sodium aluminate’ in solution is therefore a complex salt. This is a redox reaction in which hydrogen is produced by the reduction of
water; not sodium hydroxide.
Na[Al(OH)4(H2O)2] Al → Al3+ + 3e−
It is named systematically as sodium diaquatetrahydroxoaluminate(III). 2H2O + 2e− → 2OH− + H2
On evaporating a solution to dryness, water is driven off to leave a solid Al3+ + 4OH− + 2H2O → [Al(OH)4(H2O)2]−
residue of the simple salt, sodium aluminate, NaAlO2. The overall ionic equation is:
2Al + 2OH− + 10H2O → 2[Al(OH)4(H2O)2]− + 3H2
Remember - OH- serves only as a ligand; it is not the oxidant!

2
89.The Chemistry of Aluminium Chem Factsheet

The thermite reaction The colourless solution formed with excess NaOH(aq) is sodium
A strongly exothermic redox reaction occurs between powdered aluminium diaquatetrahydroxoaluminate(III), formed in a further deprotonation
and iron(III) oxide to give aluminium oxide and molten iron: reaction:

2Al(s) + Fe2O3(s) → Al2O3(s) + 2Fe(l) [Al(OH)3(H2O)3](s) + OH− (aq) ¾ [Al(OH)4(H2O)2]-(aq) + H2O(l)

This so-called ‘thermite reaction’ should be performed, with With aqueous ammonia the reaction is:
appropriate safety precautions, only by a teacher.
[Al(H2O)6]3+(aq) + 3NH3(aq) ¾ [Al(OH)3(H2O)3](s) + 3NH4+(aq)
Demonstration - The thermite reaction
Practical 3 shows that the precipitate does not dissolve in excess reagent.
Set up the apparatus as shown in the following diagram.
Further deprotonation does not occur because NH3 is a weaker base than
OH −.
magnesium ribbon
barium peroxide Important compounds of aluminium
1234567890123456789012345678
1234567890123456789012345678
Aluminium oxide, Al2O3
1234567890123456789012345678 fireclay crucible This compound, which occurs naturally in bauxite, can be prepared in the
1234567890123456789012345678
1234567890123456789012345678 pure state by heating aluminium hydroxide:
1234567890123456789012345678
1234567890123456789012345678 mixture of Al and Fe2O3
1234567890123456789012345678
1234567890123456789012345678 2Al(OH)3(s) → Al2O3(s) + 3H2O(g)
1234567890123456789012345678
1234567890123456789012345678
1234567890123456789012345678
1234567890123456789012345678
sand Like Al(OH)3, Al2O3 is amphoteric, but is more resistant than the hydroxide
1234567890123456789012345678
1234567890123456789012345678
to attack by dilute reagents.

Aluminium chloride, AlCl3

Ignite the fuse of magnesium ribbon in barium peroxide with a Bunsen Anhydrous aluminium chloride is prepared by passing dry chlorine or
burner and stand well back. When the reaction has subsided, observe hydrogen chloride over heated aluminium in the type of apparatus shown
with goggles molten iron in the bottom of the crucible. in Fig. 4.

Fig. 4 Preparation of anhydrous aluminium chloride

The thermite reaction is applied for welding in restricted places, e.g. for
making continuously welded railway track. It can also be adapted to prepare aluminium turnings
other metals below aluminium in the electrochemical series, e.g. chromium, vent to fume cupboard
by using Cr2O3 instead of Fe2O3. dry Cl2(g)
or HCl(g)
Aqueous chemistry of aluminium
Hydrolysis of aluminium salts
Aluminium salts are strongly acidic in solution due to hydrolysis.

Practical 2 - Hydrolysis of aluminium salts deposit of AlCl3

Dissolve a few crystals of an aluminium salt in water and measure the bunsen burner with fishtail
pH of the solution with universal indicator or a test paper. attachment

The reason is that the hydrated aluminium ion, [Al(H2O)6]3+, present in all
solutions, is a Brønsted-Lowry acid capable of donating protons to Solid aluminium chloride has a complex polymeric structure (not required
molecules of solvent water: at A-level). On heating, it sublimes at ~200 oC to give a dimer, Al2Cl6,
shown in Fig. 5.
[Al(H2O)6]3+(aq) + H2O(l) ¾ [Al(OH)(H2O)5]2+(aq) + H3O+(aq)
Fig. 5 The structure of Al2Cl6
Consequently, [H3O+(aq)] > [OH-(aq)], i.e. the solution is acidic. Refer to
Factsheet 85 for details Clb
Clt Clt
Deprotonation (acid-base reactions)
Al Al
Practical 3 - Aluminium salt solutions with NaOH(aq) and NH3(aq)
Pour a few cm3 of a solution of an aluminium salt into a test tube and Clt Clt
add dilute NaOH(aq), dropwise with shaking, until it is eventually Clb
present in excess. Observe the formation of a white precipitate, which
dissolves in excess reagent to give a colourless solution. Repeat the Between 200 oC and 400 oC the dimer dissociates into monomeric molecules:
experiment with dilute NH3(aq) in place of NaOH(aq).
Al2Cl6(g) ¾ 2AlCl3(g)
The white precipitate is hydrated aluminium hydroxide, which is formed A dimer can be formed by coordination between two AlCl3 molecules
in a deprotonation reaction. Protons are lost from coordinated water because:
molecules of hydrated aluminium ions and transferred to hydroxide ions: • every Cl atom has lone pairs of electrons in its outer shell;
• every Al atom has a vacant orbital in its outer shell to accept a lone pair.
[Al(H2O)6]3+(aq) + 3OH− (aq) ¾ [Al(OH)3(H2O)3](s) + 3H2O(l)
In a molecule of Al2Cl6 the four terminal chlorine atoms (Clt in Fig. 5) lie at
Because [Al(H2O)6]3+ behaves as an acid on the Brønsted-Lowry theory the corners of a rectangular plane which includes both aluminium atoms.
(i.e. proton donor), while OH− is a base, this can also be described as an The bridging chlorine atoms (Clb) lie above and below the plane respectively.
acid-base reaction. This means that the distribution of bonds about each Al atom is roughly
tetrahedral.
3
89.The Chemistry of Aluminium Chem Factsheet

Exam Hint - Do not draw molecules of Al2Cl6 as follows, because this

implies a planar structure.
Cl Cl Cl
Al Al
Cl Cl Cl

Lithium tetrahydridoaluminate(III), Li[AlH4]

This compound, commonly known as ‘lithium aluminium hydride’, is made by reacting LiH and AlH3 together in dry ether. It is one of the most powerful
reducing agents there is, with two principal uses.
• Reduction of carboxylic acids to primary alcohols, e.g. CH3COOH → C2H5OH. It is the only reducing agent able to do this. The related compound
Na[BH4] will reduce aldehydes and ketones, but is unable to attack carboxylic acids.
• Preparation of hydrides of non-metals, by reducing the corresponding chlorides, e.g. PCl3 → PH3.

Practice Questions Answers

1. Why is it that, although the aqueous chemistry of chromium closely 1 By definition, a transition element has partially filled d-orbitals in at
resembles that of aluminium, chromium is classed as a transition element least one of its stable ions. Chromium conforms to this definition but
but aluminium is not? aluminium does not.

2. How does the role of carbon in the extraction of aluminium differ from 2. In the extraction of aluminium, carbon is used for the electrolysis of the
that of extraction of iron? cell. In the extraction of iron, carbon is used as a reducing agent.

3. Why cannot aluminium be manufactured by electrolysis of either of 3 (a) For two reasons. First, aluminium chloride sublimes on heating at
the following? normal atmospheric pressure. Second, if it were melted under
pressure, the liquid would be a non-electrolyte because aluminium
(a) Molten aluminium chloride
chloride is covalent.
(b) An aqueous solution of aluminium chloride
(b) Hydrogen ions would be discharged at the cathode in preference to
4. Although the re-melting of aluminium drinks cans requires a far smaller aluminium ions.
amount of energy than obtaining the metal by the electrolysis of bauxite,
the overall energy saving may be significantly less. Explain this. 4. Energy is used in collecting, transporting and sorting scrap cans.

5. Explain why it is that aluminium fluoride is ionic, whereas aluminium 5. Two energy changes favour the formation of an ionic structure for
chloride is covalent. AlF3: (i) the relatively low bond enthalpy of the F-F bond, and (ii) the
high lattice enthalpy of AlF3.
6. Aluminium dissolves in aqueous potassium hydroxide to give a Also, the F- ion is smaller than the Cl- ion and therefore less subject to
colourless solution A and a colourless, odourless gas B. When A is polarisation by the Al3+ cation.
treated with a limited amount of dilute sulphuric acid it gives a white
precipitate C, which dissolves in excess acid to give a colourless solution 6. (a) Hydrogen
D.
(a) Identify the gas B. (b) A = [Al(OH)4(H2O)2]−
B = [Al(OH)3(H2O)3], abbreviated to Al(OH)3
(b) Write down the formulae of the aluminium-containing species
C = [Al(H2O)6]3+
present in A, C and D.
(c) Explain how first C and then D are formed from solution A. (c) Equilibria exist in solution:

7. Adding a solution of sodium carbonate to one of aluminium sulphate [Al(OH)4(H2O)2]−(aq) + H2O(l) ¾ [Al(OH)3(H2O)3](s) + OH−(aq)
gives a white precipitate X and a colourless, odourless gas Y. Predict
the identities of X and Y and suggest how these substances are formed. [Al(OH)3(H2O)3(s) + 3H2O(l) ¾ [Al(H2O)6]3+(aq) + 3OH−(aq)

8. Predict the shape of the AlCl3 molecule. On adding an acid, these equilibria are disturbed to the RHS by the
removal of OH−(aq) ions: H3O+(aq) + OH−(aq) → 2H2O(l)

7. X is aluminium hydroxide; Y is carbon dioxide.

They are formed by a deprotonation/acid-base reaction. CO32−, which
is a base, removes protons from [Al(H2O)6]3+ to give [Al(OH)3(H2O)3].
Acceptance of protons by CO32− ions does not give carbonic acid
(H2CO3) because of its instability but, instead, its decomposition
products, CO2 + H2O.
Acknowledgements: This Factsheet was researched and written by John
Brockington. Curriculum Press, Bank House, 105 King Street, Wellington, 8. Trigonal planar, due to equal repulsion between three bond pairs of
Shropshire, TF1 1NU. ChemistryFactsheets may be copied free of charge electrons and the absence of a lone pair of electrons on the Al atom.
by teaching staff or students, provided that their school is a registered
subscriber. No part of these Factsheets may be reproduced, stored in a
retrieval system, or transmitted, in any other form or by any other means,
without the prior permission of the publisher. ISSN 1351-5136
4
 Chem Factsheet
www.curriculum-press.co.uk Number 90
Complexes
To succeed in this topic you need to understand:
· coordinate bonding (covered in Factsheet 5); Remember - Iron(II) sulphate, FeSO4, is used as an antidote for
· oxidation numbers (covered in Factsheet 11); cyanide poisoning. As the toxic CN− ions coordinate to Fe2+ ions, they
· shapes of molecules and ions (covered in Factsheet 4). are converted to harmless [Fe(CN)6]4− ions.
Warning! Do not try this.
After working through this Factsheet you will:
· know that complexes are formed by the coordination of ligands to Coordination number
a cation, atom or molecule;
· know the formulae and names of common anionic and molecular
ligands; The coordination number of a central cation is defined as
· understand the following aspects of complex ions:- the number of coordinate bonds which it forms. If all the ligands are
coordination number, formulae, ionic charge, nomenclature, ‘monodentate’ , i.e. if they coordinate through only one atom,
formation, colour, shapes and isomerism; coordination number is equal to the number of ligands.
· be familiar with other types of complexes. Coordination numbers of 2, 4 and 6 are encountered in complex ions,
but 6 is by far the most common.
The term complex is used to describe a great many compounds, molecules
and ions resulting from coordination, i.e. the establishment of coordinate
Coordination number is governed by two factors.
bonds.
• Available space
Most central cations are so small that no more than six ligands can be
Remember - A coordinate (or dative covalent) bond is a special kind of
covalent bond, in which both of the bonding electrons originate from packed around them.
one atom. A coordinate bond, once formed, is indistinguishable from a • Availability of vacant orbitals
covalent bond. The central cation must have vacant orbitals at a relatively low energy
level to accept lone pairs of electrons. This explains why the
coordination number of boron in complex ions such as [BF4]- is
Complex species are formed by the coordination of one or more ligands to a restricted to 4. The central B3+ cation has the configuration 1s2.
cation, atom or molecule. Incoming electrons can enter the second shell but not the higher
energy third shell. The second shell can hold four electron pairs
A ligand is defined as an anion or molecule with a lone pair of altogether; one in the vacant 2s orbital and three in the 2p orbitals.
electrons available for donation.
Examples of anionic ligands are F−, Cl−, Br−, OH− and CN−. Similar reasoning suggests that the maximum coordination number of
Examples of molecular ligands are H2O, NH3 and CO. aluminium shouldbe nine, because electrons enter the third shell which
can hold 18 electrons (nine electron pairs), but in fact the number is
six because Al3+ is such a small cation that no more than six ligands
Complexes based on a cation can be accommodated.
When ligands coordinate to a cation (referred to as the ‘central cation’), the
product is known as a complex ion. Compex ions include: Formulae
• hydrated metal cations, such as [Al(H2O)6]3+ and [Fe(H2O)6]2+; • The symbol for the central element is written first, followed by
• other complex cations, such as [Co(NH3)6]2+; anionic ligands and molecular ligands in that order.
• complex anions, such as [Ag(CN)2]−. • Within each ligand class, the order should be alphabetical in terms of
the symbol for the donor atom of the ligand.
In order to attract lone pairs of electrons from ligands, the central • Polyatomic ligands (but not monoatomic ones) are enclosed in curved
cation needs to have a high surface charge density, i.e. a high charge (at brackets.
least 2+), a low radius or, ideally, both. • The formula of the whole complex ion is enclosed in square brackets.
• For this reason, transition metal cations are at the centre of most • The charge on the complex ion is shown superscript outside the right
complex ions. hand bracket.
• Apart from Al3+ and Be2+, cations from the main group elements do Examples are as follows,
not normally enter into complex ions. [Cr(H2O)6] 3+
• Some complex ions are based on hypothetical cations, e.g. B3+ and [Al(OH)(H2O)5]2+ (Anionic ligand before the molecular ligands)
Si4+. Such ions are said to ‘exist only in complexes’, where they are [Cu(NH3)4(H2O)2]2+ (Donor atoms are N and O; N is alphabetically
‘stabilised by coordination’. before O)
[CoCl(NH3)5]2+ (NH3 in parentheses but not Cl)

When the central cation and ligands react together, their original properties
are lost as the complex ion, with its own characteristics, is formed. For Remember - Square brackets have two main uses in chemistry.
instance, the complex salt potassium hexacyanoferrate(II) shows none of • To denote molar concentrations; e.g. [H+] represents the
the reactions of the Fe2+ and CN− ions from which it is formed, but has concentration of hydrogen ions in mol dm−3.
entirely different properties due to the complex ion [Fe(CN)6]4−. • To enclose complex ions.

1
90. Complexes Chem Factsheet

Ionic charge Table 3 Multiplying prefixes

The charge on a complex ion is the algebraic sum of that on 2 di

the central cation and the total charge carried by the ligands. 3 tri
4 tetra
When all the ligands are neutral, the overall charge of the complex ion is
simply that carried by the central cation, e.g. Cr3+ + six neutral H2O molecules 5 penta
give [Cr(H2O)6] with a charge of 3+. 6 hexa
In other cases, you should write down the charges of all the components
and then calculate the overall charge. Examples are as follows. • Ligands are listed in alphabetical order, the multiplying prefix being
ignored. For example, ‘pentaaqua’ would be cited before ‘dicyano’.
[Fe(CN)6]4− comprises an Fe2+ ion and six CN− ions.
• For all complexes, the name of the central element follows the names of
∴ overall charge = +2 -6 = -4 the ligands. For complex cations the name of the element remains
[Al(OH)(H2O)5]2+ comprises an Al3+ ion, one OH- ion and five H2O unchanged, but for complex anions thename of the element is changed
molecules. from -ium to -ate, e.g. chromium to chromate. In some cases, where the
symbol is of Latin origin, the name is more radically altered, e.g. ‘ferrate’
∴ overall charge = +3 -1 +0 = +2 for anionic complexes of iron and ‘cuprate’ for those of copper.
Exam Hint - Do not confuse ionic charge with oxidation number. • The oxidation state of the central element is indicated by a Roman
• The ionic charge is equal to the oxidation number of the central numeral in parentheses after the name of the complex.
element only if all the ligands are neutral.
• If necessary, the oxidation number of the central element can be Examples are as follows.
shown by a superscript Roman numeral to the right of the symbol, [Cr(H2O)6] 3+ hexaaquachromium(III) ion
e.g. [FeII(CN)6]4-. [Al(OH)(H2O)5]2+ pentaaquahydroxoaluminium(III) ion
(pentaaqua before hydroxo)
[CoCl4]2- tetrachlorocobaltate(II) ion
Nomenclature [Fe(CN)6]4- hexacyanoferrate(II) ion

- Ligands are named first, followed by the central element.

Remember - Complex names are written as one word, with no hyphens
and no spacing between the name and the oxidation state of the central
element.
The names of some ligands are given in Tables 1 and 2.
Formation
Table 1 Common anionic ligands with names used in complex Compex ions may be formed by two mechanisms.
nomenclature
• Deprotonation (acid-base reaction)
F− fluoro In aqueous solution cations become hydrated, i.e. surrounded by shells of
water molecules, which are attracted to the cations by partial negative
Cl− chloro
charge on oxygen.
Br− bromo δ+ δ+
H H
I− iodo
−
.. ..
OH hydroxo δ− O δ− H
H
CN− cyano O O
H H
NO 2 − nitro cation
H H
O O
H− hydrido* H O H

* IUPAC (but not ASE) recommends that ‘hydro’ is used in complexes H H

of boron.

Table 2 Common molecular ligands with names used in complex For Al3+ and transition metal cations, this ion-dipole attraction is reinforced
nomenclature by coordination. Generally, six H2O molecules are involved, to give complex
ions such as [Al(H2O)6]3+ and [Fe(H2O)6]2+. With hydroxide ions and
H 2O` aqua certain other ligands that behave as bases (e.g. NH3), new complex ions can
be formed from these hydrated cations by the process of deprotonation, in
NH 3 ammine which protons (H+) break away from coordinated water molecules to join
CO carbonyl the basic ligand. If, for example, two OH- ions were to attack a hydrated
aluminium ion, the reaction would be:
NO nitrosyl
[Al(H2O)6]3+(aq) + 2OH-(aq) → [Al(OH)2(H2O)4]+(aq) + 2H2O(l)
• The number of each type of ligand is denoted by a prefix of Greek
origin (Table 3). These prefixes are the same as those used in naming Since the hydrated cation behaves as an acid (proton donor) while OH- is a
organic compounds. ‘Mono’ is not normally used. base (proton acceptor), such changes are often described as acid-base
reactions. See Factsheet 86 for more detail.

2
90. Complexes Chem Factsheet

• Ligand substitution Table 4 Electronic configurations and colours of some hydrated

Strong ligands, i.e. those that bond strongly to the central cation, will ions, [M(H2O)6]n+, where n = 2 or 3
replace weaker ligands in ligand substitution reactions. Some of these are
reversible because it is possible for a weak ligand to replace a stronger one M Electronic configuration Colour
if the former is present in excess.
Sc3+ [Ar] 3d0 none
3+ 1
Ligand substitution may occur with or without a change in coordination Ti 3d violet
number. On boiling a mixed solution of iron(II) sulphate and potassium 3+ 2
V 3d green
cyanide, six H2O molecules are replaced by six CN− ions:
3+ 3
Cr 3d grey-blue
[Fe(H2O)6]2+(aq) + 6CN−(aq) → [Fe(CN)6]4−(aq) + 6H2O(l)
2+ 5
Mn 3d pale pink
However, when concentrated hydrochloric acid is added to a solution of a 3+ 5
cobalt(II) salt, six H2O molecules are replaced by only four Cl− ions: Fe 3d pale violet*
2+ 6
Fe 3d pale gree
[Co(H2O)6]2+(aq) + 4Cl−(aq) ¾ [CoCl4]2−(aq) + 6H2O(l)
2+ 7
Co 3d pink
The decrease in coordination number is attributed to the relatively large 2+ 8
size of Cl- ions compared with H2O molecules. Ni 3d green
Cu2+ 3d9 blue
Practical 1 - Preparation of tetrachlorocobaltate(II) ions.
Zn 2+ 3d10 none
Add concentrated hydrochloric acid slowly, with shaking, to a few cm3
of a solution of a cobalt(II) salt in a test tube and observe the colour
change. Afterwards add water, until it is present in excess, and again * The pale violet colour of [Fe(H2O)6]3+ can be seen in salt hydrates, such
observe the colour change. as Fe(NO3)3.9H2O. In aqueous solution, however, iron(III) salts are
Make sure you can write the equation for this reversible reaction. brownish yellow due to salt hydrolysis - a deprotonation reaction:
[Fe(H2O)6]3+(aq) + H2O(l) ¾ [Fe(OH)(H2O)5]2+(aq) + H3O+(aq)
Colour pale violet brownish yellow
Most, but not all, complex ions are coloured, depending on whether or not
the central cation has partially occupied d-orbitals. In a simple cation, all The colour of complex ions depends on the following factors.
five 3d orbitals are degenerate, i.e. at exactly the same energy level, but, in • Nature of the metal
the presence of ligands, this is not so. (The degeneracy is said to be Different metals produce differently coloured ions, even when those
‘relieved’.) Two of the orbitals are raised in energy level (‘upper set’) ions have identical configurations and identical ligands. (Compare
while the other three are lowered (‘lower set’), an effect known as the [Mn(H2O)6]2+ and [Fe(H2O)6]3+.)
‘splitting of d-orbitals’ (Fig. 1) • d-orbital occupation
For a particular metal, colour depends on the number of d-electrons.
Fig. 1 Splitting of d-orbitals (Compare Fe3+ and Fe2+.)
• Nature of the ligand
two 3d For a particular cation, different ligands produce different colours.
orbitals (Compare [Co(H2O)6]2+ (pink) with [CoCl4]2− (blue) and [Co(NH3)6]2+
E (upper set)
(red-brown).)
∆E
Shapes
isolated ion
five 3d three 3d
orbitals orbitals
- Shapes of complex ions
(degenerate) (lower set) • Six-coordinate complexes are octahedral.
• Four-coordinate complexes are tetrahedral, except for [Ni(CN)4]2−
which is square planar.
• Two-coordinate complexes are linear.
The energy difference between the upper set and the lower set can be
symbolised ∆E. When white light falls on a complex, the component whose Examples are shown in Table 5.
frequency (ν) corresponds to ∆E is absorbed in promoting an electron from
the lower to the upper set. (∆E and ν are related by Planck’s equation, Table 5 The geometry of some typical complex ions
∆E = hν, where h = Planck’s constant.) The other components of white Octahedral Tetrahedral Linear
light are transmitted, so that the complex appears to be coloured.
[Al(H2O)6]3+ [CoCl4]2− [Cu(NH3)2]+
Therefore, for a complex to be coloured, there must be at least one electron
[Ni(NH3)6]2+ [Cu(CN)4]3− [CuCl2]−
in the lower set (available for promotion) and at least one vacancy in the
4− 2+
upper set (to receive the promoted electron). This rules out complexes of [Fe(CN)6] [Zn(NH3)4] [Ag(NH3)2]+
Al3+ and Sc3+ (no electron in the lower set) and complexes of Cu+ and Zn2+ [Cr(OH)6]3−
(no vacancy in the upper set). However, transition element ions in general
do satisfy these conditions and their complexes are coloured (Table 4). Whenever you are asked to draw the shapes of complex ions, read the
question carefully!

3
90. Complexes Chem Factsheet

If you are asked to show the formation of a complex ion, you need diagrams
such as those shown in Figs. 2(b) and 3(b), but if you are asked to show an Exam Hint - If you are asked how you would distinguish between
ion once it has been formed, figures such as 2(a) and 3(a) are more samples of each of these, bear in mind that only ionic chlorine (i.e. Cl-
ions) will react with silver nitrate solution; not covalently bonded
appropriate because they show delocalisation of charge over the whole of
chlorine. The method therefore involves adding aqueous silver nitrate
the complex. to solutions containing equal amounts of the three isomers until there
is no further precipitation of silver chloride. The precipitates are then
Fig. 2 (a) The hexahydroxochromate(III) ion filtered off, washed, dried and weighed. Their masses will be in the
(b) Formation of the hexahydroxochromate(III) ion ratio 3:2:1, corresponding to the numbers of Cl- ions in the formulae.

3−
OH OH − Geometrical isomerism

HO OH HO− 3+ OH − - Sometimes known as cis-trans isomerism, this occurs when

Cr Cr a complex has two sorts of ligands. If two identical ligands occupy
HO OH HO− OH − adjoining positions on the complex an isomer is described as cis, but if
OH OH − they are across the complex from each other it is a trans isomer.

(a) (b)
Geometrical isomerism is encountered with both square planar and
octahedral complexes. The best known square planar examples are
Fig. 3 (a) The tetrachlorocobaltate(II) ion platinum(II) complexes such as the following:
(b) Formation of the tetrachlorocobaltate(II) ion
2−
Cl Cl− Cl II NH 3 H 3N II Cl
Pt Pt
2+ Cl NH 3 Cl NH 3
Co Co
Cl Cl Cl− Cl−
cis isomer trans isomer
Cl −
Cl
Note that these are complex molecules - not ions - because the overall
(a) (b) charge is zero.
For an octahedral example, look at the tetraamminedichlorocobalt(III) ion:
+ +
Exam Hint - ‘Octahedral’ does not mean star-shaped. NH 3 NH 3
3−
H3N III
Cl H3N III
Cl
OH Co Co
HO OH Cl Cl
H 3N NH 3
Cr NH 3 NH 3
HO OH
OH cis isomer trans isomer

If you draw an octahedral ion like this you will lose marks! Complexes based on an atom
Carbon monoxide is well known for coordinating to atoms of transition
elements to give metal carbonyls such as [Ni(CO)4], tetracarbonylnickel(0),
commonly called nickel tetracarbonyl. The molecule is tetrahedral.
Isomerism
This compound has been used in the Mond process for the purification of
Remember - Isomerism exists when two or more compounds have the nickel. Impure nickel will react with carbon monoxide at 80 oC to give
same molecular formula but different structural formulae. volatile [Ni(CO)4], which is led away and decomposed at a higher
temperature. This gives pure nickel because other metals will not form
Complexes may exhibit ionisation isomerism and geometrical isomerism. carbonyls at 80 oC.
(There is also optical isomerism but this is not required at A-level.) Complexes based on a molecule
Halides of boron, notably boron trifluoride, are very strong Lewis acids,
Ionisation isomerism forming a great many complexes by accepting a lone pair of electrons into
This occurs when two or more compounds have the same composition but the vacant p-orbital of the outer shell. This can result in the formation of
consist of different ions. The best known example concerns chromium(III) both complex ions and complex molecules, e.g.
chloride-6-water, CrCl3.6H2O, which forms three ionisation isomers or
‘hydrate isomers’ as follows: F
F−
[Cr(H2O)6]3+ (Cl-)3 grey-blue
→ [BF4]-
[CrCl(H2O)5]2+ (Cl-)2.H2O light green B
F F Tetrafluoroborate(III) ion
[CrCl2(H2O)4]+ Cl-.2H2O dark green
H F
H N → H3N→BF3
H B Ammonia-boron trifluoride(1/1)
F F

4
90. Complexes Chem Factsheet

Practice questions Answers

1 Write down the formulae of the following. 1 (a) [Co(NH3)6]3+
(a) Hexaamminecobalt(III) ion (b) [Cu(NH3)4(H2O)2]2+
(b) Tetraamminediaquacopper(II) ion (c) [Al(OH)4(H2O)2]-
(c) Diaquatetrahydroxoaluminate(III) ion
2 (a) +3
2 Calculate the oxidation number of iron in each of the following (b) 0
complexes. (c) +2
(a) [Fe(CN)6]3−
(b) Fe(CO)5 3 3d 4s 4p
(c) [Fe(OH)(H2O)5]+ [Ar]

3 Draw appropriate arrows in the following ‘boxes’ to represent orbital Electrons Electrons originating from the ligands
occupation in thehydrated chromium(III) ion. Label the diagram so as possessed
to distinguish between electrons possessed by the simple Cr3+ ion and by Cr3+ ion
those originating from the ligands.
4 (a) A = [Cu(H2O)6]2+ Hexaaquacopper(II) ion Octahedral
3d 4s 4p B = [CuCl4]2− Tetrachlorocuprate(II) ion Tetrahedral
Cr3+ [Ar] C = [Cu(OH)4]2− Tetrahydroxocuprate(II) ion Tetrahedral

4 Copper(II) sulphate was dissolved in water to give a blue solution A. (b) [Cu(H2O)6]2+(aq) + 4Cl-(aq) → [CuCl4]2−(aq) + 6H2O(l)
When A was treated with concentrated hydrochloric acid it gave a Ligand substitution
yellow solution B and when it was treated with concentrated aqueous
sodium hydroxide it gave a blue solution C. The complex ions in solutions (c) [Cu(H2O)6]2+(aq) + 4OH−(aq) → [Cu(OH)4]2−(aq) + 6H2O(l)
B and C both have a coordination number of 4. Deprotonation (acid-base reaction)

(a) Write down the formulae and names of the complex ions in A, B 5 Cl Cl
and C and state their shapes. NH 3 NH 3
II II
Ni Ni
(b) Write an ionic equation for the conversion of A to B and state the
type of reaction. H 3N Cl Cl NH 3
trans cis
(c) Write an ionic equation for the conversion of A to C and state the
type of reaction.
6 (a) NH3: lone pair of electrons on N available for donation.
5 The square planar compound [NiCl2(NH3)2] can occur as two geometric BF3: B has a vacant p-orbital.
isomers. Draw their structures and label each as cis or trans.
(b) Coordinate / dative covalent bond
6 Ammonia and boron trifluoride combine together readily to give a
white solid called ammonmia-boron trifluoride(1/1). (c) Bond angles around N are increased from 106.7o to 109.5o, while
those around B are decreased from 120o to 109.5o.
(a) What features of the NH3 and BF3 molecules make this reaction
possible? Reason The bond angle in NH3 (trigonal pyramidal) is governed
by repulsion between three bond pairs of electrons and one lone
(b) What type of bond is formed? pair: repulsion between lone pair and bond pair is greater than that
(c) State and explain how the bond angles around both the N and B between two bond pairs. In BF3 (trigonal planar) the bond
atoms are changed as a result of this combination. angle is the result of equal repulsion between three bond pairs. In
the complex, the distribution of bonds about both N and B is
tetrahedral due to equal repulsion between four bond pairs of
electrons.

Acknowledgements: This Factsheet was researched and written by John

Brockington. Curriculum Press, Bank House, 105 King Street, Wellington,
Shropshire, TF1 1NU. ChemistryFactsheets may be copied free of charge by
teaching staff or students, provided that their school is a registered subscriber.
No part of these Factsheets may be reproduced, stored in a retrieval system, or
transmitted, in any other form or by any other means, without the prior
permission of the publisher. ISSN 1351-5136

5
 Chem Factsheet
www.curriculum-press.co.uk Number 91
Naming of Organic Compounds
To succeed in this topic you need to understand: An alkyl radical (or alkyl group) is derived from an alkane by the loss of
· the difference between aliphatic and aromatic compounds; one hydrogen atom. The names of alkyl radicals commonly used in
· functional groups (covered in Factsheet 15); organic nomenclature are shown in Table 2.
· homologous series (covered in Factsheet 15);
· isomerism (covered in Factsheet 15). Table 2 - Names of alkyl radicals

Formula Name
After working through this Factsheet you will have a more detailed
knowledge of organic nomenclature, introduced in Factsheet 15. In CH 3- methyl
particular, you will: CH3CH2- or C2H5- ethyl
· understand the systematic naming of alkanes;
· understand how other aliphatic compounds are named as substituted CH3CH2CH2-* propyl
alkanes; CH3CHCH3 isopropyl (IUPAC) or 1-methylethyl
· know that international (IUPAC) names may differ from those (ASE)
used in UK schools;
· know the names of common aromatic compounds. * Never write C3H7-. This is ambiguous because it could represent
either CH3CH2CH2- (propyl) or (CH3)2CH- (isopropyl).
Although some organic compounds have trivial names (common names),
most of them have to be named systematically. Both the International CH3
Union of Pure and Applied Chemistry (IUPAC) and the Association for CH-CH3 or (CH3)2CHCH3 Compound I
Science Education (ASE) have published rules of nomenclature, but only CH3
ASE names have been adopted by schools in the UK. This Factsheet In this way, Compound I, commonly called isobutane, is named
concentrates on these but also draws your atttention to IUPAC names, systematically as methylpropane.
where they differ from ASE ones, because you may come across them in
your wider reading. For more complicated molecules, other IUPAC rules are needed.
• Consider Compound II
Aliphatic compounds
Alkanes must be studied first, because the names of other aliphatic compounds CH3
are based on those of the alkanes. CH-CH2-CH3 or (CH3)2CHCH2CH3 Compound II
CH3
Alkanes Is this methylbutane or ethylpropane?
Remember - Alkanes are saturated aliphatic hydrocarbons of general For alkanes, always select the longest carbon chain as the
formula CnH2n + 2. basis of the name.

Because the longest chain in Compound II contains four carbon atoms,

The names of the first ten unbranched alkanes are shown in Table 1.
its correct name is methylbutane. Now consider Compounds III and IV.
Table 1 - Names of unbranched alkanes CH3 CH3
 
Formula Name CH3-CH-CH2-CH2-CH3 CH3-CH2-CH-CH2-CH3
CH4 methane Compound III Compound IV
CH 3CH 3 ethane They both appear to be methylpentane, but two compounds cannot
CH3CH 2CH 3 propane have the same name.
CH3(CH2)2CH3 butane
Number the carbon atoms of the longest chain to facilitate
CH3(CH2)3CH3 pentane reference to substituent groups.
CH3(CH2)4CH3 hexane
CH3(CH2)5CH3 heptane In this way Compound III becomes 2-methylpentane while Compound
CH3(CH2)6CH3 octane IV is 3-methylpentane. Numbers used in naming are called locants.
CH3(CH2)7CH3 nonane • If the longest chain of Compound III were to be numbered from right
CH3(CH2)8CH3 decane to left, the CH3 group would appear on the fourth carbon atom to
give a name of 4-methylpentane rather than 2-methylpentane. Which
Branched chain isomers are named as alkyl-substituted alkanes. is right?

In the event of a choice, always select the name with the lower
Remember - Isomers are compounds with the same molecular formula numbering on the occasion of the first difference.
but different structural formulae.
The correct name of Compound III is therefore 2-methylpentane.
1
91. Naming of Organic Compounds Chem Factsheet

The name must always be based on the longest C chain which includes
Exam Hint - For complicated molecules you should:
• number the C atoms of the longest chain from left to right and write the C=C bond. This is not necessarily the same as the longest chain in the
down the name; molecule. Look at the following compound.
• number the atoms in the opposite direction and again write down
CH2
the name;
• choose the name with the lower numbering.
CH3CH2CCH2CH3 2-ethylbut-1-ene

• Look at Compound V. The longest chain in this molecule has five C atoms, but the compound
cannot be named as a derivative of pentane because there is no way of
CH3 CH3 CH3
referring to the =CH2 side chain.
  
CH3-CH_CH-CH2-CH-CH3 Compound V Dienes, i.e. compounds with two C=C bonds, are named as such. There
On the basis of the rules so far, the name would be 2-methyl-3-methyl-5- must be a locant to denote the position of each double bond, e.g.
methylhexane. This, however, is wrong. CH2=CHCH=CH2 buta-1,3-diene

Variations
All alkyl groups of a particular kind should be grouped The trivial names ethylene (for C2H4) and propylene (for C3H6) are in
together with a multiplying prefix; di, tri, tetra, penta and hexa for 2, 3, common use. IUPAC places locants at the beginnings of names rather than
4, 5 and 6, respectively. within them, e.g.
CH2=CHCH2CH3 1-butene
Compound V is therefore 2,3,5-trimethylhexane. CH3CH=CHCH3 2-butene
• Finally, consider Compound VI. Haloalkanes or halogenoalkanes (Formerly known as alkyl halides)

C2H5 CH3 Remember - These are compounds of the kind RX, where R stands for
  an alkyl radical, such as CH3 or C2H5, and X for a halogen atom; Cl,
CH3-CH2-CH_C-CH3 Compound VI Br or I.

CH3
Haloalkanes are given substitutive names, i.e. they are named as halogen-
Is this called 3-ethyl-4,4-dimethylpentane, or 2,2-dimethyl-3- substituted alkanes.
ethylpentane?
Write down ‘chloro’, ‘bromo’ or ‘iodo’, followed by the name
Akyl groups are referred to in alphabetical order. of the parent alkane.

This rule is applied regardless of any multiplying prefixes. It follows that

Compound VI is correctly named as 3-ethyl-4,4-dimethylpentane. Use locants, if necessary, to indicate the positions of both alkyl groups and
the halogen atom, e.g.
Exam Hint - It is impossible to have ‘2-ethyl’ anything, except when CH3Cl chloromethane
naming alkenes (see below). If ever you find yourself writing this, it CH3CH2Br bromoethane
means you’ve failed to identify the longest carbon chain.
CH 3CH2CH2I 1-iodopropane
CH3CHICH3 2-iodopropane
Alkenes
Exam Hint - Beware of the following compound:
Remember - Alkenes are unsaturated aliphatic hydrocarbons with a CH3
carbon-carbon double bond. Their general formula is CnH2n. CHCH2Cl
CH3
This is called 1-chloro-2-methylpropane;
Alkenes are treated as alkanes, with the name ending changed from ‘ane’ to NOT 2-methyl-1-chloropropane.
‘ene’, e.g. In all haloalkanes, the ‘halo’ part of the name comes first.
CH2=CH2 ethene
CH3CH=CH2 propene Variations
If necessary, locants are used to distinguish between isomers, e.g. As well as substitutive names, IUPAC also allows radicofunctional names.
On this system, the compounds are named as alkyl halides, e.g.
CH2=CHCH2CH3 but-1-ene CH3Cl methyl chloride
CH3CH=CHCH3 but-2-ene CH3CH2Br ethyl bromide
CH 3CH2CH2I n-propyl iodide*
The locant refers to the number of the C atom where the CH3CHICH 3 isopropyl iodide
double bond starts. * n stands for ‘normal’.

Branched chain alkenes are named like branched chain alkanes, e.g.
CH3
C=CH2 2-methylpropene
CH3

2
91. Naming of Organic Compounds Chem Factsheet

Alcohols For aldehydes, it is unnecessary to use a locant to show the position of the
C=O group because it is always situated at the end of the chain:
Remember - Alcohols are compounds of the kind ROH, where R HCHO methanal
represents an alkyl radical and OH (hydroxyl) is the functional group. CH 3CHO ethanal
CH 3CH 2CHO propanal
Alcohols are named as alkanols, i.e. they are treated as hydroxyl-substituted CH 3CH 2CH 2CHO butanal
alkanes.
Exam Hint - Always write the formula of an aldehyde as RCHO; not
Write down the name of the parent alkane, delete ‘e’ from the RCOH, because this implies the presence of a hydroxyl group.
end and replace it by ‘ol’.
When naming branched chain aldehydes, it is assumed that the C atom of
Use locants where necessary to refer to the positions of both alkyl side CHO is no. 1 of the longest chain, e.g.
chains and the OH group, e.g. CH3
CH3OH methanol  3-methylbutanal
CH3CHCH2CHO
CH3 CH2 OH ethanol
CH3CH 2CH2OH propan-1-ol For ketones, a locant is generally needed for the C atom of the CO group,
CH3CH(OH)CH3 propan-2-ol e.g. CH3COCH3 propanone
CH3CH 2CH 2CH2OH butan-1-ol CH3COCH2CH 3 butan-2-one
CH3CH(OH)CH2CH3 butan-2-ol CH3COCH2CH 2CH3 pentan-2-one
(CH3)2CHCH2OH 2-methylpropan-1-ol CH3CH 2COCH 2CH3 pentan-3-one
(CH3)3COH 2-methylpropan-2-ol (CH3)2CHCOCH3 3-methylbutan-2-one

Dihydric alcohols (compounds with two OH groups) are named Variations

systematically as diols, e.g. For aldehydes, IUPAC permits a series of older names based on the trivial
CH2OH names of the carboxylic acids to which they become oxidised, e.g.
 ethane-1,2-diol HCHO formaldehyde
CH2OH CH 3CHO acetaldehyde
The trivial name of this compound is ethylene glycol. CH 3CH 2CHO propionaldehyde

Variations For the substitutive names of ketones, IUPAC recommends that the locant
IUPAC substitutive names differ from ASE ones in that the locant is should be placed at the beginning of the word, e.g. 2-pentanone instead of
written at the beginning of the name, e.g. 1-propanol instead of propan-1-ol. pentan-2-one. IUPAC also allows radicofunctional names, e.g. ethyl methyl
IUPAC also allows the use of radicofunctional names, e.g. ketone for CH3COCH2CH3.
CH3OH methyl alcohol
CH 3CH 2OH ethyl alcohol For the first member of the homologous series, CH3COCH3, the trivial
CH 3CH 2CH2OH n-propyl alcohol name of acetone is still widely used, especially in industry.
CH3CH(OH)CH3 isopropyl alcohol
Carboxylic acids
The chemical industry uses some hybrid names, notably the following:
Remember - Carboxylic acids are compounds of the kind RCOOH.
CH 3CH 2CH2OH n-propanol The functional group, COOH, is called the carboxyl group.
CH3CH(OH)CH3 isopropanol
CH3CH 2CH 2CH 2OH n-butanol These compounds are named systematically as alkanoic acids.
CH3CH(OH)CH2CH3 sec-butanol
(CH3)2CHCH2OH isobutanol Write down the name of the parent alkane, delete ‘e’ from
(CH3)3COH tert-butanol the end and replace it by ‘oic acid’.

Aldehydes and ketones

As for aldehydes, a locant is not needed to show the position of the
Remember functional group. The C atom of the COOH group is assumed to be C
Aldehydes and ketones all contain the carbonyl group, C=O. atom no. 1 of the longest chain, e.g.
HCOOH methanoic acid
The difference between them is that, in an aldehyde molecule, at least CH 3COOH ethanoic acid
one bond from the carbonyl carbon atom is joined to H whereas, in the CH 3CH 2COOH propanoic acid
case of a ketone, both bonds are joined to alkyl radicals. CH 3CH 2CH 2COOH butanoic acid
O O (CH 3)2CHCOOH 2-methylpropanoic acid
Dicarboxylic acids are named as alkanedioic acids, e.g.
R-C-H R-C-R
Aldehyde Ketone COOH
 ethanedioic acid
COOH
Aldehydes are named as alkanals and ketones as alkanones.
Variations
IUPAC recommends retention of trivial names for simple aliphatic acids.
These reflect the original sources of the compounds, e.g.
Aldehydes Write down the name of the parent alkane, delete ‘e’ from
HCOOH formic acid (from the Latin formica = an ant)
the end and replace it by ‘al’.
CH3COOH acetic acid (from the Latin acetum = vinegar)
Ketones Write down the name of the parent alkane, delete ‘e’ from the
CH3CH 2COOH propionic acid (from the Greek pion = fat)
end and replace it by ‘one’.
CH3CH 2CH 2COOH butyric acid (from the Latin butyrum = butter)
3
91. Naming of Organic Compounds Chem Factsheet

Derivatives of carboxylic acids

Amides
Acyl chlorides (Formerly known as acid chlorides)
Remember - Amides have the general formula RCONH2. They are
Remember - These are compounds of the kind RCOCl, i.e. they are derived from carboxylic acids by replacing OH by NH2.
derived from carboxylic acids by replacing OH by Cl. A group of
the kind RCO is known as an acyl group. They are given substitutive names.

Acyl chlorides (and other acyl halides) are given substitutive names. Write down the formula of the parent alkane, delete ‘e’
from the end and replace it by ‘amide’.
Write down the name of the parent alkane, delete ‘e’ from
the end and replace it by ‘oyl chloride’. E.g.CH3CONH2 ethanamide
A IUPAC alternative is acetamide.
Effectively, the first member of the homologous series is CH3COCl,
ethanoyl chloride. (HCOCl is an unstable compound: it decomposes Exam Hint - Do not confuse amides with amines!
into HCl + CO.) Amides are derived from carboxylic acids:
O O
Variations R-C R-C
IUPAC permits radicofunctional names based on the trivial names of the OH NH2
carboxylic acids from which they are derived, e.g. Carboxylic acid Amide
Amines (see below) are derived from alcohols:
CH3COCl acetyl chloride
R-OH R-NH2
Alcohol Amine
Esters If in doubt, refer to amides as ‘acid amides’. This is an old-
fashioned term but it might help.
Remember - Esters are of the kind RCOOR’, i.e. they are derived
from carboxylic acids by replacing H of the carboxyl group by a Amides in which H atoms of the NH2 group are replaced by alkyl
hydrocarbon radical R’. (R and R’ may be identical radicals. radicals are named as N-substituted amides, i.e. nitrogen-substituted
amides, e.g.
Although esters are generally prepared by reacting carboxylic acids
with alcohols, for naming purposes they are regarded as derivatives of CH3CONHC2H5 N-ethylethanamide
carboxylic acids. Thus, all esters of ethanoic acid are called ethanoates, (The formula could equally well be written as C2H5NHCOCH3, but
e.g. not C2H5CONHCH3 because this represents N-methylpropanamide.)
CH3COOC2H5 ethyl ethanoate
A IUPAC variation is ethyl acetate.
Nitriles
Exam Hint - Be very careful how you write the formulae of esters:
a wrongly written formula leads to a wrong name. For instance,
Remember - Nitriles are organic cyanides; compounds of the kind
the formula of ethyl ethanoate could be written C2H5OCOCH3, RCN.
which is a contraction of
O These compounds are given substitutive names, formed by adding the
C-CH3 suffix ‘nitrile’ to the name of the parent alkane, e.g.
C2H5-O CH3CN ethanenitrile
but NOT C2H5COOCH3, which is a contraction of IUPAC also allows radicofunctional names, such as methyl cyanide for
O CH3CN.
C2H5-C
O-CH3
This is the formula of methyl propanoate (i.e. the methyl ester of Exam Hint - When looking for the longest carbon chain in a nitrile
propanoic acid), a different - although isomeric - ester. molecule, don’t forget to include the C atom of the CN group!

Amines
Remember - Aliphatic amines are alkyl derivatives of ammonia.
N N N N
H H R H R H R R
H H R R
Ammonia Primary amine Secondary amine Tertiary amine

Only primary amines are included in current A-level specifications. Both ASE and IUPAC recommend the retention of radicofunctional names rather than
the adoption of substitutive ones. Any differences between the two systems are due to variations in the names of hydrocarbon radicals, e.g.
CH3 NH 2 methylamine (not ‘aminomethane’)
CH3CH 2NH 2 ethylamine
CH 3CH 2CH 2NH2 propylamine
CH3CH(NH2)CH3 (1-methylethyl)amine - ASE
or isopropylamine - IUPAC

4
91. Naming of Organic Compounds Chem Factsheet

Difunctional aliphatic compounds Exam Hint - When writing the symbol for benzene, don’t forget to
If a molecule contains two functional groups, one of which is represented include the circle to represent the delocalised π-bond. If you leave it
by a prefix and the other by a suffix, there is no difficulty with naming, e.g. out, and draw only a hexagon, you are writing the formula of
cyclohexane.
CH3CHClCOOH 2-chloropropanoic acid
Life, however, is not always that straightforward! Other aromatic compounds are those whose molecules contain at least one
benzene ring. (Strictly, an aromatic compound is one whose molecules
If both functional groups are normally represented by suffixes, have a ring structure with a set of six π-electrons, but this definition is not
there is a problem which is overcome by citing the principal one as a required at A-level.)
suffix and the other as a prefix.
Many monosubstituted benzenes have both systematic and trivial names:
CH3 C 2H 5 Cl OH NO 2
Prefixes in common use include the following:
hydroxy for OH
amino for NH2
keto for CO Systematic name: methyl- ethyl- chloro- - nitro-
The question as to which of two groups is the principal one, for citing as benzene benzene benzene benzene
the suffix, can be resolved only by referring to the IUPAC order of priority. Trivial name: toluene - - phenol -
An abridged list is provided below.
NH2 CHO COCH3
-COOH (carboxylic acid)
-CN (nitrile)
-CHO (aldehyde)
Systematic name: phenylamine benzenecarbaldehyde phenylethanone
Decreasing
Trivial name: aniline benzaldehyde acetophenone
priority -C=O (ketone)
COOH COCl CONH2
-OH (alcohol)
-NH 2 (amine)
Look at the two difunctional compounds VII and VIII, both of which Systematic name: benzenecarboxylic benzenecarbonyl benzenecarboxamide
contain an OH group. acid chloride
OH OH Trivial name: benzoic acid benzoyl chloride benzamide
 
CH3-CH-NH2 CH3-CH-CN Although trivial names are widely used in the chemical
Compound VII Compound VIII industry, only systematic ones are used in schools in the UK. The only
trivial name that is permitted is phenol for C6H5OH.
OH has a higher priority than NH2, but a lower priority than CN. It is
therefore the principal group in Compound VII, and consequently cited as Some compounds have both substitutive and radicofunctional systematic
the suffix, but not in Compound VIII, where it is denoted by the prefix names, e.g. CH Cl CH OH
2 2
hydroxy. Compound VII is named 1-aminoethanol, and Compound VIII is
2-hydroxypropanenitrile.
Alicyclic compounds Substitutive name: (chloromethyl)benzene phenylmethanol
Radicofunctional name: benzyl chloride benzyl alcohol
Remember - Alicyclic compounds are aliphatic compounds with a ring
structure. For aromatic compounds, as for aliphatic ones, UK schools
prefer to use substitutive names.
These compounds are named in the same way as aliphatic ones, but with
the prefix ‘cyclo’. The commonest ones, with a six-membered ring, comprise When naming disubstituted and polysubstituted benzenes, a reference group
cyclohexane and its derivatives. Examples: has to be chosen as the basis of the name.
OH O
The later group alphabetically is used as a reference, from
CH2 CH CH CH
structural CH CH which position the carbon atoms of the ring are numbered from 1 to 6.
2 2 CH2 CH CH2 CH 2 CH 2 CH2 This provides locants for denoting the positions of other groups.
formula
CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH2 CH 2
Consider Compounds IX and X.
CH2 CH 2 CH 2 CH2
Cl CH 3
OH O
Br 1 3
symbol 2 6 4 2

3 5 5 1
name cyclohexane cyclohexene cyclohexanol cyclohexanone 4 6 NO 2
Aromatic compounds Compound IX Compound X
The parent compound is benzene, C6H6. For Compound IX, the reference group is Cl because C (for chloro) is later
in the alphabet than B (for bromo). The ring is numbered as shown, to give
H
a name of 2-bromochlorobenzene; not 6-bromochlorobenzene.
H C C H
C For aromatic compounds, as for aliphatic ones, numbers in
names should be kept as low as possible.
C C
H C H By similar reasoning, Compound X is regarded as a derivative of
symbol
H nitrobenzene, rather than methylbenzene, so the correct name is 3-
structural formula of bemzene methylnitrobenzene.
5
91. Naming of Organic Compounds Chem Factsheet

Practice questions Answers

1 Write down the structural formulae of five isomeric compounds of 1 CH3-CH2-CH2CH2-CH2-CH3 hexane
molecular formula C6H14 and name them on the IUPAC system.
CH3
2 Give the systematic name of each of the following compounds.
(a) (CH3)2CHCH2OH CH3-CH-CH2-CH2-CH3 2-methylpentane

(b) CH2 CH3

CH3CHCH2CH2CH 3 CH3-CH2-CH-CH2-CH3 3-methylpentane

(c) CH3CH(OH)CH2CHO CH3 CH3
(d) NO2
CH3-CH_CH-CH3 2,3-dimethylbutane
CH3
NO2
(e) CH3 CH3-C-CH2CH3 2,2-dimethylbutane

CH3

Cl 2 (a) 2-methylpropan-1-ol
3 Write down the structural formula of each of the following compounds. (b) 2-methylpent-1-ene
(a) 2-chloroethanol
(c) 3-hydroxybutanal
(b) propane-1,2,3-triol
(d) 1,3-dinitrobenzene
(c) 2-methylpent-3-enoic acid
(e) 1-chloro-4-methylbenzene
(d) phenylethene
3 (a) CH2ClCH2OH
(e) benzenecarboxamide
(b) CH2OHCH(OH)CH2OH
4 Identify which of the following names is/are wrong and then write
, (c) CH3
down the correct systematic name in each case.
(a) CH3CH(OH)COOH 2-hydroxypropanoic acid
CH3CH=CHCHCOOH
(b) (CH3)3COH 2,2-dimethylethanol
(d) CH=CH2
(c) NH2
or C6H5CH=CH2
aminobenzene
(e) CONH2
(d) NHCOCH3
or C6H5CONH2
N-phenylethanamide
4 (a) Correct
(e) OH
Br Br (b) Wrong Correct name is 2-methylpropan-2-ol
2,4,6-tribromohydroxybenzene (c) Wrong Correct name is phenylamine
Br (d) Correct
(e) Wrong Correct name is 2,4,6-tribromophenol

Acknowledgements: This Factsheet was researched and written by John

Brockington. Curriculum Press, Bank House, 105 King Street, Wellington,
Shropshire, TF1 1NU. ChemistryFactsheets may be copied free of charge by
teaching staff or students, provided that their school is a registered subscriber.
No part of these Factsheets may be reproduced, stored in a retrieval system, or
transmitted, in any other form or by any other means, without the prior
permission of the publisher. ISSN 1351-5136

6
 Chem Factsheet
www.curriculum-press.co.uk Number 92

Electrophilic Addition
To succeed in this topic you need to: Why are alkenes subject to electrophilic addition?
• understand the nature of the C=C covalent bond in terms of σ- and You need to understand the nature of both electrophiles and alkenes.
π-orbitals (covered in Factsheet 87);
• know the reactions of alkenes (covered in Factsheet 16).
An electrophile is defined as an attacking species which seeks
out, for its attack, an electron-rich centre in the substrate.
After working through this Factsheet you will:
For a species to act as an electrophile, it must satisfy the following
• understand the principles of electrophilic addition to alkenes;
three basic requirements.
• be able to write mechanistic equations for the reactions of alkenes
1 It must contain an atom with a positive electrical charge. For
with halogens, hydrogen halides and sulphuric acid;
maximum attraction to the electron-rich centre of the substrate, an
• know that carbocations (carbonium ions) are classified as primary,
electrophile should carry a full positive charge, i.e. it should be
secondary or tertiary;
ionic, but in practice most electrophiles are polar molecules in
• understand that the stability of carbocations increases from primary
which there is an atom with a partial positive charge.
to secondary to tertiary;
2 Its positively charged atom must have a vacant orbital at a relatively
• know that, when unsymmetrical alkenes react with hydrogen-
low energy level to accommodate an incoming pair of electrons.
containing reagents, there are two possible products;
3 It must be able to form a strong bond with a carbon atom, otherwise
• be able to explain the formation of one product rather than another
there cannot be a stable reaction product.
in terms of the stability of carbocations.

All organic reactions are classified on a mechanistic basis into the following The nature of the carbon-carbon double bond in alkenes is fully described
caregories: in Factsheet 87.
• substitution;
• addition; Remember - The two covalent bonds of a C=C bond are not identical
• elimination; with each other. One, called a σ-bond, is similar to a C-C single
• rearrangenent. bond. It is strong and not broken during addition reactions. The
other, called a π-bond, is relatively weak. This is the one which is
Exam Hint - Wherever possible, when you are asked to state the type broken during electrophilic addition.
of an organic reaction, you should give the mechanistic classification.
Try to avoid synthetic descriptions, such as hydrolysis, chlorination or
nitration. Alkenes undergo electrophilic addition with halogens, hydrogen halides
and sulphuric acid.
For compounds to take part in addition reactions, their molecules must
contain multiple bonds, notably C=C (in alkenes) and C=O (in aldehydes - All these reactions have the following features in common.
and ketones).
δ+ δ−
• The reagent is polarised X—Y
Remember - Addition means ‘combination’.
In an addition reaction, the reagent (i.e. the attacking molecule) combines • The atom with the partial positive charge (δ+) is attracted to,
with the substrate (molecule that is being attacked) to give one product and accepts, the two π-electrons of the C=C bond.
only, known as an addition product or ‘adduct’.
• The bond X-Y undergoes heterolytic fission, i.e. it becomes
broken in such a way that both the electrons of the bond go to Yδ−.
Addition reactions are subdivided according to the nature of the attacking
species. • X+ does not become free (too much energy is required for this)
• Electrophilic addition - shown by alkenes. but bonds permanently to one of the atoms of the C=C bond to
give a carbocation or carbonium ion, i.e. an ion in which positive
• Free radical addition - shown by alkenes under conditions that favour the charge is located on a C atom.
formation of free radicals, especially the presence of ultraviolet light.
(Not required at A-level) • Y− is a nucleophile, i.e. a negatively charged species, capable of
donating a lone pair of electrons, which will seek out a positive
• Nucleophilic addition - shown by aldehydes and ketones. centre for its attack.

• In the final stage of the mechanism, Y− coordinates to the

carbocation to give the adduct.

1
92. Electrophilic Addition Chem Factsheet

Reactions with halogens Hydrogen bromide with unsymmetrical alkenes

Bromine reacts with alkenes at room temperature to give 1,2-dibromides. When propene reacts with HBr, there are two possible adducts:
Reactions are usually carried out in an organic solvent, such as hexane or
trichloromethane. CH3CH2CH2Br 1-bromopropane
CH3CH=CH2 + HBr
E.g. CH2=CH2 + Br2 → CH2Br-CH2Br CH3CHBrCH3 2-bromopropane
1,2-dibromoethane
In fact, the product is almost entirely 2-bromopropane. Markownikoff’s
Chlorine also reacts readily, but with iodine there is no reaction. rule helps you to predict this.
The mechanism follows the principles shown above. It is perhaps
surprising that bromine, a non-polar substance, should react in this way: Markownikoff ’s rule states that, whenever a hydrogen-
indeed, it has been reported that a mixture of an alkene and pure, dry containing reagent reacts with an unsymmetrical alkene, the incoming
bromine in PTFE apparatus will not react together. However, traces of hydrogen atom goes to the carbon atom of the double bond with the
water or the surface of glass apparatus - conditions that commonly exist - most hydrogen atoms already joined to it. (As sociologists say, ‘The
are sufficient to induce temporary polarisation in the Br2 molecule. The rich get richer.’)
mechanism is summarised by the two equations shown below. Notice
particularly the use of ‘curly arrows’ to show the movement of pairs of
electrons. To understand this, you must know that carbocations vary in their stability.
They are classified as primary, secondary or tertiary, depending on whether
Exam Hint - Be very careful how you draw curly arrows! the positive charge is located on a primary, secondary or tertiary carbon
• A ‘curly arrow’ is used to show the movement of a pair of electrons. atom, and increase in stability from primary to secondary to tertiary.
• The arrow must be curved and have a complete arrowhead.
(A half-arrow is used to show the movement of a single electron.) Remember - A primary carbon atom is attached to one alkyl radical
• It must start from the original location of the electron pair and (R), a secondary carbon atom is attached to two alkyl radicals, and a
point to where it finishes up. tertiary carbon atom is joined to three.
• It must NEVER start from or point to an electrical charge.

CARBOCATIONS
δ+ δ−
Br Br Br
slow +
CH2 CH 2 CH2 CH 2 + :Br − + + +
R C H R C R' R C R'
(Examiners may allow curly arrow pointing to Brδ+.)
H H R''
Br :Br − Br Br Primary Secondary Tertiary
+
Increasing stability,
fast
CH2 CH2 CH 2 CH2 ∴ increasing ease of formation

The increase in stability is due to the fact that positive charge can be shared
(Examiners may allow curly arrow pointing to C⊕.)
with alkyl groups (R) but not with H atoms. The sharing or delocalisation
of electrical charge, anywhere in physical science, always leads to greater
Exam Hint - To make sure of maximum marks, when asked to give
this mechanism, you must: stability. Tertiary carbocations, with three alkyl groups, allow maximum
• describe the mechanism as electrophilic addition (not just delocalisation and are particularly stable. Because they are at a low energy
‘addition’); level, relatively little energy is required for their formation and they are
• write mechanistic equations; therefore formed preferentially. If a tertiary carbocation cannot be formed
• make sure the curly arrows and the carbocation are correctly you get a secondary one; failing that, a primary one.
drawn;
• mention heterolytic fission of Br2. Whenever there are competing mechanistic routes for
electrophilic addition, reaction occurs preferentially through the more
stable carbocation.
Evidence for this mechanism is provided by carrying out the reaction in the
presence of chloride ions. The product is a mixture of CH2Br-CH2Br and
In the case of propene and HBr, the main product is 2-bromopropane
CH2Br-CH2Cl, suggesting that, in the final stage, Br- and Cl- are competing
because it is formed via the relatively stable secondary carbocation,
for the carbocation, CH3CH2⊕. +
CH3-CH-CH3.
δ+ δ−
Reaction with hydrogen halides H Br
Alkenes react with concentrated hydrobromic acid at 100 oC to give +
bromoalkanes, e.g. CH3 CH CH 2 → CH3 CH CH 3 + :Br−
(Examiners may allow curly arrow to Hδ+.)
CH2=CH2(g) + HBr(aq) → CH3CH2Br(l)
+
CH 3 CH CH3 → CH3 CH CH 3
Hydriodic acid behaves in a similar manner but there is no reaction with
hydrochloric acid. (Hydrogen chloride gas will react if heated to about 200 :Br− Br
o
C.)
(Examiners may allow curly arrow to C⊕.)
The HBr molecule is permanently polarised, Hδ+—Brδ−, and reacts with
alkenes by an identical mechanism to Br2. The alternative product, 1-bromopropane, could be formed only via the
+
relatively unstable primary carbocation, CH -CH -CH .
3 2 2

2
92. Electrophilic Addition Chem Factsheet

Exam Hint - An explanation for the formation of one product of

Exam Hint - Whenever you are asked how you would carry out a
electrophilic addition rather than another is commonly asked for in
conversion, never quote an industrial process. The examiner assumes
examinations. There are three traps for the unwary.
that YOU would be working in a laboratory with the usual lab reagents
• NEVER say that one product is formed rather than another
and equipment. Students often make the mistake of saying that they
“because this is in accordance with Markownikoff’s rule.” This is
would convert ethene into ethanol by adding steam, compressing the
rather like saying that “A is formed rather than B because
mixture to 70 atm and then passing it over a phosphoric acid catalyst
Markownikoff says so.” Markownikoff does not control organic
maintained at 300 oC. This so-called direct hydration of ethene is, of
chemistry! His law is merely a statement of experimental findings
course, the industrial method of producing synthetic ethanol.
and has no regard for causes.
Conversely, never quote laboratory chemistry when asked about
• Always argue on the basis of the stability of carbocations; NOT
on the stability of final products. industrial processes.

• Tailor your answer to the question. Just saying that “A is formed

rather than B because secondary carbocations are more stable Practice questions δ+ δ−
than primary carbocations” will not get you full marks. E.g. in 1. Although the HCN molecule is polarised, H—CN, hydrogen cyanide
answer to the propene with HBr question, you should say that the
does not undergo electrophilic addition to alkenes. Explain this.
main product is 2-bromopropane because it is formed via the
⊕
relatively stable secondary carbocation, CH3CHCH3.
2. Write mechanistic equations for the following reactions.
(a) Phenylethene (styrene) with hydrogen bromide.
Reaction with sulphuric acid (b) Propene with concentrated sulphuric acid.
Electrophilic addition also occurs when alkenes are absorbed by cold
concentrated sulphuric acid. 3. Carbocations have a positive charge residing on a carbon atom. Suggest
why it is that a carbon atom can share its charge with adjoining alkyl
Exam Hint - Always distinguish between concentrated and dilute groups, such as CH3.
sulphuric acid. NEVER just write ‘sulphuric acid’.
4. Suggest why, when ethene reacts with bromine water, 2-bromoethanol
The products are alkyl hydrogen sulphates, e.g. is formed as well as 1,2-dibromoethane.

CH2=CH2 + H2SO4 → CH3CH2OSO2OH Answers

Ethyl hydrogen sulphate 1. The H-C bond is particularly strong. (Its average bond enthalpy is
412 kJ mol-1.) A prohibitively large amount of energy would be needed
Markownikoff ’s rule applies to the addition of sulphuric acid to for heterolytic fission of the bond.
unsymmetrical alkenes. Propene, for example, reacts to give 1-methylethyl
hydrogen sulphate (isopropyl hydrogen sulphate). 2. (a) H Br
Alkyl hydrogen sulphates are half-esters of sulphuric acid: +
C6H5-CH CH2 → C6H5-CH-CH3 + :Br −
O O O (Examiners may accept curly arrow to H.)
+
S S S C6H5-CH-CH3 C6H5-CH-CH3
O OH O OR O OR →
OH OH OR :Br − Br
Sulphuric acid Alkyl hydrogen sulphate Dialkyl sulphate (Examiners may accept curly arrow to C⊕.)
(Half-ester) (Full ester)
Concentrated sulphuric acid is almost pure sulphuric acid and, for all practical (b) H—OSO2OH
purposes, consists of polarised molecules;
+ −
δ+ δ− CH3-CH CH2 → CH3-CH-CH3 + :OSO2OH
H-O-SO2-OH rather than ions H+ and HSO4−. (Examiners may accept curly arrow to H.)
+
Reaction mechanisms are therefore closely similar to those shown above. CH3-CH-CH3 → CH3-CH-CH3
δ+ δ− −
H—OSO2OH :OSO2OH OSO2OH
+ − (Examiners may accept curly arrow to C⊕.)
CH2==CH2 → CH3—CH2 + :OSO2OH
(Examiners may allow curly arrow to H .) δ+ 3. Alkyl groups have a positive inductive (+1) effect,
⊕
i.e. electron releasing
effect. This reduces the positive charge on C and, at the same time,
+
CH3—CH2 CH3—CH2 causes partial positive charge to develop on the methyl group.
− → 
:OSO2OH OSO2OH 4. The H2O molecule is a nucleophile which, in the final stage of the
−
mechanism, competes with Br for the carbocation, CH2Br-CH2.
(Examiners may allow curly arrow to C⊕.) +
CH2Br-CH2 CH2Br-CH2
Like all other esters, an alkyl hydrogen sulphate can be hydrolysed to give →
an acid and an alcohol. Hot water is enough to hydrolyse ethyl hydrogen
:OH2 + OH
2
sulphate:
Loss of a proton from this protonated alcohol gives CH2Br-CH2OH.
C2H5OSO2OH + H2O → C2H5OH + H2SO4
Acknowledgements: This Factsheet was researched and written by John Brockington. Curriculum Press, Bank
Ethanol and sulphuric acid are readily separated by distillation. This House, 105 King Street, Wellington, Shropshire, TF1 1NU. ChemistryFactsheets may be copied free of charge
by teaching staff or students, provided that their school is a registered subscriber. No part of these Factsheets
provides the answer to a favourite exam question, ‘How would you convert may be reproduced, stored in a retrieval system, or transmitted, in any other form or by any other means, without
ethene into ethanol?’ the prior permission of the publisher. ISSN 1351-5136
3
 Chem Factsheet
www.curriculum-press.co.uk Number 93

Isomerism in Organic Chemistry

To succeed in this topic you need to understand: Fig 1. Structural formulas of C4H10
• homologous series (covered in Factsheet 15);
• functional groups (covered in Factsheet 15); H H H
H H H H
• empirical formulae (covered in Factsheet 02); H C C C H
• molecular formulae (covered in Factsheet 02); H C C C C H
• structural (including displayed) formulae (covered in Factsheet 15); H H
H H H H

Both are C4H10

• tetrahedral bonding shapes (covered in Factsheet 04); H C H
• naming organic molecules by I.U.P.A.C. rules (covered in Factsheet
H
15).
or CH3CH2CH2CH3 and or CH3CH(CH3)CH3
After working through this Factsheet you will be able to:
• explain what is meant by isomerism;
or or OCR only
• explain the different sub-groups of isomers; OCR only
• draw structures of isomers from their molecular formula;
• recognise different types of isomer from their structural formulae. These represent But these represent
BUTANE METHYLPROPANE
Organic molecules number many millions. Carbon, hydrogen, oxygen,
nitrogen and halogen atoms form the few basic building units of most
Note: they may take more time and effort but, unless specified
organic molecules but, by varying their numbers and how they are bonded
otherwise, full displayed structures are usually the best ones to use,
relative to each other, these millions of different molecules are possible.
especially in this context.
One of the reasons for this diversity is the occurrence of isomerism which
is concerned with the “how the atoms are bonded relative to each other”, This example illustrates what is meant by isomerism. Butane and
rather than how many are present. methylpropane are said to be “isomers of each other” or “isomeric” or
“isomers of C4H10”.
C4H10 is a molecular formula; it relates to all molecules composed of four
carbon atoms and ten hydrogen atoms. However, if all possible structural This leads to the first important definition:
formulae with this same molecular formula are drawn (Fig1)
Isomers are molecules with the same molecular formula, but
different arrangements of atoms.

Isomers may have significant differences in chemical properties only, in physical properties only or in both. Butane and methylpropane, for example have
very similar chemical properties but quite different physical properties. Mostly as a result of this, isomerism is sub-divided into various types (Fig 2).

Fig 2.

Isomers
(molecules with the same molecular formula, but different arrangements of atoms)

Structural Isomers Stereoisomers

(isomers resulting from different bonding (isomers resulting from different spatial arrangements
patterns between the atoms) of the atoms in the same structural formula)

Functional
Chain Isomers Positional Isomers Geometrical Isomers Optical Isomers (A2)
Group Isomers
are isomers are isomers resulting are isomers resulting from are isomers resulting from
are isomers
resulting from the from the atoms being the atoms being bonded to the atoms being bonded to
resulting from the
atoms being bonded so that the form different form different 3D
atoms being
bonded to form functional groups arrangements of same arrangements, around a
bonded to form
different are in different groups around a planar central carbon atom,
different
arrangements of positions on the group such as the C=C which are non-identical
functional
the carbon same carbon chain. group. mirror images of each
groups.
atoms. other.

1
93. Isomerism in Organic Chemistry Chem Factsheet

Structural Isomers 1: Chain Isomers

Remember: Isomers resulting from the atoms being bonded to form Exam Hint: If positional isomerism only is occurring, the names
different arrangements of the carbon atoms vary only in the numbering pattern. Try naming your isomers to check
they are genuine positional isomers.
Our first example showed chain isomers. Butane and methylpropane differ
only in the bonding pattern of the four carbon atoms; the former is a A2 Only: Benzene derivatives (C6H6; )commonly show positional
straight-chain isomer but the latter is a branched-chain isomer. If only isomerism.
chain isomerism applies (as here), the isomers will belong to the same
homologous series and have very similar chemistry but different physical Di-substituted benzene derivatives occur as three positional isomers. For
properties. For example, methylpropane has a noticeably lower boiling example: NO 2 NO 2 NO 2
point.
NO 2
Note: the petrochemical industry converts a lot of straight chain isomers
into branched chain isomers because the latter act as better fuels in NO 2
petrol engines. Not surprisingly, they call the process “isomerisation”! NO 2
1,2-dinitrobenzene 1,3-dinitrobenzene 1,4-dinitrobenzene
Another example of chain isomerism is C5H12.

pentane 2-methylbutane 2-2dimethylpropane One last point! Chain and positional isomerism can occur together. For
example, there are four isomers of C4H10F. These are:
CH3CH 2CH2CH 2CH3 CH3CH(CH3)CH2CH3 CH3C(CH3)2CH3
(a) 1-fluorobutane
[CH3CH2CH2CH2F] (a) and (b) are positional isomers
(c) and (d) are positional isomers
Exam Hint: Examine all the possible carbon chains in a systematic
fashion. Draw the maximum number of carbons in one continuous (b) 2-fluorobutane (a) and (c) are chain isomers
chain first (e.g. 6 in the following question). Then consider all possible [CH3CH2CHFCH3] (b) and (d) are chain isomers
variations of a 5C chain with a 1C side-chain. Then consider all but (a) and (d) and (b) and (c) are
possible variations of a 4C chain with two 1C side-chains etc. If you (c) 1-fluoro-2-methylpropane a mixture of both!
have time, naming each will show whether you have repeated a structure [CH3CH(CH3)CH2F]
because each should have a unique name.
(d) 2-fluoro-2-methylpropane
Q1 Draw and name the structures of the five chain isomers of C6H14. [CH3CF(CH3)CH3]

Structural Isomers 2: Positional Isomers A similar pattern is shown by the isomeric alcohols with molecular formula
C4H10O. The straight chain positional isomers have already been considered
Remember: Isomers resulting from the atoms being bonded so that the but the full set of isomers is:
functional groups are in different positions on the same carbon chain.
(a) butan-1-ol
[CH3CH2CH2CH2OH] Note: Isomers (a) and (c) are called
C3H7Br illustrates this type of isomerism. The three carbon atoms form a primary alcohols because both
chain but the bromine atom may be bonded to either the end (at C1) or (b) butan-2-ol contain a –CH2OH group. (b) is a
middle (at C2) of the chain. Hence, the positional isomers of C3H7Br are: [CH3CH2CH(OH)CH3] secondary alcohol since it contains a
-CH(OH)- group and (d) is a
1-bromopropane and 2-bromopropane tertiary alcohol since it contains a
CH3CH2CH2Br CH3CHBrCH3 (c) 2-methylpropan-1-ol >C(OH)- group. As you will see
If only positional isomerism applies, the isomers will again belong to the [CH3CH(CH3)CH2OH] when you study alcohols, these
same homologous series and have very similar chemistry but different different types have some
physical properties. However, for some examples, the reaction products significantly different chemical
(d) 2-methylpropan-2-ol
may vary from positional isomer to positional isomer. For example, as you reactions.
[CH3C(OH)(CH3)CH3].
will encounter when you study the halogenoalkanes, elimination of hydrogen
bromide from 1-bromobutane produces only one alkene type product
whereas its positional isomer, 2-bromobutane, produces three.
Exam Hint: Examine all the positional variations in a systematic
Here are some more examples. fashion. First draw the basic carbon chain (e.g. C-C-C in the following
(a) butan-1-ol and butan-2-ol question). Then consider all possible positional variations of the
[CH3CH2CH2CH2OH] [CH3CH2CH(OH)CH3] additional functional groups.

(b) 1,1-dicloroethane and 1,2-dicloroethane

[CHCl2CH3] [CH2ClCH2Cl] Q2 Draw and name the structures of the four positional isomers of C3H6Cl2.
(c) pentan-2-one and pentan-3-one
[CH3CO.CH2CH2CH3] [CH3CH2CO. CH2CH3]

2
93. Isomerism in Organic Chemistry Chem Factsheet

Structural Isomers 3 : Functional Group Isomers Single covalent C-C bonds (sigma bonds) are free to rotate about their axis.
However, when the Pi bond is added to form a double covalent C=C bond,
Remember: Isomers resulting from the atoms being bonded to form this ability to rotate is lost. Also the C=C atoms and the four atoms
different functional groups. directly bonded to them are forced to lie in the same plane.

For molecules with three or more carbon atoms, aldehydes and ketones can
show functional group isomerism. Similarly, carboxylic acids and esters C C C C
can show functional group isomerism whilst, in A2, you will also encounter
primary, secondary and tertiary amine functional group isomers. Of course,
Free rotation; non-planar No free rotation;planar
since organic molecules’ chemical properties are controlled by their functional
groups, functional group isomers are extremely different in their chemistry. Consider the following general structures where X and Y represent various
Also, since different functional groups often result in different inter- atoms or groups other than H that may be bonded to the C=C carbons.
molecular forces, physical properties can be very different. Because of the planar and non-rotating nature of the C=C bond, these
structures have the same molecular formula but are non-identical; in other
Aldehydes and ketones words they are isomers. In fact they are geometrical isomers. As shown,
C3H6O could be propanal [CH3CH2CHO – an aldehyde] or propanone the isomer with X and Y on the same side of the C=C bond is referred to as
[CH3CO.CH3 – a ketone]. the cis isomer whereas the other is called the trans isomer.
Similarly, C4H8O could be butanal [CH3CH2CH2CHO] or butanone
X Y X H
[CH3CH2CO.CH3].
C C C C
Linked to these, there is also a chain isomer of butanal. This is
methylpropanal, [CH3CH(CH3)CHO]. H H H Y
cis-isomer trans-isomer
Exam Hint: Draw the functional group first and then add the remaining
atoms in all their possible chain and positional variations.
Some examples of this type of isomerism include:
Q3 Draw and name the structures of the seven isomers of C5H10O. Restrict
1. Geometrical isomers of but-2-ene
your answers to aldehydes or ketones but remember to include chain and
positional variations.
CH 3 CH3 CH 3 H
Carboxylic acids and esters C C C C
C 2 H 4 O 2 could be: ethanoic acid [CH 3 CO.OH – an acid] or
methyl methanoate [HCO.OCH3 – an ester]. H H H CH3
Similarly, C 3H 6 O 2 could be: propanoic acid [CH 3 CH 2 CO.OH], cis-but-2-ene trans-but-2-ene
methyl ethanoate [CH3CO.OCH3] or ethyl methanoate [HCO.OCH2CH3]
2. Geometrical isomers of 2,3-dichloropent-2-ene
Q4 Draw and name the structures of the six isomers of C4H8O2. Restrict
your answers to acids or esters but remember to include chain and positional CH 3 CH 2CH3 CH 3 Cl
variations. C C C C
Primary, secondary and tertiary amines (A2 only): Cl Cl Cl CH 2CH3
C2H7N could be:
aminoethane (ethylamine) [CH 3 CH 2 NH 2 – a primary amine] or cis-2,3-dichloropent-2-ene trans-2,3-dichloropent-2-ene
N-methylaminomethane (N-methylmethylamine) [(CH3)2NH – a secondary
amine].
Similarly, C3H9N could be: Note: Example 2 shows that the
1-aminopropane [CH3CH2CH2NH2], 2-aminopropane [CH3CH(NH2)CH3], “similar” atoms bonded to C=C do not
N-methylaminoethane [CH3NHCH2CH3] or N,N-dimethylaminomethane have to be H atoms. However, the two H CH 2CH3
[(CH3)3N – a tertiary amine]. Note again how positional isomerism also groups bonded to any particular C=C
occurs. carbon must not be the same. This C C
occurs in but-1-ene, resulting in no
Q5 Draw and name the structures of the eight isomers of C4H11N. Restrict H H
geometrical isomers. Similar examples
your answers to amines but remember to include chain and positional would be 1,2-difluoroethene which but-1-ene
variations. does have geometrical isomers whereas
1,1-difluoroethene does not.
Stereoisomers 1 : Geometrical Isomers
Exam Hint: Draw the C=C bond with it’s four other bonds and
Remember: Isomers resulting from the atoms being bonded to form
then fit in the other atoms or groups. Remember, neither C of
different arrangements of same groups around a planar group such
the C=C bond can be bonded to the same group.
as the C=C group.

Geometrical isomerism (also known as cis-trans isomerism) can occur in Q6 (a) Draw and name the structures of geometrical isomers of (a) hex-3-ene
many types of molecules but you should concentrate on examples involving (b) 1,2-dibromoethene
alkenes. Such isomerism tends to cause the isomers to have very different (c) 2-chlorobut-2-ene.
physical properties but, since the functional groups have not changed,
very similar chemical properties.

3
93. Isomerism in Organic Chemistry Chem Factsheet

Stereoisomers 2 : Optical Isomers (A2 only) Answers to questions in text

Q1 CH3CH2CH2CH2CH2CH3 – hexane ;
Remember.: Isomers resulting from the atoms being bonded to form CH3CH(CH3)CH2CH2CH3 – 2-methylpentane ;
different 3D arrangements, around a central carbon atom, which CH3CH2CH(CH3)CH2CH3–3-methylpentane;
are non-identical mirror images of each other. CH3C(CH3)2CH2CH3 – 2,2-dimethylbutane ;
CH3CH(CH3)CH(CH3)CH3 – 2,3-dimethylbutane.
Q2 CH3CH2CHCl2 – 1,1-dichloropropane ;
Optical isomers (also known as enantiomers) always occur in pairs and
CH3CCl2CH3 – 2,2-dichloropropane ;
have identical chemical and physical properties, except that one structure
CH3CHClCH2Cl – 1,2-dichloropropane
rotates the plane of plane-polarized light (p.p.l.) clockwise and the other
CH2ClCH2ICH2Cl - 1,3-dichloropropane
rotates it anti-clockwise. This is referred to as their optical activity.
Q3 CH3CH2CH2CH2CHO – pentanal ;
Optical isomers can CH3CO.CH2CH2CH3 – pentan-2-one ;
occur if there is an CH3 CH2CO.CH2CH3 – pentan-3-one ;
W W
asymmetric (also called CH3CH2CH(CH3)CHO – 2-methylbutananal ;
chiral) carbon atom CH3CH(CH3)CH2CHO– 3-methylbutananal ;
(marked *). This is a * CH3CO.CH(CH3)CH3 – 3-methylbutan-2-one ;
* Z Z
carbon atom which is C C CH3C(CH3)2CHO – 2,2-dimethylpropanal
bonded (tetrahedrally) to
four different groups. X X Q4 CH3CH2CH2COOH – butanoic acid ;
Y Y
Consider the general CH3CH(CH3)COOH – 2-methylpropanoic acid ;
imaginary CH3CH2COOCH3 – methyl propanaote ;
structures shown, where
mirror CH3COOCH2CH3 – ethyl ethanoate ;
W-Z represent these four
different groups. HCOOCH2CH2CH3 – (1-propyl) methanoate ;
HCOOCH(CH3)CH3 – (2-propyl) methanoate ;
Q5 CH3CH2CH2CH2NH2 – 1-aminobutane ;
These are mirror images of each other, yet they are non-identical. “Chiral” CH3CH2CH(NH2)CH3 – 2-aminobutane ;
is term used to describe such molecules. Hence, they are optical isomers of CH3CH(CH3)CH2NH2 – 1-amino-2-methylpropane ;
each other. The “non-identicality” can be seen by imagining looking down CH3C(CH3)2NH2 – 2-amino-2-methylpropane ;
on the molecules from above group W. The remaining groups in clockwise CH3CH2CH2NHCH3 – N-methyl-1-aminopropane ;
order would be Z-Y-X for isomer A but Z-X-Y for B. CH3CH(CH3)NHCH3 – N-methyl-2-aminopropane ;
CH3CH2NHCH2CH3 – N-ethyl-aminoethane ;
Notes: (a) Inter-changing any two groups in isomer A produces isomer CH3CH2N(CH3)2 – N,N-dimethyl-aminoethane.
B, and vice-versa.
Q6 (a) CH3CH 2 CH2CH3 CH3CH 2 H
(b) The direction of rotation of p.p.l. cannot be predicted from
the structure. C C C C
Some examples of optical isomers are: H H H CH CH
cis-hex-3-ene trans-hex-3-ene 2 3
(1) Optical isomers of butan-2-ol
(b) H H H Br
OH OH
C C C C

* Br Br Br H
C CH 3 H 3C C*
cis-1,2-dibromethane trans-1,2-dibromethane
H H (C) CH3 CH 3 CH3
CH2CH3 CH 2CH3 H
C C C C
(2) optical isomers of 2-aminopropanoic acid
(alanine – an α-amino acid) Cl H Cl CH 3
COOH HOOC cis-2-chloro-but-2-ene trans--2-chloro-but-2-ene

Q7 (a) CH2CH 2CH 3 CH3 CH2CH 2

* CH 3 H3C C*
C
C* CH3 H3C C*
H H
H NH 2 H2N H CH3CH 2
CH 2CH3

(b) CH2OH HOH 2C

Exam Hint: When drawing optical isomers, 3D diagrams are essential.
CLEARLY draw the 3D representation for the tetrahedral carbon atom C* Cl Cl C*
with it’s four bonds and then fit in the four different atoms or groups. H
Finally, copy your first structure in an imaginary mirror (or exchange H CH 2CH3 CH3CH 2
any two groups) to obtain the second isomer. (c) Cl Cl

Q7 Marking the asymmetric carbon with an asterisk, draw structures of

the optical isomers of: C* CH3 H 3C C*
(a) 2-methylhexane (b) 2-chlorobutan-1-ol (c) 1-chloro-1-fluoroethane. H F H
F

4
93. Isomerism in Organic Chemistry Chem Factsheet

Practice Questions Answers

1. Which of the following isomers of C4H11N can exist as optical isomers? 1. CH3CH2CH(NH2)CH3 – 2-aminobutane
CH3CH2CH2CH2NH2 – 1-aminobutane
CH3CH2CH(NH2)CH3 – 2-aminobutane CH 2CH3 CH3CH2
CH3CH(CH3)CH2NH2 – 1-amino-2-methylpropane
CH3C(CH3)2NH2 – 2-amino-2-methylpropane C* CH 3 H 3C C*
CH3CH2CH2NHCH3 – N-methyl-1-aminopropane H H
NH 2 H 2N
CH3CH(CH3)NHCH3 – N-methyl-2-aminopropane
CH3CH2NHCH2CH3 – N-ethyl-aminoethane
CH3CH2N(CH3)2 – N,N-dimethyl-aminoethane 2. CH2=CHCH2Cl – 3-chloropropene ; CH2=CClCH3– 2-chloropropene;

Illustrate your answer with appropriate structures and mark the chiral Cl CH 3 Cl H
centre with an asterisk.
C C C C
2. Draw and name all the isomers of C3H5Cl. State the types of isomerism
H H N CH3
that occur.
cis-1-chloro-propene trans-1-chloro-propene
3. Draw and name
(a) a chain isomer of 1-bromobutane All four are positional isomers of each other but 1-chloroproene also
shows geometrical isomerism.
(b) a positional isomer of 2-bromo-2-methylbutane

(c) a functional straight-chain isomer (containing a single functional 3. (a) CH3CH(CH3)CH2Br – 1-bromo-2-methylbutane
group) of pentanoic acid
(b) CH3CH(CH3)CH2CH2Br - 1-bromo-3-methylbutane
4. Write down the formulae and names of the four alcohols, corresponding or CH3CH(CH3)CHBrCH3 - 2-bromo-3-methylbutane
to the formula C4H9OH, which are structural isomers of one another. or CH2BrCH(CH3)CH2CH3 - 1-bromo-2-methylbutane

5. Compounds of molecular formula C4H 10O can exhibit skeletal (c) CH3CH2CH2CO.OCH3 - methyl butanoate
isomerism, positional isomerism, functional group isomerism and or CH3CH2CO.OCH2CH3 - ethyl propanoate
stereoisomerism. or CH3CO.OCH2CH2CH3 - propyl ethanoate
(a) Write down the structural formulae of suitable pairs of compounds or HCO.OCH2CH2CH2CH3 - butyl methanoate
that show:
(i) skeletal isomerism 4. CH3CH2CH2CH2OH - butan-1-ol
(ii) positional isomerism (CH3)2CHCH2OH - 2-methylpropan-1-ol
(iii) stereoisomerism CH3CH(OH)CH2CH3 - butan-2-ol
(CH3)3COH - 2-methylpropan-2-ol
(b) Explain why it is that compounds of molecular formula C4H10O
can exhibit one kind of stereoisomerism but not another. 5. (a) (i) CH3CH2CH2CH2OH and (CH3)2CHCH2OH
or (CH3)3COH and CH3CH(OH)CH2CH3
(ii) CH3CH2CH2CH2OH and CH3CH(OH)CH2CH3
or (CH3)2CHCH2OH and (CH3)3COH

(iii) CH3 CH3

C and
C
H OH H
HO
C2H 5 C2H5

(b) Butan-2-ol has a chiral centre / asymmetric C atom ∴ can exhibit

optical isomerism / exist in two non-superimposable forms
but none of the compounds has a C = C bond (or other structural
feature) which can cause restricted rotation of atoms
∴ there is no possibility of geometrical isomerism / existence of cis
and trans isomers

Acknowledgements: This Factsheet was researched and written by Mike Hughes Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire, TF1
1NU. ChemistryFactsheets may be copied free of charge by teaching staff or students, provided that their school is a registered subscriber. No part of these
Factsheets may be reproduced, stored in a retrieval system, or transmitted, in any other form or by any other means, without the prior permission of the
publisher. ISSN 1351-5136

5
 Chem Factsheet
www.curriculum-press.co.uk Number 94
Enthalpies of Solution
To succeed in this topic you need to understand: surface and diffuse away resulting in solution formation. This
• standard enthalpy changes (covered in Factsheet 08 ); means other water molecules can bond to the ions in the newly
• Hess’s law (covered in Factsheet 08); exposed crystal surface and the processes of hydration,
• lattice energy (covered in Factsheets 28 and 29); detachment and diffusion can repeat until the whole crystal has
• how lattice energy values vary with ionic charge and radius dissolved or the solution reaches saturation.
(covered in Factsheets 28 and 29).
This is usually represented by an equation of the form:
After working through this Factsheet you will be able to:
NaCl(s) + aq ! Na+(aq) + Cl-(aq)
• define standard enthalpy of solution;
• construct energy cycles to relate lattice energy , enthalpies of Conversely for some other ionic compounds, if the energy released
hydration and enthalpy of solution; by ion hydration is insufficient to overcome the electrostatic forces
• calculate enthalpies of solution by applying Hess’s Law to such between ions, the solute will generally be less likely to dissolve.
energy cycles;
• comment on the likelihood of solubility based on enthalpy of In essence, an ionic solute is likely to be water soluble if the
solution data energy required to break up the ionic lattice is exceeded (or
• comment on solubility trends in terms of variations in lattice energy very nearly so) by the energy released by ion hydration. In
and enthalpies of hydration. short, if the overall process is exothermic (or only slightly
endothermic) solubility is likely.
Water is probably the most common solvent used in chemistry and
every day life. When water “dissolves” another substance (the
Before looking at the quantitative energetics of the dissolving
solute) they form a homogeneous mixture (the solution) at a molecular
process we need to define the relevant standard enthalpy changes.
or ionic level and, by various means, water molecules are found to
These are:
bond to the solute particles. The solute particles are said to become
solvated or hydrated. 1. Lattice Dissociation Energy, ∆Hêlatt :
However, observations tell us that not all substances will dissolve in this is the energy REQUIRED when ONE MOLE of a SOLID
water. For example, at room temperature, silicon dioxide (sand) is IONIC compound is converted to its CONSTITUENT GASEOUS
insoluble whereas ethanol (“alcohol”) is infinitely soluble and sodium IONS, measured under standard conditions of temperature and
chloride (salt) is only moderately soluble, soon becoming saturated. pressure (105 Pa and 298K).

Here, you will study what happens at a molecular and ionic level e.g. NaCl(s) ! Na+(g) + Cl-(g) ; +780 kJ mole-1
when an ionic substance (e.g. sodium chloride, Na+Cl-(s)) dissolves MgO(s) ! Mg2+(g) + O2-(g) ; +3607 kJ mole-1
in water and you will examine the energy changes involved at each (These are ALWAYS endothermic changes because bonds are
stage in order to develop a means of explaining why some ionic being broken.)
compounds are soluble and some are insoluble. It will also allow you
to explain trends in solubility. For instance, why do the group II 2. Enthalpy of Hydration, ∆Hêhydn :
sulphates become less soluble down the group whereas the this is the energy RELEASED when ONE MOLE of GASEOUS
hydroxides become more soluble? IONS dissolve in EXCESS water, measured under standard
conditions of temperature and pressure (105 Pa and 298K).
As illustrated in fig. 1, when a crystal of sodium chloride is added to
water, either end of the polar water molecules are attracted to the eg K+(g) + (aq) ! K+(aq) ; -305 kJ mol-1
oppositely charged ions at the surface of the crystal forming ion- Cl-(g) + (aq) ! Cl-(aq) ; -381 kJ mol-1
dipole bonds. (These are ALWAYS exothermic changes because bonds are being
formed.)
Fig 1 H H
Cl- δ+ O δ- Cl- δ+ O δ-
H H 3. Enthalpy of Solution, ∆Hêsoln :
Na+ This is the energy change which occurs when ONE MOLE of a
substance DISSOLVES IN EXCESS WATER, measured under
Cl-
Separated solvated standard conditions of temperature and pressure (105 Pa and
H
Na+ δ- O δ+ ions in solution 298K).
H
Cl- e.g. CaCl2(s) + (aq) ! Ca2+(aq) + 2Cl-(aq) ; -83 kJ mole-1
H NaCl(s) + (aq) ! Na+(aq) + Cl-(aq) ; +10 kJ mole-1
Dipole of water
Na+ δ- O δ+ (These may be exothermic or slightly endothermic changes .)
attracted to ion Na+
H
Exam Hint : Many marks are lost by incomplete or inaccurate
This bond formation is an exothermic process and the energy released definitions of standard enthalpy changes. Each definition should
is sufficient to overcome the ionic bonding forces holding the ions in include three elements; quantity, process and conditions.
their lattice positions. Hence, the hydrated ions detach from the crystal
1
94. Enthalpies of Solution Chem Factsheet

These three quantities can be connected in an energy cycle as shown in Fig 2.

Fig 2 Hess’s Law can then be applied giving :

Separate gaseous ions
Enthalpy Lattice Dissociation Sum of the Hydration
Lattice = +
of Solution Energy Enthalpies of ALL ions
Dissociation
Hydration Energy
enthalpies of This is a general energy cycle which can be used to calculate
cations and One mole of ∆Hêsoln , ∆Hêhydn of anion or cation or ∆Hêlatt provided all other
anions ionic compound values are available.

Enthalpy of
solution Exam Hint : To avoid errors in applying Hess’s Law, a simple device
is to use the fact that the sum of the clockwise enthalpy changes
Aqueous ions (solution) must equal the sum of the anti-clockwise enthalpy changes.

Data: HYDRATION ENTHALPIES (/kJ mole-1) LATTICE DISSOCIATION ENTHALPIES (/kJ mole-1)
H+(g) -1075 F-(g) -457 F- Cl- Br- I-
Li+(g) -499 Cl-(g) -381 Li+ +1031 +848 +803 +759
+ - +
Na (g) -390 Br (g) -351 Na +918 +780 +742 +705
+ - +
K (g) -305 I (g) -307 K +817 +711 +679 +651
2+ - 2+
Mg (g) -1891 OH (g) -460 Mg +2957 +2526 +2440 +2327
2+ 2+
Ca (g) -1562 Ca +2630 +2258 +2176 +2074
< Sr2+(g) -1337 Sr2+ +2492 +2156 +2075 +1963

Example 2 Using the data table, calculate the heat of solution

Example 1 Using the data table, calculate the heat of solution of
of calcium chloride, CaCl2(s)
potassium bromide, KBr(s)

Applying the general energy cycle seen in fig.2 to potassium Again, applying the general energy cycle and inserting the
bromide and inserting the relevant data using the data table relevant data using the data table, produces the cycle shown:
produces the cycle:
Ca2+(g) + 2Cl-(g)
K+(g) + Br-(g)
+ 2258
+ 679
(-1562) + 2(-381) CaCl2(s)
(-305) + (-351) KBr(s)
Enthalpy of
Enthalpy of solution of CaCl2
solution of KBr
Ca2+(aq) + 2Cl-(aq)
+ -
K (aq) + Br (aq)
Applying Hess’s Law, gives:
Exam Hint: Take care to show the correct states of matter for
each species in the cycle. ∆Hêsoln[CaCl2(s)] = (+2258) + (-1562) + 2(-381)
= -66 kJ mole-1

Applying Hess’s Law, gives:

Exam Hint: Make sure you allow for the number of moles of ions
∆Hêsoln[KBr(s)] = (+679) + (-305) + (-351)
being hydrated. In this example 2 x (-381) is needed because
= + 23 kJ mole-1 calcium chloride contains 2 moles of chloride ions per mole.

Exam Hint: Make sure you include units with your final answer.

2
94. Enthalpies of Solution Chem Factsheet

Relating Enthalpies of Solution to Trends in Solubility

Sulphate Solubility (/mol dm-3) at 25°C Hydroxide Solubility (/mol dm-3) at 25°C

MgSO 4 1.83 Mg(OH)2 2.00 × 10-4

CaSO4 4.66 × 10-2 Ca(OH)2 1.53 × 10-2

SrSO4 7.11 × 10-4 Sr(OH)2 3.37 × 10-2

BaSO4 9.43 × 10-6 Ba(OH)2 0.150

These data show that the solubilities of the group II sulphates decease down the group whereas the solubilities of the corresponding
hydroxides increase. This suggests that the enthalpy of solution becomes more endothermic for the sulphates causing them to become
less likely to dissolve. However, the enthalpy of solution must become more exothermic for the hydroxides causing them to become more
likely to dissolve. Why do these opposite trends occur?

Remember, enthalpies of solution are calculated from two basic factors:

∆Hêsoln = ENDOTHERMIC Lattice Dissociation Energy + EXOTHERMIC Hydration Enthalpies.

In order to account for the different trends in solubility for the group II sulphates and hydroxides it is necessary to look at the relative
trends in lattice energies and hydration energies down the group.

Ion ∆Hêhydn(/kJ mole-1) Sulphate Lattice Energy (/kJ mole-1) Hydroxide Lattice Energy (/kJ mole-1)

Mg2+(g) -1891 MgSO 4 +2999 Mg(OH)2 +3087

Ca2+(g) -1562 CaSO4 +2710 Ca(OH)2 +2628

Sr2+(g) -1337 SrSO4 +2550 Sr(OH)2 +2333

Ba2+(g) -1128 BaSO4 +2427 Ba(OH)2 +2053

Using these data, the enthalpy of solution can be estimated for each compound.

∆Hêsoln for MgSO4 = +2999 – 1891 + (∆Hêhydn[SO42-]) = +108 + a constant

∆Hêsoln for CaSO4 = +2710 – 1562 + (∆Hêhydn[SO42-]) = +1148 + a constant
∆Hêsoln for SrSO4 = +2550 – 1337 + (∆Hêhydn[SO42-]) = +1213 + a constant
∆Hêsoln for BaSO4 = +2427 – 1128 + (∆Hêhydn[SO42-]) = +1299 + a constant

∆Hêsoln for Mg(OH)2 = +3087 – 1891 + (2∆Hêhydn[OH-]) = +1196 + a constant

∆Hêsoln for Ca(OH)2 = +2628 – 1562 + (2∆Hêhydn[OH-]) = +1066 + a constant
∆Hêsoln for Sr(OH)2 = +2333 – 1337 + (2∆Hêhydn[OH-]) = +996 + a constant
∆Hêsoln for Ba(OH)2 = +2053 – 1128 + (2∆Hêhydn[OH-]) = +925 + a constant

These calculations show that the enthalpies of solution of the sulphates become more endothermic, resulting in a decrease in solubility.
However, those of the hydroxides become more exothermic, resulting in an increase in solubility.

In both cases the endothermic lattice energy contribution decreases (becomes more exothermic) as the cation size increases but, because
of the smaller size of the hydroxide ion, the decrease is more rapid for the hydroxides than for the sulphates. This more than compensates
for the corresponding decrease (becoming less exothermic) in the hydration energies as the cations increase in size. Overall, the endothermic
contributions by the lattice energies become less significant in the enthalpy of solution calculations for the hydroxides than for the
sulphates.

3
94. Enthalpies of Solution Chem Factsheet

Practice Questions
1. Using the data tables and an appropriate energy cycle, calculate a value for the molar enthalpy of a solution of magnesium iodide,
MgI2(s).

2. Using the data tables and an appropriate energy cycle, calculate a value for the molar enthalpy of a solution of lithium chloride, LiCl(s).

3. (a) Write equations, including state symbols, for which the enthalpy change is

(i) the enthalpy of hydration of an ion M+

(ii) the enthalpy of solution of a salt MX

(b) The standard enthalpy change for

NaF(s) → Na+(g) + F-(g) is + 918 kJmol-1 .
Name this standard enthalpy change.

The enthalpy of solution of sodium fluoride is +71 kJ mol-1. The enthalpy of hydration of a fluoride ion is -457 kJ mol-1. Use these
data, an appropriate energy cycle and the enthalpy value given in part (b) to calculate the enthalpy of hydration of a sodium ion.

Answers

1.
Mg2+(g) + 2I-(g)

+ 2327
Enthalpy of solution of MgI2
(-1891) + 2(-307) MgI2(s) = +2327 -1891 – 614
= -178 kJ mole-1
Enthalpy of
solution of MgI2

Mg2+(aq) + 2I-(aq)

2.
Li+(g) + Cl-(g) Enthalpy of solution of LiCl
= +848 - 499 – 381
+ 848 = - 32 kJ mole-1
(-499) + (-381) LiCl(s)
Enthalpy of
solution of LiCl

Li+(aq) + Cl-(aq)

3. (a) (i) M+(g) + aq ! M+(aq)

(ii) MX(s) + aq ! M+(aq) + X-(aq)
(-499) + (-381)
(b) The lattice dissociation energy

Na+(g) + F-(g)

+17 = +918 + ∆Hêhydn[Na+] -457

+ 918
Hydration
enthalpy of NaF(s) ∆Hêhydn[Na+] = +71 - 918 + 457
Na+ + (-457) = -390 kJ mole-1
+ 71

Acknowledgements: This Factsheet was researched and written by Mike Hughes. Curriculum Press, Bank
Na+(aq) + F-(aq) House, 105 King Street, Wellington, Shropshire, TF1 1NU. ChemistryFactsheets may be copied free of charge
by teaching staff or students, provided that their school is a registered subscriber. No part of these Factsheets
may be reproduced, stored in a retrieval system, or transmitted, in any other form or by any other means, without
the prior permission of the publisher. ISSN 1351-5136

4
 Chem Factsheet
www.curriculum-press.co.uk Number 95

Rearranging Formulae
Two methods are given for rearranging formulae. The first method Cross multiplying
shows mathematically how the rearrangement is done; the second Another way to rearrange the equation is by ‘cross multiplying’.
method, sometimes called ‘cross multiplying’, is a short cut. You
should study and practise both methods but you may find it easier to 1. Swap the two sides of the equation so that the term containing
use the method of cross multiplying for rearranging chemical formulae what we want, m, is on the left hand side of the equation
quickly.
m/M=n
Mole calculations
Perhaps the most important formula which is met in the early stages 2. We need to ‘get rid of’ M on the left hand side of the equation
of a chemistry course is the one which relates the number of moles to leave us with m. Take the M which is on the bottom of the
(n) of a substance to the mass of the substance (m) and the mass of fraction on the left hand side of the equation and move it
one mole of substance (M), (the atomic or molecular mass expressed across to the the top of the fraction on the right hand side of
in grams). The formula is the equation.

m
n=m/M (i) = n
M
m = nM
Example 1. Suppose we want to find the number of moles in 9 g of
water. The molecular mass of water is (2 x 1 + 16) =18. To find the The rule for cross multiplying: if it is ‘divide’ on one side it
number of moles of water we simply substitute in the equation using becomes ‘multiply’ when you swap it to the other side of the
m = 9 and M = 18 to give equation and vice versa.

n=9/18
n=0.5 mols Example 3. Rearrange formula (i) so that M is the subject of the
formula. Hence calculate the molecular mass of a substance, 2
i.e. the number of moles in 9 g of water is 0.5 moles moles of which have a mass of 48 g.
n=m/M
Example 2. Suppose, however, we need to use the formula to
calculate the mass of 3 moles of sulphur atoms. The atomic mass of 1. Multiply both sides of the equation by M
sulphur is 32 so M = 32. We must now rearrange the formula to give n × M = M × m/M
us m as the subject of the formula.
2. Cancel the Ms on the right hand side of the equation
1. Swap the two sides of the equation so that the term we want, m, is
on the left hand side of the equation n × M = M × m/M
n×M=m
m/M=n
This gives us M on the left hand side but we now have to get
2. M is dividing on the left hand side of the equation. To ‘get rid of rid of n on the left hand side.
‘ the M on this side carry out the opposite mathematical operation.
That is multiply both sides of the equation by M 3. Since n is multiplied we do the opposite and divide both
sides of the equation by n
M × m/M = M × n (because both sides of an equation are equal, n×M=m
if you do the same thing to both sides of the n x M/n = m/n
equation they remain equal) 4. Cancel the n’s on the left hand side of the equation
n x M/n = m/n
3. Cancelling the M’s on the left hand side gives: M = m/n
m = M × n which is the rearranged formula that we require.
This is the equation we want and so we can substitute the
We now put in the quantities we are given: values we are given:

m = 32 × 3 M = 48/2 =24
= 96 g
i.e. the molecular mass of the substance is 24.
i.e. the mass of 3 moles of sulphur atoms is 96 g.

1
95. Rearranging Formulae Chem Factsheet

Example 4. Rearrange the general gas equation to make T the subject

Cross multiplying
of the formula, pV= nRT
It is quicker to rearrange the equation by cross multiplying.
Swap the two sides of the equation over so that the left hand side
n=m/M
contains the term we want, T
1. Move the M on the bottom of the right hand side fraction to
nRT = pV
the top of the left hand side fraction.
m T is multiplied by n and R so divide both sides by nR to ‘get rid of’
n= n and R on the left hand side
M
Mn = m nRT pV
=
2. Move the n on the top of the left hand side to the bottom of nR nR
the right hand side fraction
Cancel the n’ and R’s on the left hand side
M = m/n This gives the equation we need. nRT pV pV
= T=
nR nR nR
Questions Using the cross multiplying method,
The number of moles of a solute in a solution is give by the
pV= nRT
formula:
C×V Swap the two sides of the equation over so that the left hand side
n=
1000 contains the term we want, T
where n is the number of moles, C is the concentration of the nRT = pV
solution (in mol dm-3) and V is the volume of the solution (in cm3)
1. Rearrange the equation to make C the subject of the formula. Move the n and R from left hand side to the bottom of the right
Hence find the concentration of a solution of sodium hand side fraction.
hydroxide which contains 2 moles of solute in 500 cm3 of pV
solution. T=
nR
2. Rearrange the equation to make V the subject of the formula.
Hence find the volume (in cm 3) of a 3M solution of Questions
hydrochloric acid which contains 0.3 moles of solute. 3. Rearrange the equation pV=nRT to make (a) p, (b) n and (c) R
the subjects of the formula.
Gas law calculations
4. Calculate the number of moles in 0.1 m3 of oxygen at a
Another important equation which often needs to be rearranged is
pressure of 90955 Pa and a temperature of 547 K
the General Gas Equation,
(R = 8.314 J mol-1 K-1)
pV=nRT
Energy calculations
When we use Hess’s Law to work out energy changes we often end
This equation can be rearranged to give each of the terms, p, V, n, R up with an equation which needs rearranging to give us the answer.
and T. The methods are exactly the same as those used above.
Example 5
Example 4. Rearrange the general gas equation to make V the subject In a calculation to find the enthalpy of formation of methane we
of the formula. pV=nRT might end up with the following equation:
The term containing V is already on the left hand side of the formula.
-393 + 2 (-286) = -890 + ∆Hf[CH4(g)]
V is multiplied by p so, to ‘get rid of’ p, divide both sides of the
equation by p (where ∆Hf[CH4(g)] is the enthalpy of formation of methane)
pV nRT We need to rearrange the equation to make the enthalpy of formation
=
p p of methane, ∆Hf[CH4(g)], the subject of the equation.
Then cancel the p’s on the left hand side of the equation to give
1. Swap the two sides of the equation over so that the term we
nRT need, ∆Hf[CH4(g)], is on the left hand side of the equation.
V =
p
-890 + ∆Hf[CH4(g)] = -393 + 2 × (-286)
Or using the cross multiplying method,
Move the p on the left hand side of the equation to the bottom of 2. ‘Get rid of’ the term -890 by adding +890 to both sides of the
the fraction on the right hand side equation. (As before, if you do the same thing to both sides of
the equation they remain equal)
pV=nRT
-890 + ∆Hf[CH4(g)] + 890 = -393 + 2 × (-286) + 890
nRT
V =
p

2
95. Rearranging Formulae Chem Factsheet

3. The -890 and the +890 on the left hand side cancel each other 10 (1-3x)
p=
out leaving the equation: 7
∆Hf[CH4(g)] = -393 + 2 × (-286) + 890 (Equations similar to this may arise in calculations involving partial
pressures)
And this equation can be worked out to give:
1. Cross multiply to put the 7 on the left hand side of the equation
∆Hf[CH4(g)] = -393 + - 572 + 890 7p = 10(1 - 3x)
∆Hf[CH4(g)] = -75 kJ mol-1 2. Multiply out the brackets
7p = 10 - 30x
A Short Cut
3. Put all the terms containing x on the left hand side and all the
If we move a term from one side of the equation to the other we terms which do not contain x on the right hand side. Change
change its sign. Starting with the same equation: the signs where necessary.
30x = 10 - 7p
-393 + 2 x (-286) = -890 + ∆Hf[CH4(g)] Cross multiply to put the 30 on the right hand side
1. Again swap the two sides of the equation so that the term we 10-7p
x=
require is on the left hand side: 30
-890 + ∆Hf[CH4(g)] = -393 + 2 x (-286) Example 8
Equations with roots or powers can be rearranged using the same
2. Move the -890 from the left hand side of the equation to the
principles
right and change its sign:
Rearrange the following equation to make [H+] the subject of the
∆Hf[CH4(g)] = -393 + 2 × (-286) + 890 formula:

3. Work out this equation as before to give: [H+]2

= Ka
C
∆Hf[CH4(g)] = -393 + - 572 + 890 (This equation usually arises in second year modules. It relates the
∆Hf[CH4(g)] = -75 kJ mol -1 hydrogen ion concentration, [H+], to the concentration of a weak
acid, C, and the acid dissociation constant, Ka)
Questions Move the C over to the right hand side of the equation (bottom to
5. Rearrange the following equations and find the value of the top!) so that the squared term is by itself)
unknowns x, y and z: [H+]2 = Ka × C
(a) 248 - 376 = x + 202
(b) y + 123 = -478 +1020 Since square rooting is the inverse of squaring, take the square
(c) 102 + 2(-346) = -135 - z root of both sides of the equation (As before, if you do the same
thing to both sides of the equation they remain equal)

More complex rearrangements [H+] = √( Ka × C)

The same principles as shown above can be used to rearrange more Questions
involved equations 6. Make T the subject of the formula: ∆G = ∆H - T ∆S
7. Make the concentration of NO2 , [NO2], the subject of the formula:
Example 6 [NO ]2
Find the value of ∆H from the following equation: Kp = [N O2 ]
2 4
124 -376 = 246 + 3∆H 8. Rearrange the following to make x the subject of the formula
1. Swap over the two sides of the equation so that the unknown is (3 - x)
on the left hand side. K=
8
246 + 3 ∆H = 124 -376 9. Make k the subject of the formula: R= k[NOCl]2
10. Make p(H2) the subject of the equation
2. Move the 246 to the right hand side and change its sign p(NH3)2
Kp = p(H )3p(N )
3 ∆H = 124 -376 - 246 2 2

4. Work out the right hand side Answers to questions

1. C = 1000 × n/V 4 mol dm-3
3∆H = 124 -376 - 246 2. V = 1000 × n/C 100 cm3
= -498 3. (a) p = nRT/V (b) n = pV/RT (c) R = pV/nT
5. ∆H is multiplied by 3, so to obtain ∆H divide both sides by 3 4. 2 mol
∆H = -498/3 5. (a) x = 248 - 376 -202 = -330
∆H = -166 (b) y = -478 + 1020 -123 = +419
(c) z = -102+ 2 × 346 -135 = +455
∆H - ∆G
Example 7 6. T=
∆S
If an expression contains brackets these should be worked out
7. [NO2] = √( Ka × [N2O4] )
before the addition and subtraction.
8. x = 3 -8K Acknowledgements: This Factsheet was
Make x the subject of the equation: 9. k = R/[NOCl]2 researched and written by Chris Senior Curriculum
10. p(H2) = 3√p(NH3)2/(Kp × p(N2)) Press, Bank House, 105 King Street, Wellington,
Shropshire, TF1 1NU. ISSN 1351-5136
3
 Chem Factsheet
www.curriculum-press.co.uk Number 96
Relating the Properties of Crystal
Structures to Structure and Bonding
This topic builds on the work covered in; Relating Properties of Diamond to Structure and Bonding
Factsheet 05- Bonding • Very strong and rigid structure which is very difficult to distort
Factsheet 06 – Structure of Elements and Compounds or break because of the 3-dimensional pattern of strong
covalent bonds. In fact, diamond is the hardest natural material
To succeed in this topic you need to: known.
Understand what is meant by ionic, covalent and metallic bonding • Very high melting point (3823K) because a lot of energy is
Understand the different types of intermolecular forces needed to break the strong covalent bonds. In order to reach
the liquid state most of the covalent bonds would need to be
Introduction broken.
All materials are made up from atoms. There are only about 100 kinds • Does not conduct electricity because all the electrons are held
of atom in the entire universe. These atoms are the building blocks tightly in the bonds between the atoms and are not free to
that make all the plants and animals, solids liquids and gases that we move.
encounter everyday. Bonding of atoms in different ways creates
various structural forms. The bonding and structure determine the Note: Silicon can also exist in the same crystalline structure as
appearance of any material but also all its other physical properties. diamond. It is not as hard as diamond because the covalent
bonds are longer and therefore weaker. Silicon has a high melting
This Factsheet will concentrate on crystalline structures which you point but it is only 1683K.
are most likely to meet in examination question papers.
2) Graphite
You will need to know about the following examples of crystalline
structures: diamond, graphite, sodium chloride, ice, iodine and metals.

1) Diamond weak van der Waals' forces

between layers
strong covalent bonds
carbon atoms arranged
carbon atom in hexagons
strong covalent bonds

Structure and Bonding

• Layers of carbon atoms arranged in hexagons joined together
by strong covalent bonds.
• Each carbon uses 3 out of 4 outer electrons to bond covalently
Structure and Bonding to three others.
• Giant covalent lattice structure • Fourth electrons from each atom are delocalised throughout
• Millions of carbon atoms bonded directly or indirectly to each the layer of C atoms.
other by strong covalent bonds. • Weak van der Waals’ forces hold the layers together.
• Every carbon atom forms four covalent bonds by sharing electrons
Relating Properties of Graphite to Structure and Bonding
with each of its four nearest neighbours.
• Conducts electricity very well because the delocalised electrons
• Every carbon atom can be imagined to be at the centre of a regular
are free to move throughout the layers.
tetrahedron surrounded by four other carbon atoms whose
• High melting point (3925K) because, in order to melt graphite, it
centres are at the corners of the tetrahedron.
is not sufficient to loosen one layer from another by breaking
the Van der Waal forces. To achieve melting it is necessary break
Common errors: Terms such as “ions”, free electrons”,
much of the strong covalent bonding throughout the whole
“molecular” and “intermolecular forces” are NEVER applicable
structure.
when describing the structure and bonding in diamond.
• Soft, slippery texture and can be used as a lubricant because the
weak Van der Waal forces are easily overcome allowing the layers
to slide over each other like cards in a pack of playing cards.
1
96. Relating the Properties of Crystal Structures to Structure and Bonding Chem Factsheet

3) Sodium chloride Structure and Bonding

• Covalently bonded molecules, H-O-H.
Na+ Cl− Na+ • Simple molecules in hydrogen bonded crystal structure.
Cl− • Hydrogen bonds between neighbouring H2O molecules. These
Na+ Cl−
are caused by the very highly electronegative oxygen atom which
Na+ Cl− Na+ attracts most of the electron cloud away from the hydrogen
Cl− Na + atom. A hydrogen bond is then the electrostatic attraction
Cl−
between the δ+ hydrogen atoms in one molecule and a lone pair
Na + −
Cl Na+ on the oxygen atom in a neighbouring molecule.
Cl− Na+ Cl− • Two hydrogen bonds per water molecule maintain the crystal
− structure below 273K.
Na +
Cl Na+ dashed lines are
− +
Cl Na Cl − not physical Relating Properties of Ice to Structure and Bonding
Na+
bonds • Relatively high melting point, 273K for such a small molecule
Cl− Na+
because the relatively strong hydrogen bonds need to be broken.
• Less dense than water because the long hydrogen bonds in ice
Structure and Bonding hold the water molecules further apart than in the liquid. Thus
• Giant ionically bonded lattice. the same mass occurs in a larger volume.
• Electrons have been transferred from the sodium atoms to form • Remains solid below 273K because the hydrogen bonds are
sodium ions. strong enough to resist the thermal vibrations of the water
• Electrons have been transferred to the chlorine atoms to form molecules
chloride ions. • Fairly easily crushed because the crystal will sheer where it is
• The sodium ions carry a positive charge; Na+ (cation). hydrogen bonded.
• The chloride ions carry a negative charge; Cl- (anion). • Non-conducting because no free electrons or ions exist in ice.
• Each positive sodium ion is surrounded by 6 chloride ions and The molecules are polar but neutral overall.
vice versa.
• Overall, the ions are arranged to form a cubic crystal with cations Note: The physical properties of such molecular crystals are
and anions alternating along any edge of the cube controlled by the inter-molecular forces not the intra-molecular
• The oppositely charged ions are held together by strong covalent bonds. The latter remain intact during melting,
electrostatic forces of attraction. crushing etc.
• The net electrical force binding the ions together is described
as ionic bonding. 5) Iodine
Note: “an ionic bond” is a meaningless term because, unlike the
atoms involved in a covalent bond, each cation attracts every
anion and vice versa. “Ionic bonding” describes the net
attractive forces between the ions. = I2 molecule

Relating Properties of Sodium Chloride to Structure and Bonding

• High melting point, because a lot of energy is needed to
overcome the strong electrostatic forces between the cations
and anions.
• Soluble in water because, when the positive and negative ions
attract polar water molecules, sufficient energy is released to
break the ionic bonding forces. Structure and Bonding
• Conducts when molten or in solution because the ions are then • Covalently bonded molecules, I-I.
free to move. • Simple non-polar molecules in crystal structure.
• Brittle because any stress will cause the crystal to cleave along • Van der Waal forces between neighbouring I2 molecules maintain
planes parallel to the face of the crystal cube. the crystal structure at room temperature.
4) Ice Relating Properties of Iodine to Structure and Bonding
• Low melting point, 387K, because relatively little energy is
needed to break the weak Van der Waal intermolecular forces.
• Non-conducting because no free electrons or ions exist in the
= hydrogen atom crystal. The I2 molecules are neutral overall.
= oxygen atom
= hydrogen bond Note: Again, the physical properties of such molecular crystals
are controlled by the inter-molecular forces not the intra-molecular
covalent bonds.

Note: Van der Waals’ forces increase with increasing size of the
molecules. This is why, at room temperature, chlorine is a gas,
bromine is a liquid but iodine is a crystalline solid.

2
96. Relating the Properties of Crystal Structures to Structure and Bonding Chem Factsheet

6) Metals heat energy required to melt one mole of sodium

chloride.Why should this be so?
_ _ _ _ (i) Why do you think graphite remains as a solid at very
+ + +_ + + high temperatures? Answer in terms of the structure and
_ _ _ _ bonding of graphite.
_ __ _ _ _
+ + + + + + Another approach is to talk about bonds and then link it in with the
_ _ _ _ _ physical properties of contrasting substances.
_ _ _ _
+ + + + + 2. Graphite and iodine crystals both contain covalent bonds.
_ _ _ _ However the physical properties of their crystals could hardly
_ _ _ _ _
+ + + + + + be more different. Compare their melting points and their electrical
_ _ _ _ _ conductivities and say how these differences can be explained
electron sea
by referring to their bonding and structures.
Next a question comparing the structure of contrasting substances
Structure and Bonding and relating these with the physical properties.
• Strong metallic bonding.
3. Crystals of sodium chloride melt at 801oC and diamond melts at
• Giant lattice structure of cations (+) surrounded by a ‘sea of
3554oC. Compare their structures and explain why the melting
delocalised electrons’.
point of diamond is so high.
• The free, delocalised electrons come from the outer or valence
shell of each atom. Here is a question comparing diamond and iodine. This time looking
• Metallic bonding is the net attraction between the cations and at similarities in bonding but contrasting the differences in their
the delocalised electrons. The electrons are the ‘glue’ which structure and properties.
hold the metal ions in place. 4. Diamond and iodine are both crystalline solids at 25 oC. What
• The metal lattice is usually close packed. type of bonding do they have in common, and what is the
Relating Properties of Metals to Structure and Bonding difference in their structures. How does the difference in their
• High melting points (usually) because the strong metallic structures account for their different melting points.
bonding requires a large amount of energy to be weakened to Some questions may simply ask you to recall information and be
the point where the cation are free to move. able to draw labelled diagrams.
• The free delocalised electrons make all metals very good
conductors of electricity in both solid and liquid state. 5. Draw labelled diagrams to illustrate the structure and type of
• Metals are malleable and ductile (not brittle) because the layers bonding found in (a) Graphite and (b) Sodium chloride
of cations can slip over each other without cleaving because
the delocalised electrons maintain the bonding between layers. Some questions might approach the subject via electrical
• High density due to the close packing resulting from the strong conductivity.
metallic bonding and the spherical shape of the ions. 6. How can the electrical conductivities of sodium chloride,
diamond and graphite be explained by looking at their structure
Practice Questions and bonding.
There are many different approaches for examination bodies to test
your understanding of crystalline structures. 7. Aluminium it conducts electricity very well. Explain why this is
so by describing its bonding and crystalline structure.
They may provide information of the physical properties of relevant
materials and then ask how this links in with the crystalline structures Answers
of those materials. 1 (a) Force 1 .........van der Waals’
Force 2 .........dipole –dipole
1. The table below shows some values of melting points and some Force 3 ..........hydrogen bonding
heat energies needed for melting.
Remember:
Substance I2 NaCl Carbon (graphite) • Not ionic because these are forces between ions not between
Melting point / oC 114 801 Sublimes at 3652 molecules
Heat energy for melting / kJmol-1 7.9 28.9 ——- • Not covalent as this would be intra-molecular, that is to say
within a molecule, not between molecules.
(a) Name three types of forces between molecules.
(b) Describe the bonding between the atoms and between the
(b) Covalent between the atoms, I-I
molecules in a crystal of iodine.
and van der Waals’ between the I2 molecules
(c) An iodine crystal is said to have what crystal type?
(d) To melt iodine crystals requires heat energy. Why is this
Remember:
energy needed?
• The covalent bonds are intra-molecular between the paired
(e) Sodium chloride crystals are held together by what bonds?
atoms of iodine that make up the iodine molecule.
(f) A sodium chloride crystal is said to have what crystal type?
• The van der Waals’ forces hold the iodine molecules in
(g) To melt one mole of sodium chloride requires a lot of energy.
position in the crystal of iodine.
Explain why.
(h) The heat energy needed to vaporise one mole of sodium
chloride, (171kJmol–1), is almost 6 times greater than the
3
96. Relating the Properties of Crystal Structures to Structure and Bonding Chem Factsheet

(c) Molecular. Diamond has a giant covalent lattice structure

Remember: Remember
• There are no ions present so it cannot possibly be described • You will lose marks if you use the term molecular rather than
as ionic. giant.
• Iodine molecules are held in place by intermolecular van • You will also lose marks if use the term ionic as there are no
der Waals’ forces. So it is certainly a molecular crystal type. carbon ions involved.
• You will lose marks if you mention van der Waals’ because
(d) Van der Waals’ forces between the molecules must be you could be confusing the structure of diamond with the
broken. structure of iodine or graphite crystals.

Remember:
• There are no ions in iodine crystals, if you mention them Many strong covalent C-C bonds need to be broken if the
you will lose marks. structure of diamond is to break down. This takes much energy.
• If you suggest that covalent bonds between the iodine at- Remember.
oms must be broken you will also lose marks. • Don’t talk about the bonds being weakened they would
have to be broken for melting to take place.
(e) Ionic bonding • If you are certain you can draw the structure of diamond
(f) Giant ionic lattice structure then you can get these ideas across with a diagram.
(g) Ionic bonding involves very strong electrostatic forces • Don’t draw unwanted diagrams which may confuse the issue,
between ions. A large amoun of energy is needed to overcome for example the structure of graphite.
these forces. • Again talk only about covalent bonds not van der Waals’
(h) All bonding must be broken rather than weakend. or you will lose marks.
Remember: 4. Both have covalent bonds BUT the structure of iodine is simple
• When you melt a crystal of sodium chloride you put in energy molecular with the iodine molecules (I ) kept in place in the
until the lattice is broken up and the ions are free to move 2
lattice by weak van der Waals’ forces. However, diamond is a
around. But they are still very close to each other. The giant covalent lattice with each atom bonded to four others in a
electrostatic forces are still acting keeping the ions together tetrahedral arrangement.
to form molten sodium chloride. To vaporise the sodium
chloride you have to provide a much greater amount of Iodine melts easily because only weak inter-molecular forces
energy to overcome the electrostatic forces and completely need to be broken whereas, in diamond, many strong covalent
separate the sodium and chloride ions. bonds would need to be broken so it has a very high melting
• Do not mention sodium chloride molecules or you will lose point.
marks.
Remember:
If you go on to draw a diagram make sure it is correct and does
not contradict your written answer.
(i) Giant covalent lattice. The strong covalent bonds need a lot
of energy to break them.
2. Iodine sublimes on heating and has a low melting point. Graphite 5. See previous notes on these materials.
has a very high melting point. 6. Sodium chloride is a giant ionic lattice. In the solid state the ions
Iodine does not conduct electricity ; graphite does are fixed and therefore sodium chloride does not conduct when
Iodine has a simple molecular covalent lattice structure. solid. However it does conduct when aqueous or molten because
Molecules consist of two iodine atoms held together by a single there are mobile ions in solution or when molten.
covalent bond. Diamond is a giant covalent lattice structure. There are no free
Van der Waals’ forces hold the iodine molecules in place in its electrons or ions so it does not conduct at all.
lattice.
Graphite is a giant covalent layer lattice structure but it has
Iodine has a low melting point because the van der Waals’ inter-
delocalised electrons and it therefore conducts electricity.
molecular forces are weak and require only a small amount of
energy to break them. 7. The structure is a lattice of positive ions surrounded by a
Iodine has no free electrons or free ions to conduct electricity. delocalised “sea of electrons”. These delocalised electrons (3
Iodine crystals are therefore non-conducting. per atom) are free to move and responsible for aluminium’s very
high conductivity.
Graphite has a giant covalent layer lattice structure with three
covalent bonds and one delocalised electron per carbon atom. Remember.
• Refer to positive ions not nuclei.
Graphite has a very high melting point because many strong
• Refer to the lattice structure of the metal.
covalent bonds need to be broken which takes much energy.
• Refer to the ability of the delocalised electrons to move.
Graphite conducts because it has delocalised free electrons.
3. NaCl is a giant ionic lattice structure. Acknowledgements: This Factsheet was researched and written by Brian Egan. Curriculum
Press, Bank House, 105 King Street, Wellington, Shropshire, TF1 1NU. ChemistryFactsheets
Remember may be copied free of charge by teaching staff or students, provided that their school is a
You lose marks if you use the terms atoms and molecules when registered subscriber. No part of these Factsheets may be reproduced, stored in a retrieval
describing the sodium chloride lattice structure. system, or transmitted, in any other form or by any other means, without the prior permission
of the publisher. ISSN 1351-5136
4
 Chem Factsheet
www.curriculum-press.co.uk Number 97

Oxidation and Reduction in Organic Chemistry

Tosucceed in this topic you need to understand: Thus, if the structures of the starting material and the product are
• homologous series (covered in Factsheet 15); clearly drawn, applying these definitions will lead to an easy
• functional groups (covered in Factsheet 15); classification by simply noting the changes in structure in terms
• structural (including displayed) formulae (Factsheet 15); of addition or loss of either oxygen or hydrogen.
• naming organic molecules by I.U.P.A.C. rules (Factsheet 15);
e.g.1 CH3CH2OH (ethanol) ! CH3CHO (ethanal)
• the basic definitions of oxidation and reduction (Factsheet 11);
is an oxidation because 2H atoms are removed.
• the term “redox reaction” (Factsheet 11);
• the terms “oxidant” (oxidising agent) and “reductant” (reducing e.g.2 CH3CHO (ethanal) ! CH3COOH (ethanoic acid)
agent) (Factsheet 11); is an oxidation because one O atom is added.
• oxidation states / numbers for defining oxidation and reduction
(Factsheet 11) e.g.3 CH2=CH2 (ethene) ! CH3CH3 (ethane)
is a reduction because 2H atoms are added.
After working through this Factsheet you will be able to: This is commonly applied in simplified equations used to represent
• recognise reactions of organic molecules as either oxidation or the organic redox reactions.
reduction;
• state the reagents and conditions used to achieve a particular [O] represents the oxygen being added or the agent responsible
oxidation or reduction reaction; for removing hydrogen. For example
• predict the oxidation and / or reduction products given a particular
CH3CH2OH + [O] ! CH3CHO + H2O
starting material.
CH3CHO + [O] ! CH3COOH
Introduction
The usual definitions for reduction and oxidation are “gain of Similarly, [H] represents the hydrogen being added or the agent
electrons” and “loss of electrons” respectively. For organic redox responsible for removing oxygen. For example
reactions, although these definitions are still applicable, it is usually CH3COOH + 2[H] ! CH3CHO + H2O
easier to recognise them in terms of loss or gain of hydrogen or
oxygen. CH3CHO + 2[H] ! CH3CH2OH

Oxidation = gain of oxygen or loss of hydrogen Note: Water is always formed if removal of hydrogen or
Reduction = gain of hydrogen or loss of oxygen oxygen occurs

Having decided that an organic conversion involves either oxidation or reduction, the next problem is to make an appropriate choice of
oxidising agent (oxidant) or reducing agent (reductant). The most common reagents you are likely to meet in A-level chemistry are
summarised in Table 1.

Table 1. Common Oxidants and Reductants

Oxidants Reductants
Acidified (H2SO4) potassium dichromate (K2Cr2O7) Hydrogen (H2) with nickel catalyst

Alkaline (NaOH) potassium manganate(VII) (KMnO4) Hydrogen (H2) with platinum catalyst

Fehling’s solution – alkaline (NaOH) copper sulphate (CuSO4) Hydrogen (H2) with palladium catalyst
Tollen’s reagent – alkaline (NH3) silver nitrate solution (AgNO3) Lithium aluminium hydride (LiAlH4) in dry ether
Atmospheric oxygen Sodium borohydride (NaBH4) in aqueous solution

Tin and hydrochloric acid

Finally you need to know of specific experimental conditions (e.g. temperature, reflux etc.) that are needed to achieve an efficient conversion.

Note: All organic compounds are combustible in the presence of oxygen and such reactions can be classified as oxidations of these
organic molecules. However, even though these reactions are vitally important in providing usable energy but, at the same time, adding
to pollution and global warming, they are not of much interest in organic synthesis because combustion invariably destroys the
carbon skeleton and functionality of the molecule.

1
97. Oxidation and Reduction in Organic Chemistry Chem Factsheet

The common, synthetically-useful oxidation and reduction reactions can now be summarized.

Functional Group Oxidation? Reduction? Functional Group Oxidation? Reduction?

Alkane No No Carboxylic acid No Yes
Alkene Yes Yes Amine No No
Alkyne No Yes Amide No Yes
Halogenoalkane No Yes Nitrile No Yes
Primary alcohol Yes No Arene Yes Yes
Secondary alcohol Yes No Acyl chloride No Yes
Tertiary alcohol No No Acid anhydride No Yes
Aldehyde Yes Yes Ester No Yes
Ketone No Yes Nitro compounds No Yes

Oxidation of Alkenes Reduction of Alkynes

1. By atmospheric oxygen in the presence of a silver catalyst By hydrogen in the presence of a finely divided nickel catalyst at
at around 200°C to produce epoxyalkanes 150°C to produce alkanes.
>C=C< + ½ O2 ! >C-C< H H
\ /
O −C=C− + 2H2 ! −C−C−
e.g. Ethene will convert to epoxyethane H H

H2C=CH2 + ½ O2 ! H2C-CH2 e.g. Ethyne will convert to ethane

\ / CH=CH + 2H2 ! CH3CH3
O
2. By heating with alkaline potassium manganate(VII) to
Note: this reaction is exactly parallel to that of alkenes because
produce diols >C=C< + [O] + H2O ! >COH-COH<
both involve hydrogenation of unsaturated carbon-to-carbon
e.g. Propene will convert to propan-1,2-diol bonds.
CH3CH=CH2 + [O] + H2O ! CH3CH(OH)-CH2OH

Note: Since this diol is both a primary and a secondary alcohol Reduction of Halogenoalkanes
it can oxidize further to a ketone and carboxylic acid. The By refluxing with lithium aluminium hydride in dry ether followed
diol is best made by producing the epoxyalkane as described by acidification to produce the corresponding alkane
in reaction 1, followed by hydration. C−Cl + 2[H] ! C−H + HCl
e.g. To make ethan-1,2-diol, prepare epoxyethane as
described and then react with dilute sulphuric acid at 60°C e.g. Bromomethane will convert to methane
CH3Br + 2[H] ! CH4 + HBr
H2C-CH2 + H2O ! HOCH2CH2OH
\ /
O
Oxidation of Primary Alcohols
By heating with acidified (H2SO4) potassium dichromate solution
Reduction of Alkenes to produce aldehydes (−CHO) and carboxylic acids (−COOH).
By hydrogen in the presence of a finely divided nickel catalyst −CH2OH + [O] ! −CHO + H2O
at 150°C to produce alkanes. then −CHO + [O] ! −COOH
>C=C< + H2 ! >C-C< e.g. Butan-1-ol will convert to butanal and then butanoic acid
HH CH3CH2CH2CH2OH + [O] ! CH3CH2CH2CHO + H2O
then CH3CH2CH2CHO + [O] ! CH3CH2CH2COOH
e.g. Propene will convert to propane
CH3CH=CH2 + H2 ! CH3CH2CH3
Note: The yield of aldehyde rather than acid can be maximized
Note: this reaction is of particular significance in the by reducing the time the alcohol is in contact with the oxidant
hydrogenation of vegetable oils to produce soft margarines. and avoiding an excess of oxidant. These are achieved by
immediate distillation of the reaction mixture and adding the
Note: other catalysts (Pt, Pd) can be used but nickel is oxidant to the alcohol in small controlled amounts during
preferred in most cases because of its lower cost. the course of the reaction. Conversely, acid production is
maximized by refluxing the reaction mixture and using excess
oxidant right from the start.

2
97. Oxidation and Reduction in Organic Chemistry Chem Factsheet

Oxidation of Secondary Alcohols Reduction of Carboxylic Acids

By heating with acidified (H2SO4) potassium dichromate solution By refluxing with lithium aluminium hydride in dry ether followed
to produce ketones by acidification to produce the corresponding primary alcohol.

(C−CO−C). C−CHOH−C + [O] ! C−CO−C + H2O −COOH + 4[H] ! −CH2OH + H2O

then −CHO + [O] ! −COOH e.g. Ethanoic will convert to ethanol

CH3COOH + 4[H] ! CH3CH2OH + H2O
e.g. Propan-2-ol will convert to propanone
CH3CHOHCH3 + [O] ! CH3COCH3 + H2O Note: Acids are reduced by LiAlH 4 but not by NaBH 4.
Aldehydes and ketones are reduced by both.
Note: Reflux is the standard technique here because ketones
do not oxidize further.

Reduction of Ketones
Oxidation of Tertiary Alcohols By refluxing with lithium aluminium hydride in dry ether or sodium
None borohydride in aqueous solution followed by acidification to
produce the corresponding secondary alcohol.
Note: No easy oxidation because tertiary alcohols do not
contain the −CHOH − group seen in both primary and C−CO−C + 2[H] ! C−CH(OH)−C
secondary alcohols. Both H atoms are needed for oxidation
to C=O to occur. e.g. Butan-2-one will convert to butan-2-ol
CH3CH2COCH3 + 2[H] ! CH3CH2CH(OH)CH3
Note: This can be used as a test to distinguish tertiary
alcohols from primary and secondary alcohols. When heated Note: The fact that ketones are not easily oxidized means
with orange acidified dichromate, tertiary alcohols will have that, unlike aldehydes, they are not reducing agents. This is
no effect on this colour but primary and secondary alcohols used to distinguish aldehydes from ketones. These tests were
will cause an orange to green colour change. discussed earlier.

Note: Vigorous oxidation by potassium manganate(VII)

causes the carbon chain to break down. This is not
synthetically useful. Reduction of Amides
By refluxing with lithium aluminium hydride in dry ether followed
by acidification to produce the corresponding primary amine.
Oxidation of Aldehydes −CONH2 + 2[H] ! −CH2NH2
By heating with acidified (H2SO4) potassium dichromate solution
to produce carboxylic acids e.g. Ethanamide will convert to aminoethane
CH3CONH2 + 2[H] ! CH3CH2NH2
(−COOH). −CHO + [O] ! −COOH
e.g. Ethanal will convert to ethanoic acid
CH3CHO + [O] ! CH3COOH
Reduction of Nitro Compounds
Note: This is related to Tollen’s test (ammoniacal silver nitrate By refluxing with granulated tin or iron filings and concentrated
solution) and Fehling’s test (alkaline copper(II) sulphate). hydrochloric acid, followed by addition of sodium hydroxide to
These are used as tests to distinguish aldehydes from produce the corresponding primary amine.
ketones. The emphasis is given to the visible reduction of
C−NO2 + 6[H] ! C−NH2 + 2H2O
Ag+ to Ag (mirror) or Cu2+ to Cu+ (red precipitate) by an
aldehyde but not a ketone. But don’t forget when the metal e.g. Nitrobenzene converts to aminobenzene
ions are reduced something, in this case an aldehyde, has to C6H5−NO2 + 6[H] ! C6H5−NH2 + 2H2O
be oxidized

Reduction of Nitriles
By refluxing with lithium aluminium hydride in dry ether followed
Reduction of Aldehydes by acidification to produce the corresponding primary amine.
By refluxing with lithium aluminium hydride in dry ether or sodium
borohydride in aqueous solution followed by acidification to −C≡N + 4[H] ! −CH2NH2
produce the corresponding primary alcohol. e.g. Propanamide will convert to 1-aminopropane
−CHO + 2[H] ! −CH2OH CH3CH2CN + 2[H] ! CH3CH2CH2NH2
e.g. Propanal will convert to propan-1-ol
CH3CH2CHO + 2[H] ! CH3CH2CH2OH

3
97. Oxidation and Reduction in Organic Chemistry Chem Factsheet

Oxidation of Arenes Related to this is the idea of selective oxidation or reduction.

The benzene ring structure is very stable and not easily oxidized. This will not concern you at A-level but, by choice of an
However, any carbon-based side-chains are oxidized to −COOH appropriate oxidant or reductant it is possible to reduce one
when arenes are refluxed with alkaline potassium manganate(VII). group and not another. In fact, this applied to an earlier example
where nitrobenzene is reduced to amino benzene using tin and
Cn COOH hydrochloric acid. Note that the NO2 group is reduced but the
benzene ring is not.
In this context, look back at the point about NaBH4 compared to
LiAlH4 made earlier!
e.g. Ethyl benzene converts to benzoic acid
3. Acid derivatives such as acyl chlorides, acid anhydrides and
CH2CH3 COOH
esters undergo reductive hydrolysis with lithium aluminium in
dry ether. This means they are hydrolysed to the corresponding
acid which is then reduced to the corresponding primary alcohol.

e.g. 2-(4-methylphenyl)-ethanol converts to e.g. CH3COCl ! CH3COOH ! CH3CH2OH

benzene-1,4-dicarboxylic acid
(CH3CO)2O ! 2CH3COOH ! 2CH3CH2OH
CH2 CH 3OH COOH
CH3COOCH3 ! CH3COOH + CH3OH ! CH3CH2OH + CH3OH
4. Simultaneous oxidation and reduction of the same organic
molecule is also possible. This is called disproportionation.
The best example is the disproportionation of two aldehyde
CH3 COOH groups to a primary alcohol and a carboxylic acid. In effect, one
aldehyde group oxidizes the other and so becomes reduced
Note: Writing balanced equations here is difficult because so itself.
many other products are formed. Most significantly, the These are specialized reactions which you probably would not
remaining C atoms from each side-chain are converted to CO2. be expected to “know” but you can now use the principles of
this Factsheet to recognize them!
e.g. 2C6H5CHO + H2O ! C6H5CH2OH + C6H5COOH
Reduction of Arenes
Benzene rings and related aromatic structures are reduced by This is achieved by heating the aldehyde with potassium
hydrogen in the presence a nickel catalyst at 150°C to produce hydroxide solution.
the corresponding cycloalkanes.
Practice Questions
1. Classify each of the following as oxidation, reduction,
+ 3H2 disproportionation or not redox
(a) CH3OH ! HCHO
(b) C6H5CH2CH2CH2COOH ! C6H5COOH
(c) CH3CH2CN ! CH3CH2CH2NH2
e.g. Methylbenzene converts to methylcyclohexane
(d) CH3COOH ! CH3COCl
CH 3 CH 3 (e) Cyclohexanol ! cyclohexanone
(f) C6H5CHO ! C6H11CH2OH
+ 3H2 (g) CH3CHO ! CH3CH2OH + CH3COOH
(h) CH3COCH2CH3 ! CH3CH(OH)CH2CH3
(i) CH3CH2Br ! CH3CH2OH
(k) CH3COCH2COCH3 ! CH3CH(OH)CH2CH(OH)CH3
Additional Points:
1. Remember to classify any given reaction in terms of loss or gain 2. Explaining your choice, classify each of the following as oxidation
of oxygen or hydrogen before attempting to select appropriate or reduction and then write an appropriate equation for the
reagents and reaction conditions. conversion described. Use [O] and [H] where appropriate.
2. Be aware that more than one functional group may be oxidized (a) CH3CH(OH)CH2CH3 ! CH3COCH2CH3
or reduced. (b) CH3CH2CH2NO2 ! CH3CH2CH2NH2
(c) C6H5CHO ! C6H11CH2OH
e.g. 1 Propan-1,2-diol has two alcohol groups, one primary and (d) C6H5CH2CH2OH ! C6H5CH2COOH
one secondary. Under prolonged oxidation these will convert to (e) CH3COCH2COCH3 ! CH3CH(OH)CH2CH(OH)CH3
ketone and carboxylic acid groups respectively.
CH3CH(OH)CH2OH + 3[O] ! CH3COCOOH + 2H2O
Acknowledgements: This Factsheet was researched and written by Mike Hughes Curriculum Press, Bank
e.g.2 Phenyl ethene has a benzene ring and an alkene group. House, 105 King Street, Wellington, Shropshire, TF1 1NU. ChemistryFactsheets may be copied free of charge
When reacted with hydrogen and a nickel catalyst at 150°C it by teaching staff or students, provided that their school is a registered subscriber. No part of these Factsheets
may be reproduced, stored in a retrieval system, or transmitted, in any other form or by any other means, without
will covert to ethylbenzene. the prior permission of the publisher. ISSN 1351-5136

4
 5
Answers
1. (a) Oxidation (b) Oxidation (c) Reduction (d) Not redox (e) Oxidation (f) Reduction
(g) Disproportionation (h) Reduction (i) Not redox (k) Reduction
2. (a) Oxidation because H removed: CH3CH(OH)CH2CH3 + [O] ! CH3COCH2CH3 + H2O
(b) Reduction because H added: CH3CH2CH2NO2 + 6[H] ! CH3CH2CH2NH2 + 2H2O
(c) Reduction because H added: C6H5CHO + 8[H] ! C6H11CH2OH
(d) Oxidation because H removed: C6H5CH2CH2OH + 2[O] ! C6H5CH2COOH + H2O
(e) Reduction because H added: CH3COCH2COCH3 + 4[H] ! CH3CH(OH)CH2CH(OH)CH3
3. (a) Reduction because H is added; aldehyde to primary alcohol and arene to cyclohexane
C6H5CHO + 8[H]! C6H11CH2OH
Hydrogen gas with nickel catalyst at 150°C.
Note: Use of lithium aluminium hydride in dry ether would reduce only the aldehyde group.
(b) Reduction because H is added; amide to primary amine
CH3CH2CONH2 + 4[H] ! CH3CH2CH2NH2
Reflux with lithium aluminium hydride in dry ether, followed by aqueous acid. Then add aq NaOH to release the amine
(c) Oxidation because H removed; secondary alcohol to ketone
C6H5CH(OH)CH2CH3 + [O] ! C6H5COCH2CH3 + H2O
Heat under reflux with excess acidified potassium dichromate
(d) Oxidation with degradation of aryl side-chain.
C6H5CH2CH2CH2CHO + 10[O]! C6H5COOH + 3CO2 + 3H2O
(Note : this is a much simplified equation)
reflux with alkaline potassium permanganate
(e) Reduction because H is added; trione to triol
CH3COCH2COCH2COCH3 + 6[H] ! CH3CH(OH)CH2CH(OH)CH2CH(OH)CH3
Reflux with lithium aluminium hydride in dry ether, followed by aqueous acid.
4. (a) This primary alcohol is oxidized to butanoic acid, CH3CH2CH2COOH, because the oxidant is in excess and reaction is prolonged. The
dichromate mixture will change from orange to green.
(b) This secondary alcohol is oxidized to butanone, CH3CH2COCH3, because the oxidant is in excess and reaction is prolonged.
Ketones do not oxidize further. The dichromate mixture will change from orange to green.
(c) This primary alcohol is oxidized to butanal, CH3CH2CH2CHO, because the oxidant is not in excess and the contact time is short. The
dichromate mixture will change from orange to green.
(d) This tertiary alcohol is not oxidized. The dichromate mixture will remain orange.
(e) To avoid the presence of excess oxidant.
Aldehydes have much lower boiling points than the corresponding alcohol because alcohol molecules are attracted to each other
by stronger inter-molecular forces. Hydrogen bonds exist in alcohols but only dipole-dipole forces in aldehydes.
5. (a) Reflux in dry ether, followed by aqueous acid.
(b) CH3CH(OH)CH2OH ; propan-1,2-diol
(c) Use a milder reductant such as sodium borohydride in aqueous solution. This selectively reduces the ketone group.
(c) How would you obtain X from Y?
(b) Give the name and structure of the product if this reagent is used?
X may be produced from Y by reduction, but this cannot be achieved using lithium aluminium hydride
X = CH3CH(OH)COOH Y = CH3COCOOH
(a) State the conditions under which this reagent is used.
5. Aldehydes and ketones can both be reduced to alcohols by lithium aluminium hydride, LiAlH4.
is possible to distil out the product as it is formed.
(e) With reference to (c), explain why the sodium dichromate(VI) is added to butan-1-ol (rather than the other way round) and why it
(d) 2-Methylpropan-2-ol is boiled under reflux with excess acidified sodium dichromate(VI).
(c) Butan-1-ol is heated and distilled whilst acidified sodium dichromate(VI) is added slowly.
(b) Butan-2-ol is refluxed with excess acidified sodium dichromate(VI).
(a) Butan-1-ol is refluxed with excess acidified sodium dichromate(VI).
appropriate.
conditions and method. Describe the results of each of the following reactions, giving the names and structures of the products where
4. Alcohols react with acidified dichromate(VI) solution in various ways depending on the type of alcohol used and the reaction
(e) CH3COCH2COCH2COCH3!CH3CH(OH)CH2CH(OH)CH2CH(OH)CH3
(d) C6H5CH2CH2CH2CHO ! C6H5COOH
(c) C6H5CH(OH)CH2CH3 ! C6H5COCH2CH3
(b) CH3CH2CONH2 ! CH3CH2CH2NH2
(a) C6H5CHO ! C6H11CH2OH
conversion described
3. Explaining your choice, classify each of the following as oxidation or reduction and then select reagents and conditions to achieve the
Chem Factsheet 97. Oxidation and Reduction in Organic Chemistry
 Chem Factsheet
www.curriculum-press.co.uk Number 98
Improve Your Mark: AS Energetics
This Factsheet aims to give you tips to help improve your marks break between atoms in some methane and oxygen molecules.
when answering AS Energetics questions. The areas covered are:- The “free” atoms so formed then react together, forming new bonds
Check your understanding of basic energetics ideas as molecules of water and carbon dioxide with lower energy levels
• Defining energetics terms than the reactant molecules. Excess energy is released to the
• Using signs and units correctly surroundings, lighting up carbon particles (making a visible flame)
• Putting it into practice and heating up particles in the area around the reaction (hence a
saucepan and its contents get hot when placed on a lit gas burner).
Some excess energy breaks bonds in more molecules, creating a
Answer these questions as best you can:- “chain” effect that ends only when the supply of a reactant is cut
1. Combustion of Methane off (such as by turning off the gas), or by cooling the reaction
Methane burns according to the equation:- mixture.
CH4(g) + 2O2 (g) → 2H2O(l) + CO2 (g) The reaction is exothermic, 2. The energy comes from bond formation in the reaction products.
releasing energy to the surroundings. The stronger the bond being formed, the more energy is released.
(a) Why is a spark or match needed to start methane burning? Of course, the net energy release is what remains after allowing for
(b) Where does the energy come from when methane burns? the energy to break bonds in the reactant molecules.
2. Reaction of Sodium with Chlorine Sodium and Chlorine
Sodium and chlorine react to make sodium chloride:- 3. As the reaction is exothermic, the enthalpy level of the products
2Na(s) + Cl2 (g) → 2NaCl(s) The reaction is exothermic, releasing must be lower than that of the reactants. The difference is energy
energy to the surroundings. is released to the surroundings.
(a) Draw an energy level diagram to show the reaction between 4. Energy cannot be created or destroyed. We only transfer energy
sodium and chlorine to make sodium chloride. from one form to another. This is the “First Law of
(b) Where was the energy before it was released? Thermodynamics”. The energy must have existed before the
reaction occurred, but we couldn’t “see” it. In an exothermic
Answers are available at the end of the factsheet.
chemical reaction energy is transferred from the reactants to the
Explanations products and surroundings. Conversely, in an endothermic
It would be a safe bet that you got one or more of these questions chemical reaction energy is transferred from the reactants and
”wrong”! This does not matter – the point of these questions is to surroundings to the products.
sort out your understanding. Now read the following extended These introductory questions covered important ideas. If you don’t
explanations and check your understanding. understand them, this is likely to affect your ability to answer
examination questions, as these often assume you understand these
Combustion of Methane basic ideas behind them.
1. The spark or match supplies activation energy. The vast majority
of methane molecules and oxygen gas molecules are energetically Defining energetics terms
“stable” since they do not have enough energy to react. A spark Energetics questions often begin by asking you to “define a term”.
or match puts energy into the reaction system, causing bonds to Common terms and their definitions are shown in the following
table. The key points that usually score marks are highlighted.
Energetics term Definition Symbol and units Sign
Standard enthalpy change of formation The enthalpy change occurring when 1 mole ∆Hêf kJmol-1 Can be a +ve
2 marks are usually available (1 mark) of a compound / substance is formed from or –ve value
its elements under standard conditions (1 mark)
Standard enthalpy change of reaction The enthalpy change occurring when the mole ∆HêR kJmol-1 Can be a +ve or –ve
2 marks are usually available quantities written in the balanced reaction equation value
(1 mark) react under standard conditions (1 mark)
Standard enthalpy change of combustion The enthalpy change occurring when 1 mole ∆Hêc kJmol-1 Always a –ve value
3 marks are usually available (1 mark) of a compound / substance is completely
burned in oxygen (1 mark) under standard
conditions (1 mark)
Average (or mean) bond enthalpy The energy required to break 1 mole of specific ∆Hêbe kJmol-1 Always a +ve value
2 marks are usually available covalent bonds in the gaseous state (1 mark)
averaged over a range of similar compounds
(1 mark)
Bond dissociation enthalpy (or standard The energy required to break 1 mole of specific ∆HêD kJmol-1 Always a +ve value
bond enthalpy) 1 mark is usually available covalent bonds in the gaseous state

1
98. Improve Your Mark: AS Energetics Chem Factsheet

Remember: Remember: Examiners always expect you to give the sign at

• Energy is released when chemical bonds form. the end of a calculation. This is good practice, as it shows you
• Energy is needed to break chemical bonds. understand the point about enthalpy change! Don’t forget the
• Energy cannot be created or destroyed, but we can transfer sign.
energy from one form to another.
Remember: Since your calculator will not show a “+” sign for
“Under standard conditions” is vital to score the final mark an endothermic reaction, you must remember to insert the “+”
available for the first three enthalpy changes in the table. sign.
“Standard conditions” means “298K and 100 kPa”. You can give
the values instead of simply stating “standard conditions”.
Why do bond dissociation enthalpies always have positive
There is almost no leeway in responses to these questions. Using
the phrase “enthalpy change” as stated is strongly recommended.
values?
Phrases such as “heat evolved”, “energy evolved” and “energy We can answer this using “Why ‘enthalpy change’?” and the
change” are regarded as “vague”, and although not always explanation for signs, above. The system in this case consists of
detrimental to your mark, tend to put examiners in negative frames the molecules of substance, let’s say, methane, formula CH4.
of mind. “Why ‘enthalpy’ change?” is discussed later in this
Factsheet. Methane molecules are “stable” – simply, under atmospheric
pressure and range of temperatures, they don’t break up into atoms
Defining average (or mean) bond enthalpy often signals a request spontaneously. To make a reaction happen, energy needs to be put
later in the question to calculate the average value for the C-H into the system. This means that the enthalpy level of the system
bond enthalpy in methane. This is +412 kJmol-1. This value is has increased, so the sign is positive.
worth remembering as a way of checking your answer. The value
is obtained by calculating the average of the 1st, 2nd, 3rd and 4th Why do enthalpy changes of combustion always have a
bond dissociation enthalpies of the C-H bonds in the methane negative value?
molecule. When each bond is broken separately, the potential Combustion reactions are exothermic so must always have negative
energy of the remaining particle (-CH3, =CH2 and =CH) changes, signs. Overall, the system loses energy, mostly as heat, to the
altering the energy required to break any remaining bonds. So, surroundings – if you are part of the surroundings then you can
each C-H bond has a different bond enthalpy. The average is feel the heat! The internal energy decreases so the enthalpy level is
+412 kJmol-1. lower after the reaction.

Why “enthalpy change”? Why can an enthalpy change of formation or reaction be

Enthalpy is a measure of how much energy there is in total in the either positive or negative?
volume of space occupied by chemical reactants / products at a This depends on the enthalpy values relating to the reactants and
specific pressure. Chemists want to know how enthalpy changes products. There is no fixed “rule” – a reaction system can take in
when a reaction occurs. The Greek symbol “∆” (called “delta”) energy or lose energy overall, resulting in a higher or lower internal
represents change, hence “∆H” is the symbol for “enthalpy energy level. When calculating these, take note of the type of reaction
change”. As chemists use moles as their way of counting amounts to help decide what the sign may be.
of substance, a standard reference is the “enthalpy change per
mole”, with units “kJmol-1”. Examiners like accuracy, so “enthalpy Neutralisation and combustion reactions, for example, are exothermic,
change” is correct. while dissolving may be either depending on the solute. In general,
if reaction results in an increase in the number of molecules, you
Using signs and units correctly should expect the enthalpy change to be positive since there is a
net decrease in bonding. Similarly, a decrease in the number of
Signs molecules would be associated with a negative enthalpy change.

The sign refers to the enthalpy change of the system involved in Units
the reaction. “System” means the reactants and products. The
“surroundings” is everything other than the reactants and products. The units examiners look for are “kJmol-1”. This reads as “kiloJoules
per mole”. The units tie in with the definitions, so must be consistent
If a reaction GIVES OUT energy, this must have come
– if you look back at the table, you will see the reference to “enthalpy
from the system. The system has LOST ENERGY so the sign is
change” and “1 mole”. Enthalpy is measured in Joules, but as the
NEGATIVE. We call this an “EXOTHERMIC” reaction –
numbers are usually large “kilo” is used as the prefix. “1 mole” is
literally “HEAT OUT”.
the amount of substance involved in a standard enthalpy change.

Remember: The units are essential. If you get a calculation

If a reaction TAKES IN energy from the surroundings,
correct, but forget the units, you can lose a mark. Don’t forget
the enthalpy level of the system has INCREASED so the sign is
the units.
POSITIVE. We call this an ENDOTHERMIC reaction –
literally “HEAT IN”.

2
98. Improve Your Mark: AS Energetics Chem Factsheet

Putting it into practice In this example you may be given:

You need to be able to do two main types of calculation. The first is
∆Hêf [CO2(g)] = -393.5 kJ mol-1 , ∆Hêf [H2O(l)] = -285.8 kJ mol-1 and
from experimental data. The remaining four (2-5 in the list below) are
∆HêC [CH4(g)] = -890.3 kJ mol-1 which means :
applications of Hess’s Law, although it is not always necessary to
draw a full cycle to get the answer. ∆H2 = (-393.5) + 2(-285.8) = -965.1kJ mol-1 and ∆H3 = -890.3 kJ mol-1
Giving -965.1 = ∆H1 + -890.3 and hence, ∆H1
1. Enthalpy change of combustion from quantitative data
= ∆Hêf [CH4(g)] = + 890.3 - 965.1 = -74.8 kJ mol-1
Remember that combustion reactions are always EXOTHERMIC.
Heat is given out to surroundings. We can measure this using a
3. Enthalpy change of reaction from enthalpy change of formation
“calorimeter”, literally a “heat measurer”. The heat energy transferred
values
to a fixed mass of water (m H O) is measured by finding the change in
2
temperature of the water (∆TH O) when a known number of moles (n)
2 Remember: “enthalpy change” measures the loss or gain in
of a fuel is burned.
internal energy of the system.
- m H O × ∆T H O × C H O
∆Hc = 2 2 2 So, the enthalpy change for a reaction will be, very simply:-
1000 × n The “energy level” of the products – “energy level” of the reactants
In “exam-speak”, this is:- ∆HR = Σ∆Hf (products) - Σ∆Hf (reactants)
(a) CH O is the specific heat capacity of water i.e. the number of
2
Joules needed to raise the temperature of 1g of water by 1K It is useful to remember this equation to allow quick calculation of
∆HR when ∆Hf values are available. However, remember this is the
(b) The “1000” is included to convert the Joules of “CH O” to kJ result of an application of Hess’s Law as shown in the following
2
cycle:
(c) The negative sign is inserted to show the combustion is
exothermic. Reactants Products
∆HR
∆H2 ∆H3
2. Calculations involving a Hess’s Law cycle
Hess’s law puts the First Law of Thermodynamics in chemical terms,
by saying : Component Elements

∆HR = ∆H2 + ∆H3

The total enthalpy change occurring in a reaction is
= - Σ∆Hf (reactants) + Σ∆Hf (products)
independent of the route taken.
= Σ∆Hf (products) - Σ∆Hf (reactants)

In other words, energy is conserved when we get the same product Note the “-“ sign before ∆Hf (reactants) because the reactants are
(or products) from the same starting materials regardless of what being converted to elements which is the opposite direction to
we do to the starting materials in between. In exam questions, the the definition of ∆Hf .
principle is to react two different substances or sets of substances
to make the same product. If you put the two substances / sets of 4. Enthalpy change of reaction from bond enthalpy values
substances in an equation across the top and the product(s) Again, remember that “enthalpy change” measures the loss or gain
underneath, you get a triangle. You will always be given data for in internal energy of the system. If this is given as bond enthalpy
two “sides” of the triangle and have to work out the value for the values, we are looking at, very simply:-
third “side”. This is illustrated as follows :
The energy needed the energy released when
–
to break bonds bonds are formed.
Substances 1 Substances 2
e.g. C(s) + 2H2(g) + 2O2(g) e.g. CH4(g) + 2O2(g)
∆H1 In “exam-speak”, this is:- ∆HR = Σ∆Hbe (broken)- Σ∆Hbe (formed)

∆H2 ∆H3 It is also useful to remember this equation to allow quick calculation
of ∆HR when ∆Hbe values are available. Again, it is also the result of
Products an application of Hess’s Law as shown in the following cycle:
e.g. CO2(g) + 2H2O(l)
Reactants Products
Any one of the three enthalpy changes can be calculated by ∆HR
substituting two given values into : ∆H2 ∆H3
∆H
(
2
= ∆H1 + ∆H3 and then calculating the third.
Individual Atoms
Remember: When applying Hess’s Law to such a cycle, it is
∆HR = ∆H2 + ∆H3
often useful to use “sum of clockwise ∆H = sum of anti-clockwise
= Σ∆Hbe (reactants) - Σ∆Hbe (products)
∆H” to help you get the arithmetic correct.
Note the “-“ sign before − ∆Hbe (products) because the here bonds
are being formed which is the opposite direction to the definition
of ∆Hbe .
3
98. Improve Your Mark: AS Energetics Chem Factsheet

5. Enthalpy change of reaction from enthalpy of combustion values

This applies when the reactants and products are both combustible. Reactants + O2(g) Products + O2(g)
Again, you may care to remember: ∆HR
∆H2 ∆H3
∆HR = ∆Hc (reactants) - ∆Hc (products)
Oxides of Component Elements
to allow quick calculation of ∆HR when ∆HC values are available
but remember it is also the result of an application of Hess’s Law ∆HR = Σ∆H2 + Σ∆H3
as shown in the following cycle: = Σ∆Hc (reactants) - Σ∆Hc (products)

Finally, here are examples of the different types of calculation with a sample answer, mark scheme and examiner’s notes in the same order
as above.

Question Answer Mark scheme and Examiner’s notes

Enthalpy change of combustion from Moles = mass / relative molecular mass 1 mark for relative molecular mass
experimental data 1 mark for mole calculation
1.45 g propanone were completely burned Propanone formula CH3COCH3 Mr = 58
in oxygen. The energy was used to raise Moles = 1.45 / 58 = 0.025
the temperature of 100 g water from 293.1 K
to 351.2 K. Heat energy = 100 × 4.12 × 58.1 1 mark for this line
= 24300 J 1 mark for this line, could be 24.3 kJ, but
Calculate the number of moles of not 24.3 without units
propanone. Enthalpy change of combustion
= -24.3/ 0.025 = - 972 kJmol-1 1 mark for this line
Calculate the heat energy used to raise the
temperature of 100 g water from 293.1 K to
Check:- Notes:-
351.2K. The specific heat capacity of water
• Formula of propanone • If the wrong Mr value is used, all other
is 4.18 J K-1 g -1.
• 100 used as mass of water needed, marks are awarded consequentially
Calculate a value in kJmol-1 for the NOT mass of propanone • If the mass of propanone is used
enthalpy change of combustion of • 58.1 is the temperature rise instead of water, no marks awarded for
propanone • sign negative as this is COMBUSTION this part, but if the value is used in the
final stage then one consequential
5 marks available mark is given

Enthalpy change of combustion from Using a Hess’s Law cycle:-

other enthalpy change of combustion -91
values CO(g) + 2H2 (g) → CH3OH (g)
Calculate the enthalpy change of (-283 +
x 1 mark for correct cycle
combustion for gaseous methanol using 2x-286)
the following data:
CO2 (g) + 2H2O (g)
CO(g) + 2H2 (g) → CH3OH (g) ∆H = -91 kJmol -1

x = (-283+2x-286) - -91 1 mark for this line

∆Hc/kJmol-1 CO(g) -283 = -855 + 91
H2 (g) -286 = -764 kJmol-1 1 mark for this line
Check:-
• By Hess’s law: the enthalpy change Notes:-
for the direct route from carbon • The sign on the ” – 91” is vital to get
monoxide and hydrogen to carbon the right answer
3 marks available • +764 scores 1 mark
dioxide and water must be the same
as that for the formation of methanol • Units are not essential, but one mark
first, then the combustion of is lost if incorrect units are given
methanol
• 2 x -286 as 2 moles of hydrogen are
in the equation
• sign and units

4
98. Improve Your Mark: AS Energetics Chem Factsheet

Question Answer Mark scheme and Examiner's notes

Enthalpy change of reaction from ∆HR = Σ∆Hf (products)

− Σ∆Hf (reactants)
enthalpy changes of formation values = - 394 - (-75 + 2 × -286) 1 mark for this line
Calculate the enthalpy change of reaction = -394- -647
= +253 kJmol-1 1 mark for the correct answer
for the reaction:-
1 mark for correct +/- signs
CH4 (g) + 2H2O(l) → CO2 (g) +4H2 (g) Check:-
• Sign and units Notes:-
Using:-
• Multiply by 2 as 2 moles of water • 2 marks awarded for values -33, +103,
∆Hf/kJmol-1 CH4(g) -75
involved -253, -891, + 1041
H2O (l) -286
CO2 (g) -394 • Hydrogen is an element so ∆Hf = 0 • 1 mark awarded for values +33, -183, -
• All working shown 605, +755, -1041
3 marks available

Enthalpy change of reaction from ∆HR = Σ∆Hbe (broken) - Σ∆Hbe (formed) 1 mark for the sum of bonds broken
average bond enthalpy values
= 4 × 255 – (2 × 255 + 266 + 242) 1 mark for the sum of bonds formed
Calculate the enthalpy change of reaction = 1020 – 1018
= + 2 kJmol-1 1 mark for the correct answer
for the reaction:-
Check:-
2Cl-S-Cl(g) → Cl-S-S-Cl (g) + Cl-Cl(g) • Sign and units Notes:-
• Multiply by 4 as 2 moles of SCl2 • 2 marks awarded for values -2, +268, +/-
Using:- involved 2038, +/- 1018
∆Hbe/kJmol-1 Cl-Cl +242 • Small value sensible as this is an • 1 mark awarded for value -268
S-Cl +255 equilibrium reaction other values may also score
S-S +266
3 marks available

A mean bond dissociation enthalpy value ∆HR = Σ∆Hbe (broken) - Σ∆Hbe (formed)
Calculate a value for the C-H bond -136 = 4 × C-H + 612 + 436 – (6 × C-H +348) 1 mark for this line OR
enthalpy in ethane from the equation:- -136 = 2 × C-H +612 + 436 – 348 1 mark for this line
C=C + H-H → H-C-C-H ∆Hr = -136 kJmol-1
2 × C-H = + 836 1 mark for this line
Using:- 1 × C-H = + 418 kJmol-1 1 mark for this line
∆Hbe/kJmol-1 H-H = +436
C-C = +348 Check:- Notes:-
C=C = +612 • Value is close to the +412 for C-H in 1 mark only awarded for -836 or -418
methane
3 marks available
• Divide by 2 at the end to get value for 1
bond
• Sign and units

Answers to Introductory Questions

1. The spark or match is needed to initiate the reaction. That is, 4. The energy must have existed (as potential energy) in the chlorine
supply energy which is used to break bonds in methane gas molecules and sodium atoms
molecules and in oxygen gas molecules and so begin the
transformation to products.

2. The energy comes from bond formation. Energy is released when

chemical bonds form. New bonds are formed making carbon
dioxide gas molecules and water molecules.
3.
Ea = activation energy

Enthalpy Ea
Acknowledgements: This Factsheet was researched and written by Vanessa
Na(s) + Cl2(g) Kind. Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire,
Energy released TF1 1NU. ChemistryFactsheets may be copied free of charge by teaching
staff or students, provided that their school is a registered subscriber. No part
of these Factsheets may be reproduced, stored in a retrieval system, or
NaCl(s) transmitted, in any other form or by any other means, without the prior
permission of the publisher. ISSN 1351-5136
Time
5
 Chem Factsheet
www.curriculum-press.co.uk Number 99

Why Students Lose Marks:

A2 Acid Base Calculations
This Factsheet analyses students’ answers to A2 exam questions on Example 1
Acid-Base Equilibria. It aims to make you confident in In a buffer solution, the concentration of ethanoic acid is 0.250 mol
• knowing what the examiners expect from a good answer dm-3 and the concentration of sodium ethanoate is 0.200 mol dm-3.
• the type of questions you are likely to be asked
• common mistakes and misunderstandings The dissociation constant of ethanoic acid Ka has the value
1.74 × 10-5 mol dm-3 at 25ºC.
As you read the students answers to the questions and the comments,
try to work out what the student should have done – using the hints [H+ ] [CH3 COO− ]
and comments if necessary – before you read the correct answer. Ka =
[CH3 COOH]
You will find the background knowledge needed is covered in
Factsheets 25, 26, and 64. Calculate the pH of the buffer solution.

To approach this type of question you will need to be able to: Suppose the student rearranged the Ka expression to give
• Identify acid-base behaviour by use of Brønsted Lowry Theory
• Recall (see below) definitions of pH, Ka, Kw, pKa, pKw and calculate [CH3 COO− ]
these [H+ ] =
Ka [CH3 COOH]
• Calculate the pH of solutions
• Sketch pH curves accurately. This is an incorrect rearrangement of the equation and means that
the student can gain no marks, as the subsequent calculation
would be based on incorrect science and would thus not be
1. pH = -log10[H+]
creditworthy. There is no unit mark available.
2. If the dissociation of a weak acid is represented by
The correct rearranged equation is:
HA(aq) ¾ H+(aq) + A-(aq)
[H+(aq)] × [A-(aq)] Ka [CH3 COOH] (1 mark)
then Ka = [H+ ] =
[HA(aq)] [CH3 COO- ]
3. pKa = -log10Ka
0.25
4. Kw = [H+(aq)] × [OH-(aq)] = 1.0 × 10-14 mol2 dm-6 at 25°C = 1.74 × 10-5 × = 2.175 × 10-5 mol dm-3 (1 mark)
0.20
5. pKw = -log10Kw = 14 at 25°C One mark is awarded for the correct equation and a correct
substitution gains one more mark.
Note: As seen in 1, 3 and 5, “p” is a general mathematical operator
which means “take the log to base 10 of a number (e.g. Ka) and then pH = -log10[H+] = -log10[2.175 × 10-5] = 4.663
take the negative of the answer”
The pH is correctly calculated, but the degree of accuracy is too
high, and the student loses this mark.
In general there may be marks available for showing a clear method,
and if an arithmetic slip has been made which the examiner can clearly The pH should always be given to 2 decimal places, 4.66. (1 mark)
see, then only one mark may be lost.
However, this type of error is only penalised once. If there were
There are often marks available where an incorrect answer is the other calculations of pH in the same question and the final answers
result of incorrect working in a previous part of the question. However, were also given to 3 decimal places, this would be condoned and
if the incorrect answer is based on an incorrect formula or incorrect only one mark lost for this type of error.
science, then ‘error carried forward’ marks may not be available.

Rearranging equations and balancing equations are important skills

and may be seen as part of the calculation. However, if a unit mark is
available and the unit is correct (for a correct formula), then this mark
will be awarded. Missing brackets or charges are penalised once in a
question and result in the loss of one mark.

1
99. Why Students Lose Marks: A2 Acid Base Calculations Chem Factsheet

Example 2 If the student’s answer then continues:

(i) The value of the acid dissociation constant for a weak acid
HA at 298K is 1.74 × 10-5 mol dm-3. Ka [HA] (1 mark)
[A−] =
[H+]
Calculate the pH of a 0.350 mol dm-3 solution of HA at 298 K.
(1.74 × 10-5) × 0.35
=
0.562
[H+]² (1 mark)
Ka =
[HA] = 1.08 × 10-5 mol dm-3

The student gains one mark for realising that [H+] = [A−] The correct calculation should have been

This gives [H+] = √{(1.74 x 10-5) × 0.350} mol dm-3 (1 mark) (1.74 × 10-5) × 0.35 (1mark)
[A−] =
2.239 × 10-4
The student has correctly rearranged the equation and applied the
approximation that, as the acid is weak, the acid which is dissociated = 0.0272 (mol dm-3) (1mark)
can be counted as negligible, so the value of [HA] at equilibrium is
taken to be 0.350 mol dm-3. The correct equation for calculating [A−] would gain one mark but,
although the student correctly substitutes the (incorrect) value for
This approximation is expected, and the failure to use it would result [H+], this mark is lost because the value is based on a scientifically
in the student being faced with a difficult quadratic expression. incorrect method for calculating the hydrogen ion concentration.
One mark is given.
The correct formula has allowed the student to gain a follow through
mark for his incorrect value for the concentration of A−.
Suppose this gave [H+] = 6.09 x 10-6 mol dm-3
Example 3
This would mean that the student has forgotten to square root his
At 40ºC, the ionic product of water is 2.92 x 10−14 mol2dm-6
correct expression causing this mark to be lost. This should have
(i) Calculate the pH of pure water at 40ºC.
been evident, as square rooting a calculation containing 10-5 or 10-6
will give an answer of the order of 10-3 so it is well worth checking Suppose the student wrote:
that the answer is sensible. 2.92 × 10−14 mol2dm-6 = [H+]
and so pH = -log10 [H+] = -log10 2.92 x 10−14 = 13.53
The correct answer at this stage should be 2.468 × 10-3 mol dm-3.
(1 mark) The student has used the data given incorrectly having forgotten
that Kw = [H+][OH−] and for pure water [H+] = [OH−].
However, if the student continues the calculation using
[H+] = 6.09 × 10-6 mol dm-3 Thus the square root of the value for Kw should be used to calculate
[H+] and hence, the pH. Again, the student would gain no marks, as
pH = -log10[H+] = -log10[6.09 × 10-6] = 5.22 incorrect science gave an incorrect value for [H+], even though the
correct formula for the pH is used. If the value for [H+] had been the
One mark is still awarded as the pH calculation method is correct result of incorrect use of the calculator but the correct use of the
even though the answer is incorrect. data then the mark for the calculation of pH would have been given
and only one mark lost.
The correct answer should be
The correct response would be:
+ -3
pH = -log10[H ] = -log10[2.468 x 10 ] = 2.61 (1 mark) [H+] = √{ 2.92 × 10−14} = 1.7088 × 10−7 mol dm-3 (1 mark)
pH = -log10 [H+] = -log10 1.7088 × 10−7 = 6.77 (1 mark)

(ii) A mixture of this acid, HA and the sodium salt of this acid,
NaA can be used to prepare a buffer solution. Calculate the The incorrect value obtained is that of a strong alkali, not pure
concentration of A− in the buffer solution if the pH is 3.65 water. This should have alerted the student to the fact that
something had gone wrong! Always ask yourself, “is my answer
reasonable?”
Exam Hint: A common error in this type of calculation is to say that
[H+] = [A-]. This is true only in a solution of the pure acid!
Remember: Unlike most K values you will meet, you are often expected
to remember the value of Kw at 25 ºC. i.e. 1.00 x 10-14 mol2dm-6
Suppose the student’s first calculation step showed:

[H+] = log10 3.65 = 0.562

At 25 ºC, the value of Kw = 1.00 x 10¯14 mol2dm-6
The student has incorrectly tried to calculate [H+] by taking the log (ii) Calculate the pH at 25ºC of
of the pH and so loses this mark. (a) a 0.140 mol dm-3 solution of potassium hydroxide.

The correct answer should have been This requires the use of Kw to link [OH-] to [H+] and hence, pH. It is
also important to know that KOH is a strong base (fully ionised)
[H+] = 10-pH = 10-3.65 = 2.239 x 10-4 mol dm-3. (1 mark) which means that
2
99. Why Students Lose Marks: A2 Acid Base Calculations Chem Factsheet

[OH-] = [KOH] = 0.140 mol dm-3 If the 1000 is missing then the 1st 2nd 3rd 4th and 6th marks can be
gained.
Kw 1 × 10−14
[H+] = = = 7.143 × 10−14 mol dm-3 (1 mark) If the excess is used as acid, then the 1st, 2nd 4th and 6th marks can be
[OH−] 0.140
gained.
One mark is gained for the correct use of Kw
If the excess is used as acid and the volume is not used, then the 1st
and 2nd marks only can be gained.
pH = -log10 [H+] = -log10 (7.143 × 10-14) = 13.15 (1 mark)
Minor errors, such as missing square brackets or charges may be
The correct value for pH given to the correct degree of accuracy condoned in an otherwise correct calculation, and full marks given.
gains another mark.
Question 4
(b) The solution formed when 45 cm³ of this solution of potassium Acid-base indicators can be represented as HIn. In aqueous
hydroxide is mixed with 50 cm³ of a 0.115 mol dm-3 solution of solution: HIn(aq) ¾ H+ (aq) + In− (aq)
hydrochloric acid. The pH is related to pK In , the dissociation constant for the
indicator equilibrium, by the equation
Suppose the student’s answer begins:
[In−]
pH = pKIn + log10
Moles OH− used: [HIn]
V×C For bromothymol blue KIn = 1 × 10−7 mol dm-3
= = 45 × 10-3 × 0.140 = 6.30 × 10-3 (1 mark)
1000
Calculate the pH of a solution in which [In − ] = [HIn] for
Moles H+ used: bromothymol blue.
V×C
= = 50 × 10-3 × 0.115 = 5.75 × 10-3 (1 mark) Suppose a student’s answer showed
1000
Since H+ and OH− react 1:1 pH = pKIn + 1 ; pH – 1 = pKIn = 7 ; pH = 8
the excess moles of OH− in the resultant mixture
= 6.30 × 10-3 – 5.75 × 10-3 The student has forgotten to take the log of one so loses the first mark
= 5.50 × 10-4 (1 mark)
The incorrect value for the pH loses the second mark.
The student gains three marks, one for each correct moles calculation A correct response would have been:
and one for the correct excess moles. [In−]
log10 = 0 and therefore pKIn = pH (1 mark)
[HIn]
It is important to realise that the rest of the calculation is the
same as part (a) because, in effect, you are dealing with a solution pH = 7 (1 mark)
of potassium hydroxide with added potassium chloride.
Question 5
Suppose the student’s answer continued with: The change in pH as a 0.0550 mol dm-3 solution of potassium
hydroxide is added to 30 cm³ of a solution of ethanedioic acid
Kw = 1.00 × 10−14 mol2dm-6 = [H+] [OH−] gives a titration curve which has two equivalence points.
When the second equivalence point is reached, a total of 36.7 cm³
1.00 × 10−14
[H+] = = 1.818 × 10−11 mol dm−3 of the 0.0550 mol dm -3 potassium hydroxide has been added.
5.50 × 10−4
Calculate the concentration of the ethanedioic acid solution.
So pH = -log10 [H+] = -log10 1.818 × 10−11 = 10.74
The student begins with:
This is incorrect because the student has used “moles” instead of Moles of OH− added = (36.7 / 1000) × 0.0550 = 2.0185 × 10−³ (1 mark)
“mol dm-3” for [OH−]. This is a common error! The student should which is correct and gains one mark.
have realised that the excess moles of KOH were present in 95 cm3
of solution which allows [OH−] to be calculated. The answer then continues:
Thus moles of ethanedioic acid present = 2.0185 × 10−³
Two of the final three marks are lost but one follow through mark for Thus the concentration of ethanedioic acid = 2.0185 × 10−³ × (1000 / 30)
the (incorrect) pH value is gained. = 0.0673 mol dm-3
This is incorrect because the student has failed to recognise that
The correct solution should have been: the ratio of hydroxide to acid at the second end point is 2:1 and so
does not halve the moles of OH−.
[OH−] = 5.50 × 10−4 × 1000 ÷ 95 (1 mark)
= 5.789 × 10−3 mol dm−3 (1 mark) Although the student follows through correctly, there is no follow
through mark available and the student loses the final two marks.
1 × 10−14 mol dm-3
[H+] = = 1.727 × 10−12 ; pH = 11.76 (1 mark) The final answer should have been:
5.789 × 10−3
Thus moles of ethanedioic acid present = 2.0185 × 10−³ / 2 (1 mark)
If the volume is wrong the 4th mark is lost. = 1.009 × 10−³
If the subtraction is missing from the calculation of the excess moles, [H2C2O4] = 1.009 × 10−³ × (1000 / 30) = 0.0336 mol dm-3 (1 mark)
then only the 1st 2nd and 4th marks can be gained.
3
99. Why Students Lose Marks: A2 Acid Base Calculations Chem Factsheet

Question 6 This does not gain credit because the student assumes that only a
Using a burette, a 0.235 mol dm−³ solution of sodium hydroxide weak acid is present, rather than an acidic buffer solution, and
was added to 30cm³ of a 0.180 mol dm− ³ solution of ethanoic attempts to solve the problem in a similar way to the first part.
acid.
This gives [H+] = √{1.74 × 10-5 × 3.05 × 10-3} = 2.304 × 10-4 mol dm-3
Calculate the pH at 298K of the solution in the flask at the pH = 3.64
following points:
The student fails to notice that, according to his / her calculations,
(i) before any sodium hydroxide had been added the addition of NaOH has made the solution more acid! This cannot
(ii) after 10.0 cm³ of sodium hydroxide had been added be correct.
(iii) after 50 cm³ of sodium hydroxide had been added
The calculation should have been done as follows:
The value of the acid dissociation constant for ethanoic acid is [CH3COOH]
Ka = 1.74 × 10-5 at 298K. [H+] = Ka × (1 mark)
[CH3COO-]
The student’s response begins: 3.05 × 10-3 × (1000 / 40)
= 1.74 × 10-5 ×
2.35 × 10-3 × (1000 / 40)
[H+][CH3COO− ] (1 mark)
(i) Ka = = 2.258 × 10-5 mol dm-3 (1 mark)
[CH3COOH]
pH = 4.65 (1 mark)
Stating the fundamental equation gains one mark and realising that
[H+] = [CH3COO−] gains another mark.
(iii) The student’s answer to (iii) begins
Total moles of NaOH added = (50 / 1000) × 0.235 = 1.175 × 10-2
[H+]²
Thus Ka = (*) (1 mark) (1 mark)
[CH3COOH]
Therefore pOH = 1.93

And pH = 14.00 – 1.93 = 12.07

The first mark would not have been awarded had the student
jumped straight to the approximation (*) which is commonly used
The student has failed to allow for the fact that some of the sodium
for such calculations. It is always a good idea to state fundamental
hydroxide has been used by reaction with the acid. The number of
equations even if you are not too sure how to use them! They
moles of NaOH is excess needed to be calculated.
are often credited in the mark scheme.
Also, he / she has forgotten that the excess NaOH is now present in
The student then continues:
a new total volume of 30 + 50 = 80 cm3 which has to be used when
[H+] = 1.74 × 10-5 × 0.180 = 3.132 × 10-7 calculating its concentration.
pH = 6.50
This results in no further marks being gained.
However, the student fails to square root and also gives an incorrect
power of ten in his value. Both marks for this section are lost. The correct solution would have continued:
The nearly neutral pH should have alerted the student to the errors.
Excess moles of NaOH = (11.75 – 5.40) × 10−3 = 6.35 × 10−3 (1 mark)
The correct response should have been:
Total volume of mixture = 30 + 50 = 80 cm³ (1 mark)
[H+] = √{1.74 × 10-5 × 0.180} = 1.770 × 10-3 mol dm-3 (1 mark)
pH = 2.75 (1 mark)
Therefore [OH−] = 6.35 × 10−3 × (1000 / 80) = 0.0794 (1 mark)
(ii) The student’s response to part (ii) begins:
Therefore pOH = 1.10
Moles of NaOH added = (10 / 1000) × 0.235 = 2.35 × 10-3 (1 mark)
or [H+] = 10−14 ÷ 0.0794 = 1.259 × 10−13 mol dm-3 (1 mark)
Moles of CH3COO formed = 2.35 × 10
− -3
(1 mark)
Therefore pH = 12.90 (1 mark)
-3
Original moles of CH3COOH = (30 / 1000) x 0.180 = 5.40 x 10
(1 mark)

Moles of CH3COOH left = (5.40 – 2.35) x 10-3 = 3.05 x 10-3 (1 mark)

[H+]²
Ka =
[CH3COOH]

4
99. Why Students Lose Marks: A2 Acid Base Calculations Chem Factsheet

Practice Questions
1. Citric acid acts as an antioxidant used in food. If it is used together with its sodium salt, it can also act as an acidity regulator.

CH2CO2H

The formula of citric acid is HO–C–CO2H

CH2CO2H

(a) Assuming citric acid behaves as a monoprotic acid when in aqueous solution, the equation for its dissociation is:
RCO2H + H2O ¾ RCO2− + H3O+
Give the expression for Ka for citric acid. (1)

(b) If Ka for citric acid at 298K is 7.4 × 10-4 mol dm-3calculate the pH of lemon juice which contains citric acid at a concentration of 0.250 mol dm-3.
(3)

(c) Calculate the pH of a buffer solution containing 0.250 mol dm-3 of citric acid and 0.450 mol dm-3 of sodium citrate. (3)

2. (a) Calculate the pH of 0.150 mol dm-3 potassium hydroxide solution at 25°C. (Kw at 25°C is 1.0 × 10-14) (2)

(b) 100 cm³ of 0.100 mol dm-3 potassium hydroxide solution was added to 100 cm³ of 0.200 mol dm-3 ethanoic acid.
(Ka for ethanoic acid at 25ºC is 1.80 × 10-5 mol dm-3.)
(i) Find the concentration of ethanoic acid in the mixture. (2)
(ii) Calculate the concentration of potassium ethanoate in the mixture. (2)
(iii) Calculate the pH of the mixture at 25ºC. (2)

Answers
[RCO2−][ H3O+ ] 2. (a) [OH-] = 0.100 mol dm-3
1. (a) Ka = [RCO2H] (1) allow [H+] for [H3O+]
[H+] = 10-13 mol dm-3 (1)
pH = 13.00 (1)
[H3O+]² Must have working for 2 marks
(b) 7.4 × 10-4 = 0.25 (1) allow [RCO2H] = [H3O+]
[H3O+] = √{0.25 × 7.4 × 10-4 } (b) (i) Half the ethanoic acid will have reacted and the total
= √{1.85 × 10-4 } volume of the mixture will have doubled.
= 0.0136 mol dm-3 (1)
pH = 1.87 (1) must be given to 2 d.p. or Therefore the concentration is a quarter of the original. (1)
this mark is lost. (This can be shown by a suitable calculation.)
Correct answer with no working (1) only for part (b). Concentration of ethanoic acid = 0.05 mol dm-3 (1)

0.45 × [H3O+] (ii) Number of moles of salt produced = 0.01 (1)

(c) 7.4 × 10-4 = 0.25 (1)
Therefore concentration of salt = 0.05 mol dm-3 (1)
0.25
[H3O+] = × 7.4 × 10-4
0.45 [salt]
= 0.556 × 7.4 × 10-4 (iii) pH = pKa + log10 (1)
[acid]
= 4.1 × 10-4 mol dm-3 (1)
pH = 3.39 (1) This mark can be gained either for correct equation or
correct substitution
If not 2 d.p. then one mark lost unless this type of error was
penalised in part (b). 0.05
pH = -log10 1.8 × 10-5 + log10
0.05

pH = 4.74 (1)

Acknowledgements: This Factsheet was researched and written by Christine Collier. Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire,
TF1 1NU. ChemistryFactsheets may be copied free of charge by teaching staff or students, provided that their school is a registered subscriber. No part of these
Factsheets may be reproduced, stored in a retrieval system, or transmitted, in any other form or by any other means, without the prior permission of the
publisher. ISSN 1351-5136

5
 Chem Factsheet
www.curriculum-press.co.uk Number 100

Organic Functionality and Structure – Part I (AS)

To succeed in this topic you need to: There are many other functional groups. Each of them imparts its
• remember that carbon atoms form the backbone of all organic own particular properties to the molecule it is part of. The organic
molecules molecules that you find in nature, in your body, your food, your
• understand why and how carbon atoms form four covalent bonds shampoo or your medicine are built from a basic carbon backbone
• remember the structures and properties of simple organic with all the functional groups hanging off it.
compounds like alkanes, alkenes, alcohols etc.
• understand that the chemical and physical properties of a The carbon backbone gives the molecules their shape and
compound depend on the elements that the compound is made of structure (and if you think about enzymes, or DNA, you will
and how they are bonded together understand why shape and structure are important), but the
functional groups give them their reactivity and enable them to
After working through this Factsheet you will: interact both physically and chemically with other substances.
• understand why functional groups are important features of
organic molecules In the picture of Vitamin B5 (Fig 3) some of the functional groups
• be able to recognise the key functional groups in AS Chemistry are labelled: alcohol (only one of the alcohol groups is labelled –
• be able to predict chemical and physical properties of the key can you spot the other one?), amide and carboxylic acid.
functional groups encountered in AS Chemistry
There is also an alkyl group. This is the name given to the bits of
In your GCSE course you were introduced to organic chemistry the molecule that resemble simple alkanes (in this example, the
through the study of two families of molecules, the alkanes and the alkyl group is actually a methyl group, -CH3). Alkyl groups are
alkenes (Fig 1). Like all organic molecules, these families of molecules functional groups since they can also contribute their properties
(also called homologous series) are built around a framework of carbon to a molecule, such as reducing the solubility of a drug in your
atoms. bloodstream so that it stays in your body longer.

Fig 1. Some simple alkanes and alkenes Fig 3. Vitamin B5 (pantothenic acid)
H H H H H H

H C H H C C H H C C C H
alkyl
amide
H H H H H H H
H H H H O
methane ethane propane H C H
H O N C C C
H H H
H H H O C C C C H H O H
C C C C C H alcohol O
H H carboxylic acid
H H H H C H
H H
ethene
propene H

Alkanes and alkenes contain only carbon and hydrogen atoms, which
is why they are known as hydrocarbons. Remember that each carbon
atom forms four covalent bonds (a double bond counts as two), with Functional groups can contain many different elements – sulphur,
hydrogen atoms hanging off the carbons wherever there is a free phosphorus or magnesium, for example – but the most common
bond available. ones contain oxygen, nitrogen and halogen atoms. Table 1. shows
the ones that you will encounter most commonly, along with the
Alkanes are relatively unreactive molecules. They don’t do many suffix or prefix used in the systematic naming of the group.
interesting reactions apart from combustion – which they do very
well (Fig 2) and the free radical substitution reaction described later. The functional groups are highlighted in the examples. Notice
that in some of the structures the abbreviation R is used. This is
Fig 2. The complete combustion of methane the conventional way to show that a carbon-containing group,
linking to the rest of the molecule, is attached to the atom we are
CH4 (g) + 2O2 (g) → CO2 (g) + 2H2O (g) interested in.

Alkenes are a bit more interesting than alkanes because they contain
a functional group. This is what we call the part of a molecule that
makes it different from an alkane. In an alkene, the functional group
is the carbon-carbon double bond.
1
100. Organic Functionality and Structure – Part I (AS) Chem Factsheet

Table 1. Some common functional groups

Name Suffix or prefix* Structure Example

H
Alkene -ene C C
C H
H3C C
CH 2
H
But-1-ene

H
Halogenoalkane fluoro-, chloro-, bromo- C Halogen H C Br
or iodo-
H
Bromomethane

H H
Alcohol -ol or hydroxy- C OH H C C OH

H H
Ethanol

O O
Ketone** -one

C C

R1 R2 H3C CH3
Propanone

Aldehyde** -al O O

C H 3C C
R H CH 2 H

Propanal

O O
Carboxylic acid** -oic acid
C C
R OH H3C OH

Ethanoic acid

Ester** -oate O O

C C C2H5
R1 OR 2 H3C O

Ethyl ethanoate

Amine amino- or –amine H H

H
C NH 2
H C C N
H
H H
Aminoethane or ethylamine
*Naming of functional groups is covered in detail in Factsheet 15.
** Note that these compounds all contain C=O, called the carbonyl group.
2
100. Organic Functionality and Structure – Part I (AS) Chem Factsheet

Reactions and properties of functional groups The carbon atom is therefore open to attack by nucleophiles such
Below we look at the key properties of these functional groups. as hydroxide ions, ammonia and water. These nucleophiles donate
This should enable you to predict their behaviour even in more electron pairs to the electron-deficient carbon atom. Since
unusual molecules. For practice in this, try the questions at the end halogenoalkanes are already saturated, they usually react by
of the Factsheet. substitution to make another saturated molecule. These reactions
are therefore called nucleophilic substitutions (Fig. 7).
Free Radical Substitution of Alkanes
Alkanes are non-polar, saturated molecules, so they tend not to Fig 7. Nucleophilic substitution of halogenoalkanes
interact with most reagents. However, they will react with halogens
by the free radical substitution reaction (Fig 4).This reaction takes δ+ δ−
place through a chain reaction involving highly reactive free radicals C X + Nu− C Nu + X−
(species with a single unpaired electron). It is initiated by ultra-
violet light, which provides the energy to split the chlorine molecule halogenalkane nucleophile
into two free radical chlorine atoms. These atoms are so reactive
that they can break the strong C-H bonds and thereby react with The reactivity of the halogenoalkanes in these reactions varies with
the alkane (see Factsheet 16 for more information). the halogen in the following order; C-I > C-Br > C-Cl > C-F. This is
due to the increasing bond strength of the carbon-halogen bonds,
Fig 4. Free Radical Substiution of Methane by Chlorine with carbon-iodine being the weakest and carbon-fluorine the
strongest. The weakest bond is broken most easily resulting in the
H H
greatest reactivity.
C uv light C
H H + Cl2 H Cl + HCl If the cyanide ion CN- (found in HCN and KCN, for example) is used
as the nucleophile, the product is a nitrile which contains an
H H
additional carbon atom (Fig 8). This is an important process in
Although this reaction can be difficult to control because multiple organic synthesis since it allows us to increase the length of the
substitutions will occur, it is important because it provides a route carbon chain. The nitrile group can be easily converted to other
from an alkane to a halogenoalkane and thereby provides access to functional groups such as carboxylic acids and amines.
the whole range of functional groups, using some of the
transformations described below. Fig 8. Nucleophilic substitution of a bromoalkane by CN-

Electrophilic Addition to Alkenes δ+ δ−

C Br + CN− C CN + Br−
Double bonds are areas of high electron density (four electrons
shared between just two atoms). This means that they react readily
with electrophiles, species which seek out electron density. Some
commonly used electrophiles are H+ ions (from hydrogen halides Nucleophilic Substitution of Alcohols
and acids) and Br+(from Br2). When the electrophile reacts it accepts The polar nature of the C-O bond in alcohols, combined with the
an electron pair from the alkene. Since an alkene is unsaturated, it is fact that they are saturated molecules, suggests that they are also
most likely to react by addition to form a more stable saturated likely to react by nucleophilic substitution. As seen in Figure 10,
compound. These reactions are therefore called electrophilic alcohols can react with the nucleophilic Br- ion from HBr to form the
additions (Fig 5). corresponding bromoalkane.

Fig 5. Electrophilic addition of HBr to an alkene Fig 9. Nucleophilic substitution of an alcohol by Br-

δ+ δ−
C OH + Br− C Br + OH−
C C + HBr C C
alkene electrophile H Br
Nucleophilic behaviour of alcohol and amines
The test for an alkene, where orange-brown bromine solution is As discussed above, alcohols can undergo nucleophilic substitution
shaken with the alkene, producing a colourless product, is similarly of their OH group, but the lone pairs of electrons on the O of alcohols,
an electrophilic addition reaction (Fig 6). and also on the N of amines, mean that they can behave as
nucleophiles themselves and take part in nucleophilic substitution
Fig 6. Electrophilic addition of bromine to ethane reactions as the nucleophile. Alcohols can make esters by reacting
H H with carboxylic acids (see Fig 15 below) and amines make secondary
H H
amines by substitution of halogenoalkanes (Fig 10).
C C + Br2 H C C H
H H Fig 10. Nucleophilic substitution of a bromoalkane by an amine
ethene Br Br
H
δ+ δ−
Nucleophilic Substitution of Halogenoalkanes C Br + RNH2 C N + Br−
The halogen atom is more electronegative than the carbon atom.
R
This means that the carbon-halogen bond is polar, with the carbon
holding a partial positive charge (δ+).

3
100. Organic Functionality and Structure – Part I (AS) Chem Factsheet

Hydrogen Bonding in Alcohols, Amines and Carboxylic Fig 14. Reduction of an aldehyde
Acids Oδ
-
OH
The polar nature of the bonds in these functional groups means δ+ +2[H]
that they tend to be more soluble in water than similar sized alkanes R C R C H
since they can form hydrogen bonds to water molecules (Fig 11).
H H
Fig 11. Hydrogen bonds between water and an alcohol Fig 15. Conversion of carboxylic acid to methyl ester by addition-
elimination
δ−
O
Oδ
-
δ+ H O
δ−
H
δ+
R O R C + CH3OH R C + H2O

:
δ+ OH OCH 3
H

These compounds can also form intermolecular hydrogen bonds, Fig 16. Testing for a ketone with 2,4-dnp
which strengthen the forces between molecules, leading to relatively
Oδ
-
higher boiling points. This is especially true of carboxylic acids, NO 2 N NH NO 2
O 2N
which can form dimeric structures (Fig 12) consisting of two δ
+
R1 C
molecules hydrogen bonded together. Carboxylic acids thus have R1 C + H2N

:
even higher boiling points. NH R2
R2
NO 2
orange
Fig 12. Intermolecular hydrogen bonds in carboxylic acids 2,4-dinitrophenylhydrazine precipitate
+ H2 O

δ− δ+ Interconversion of Functional Groups

Oδ
−
O H Perhaps the most significant reactions of functional groups are
those which allow conversion of one to another. This is a powerful
C R
R C tool for organic chemists since it allows them to manipulate the
δ+ functionality of a molecule, firstly to reach their target molecule,
O H O and secondly to adapt it, thereby enabling the testing of new
δ −
δ−
functional groups in a particular position of the molecule. This is
often vital in the development of new therapeutic drugs.
Nucleophilic Addition to Carbonyl Groups
By combining the reactions of functional groups it is possible to
The carbonyl group, C=O, is found in a number of functional groups
convert, either directly or indirectly, any functional group to any
– aldehydes, carboxylic acids, ketones and esters are the ones you
other. For example, a halogenoalkane can be converted to an alcohol
are most likely to encounter in AS Chemistry. Like an alkene, the
or an amine by nucleophilic substitution, as described above, or to
carbonyl group is unsaturated, with a high electron density. Its
an alkene by elimination of a hydrogen halide (HX). These reactions
functionality, though, is usually determined by the polarity of the
can also be reversed, or bypassed by direct conversion of alkene to
C=O bond (although this can be modified by the other part of the
alcohol (Fig 17).
functional group). Oxygen is more electronegative than carbon, so
the carbon is δ+. As in a halogenoalkane, this makes it susceptible Fig 17. Interconversion of halogenoalkanes, halides and alkenes
to attack by nucleophiles (Fig 13), giving rise to nucleophilic addition
nucleophilic
reactions. subsitution elimination
C C C C C C
Fig 13. Nucleophilic addition to the carbonyl group nucleophilic electrophilic
H OH subsitution H Br addition
δ− −
O O
elimination
δ+
+ Nu −
R C Nu
R C
electrophilic addition
nucleophile
Alcohols, aldehydes and carboxylic acids can be interconverted by
oxidation and reduction (Fig 18).

This is a reaction that you will come across in many guises: reduction Fig 18. Interconversion of alcohols, aldehydes and carboxylic
of aldehydes by hydride ions (H−, provided by NaBH4 and LiAlH4)
(Fig 14), interconversion of carboxylic acids and esters (Fig 15), and R R R
oxidation oxidation
testing for aldehydes and ketones with 2,4-dinitrophenylhydrazine
CH 2 OH C O C O
(Fig 16), for example. It may not always be easy, at first glance, to reduction reduction
recognise the nucleophilic addition, but if you draw out the H HO
mechanism it should become clear.

4
100. Organic Functionality and Structure – Part I (AS) Chem Factsheet

Acids
There are many other functional group reactions, and you will need 7. The molecules below contain some other functional groups.
to learn them to succeed in A Level Chemistry, including the Predict whether you think they will react predominantly with
reagents and conditions necessary to make them work well. nucleophiles or electrophiles.
However, the principles behind them are the same and you should
get into the habit of looking at a molecule and making predictions O
about its reactions and properties based on the structure, degree of
saturation and polarity of the functional groups it contains. O H3C C N
C
H3C Cl H 2C CH2
Practice Questions
1. Name the functional group in each of these organic molecules Acyl chloride Epoxide Nitrile

O H O H
CH 3 8. The diagram below shows the structure of two commonly used
analgesics (pain killers), aspirin and ibuprofen.
C C CH 3 CH C C CH 3
H2C
H 3C H CH CH 3 HO CH 3 O
O OH H 3C C
O C OH
CH
H 3C CH3 CH2 H O CH 3
H 3C CH3 H 3C C CH2
CH C C
CH2 O H 3C
O O
NH 2
CH
aspirin ibuprofen
H 3C
2. Name the functional group in each of these compounds:
(a) Propan-2-ol
(b) 2-Methylpropene (a) Name one functional group found in both molecules.
(c) Propanone (b) Name one functional group found in aspirin but not in
(d) Butanal ibuprofen.
(e) Ethyl ethanoate (c) Ibuprofen is a drug that was designed and synthesised in
(f) Hexanoic acid the research labs of Boots the chemists. Suggest a reason
why the research chemists included the alkyl chain labelled
3. Ethanol, C2H5OH, chloromethane, CH3Cl, and propane, C3H8, in the molecule, rather than an alcohol group in the same
have similar molecular masses (46, 51 and 44 respectively), but position.
their boiling points are very different (79, -24 and -42°C
respectively). Explain why.

4. Amines are more soluble in water than alkanes. Why is this?

5. (a). The test for an alkene is the addition of bromine solution.

What would you observe in this reaction?
(b).What type of reaction is this?
(c). What functional group does the product of this reaction
contain?

6. The diagram shows the structure of aspartame, a controversial

synthetic sweetener that is nearly 200 times sweeter than sugar.
Name four functional groups in the molecule.

C
H2C OH O

NH C CH 3
CH
H2N C O
CH

O H2C

Aspartame
5
100. Organic Functionality and Structure – Part I (AS) Chem Factsheet

Answers 7. All these molecules will be susceptible to nucleophilic attack on

1. the δ+carbon atoms.
H H
Oδ
−
O CH 3 O
δ−
C C CH3 CH C C CH3 O δ+ δ−
Cδ
H2C +
δ+ H 3C C N
CH H2C CH 2
H 3C H CH 3 HO CH3 H3C Cl Nu−
Ketone Alkene Carboxylic acid Nu−
Nu−
O
H 3C CH3 CH2 H
H 3C CH3 H 3C C
CH C
8. (a) Carboxylic acid
CH2 O
O (b) Ester
NH 2
(c) To reduce water solubility of the drug. Using an alcohol
Amine Ester Aldehyde group here would make the molecule much more water-
soluble. This would lead to it staying dissolved in the
bloodstream and passing straight through the body, rather
2. (a) Alcohol (secondary) than passing into cells where it can work as a painkiller.
(b) Alkene
(c) Ketone
(d) Aldehyde
(e) Ester
(f) Carboxylic acid

3. Ethanol contains intermolecular hydrogen bonds, due to the

polar nature of the O-H bond, which increase the strength of
their intermolecular forces. Remember that ethanol will also
have permanent dipole and van der Waal’s interactions as well.
Chloroethane contains polar C-Cl bonds, which lead to
permanent dipole-dipole interactions between molecules (as well
as van der Waal’s), making intermolecular forces stronger than
in non-polar molecules. Propane is an alkane, a non-polar
molecule, with only weak van der Waal’s forces holding the
molecules together.

4. Amines can form hydrogen bonds with water molecules due to

the polar N-H bonds. Alkanes cannot since they do not contain
polar bonds.

5. (a) The brown/orange bromine solution would turn colourless

(b) An electrophilic addition reaction
(c) The product is a (di)bromoalkane

6.

O
carboxylic acid
ester
C
H2C OH O

C CH3
CH NH
H 2N C O
CH
amine
O
H2C
amide
benzene
Acknowledgements: This Factsheet was researched and written by Emily Perry.
ring
Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire, TF1
1NU. ChemistryFactsheets may be copied free of charge by teaching staff or
students, provided that their school is a registered subscriber. No part of these
Factsheets may be reproduced, stored in a retrieval system, or transmitted, in
Aspartame any other form or by any other means, without the prior permission of the
publisher. ISSN 1351-5136

6
 Chem Factsheet
www.curriculum-press.co.uk Number 101
Organic Functionality and Structure – Part 2 (A2)
To succeed in this topic you need to: In your AS Chemistry course you have developed some important skills
• remember that carbon atoms form the backbone of all organic molecules of organic chemistry. You should now be able to look at the structure of
• understand why and how carbon atoms form four covalent bonds any organic compound and pick out the key functional groups.
• understand the properties and reactivity of simple functional groups You should also be able to predict the chemical and physical properties of
like alcohols and alkenes the compound based on those functional groups. In A2 Chemistry you
• be comfortable with the naming and testing of functional groups meet a wider variety of functional groups, but you still need to be able to
name them, describe tests, suggest ways of making them and predict their
After working through this Factsheet you will: physical properties and chemical reactions.
• be able to recognise the key functional groups in A2 Chemistry
• be able to predict chemical and physical properties of the key functional Table 1 shows the functional groups that most commonly occur in A2
groups in A2 Chemistry Chemistry, along with the suffix or prefix used in the systematic naming of
the group. The functional groups are highlighted. Remember that the
Not all A2 courses cover all the functional groups mentioned in this abbreviation R is used to show that a carbon-containing group, linking to
Factsheet, so make sure you have checked your notes and your syllabus the rest of the molecule, is attached to the atom we are interested in.
to be clear about which ones you need to study.

Table 1. A2 Functional groups

Name Suffix or prefix* Structure Example

R C N H3C C N
Nitrile -nitrile
Ethanonitrile

Grignard reagent -magnesium iodide or bromide R MgBr H3C MgBr

Methyl magnesium bromide
O O
Propanone
Ketone** -one
C C
R1 R2 H3C CH3
O Propanal O
Aldehyde** -al H3C
C C
R H CH2 H
O Ethanoic acid O
Carboxylic acid** -oic acid C C
R OH H3C OH
O Ethyl ethanoate O
Ester** -oate C2H5
C C
R1 OR2 H3C O
O O Ethanoic O O
Acid anhydride** -oic anhydride anhydride
C C C C
R1 O R H3C O CH3

O Ethanoyl chloride O
Acid chloride** -oyl chloride C C
R Cl H3C Cl

O Ethanamide O
Amide** -amide
C C
R NH2 H3C NH2
R Methyl benzene CH3
Benzene ring -benzene or phenyl-

* Naming of functional groups is covered in Factsheet 15. ** These functional groups contain the carbonyl group, C=O.
1
101. Organic Functionality and Structure – Part 2 (A2) Chem Factsheet

Carboxylic acids, aldehydes and ketones

Carboxylic acids, aldehydes and ketones are made by oxidation of alcohols (Fig 1). The oxidising agent most commonly used is acidified
potassium (or sodium) dichromate(VI), K2Cr2O7 (or Na2Cr2O7). Oxidation of a primary alcohol produces an aldehyde, which must be
distilled off as it forms or it will be further oxidised to the carboxylic acid. Secondary alcohols produce ketones. Tertiary alcohols cannot
be oxidised under these conditions since the carbon atom of the alcohol is not bonded to a hydrogen atom.

Fig 1. Oxidation of alcohols

R R R
K2Cr2O7 dil.H2SO4 heat K2Cr2O7 dil.H2SO4
CH2 OH + [O] C O + H2O + [O] C O
distil aldehyde as it forms heat under reflux
H HO
R1
R1
K2Cr2O7 dil.H2SO4
H C OH + [O] C O + H2O
heat under reflux
R2
R2

Carboxylic acids, aldehydes and ketones can be reduced back to Acyl chlorides and acid anhydrides
their respective alcohols by reaction with reducing agents such as Acyl chlorides are synthesised from carboxylic acids by reaction
sodium tetrahydridoborate, NaBH4, or lithium tetrahydridoaluminate, with PCl5 or SOCl2 (Fig 5). Acyl chlorides are more reactive than
LiAlH4. These reductions can be viewed as nucleophilic addition carboxylic acids because the C-Cl bond is weaker than the C-OH
reactions because the metal hydrides are sources of nucleophilic H- bond of the carboxylic acid.
ions which attack the unsaturated δ+ carbonyl carbon atom (Fig 2).
Fig 5. Synthesis of acyl chlorides
Fig 2. Reduction of carboxylic acids and ketones
O δ−
O
PCl5 or SOCl2 δ+
R R C C C C
LiAIH4 or NaBH4 δ−
C O + 4[H] CH2 OH + H2O OH Cl
HO carboxylic acid acyl chloride
R1
R1
LiAIH4 or NaBH4
C O + 2[H] H C OH Thus, acyl chlorides also react with nucleophiles, as shown in Fig
R2 6, which attack the δ+ carbon atom, ultimately breaking the weaker
R2 carbon-chlorine bond, but leaving intact the unsaturated C=O bond.

It is difficult to stop the reduction of a carboxylic acid at the aldehyde Fig 6. Nucleophilic addition-elimination reactions of acyl chlorides
stage, so if this transformation is required, a more effective approach −
O :O
is to reduce to the primary alcohol and then re-oxidise to the aldehyde δ + O
nucleophilic
(Fig 3). R C + Nu− addition R C Nu elimination R C + Cl−
of Cl-
:

Cl Nu
Fig 3. Conversion of a carboxylic acid to an aldehyde Cl

R R R
[H] [O] The nucleophiles commonly used in this reaction are species with
C O CH2 OH C O lone pairs such as ammonia, amines, water and alcohols, which
HO H convert acyl chlorides into amides, substituted amides, carboxylic
acids and esters respectively, as shown in Fig 7. Note that in each
Aldehydes and ketones react similarly with other nucleophiles, like of these reactions, HCl is produced as well.
hydrogen cyanide, HCN (Fig 4). These reactions are also nucleophilic Fig 7. Reactions of acyl chlorides
additions where the unsaturated carbonyl group is transformed to
a saturated single C-O single bond as a result of the nucleophilic O
CN- ions attacking the unsaturated δ+ carbonyl carbon atom. The amide C C
nitrile group can be further manipulated to make carboxylic acids NH2
and amines.
:NH3
Fig 4. Nucleophilic addition of HCN to aldehydes and ketones O O O
H2O:
C C C C C C
R R R NHR Cl OH
δ+ δ− −
HCN H+
:

C O NC C O NC C OH substituted amide ROH carboxylic acid

R :CN − R R O
C C ester
OR
2
101. Organic Functionality and Structure – Part 2 (A2) Chem Factsheet

Acid anhydrides are synthesised from acyl chlorides by reaction Acid anhydrides are also more reactive than carboxylic acids and
with the sodium salt of a carboxylic acid (Fig 8). This is also a can be used in similar ways to acyl chlorides. The example (Fig 9)
nucleophilic attack on the δ+ carbonyl carbon by the alkanoate shows the synthesis of an amide by reaction with nucleophilic
ion (RCO2−). ammonia. Substituted amides, esters and acids can be made from
amine, alcohol, and water nucleophiles respectively.
Fig 8. Synthesis of an acid anhydride from acyl chloride
Fig 9. Reaction of an acid anhydride with ammonia
O O O O
C C + RCO2−Na+ C C + NaCl C C + NH3 C C + RCOOH
Cl OCOR OCOR NH2
acid anhydride

Grignard Reagents
Grignard reagents contain a nucleophilic carbon atom because of the electropositive nature of the magnesium atom, which increases the
electron density around the carbon atom. Hence, they also react with polar carbonyl groups by nucleophilic addition as shown in Fig 10.

Fig 10. Reactivity of a Grignard reagent

δ− δ+ δ−
:
δ+ H2O
C MgBr C O C C OMgBr C C OH + Mg(OH)Br

The resulting addition product can be hydrolysed to form various products depending on the nature of the original carbonyl molecule.
Fig 11 shows some examples. Methanal produces a primary alcohol, other aldehydes produce secondary alcohols and ketones
produce tertiary alcohols. They also react with the C=O bond in carbon dioxide to make carboxylic acids, and with water to make
alkanes.

Fig 11. Nucleophilic reactions of Grignard reagents

R
C C OH secondary alcohol
H

O
C
R H
O
O C H
CO2 H H
C C C MgBr C C OH
OH H
carboxylic acid O primary alcohol

C
R1 R2

R1
C C OH tertiary alcohol
R2

3
101. Organic Functionality and Structure – Part 2 (A2) Chem Factsheet

Amides Nitriles
Amides, which also contain a carbonyl group, are a common feature Reactive carbon atoms tend to be δ+ since they are usually attached
of many biological molecules. They can be produced by the reaction to electron-withdrawing halogens, oxygen or nitrogen. However, it
of acyl chlorides with ammonia and amines (see Fig 7), or by is possible to reverse this reactivity and produce a nucleophilic
hydrolysis of nitriles (see Fig 18). Another route to amides is the carbon atom. The nitrile ion, CN−, found in compounds like KCN, is
dehydration of the ammonium salt of a carboxylic acid, as seen in an example of this reversed reactivity since the lone pair of the
Fig 12. negatively charged carbon atom will attack the δ+ carbon atoms of
halogenoalkanes. This, as shown in Fig 17, is a nucleophilic
Fig 12. Synthesis of an amide from a carboxylic acid substitution reaction.

O O O Fig 17. Nucleophilic substitution of a halogenoalkane by a cyanide ion

(NH4)2CO3 heat
C C C C C C + H2O
− +
OH O NH4 NH2 C Br + KCN (in ethanol solution) C CN + KBr

Unlike amines, amides are not basic since, as shown in Fig 13, the Nitrile groups extend the carbon chain by one atom. The group can
electron-withdrawing nature of the carbonyl group reduces the then be reduced to an amine (again by reaction with lithium
electron density of the nitrogen atom, making it less able to use its tetrahydridoaluminate, LiAlH4) or hydrolysed under acidic or alkaline
lone pair to accept a proton. conditions to an amide and subsequently to a carboxylic acid, as
shown in Fig 18.
Fig 13. Reduced basic character of the amide nitrogen atom
_ Fig 18. Reactions of the nitrile group
O O
H R
C C C C LiAlH4 H2O R H2O
+
R C NH2 R C N C O C O
:NH2 :NH2
H H2N HO
Like acyl chlorides and acid anhydrides, amides react by These reactions all involve nucleophilic attack on the carbon of the
nucleophilic attack on the carbonyl carbon atom. As shown in Fig CN group, which, due to the electron-withdrawing nature of the
14, they can be hydrolysed to carboxylic acid salts by reaction with nitrogen atom, behaves in a similar way to the carbon of a carbonyl
either acid or base. In these processes, H 2O and OH − are the group (Fig 19). In the reduction, LiAlH 4 acts as a source of
nucleophiles. nucleophilic H− ions, while in the hydrolysis, water is the nucleophile.
Fig 14. Hydrolysis of an amide Fig 19. Nucleophilic attack on carbonyl and nitrile groups
O O R
H2O δ+ δ- δ+ δ-
C C C C C O R C N
− +
R Nu− Nu−
NH2 O NH4

They can also be reduced to amines using lithium tetrahydridoaluminate. Reactions of the benzene ring
This is seen in Fig 15 and is analogous to the nucleophilic addition of Benzene rings are a common feature of naturally occurring organic
hydride to aldehydes, ketones and acids (Fig 2). compounds. It is important, therefore, to have synthetic methods
which can provide routes to the whole range of substituted rings.
Fig 15. Reduction of an amide
Benzene’s stability means that, unlike alkenes, it does not readily
O H undergo electrophilic addition reactions, but it can be forced to
LiAlH4 react with hydrogen by using a high temperature and nickel catalyst
C C + 4[H] C C NH2 + H2O
(see Fig 20). This is a free radical addition reaction and a reduction,
NH2 H since it involves the addition of hydrogen.
The Hofmann degradation (Fig 16) is another reduction reaction,
Fig 20. Reduction of benzene
this time producing an amine with one less carbon atom than the
original amide. H H
H C H
H2 150oC C C H
Fig 16. The Hofmann degradation reaction H
Ni catalyst H C C H
O H C
H H
Br2(aq)
R C C R C NH2 H H
conc alkali
NH2 H The benzene ring is most often involved in electrophilic substitution
reactions (see Fig 21) which retain the stable benzene ring structure.
After the initial electrophilic addition, an H+ ion is eliminated, and
so this process can be viewed as an addition-elimination reaction.
4
101. Organic Functionality and Structure – Part 2 (A2) Chem Factsheet

Fig 21. Electrophilic substitution of the benzene ring

CH3
E
H
+ E+ addition + elimination + H+

The benzene ring can be substituted by electrophilic halogens (e.g. Cl+), NO2+, alkyl groups (e.g. CH3+) and carbonyl groups (e.g. CH3C+O).
These are all generated in-situ as shown in Fig 22.

Fig 22. Electrophilic substitution reactions of the benzene ring

NO2

conc. HNO3 and conc. H2SO4 nitration O

R C
RCl, AlCl3 RCOCl, AlCl3 R
alkylation acylation

Cl2, AlCl3 halogenation

Cl

Questions 3. The diagram shows a substituted benzene compound.

1. Put these molecules in order of reactivity with nucleophiles, NH2
least reactive first. Justify your choice.
H H Cl
O O O
(a) (b) (c)
C C CH3 C C CH3 C C CH3 CH3
Cl HO Cl (a) Draw the organic product of the reaction of this compound
H H H
with the acyl chloride CH3CH3COCl.
H (b) What is the other product?
(d) O
(c) Name and draw the mechanism of this reaction.
C C CH3 (d) Which species in this reaction is behaving as a nucleophile?
H3C What feature of this species enables it to do so?
H
4. Look at the reaction sequence below.
2. The diagram shows the structure of Vitamin A. H H OH H OH
O
H3C CH3 HCN step 2
CH3 CH3 H3C C C H3C C C CN H3C C C NH2
C CH C CH C CH2 H
H2C C H H H H H
CH CH CH CH OH
C (a) Name the starting aldehyde.
H2C
CH2 CH3 (b) Is the second step a nucleophilic addition or substitution?
Explain your answer.
(c) Which species is acting as the nucleophile in this reaction?
(a) Draw the product that would be made on complete oxidation (d) Name and give the formula of a reagent which could be used
of this compound by dichromate(VI). to carry out Step 2.
(b) What conditions would you need to carry out this oxidation? (e) What type of reaction is Step 2?
(c) Partial oxidation of Vitamin A would produce an aldehyde.
Draw this aldehyde.
(d) Name and give the formula of a reagent that could be used
to convert this aldehyde back to Vitamin A.
5
101. Organic Functionality and Structure – Part 2 (A2) Chem Factsheet

Answers
1. d – b – a – c
The ketone is the least reactive, then the carboxylic acid, with its electron-withdrawing OH group, then the unsubstituted acyl chloride
(a), with its weaker C-Cl bond. The most reactive is the chloro-substituted acyl chloride because the electronegative chlorine atoms
withdraw electron density from the carbonyl carbon, enhancing its δ+ charge.

2. (a) H3C CH3 CH3 CH3 O

C CH C CH C C
H2C C
CH CH CH CH OH
H2C C
CH2 CH3

(b) H2SO4 (aq), heat and reflux.

(c) H3C CH3 CH3 CH3 O

C CH C CH C C
H2C C
CH CH CH CH H
H2C C
CH2 CH3

(d) Lithium tetrahydridoaluminate, LiAlH4

or sodium tetrahydridoborate, NaBH4.

3. (a) NH CH2CH3
C
O
CH3
(b) HCl

(c) The mechanism is a nucleophilic addition-elimination

H H
O N CH2CH3 N CH2CH3
NH
C C
:

C + HCl
Cl CH2CH3 −
Cl O
:O
CH3 CH3
CH3

(d) The amine-substituted benzene is the nucleophile. It is the lone pair of the amine nitrogen atom which enables it to act in this way.

4. (a) Propanal
(b) It is a nucleophilic addition because one product is made from the two starting materials.
(c) The nucleophile is the CN- ion.
(d) Lithium tetrahydridoaluminate, LiAlH4 or sodium tetrahydridoborate, NaBH4.
(e) Step 2 is a reduction, or a nucleophilic addition of H- ions.

Acknowledgements: This Factsheet was researched and written by Emily Perry. Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire,
TF1 1NU. ChemistryFactsheets may be copied free of charge by teaching staff or students, provided that their school is a registered subscriber. No part
of these Factsheets may be reproduced, stored in a retrieval system, or transmitted, in any other form or by any other means, without the prior permission
of the publisher. ISSN 1351-5136

6
 Chem Factsheet
www.curriculum-press.co.uk Number 102

Improve Your Marks:

A2 Energetics- Born-Haber Cycles
This Factsheet aims to give you tips to help improve your marks ∆HL) is defined as the
The lattice dissociation enthalpy change (∆
when answering A2 Energetics questions about Born-Haber cycles. enthalpy change occurring when 1 mole of solid ionic lattice is
The areas covered are:- separated into its gaseous ions under standard conditions of
temperature and pressure.
• A check of your understanding about the formation of an ionic
compound e.g. NaCl (s) ! Na+ (g) + Cl−(g)
• Born-Haber Cycles
• Defining Born-Haber Cycle terms Conversely, the lattice formation enthalpy change (also ∆HL) is
• Getting each point right in the exam defined as the enthalpy change occurring when 1 mole of solid
• Applying the knowledge ionic lattice is formed from its gaseous ions under standard
conditions of temperature and pressure.
Check your understanding about the formation of an ionic compound
e.g. Na+ (g) + Cl-(g) ! NaCl (s)
Sodium and chlorine
When a piece of hot sodium metal is lowered Be sure you know which of these definitions is favoured by
into a gas jar of chlorine, a violent reaction your specification. They are equal in magnitude but opposite
takes place and spots of a white substance in sign. Lattice dissociation is always endothermic because
are spattered inside the jar. bonds are being broken whereas lattice formation is always
exothermic because bonds are being formed.
Explain as fully as you can what is e.g. NaCl (s) ! Na+ (g) + Cl-(g) ; + 780 kJ mole-1
happening in the gas jar.
but Na+ (g) + Cl-(g) ! NaCl (s) ; - 780 kJ mole-1

Check your answer against the full answer at the end of the factsheet. In either case, the magnitude indicates the strength of the
ionic bonding; the larger the value the stronger the ionic
Background to the answer bonding.
How much detail did you include? Read the answer - a lot of processes
occur in a very short period of time in the reaction:- If anything, dissociation is the favoured definition because it
is parallel to the definitions of bond dissociation energy and
2Na (s) + Cl2(g) ! 2NaCl (s) mean bond enthalpy as applied to covalent bonds.

The product is an ionic lattice – a 3-D crystalline solid consisting of

millions of sodium and chloride ions packed in a 1:1 ratio. The “ionic
Born-Haber Cycles apply Hess’s Law (see FactSheet 98 Improve
bond” formed between them holds the lattice together. The bond is
your marks: AS Energetics). Two differences between a standard
multi-directional – the charge on ions is all over, so isn’t directed
Hess’s Law cycle and a Born-Haber cycle are:-
towards one specific ion of opposite charge. This makes the strength
of ionic bonds much harder to study – where do you start? How
1. Born-Haber cycles are presented vertically so they look
many ions should be included? On what basis should comparisons
different. This is a convention arising because of point 2.
be made? It is difficult to answer these questions by experiment.
Instead, chemists investigate, measure and compare ionic bond
2. Born-Haber cycles have a lot more component parts than most
strength and ionic compound formation using Born-Haber energy
Hess’s Law cycles.
cycles.
To illustrate the points, we will use a Born-Haber cycle for the
Born-Haber Cycles
formation of sodium chloride (look back at the starting question
Born-Haber Cycles enable us to calculate the lattice enthalpy change
and its answer).
∆HL) for ionic solids which gives an indication of the overall strength
(∆
and nature of the ionic bonding in the compound. The cycles were
The enthalpy change for the formation of sodium chloride can be
developed around 1917 by Max Born and Fritz Haber, two scientists
determined by experiment and the enthalpy changes of the separate
famous for other work: Max Born contributed to our understanding
steps involved in making ions from the elements and reacting
of atomic structure and Fritz Haber developed the “Haber-Bosch
them together can also be measured. This means we can set up
Process” (now usually called the Haber Process) for making ammonia.
the following energy diagram:-

1
102. Improve Your Marks: A2 Energetics- Born-Haber Cycles Chem Factsheet

This should look familiar – it’s simply a Hess’s Law cycle. Born-Haber cycle
Na+(g) + Cl(g) + e−
Hess's Law cycle Route 1
Na(s) + ½Cl2(g) → NaCl(s) (3)
(4)
Na+(g) + ½Cl2(g) + −
Na (g) + Cl (g)
+ −
Na (g) + Cl (g) (2)
Route 2 Na(g) + ½Cl2(g)
(1) (5)
Route 1 is direct, but can be measured. Route 2 goes through many
steps each of which can be measured except for the lattice enthalpy. Na(s) + ½Cl2(g)
The enthalpy changes for Routes 1 and 2 must be equal. If we know
Route 1
all the other enthalpy changes of the steps involved in creating the
Enthalpy change
gaseous ions (route 2) and the enthalpy change involved in forming
of formation of
the lattice from the elements (route 1), we can calculate the lattice NaCl(s)
enthalpy for sodium chloride (part of route 2). = -441 KJmol-1
NaCl(s)
This Hess’s Law cycle is shown opposite in a Born-Haber cycle
format. The bold parts are the Hess’s Law cycle components. The The components for route 2 are:-
starting point, the chemical elements in their standard states, is on Endothermic changes: (1) Atomisation enthalpy of sodium
the left-hand side. Usually, endothermic changes are placed on the (2) First Ionisation enthalpy of sodium
left, while exothermic changes are on the right. The only exception (3) Atomisation enthalpy of chlorine
is the enthalpy change of formation (route 1), which can be either
Exothermic changes: (4) Electron affinity of chlorine
exo- or endothermic, and is also shown on the left. Route 2 is made
(5) Lattice dissociation enthalpy of NaCl
up of all the other enthalpy changes added together.
We will refer to these numbered points in the next sections.

Defining Born-Haber cycle terms

No. Term Definition Symbol Sign

1 Atomisation enthalpy (For solids this is The standard enthalpy change occurring when ∆Hêat ALWAYS +ve
also known as the enthalpy change of 1 mole of gaseous atoms is formed from 1 mole ∆Hêsub
sublimation) of atoms in its standard state
e.g. Na(s) ! Na(g)

2 First ionisation enthalpy The standard enthalpy change occurring when 1 ∆Hêi1 ALWAYS +ve
mole of unipositive ions is formed from 1 mole of
gaseous atoms
e.g. Na (g) ! Na+(g) + e-

3 Atomisation enthalpy The standard enthalpy change occurring when 1 ∆Hêat ALWAYS +ve
(For diatomic gases this is also HALF of mole of gaseous atoms is formed from the element ½∆HêD
the bond dissociation enthalpy) in its standard state
e.g. ½ Cl2 (g) ! Cl (g)

4 First Electron affinity The standard enthalpy change occurring when 1 ∆Hêea(1) ALWAYS −ve
mole of electrons reacts with 1 mole of gaseous
atoms to produce 1 mole of gaseous 1- ions e.g.
Cl (g) + e- ! Cl-(g)

5 Lattice dissociation enthalpy The standard enthalpy change occurring when 1 ∆HêL ALWAYS −ve
mole of solid ionic lattice is separated into its
gaseous ions
e.g. NaCl (s) ! Na+ (g) + Cl-(g)

Exam Hint:- Questions often refer simply to a “lattice enthalpy”.

First electron affinities are always exothermic but second electron Strictly, “lattice enthalpy” is defined in two different ways depending
affinities are always endothermic because work needs to be done on whether the ionic lattice is being formed or broken up as described
to overcome the repulsions between the added electron and the earlier. Use the sign of the enthalpy change to decide which is being
1- ion. used. If lattice formation ethalpy change is given, the arrow in the
e.g. O−(g) + e− ! O2−(g) ; + 798 kJ mol-1 previous diagram will need to be reversed.

2
102. Improve Your Marks: A2 Energetics- Born-Haber Cycles Chem Factsheet

Definitions are normally worth 2 marks each in an exam question. The details of the defined processes are important but “1 mole” is
essential because the units throughout are “kJmol-1” and you should always refer to a “standard enthalpy change” .

Getting each point right in the exam

Next we will take each point from an exam perspective. What do you need to look for?

No. Name and where to find it Do’s and Don’ts Remember to

1 Atomisation enthalpy of a solid Don’t call it “enthalpy of vapourisation”. Include “standard state” in a definition.
First step going upwards from the This scores no marks. This scores 1 mark. Include state
element in its standard state symbols (s) and (g) when drawing a BHC.
2 Ionisation enthalpy Do check the charge on the ion! Check: Some BHC diagrams combine first
Second step going upwards Magnesium and calcium will be 2+. and second ionisation energies together,
on the left-hand side. This will require you to use ∆Hêi1 + ∆Hêi2 others show them separately.
3 Atomisation enthalpy of a diatomic gas. Do check the symbols: “ ½Cl2” and “Cl2” use +121 kJ mol-1 in a calculation using
Final left-hand step going to the top of are possible ½Cl2 (e.g. NaCl(s)) but 2(+121) kJ mol-1
the BHC diagram. in a calculation using Cl2 (e.g. MgCl2(s)).
4 Electron affinities Do check the number of atoms: use -349 kJ mol-1 in a calculation using
First step down on the right hand side Cl and 2Cl are possible Cl (e.g. NaCl(s)) but use 2(-349) kJ mol-1 in a
Normally chlorine but other elements calculation using 2Cl (e.g. MgCl2(s)).
such as sulphur may be used Try to memorise these values – you may
Do check the charge on the final ion: e.g. be asked to calculate them, so you will
sulphur is S2-. This will require you know the right answer.
to use ∆Hêea1 + ∆Hêea2 Check: a second electron affinity is
endothermic due to repulsion
5 Lattice dissociation enthalpy Do check you use a positive value Compare values: highest values imply the
Lowest step on right hand side strongest ionic bonds

Applying the knowledge Remember:

Let’s use figures for the sodium chloride BHC diagram to illustrate • Look for the two routes on a BHC diagram. The “clockwise
the kinds of questions examiners like to ask. The numbers and names route” and the “anticlockwise route”.
in the table below give the data we need and correspond with the • Check the sign of your answer – the correct sign is vital and
BHC diagram above. worth 1 mark! Use the definitions table to help you learn
what the signs should be.
No. Name Value / kJmol-1 • State the units – this is good practice, even though marks
may not be awarded for them.
1 Atomisation enthalpy of sodium + 107
2 First ionisation enthalpy of sodium +496
• Note that answers can vary within +/- 2kJmol-1 – this is due
to rounding up and down and use of different databook
3 Atomisation enthalpy of chlorine +121
values.
4 Electron affinity of chlorine -349
5 Lattice dissociation enthalpy +786
Related Data:

Exam Hint:- When applying Hess’s Law to such a cycle, it is often Element ∆Hêat Element ∆HêI1 ∆HêI2 ∆HêI3 ∆Hêea1 ∆Hêea2
useful to use “sum of clockwise ∆H = sum of anti-clockwise ∆H” to
Li(s) +159 Li(g) +520
help you get the arithmetic correct.
Na(s) +107 Na(g) +496
• Calculate the lattice dissociation enthalpy for sodium chloride K(s) +89 K(g) +419
Route 1 = Route 2 Cs(s) +76 Cs(g) +376
-411 + ∆HLE = +107 + 496 + 121 + (-349 )
∆
∆HLE = +786 kJmol-1 Mg(s) +148 Mg(g) +738 +1451
Ca(s) +178 Ca(g) +590 +1145
• Calculate the first electron affinity for chlorine Al(s) +326 Al(g) +578 +1817 +2745
Route 1 = Route 2
-411 + 786 = +107 + 496 + 121 + ∆Hea ½F2(g) +79 F(g) -328
∆Hea = -411 + 786 -107 -496 -121 ½Cl2(g) +121 Cl(g) -349
∆Hea = -349 kJmol-1 ½Br2(l) +112 Br(g) -325
½I2(s) +107 I(g) -295
½O2(g) +249 O(g) -141 +798
1/8S8(s) +279 S(g) -200 +640

3
102. Improve Your Marks: A2 Energetics- Born-Haber Cycles Chem Factsheet

Example 2 Answers
Calculate the lattice dissociation energy of lithium sulphide given 1.
Ca2+(g) + 2F-(g)
that its standard enthalpy of formation is -430 kJ mol-1.
+590 + 1145
2Li+(g) + S2-(g) +2(-328)
+2(520) Ca(g) + 2F(g)
+(-200) + 640 By Hess's Law:
+178
2Li(g) + S(g) ∆HêLE[Li2S(s)] + (-430) ∆HêLE
+2(+79)
+2(159) = +279 +2(159) + (-200) Ca(s) + F2(g)
+279 ∆HêLE +640 + 2(520)
-1220
2Li(s) + 1/8 S8(s) CaF2(s)
∆HêLE[Li2S(s)] = +2507 kJ mole-1
-430
Li2S(s) By Hess's Law:
∆HêLE[CaF2(s)] + (-1220)

Example 3 = +178 +2(79) + 2(-328)

Calculate the lattice dissociation energy of magnesium oxide given +590 + 1145
that its standard enthalpy of formation is -602 kJ mol−1.
∆HêLE[CaF2(s)] = +2635 kJ mole-1
+ 2-
Mg (g) + O (g)
+738 + 1451 2.
+(-141) + 798 By Hess's Law:
2Al3+(g) + 3O-(g)
Mg(g) + O(g) ∆HêLE[MgO(s)] + (-602)
2(+578 + 1817 + 2745)
+148 = +148 +249 + (-141) + +3(-141) + 3(+798)
+249 ∆HêLE 798 + 738 + 1451
2Al(g) + 3O(g)
Mg(s) + 1/2 O2(g)
∆HêLE[MgO(s)] = +3845 kJ mole -1
+2(+326)
-602 +3(+249) ∆HêLE
MgO(s) 2Al(s) + 1.5 O2(g)

-1676
Answer to the introductory question Al2O 2(s)
Sodium and chlorine react to form an ionic lattice. In the process,
sodium metal is sublimed to sodium gas. In this example, liquid
sodium metal is used. In the reaction, sodium atoms lose one electron By Hess's Law:
each becoming sodium ions. Chlorine gas molecules split apart, ∆HêLE[Al2O3(s)] + (-1676)
making chlorine atoms. Each chlorine atom accepts one electron
from a sodium atom becoming a chloride ion. The sodium ions and = +2(326) +3(249) + 2(+578)
+2(+1817) + 2(+2745)
chloride ions come together releasing energy as a solid ionic lattice
+3(-141) + 3(+798)
of sodium chloride forms. This is the white stuff observed at the
end of the reaction.
∆HêLE[Al2O3(s)] = +15326 kJ mole-1

Practice Questions
1. Calculate the lattice dissociation energy of calcium fluoride given
that its standard enthalpy of formation is -1220 kJ mol-1.

2. Calculate the lattice dissociation energy of aluminium oxide given

that its standard enthalpy of formation is -1676 kJ mol-1.

Acknowledgements: This Factsheet was researched and written by Vanessa

Kind. Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire,
TF1 1NU. ChemistryFactsheets may be copied free of charge by teaching
staff or students, provided that their school is a registered subscriber. No part
of these Factsheets may be reproduced, stored in a retrieval system, or
transmitted, in any other form or by any other means, without the prior
permission of the publisher. ISSN 1351-5136

4
 Chem Factsheet
www.curriculum-press.co.uk Number 103
Let EMMA Do Your Mole Calculations For You
After studying this Factsheet you should be able to successfully
complete any calculation based on moles that you meet. Note: Be sure that the units given are appropriate. In particular,
gaseous pressures are usually given in kilopascals (kPa) – these
This Factsheet deals with how to get your calculation steps in the would need to be converted to Pascals (Pa) by multiplying by
right order to get you from the problem to the answer. However, in 1000 before using 3(a). Similarly, volumes may need to be
order to do so, it is essential that you are able to calculate the number converted to cm3, dm3 or m3 as appropriate for 2, 3(a) or 3(b).
of moles of a substance in any given sample. These will usually be This can be done using:
one of three types: ×1000000

×1000 ×1000
1. A given mass (e.g. w g) of the sample of known relative molecular Volume in m3 Volume in dm3 Volume in cm3
mass (e.g. Mr). ÷1000 ÷1000

÷1000000
Number of moles (n) in sample = w ÷ Mr

Now you are confident that you can use (1)-(3) to calculate a
e.g How many moles of CaCO3 are present in a 2.735g sample? number of moles it is time to apply this to real problems where
information about one substance involved in a chemical reaction
Mr (CaCO3) = 40.1 + 12.0 + 3(16.0) = 101.1 allows you to calculate information about any other reactant or
Î Number of moles in sample = 2.735 ÷ 101.1 = 0.02705 product.

2. A given volume (e.g. V cm3) and molar concentration (e.g. It is the order of the calculation steps which often causes problems
C mol dm-3) for a sample in solution form. but this can be remembered using the acronym EMMA. This is
illustrated in the following table:
Number of moles (n) in sample = C × V
1000
E Write the balanced Equation for the reaction

e.g How many moles of NaOH are present in a 27.3 cm3 sample of Decide which reactant or product you know enough about
solution with concentration 0.0820 mol dm-3? to calculate it’s number of Moles (n). You will need :
(1) a formula to calculate Mr and a mass (w/g)
Number of moles in sample = 0.0820 × 27.3 ÷ 1000 = 2.24 × 10-3 or (2) a concentration, C (mol dm-3) and volume, V(cm3) for
3. (a) A volume (e.g. V m3), temperature (e.g. T K) and pressure a solution
(e.g. P Pa) for a sample in gaseous form [this may not apply to or (3a) a pressure, P(Pa), a volume, V(m3) and a temperature,
your syllabus – 3(b) may be used instead]. T(K) for a gas
or (3b) a volume, V(dm3) at room temperature and pressure
Number of moles (n) in sample = PV for a gas
RT
M Calculate the number of Moles for that known substance
e.g How many moles of gas are present in a 2343 cm3 sample at
300K and 95.0kPa? Decide which reactant or product is the target of your
calculation
Volume in m3 = 2343 ÷ 1000000 = 2.343 × 10-3 M Use the mole ratio from the balanced equation to calculate
Pressure in Pa = 95 ×1000 = 95000 the number of Moles of the target substance relative to the
95000 × 2.343 × 10-3 number of moles of the known substance calculated in the
Î Number of moles in sample = 8.31 × 300 = 0.0893
previous step
(b) A volume (e.g. V dm3) at room temperature and pressure for a Note : The equation is often given in the question. If not,
sample in gaseous form [this may not apply to your syllabus – ALWAYS attempt to write an equation because, even if
3(a) may be used instead. you get it wrong, use of the wrong reacting ratio will usually
cause you to lose only one of 4 or 5 marks.
e.g How many moles of gas are present in a 856 cm3 sample at
room temperature and pressure? A If required, convert this number of moles to the Answer
required by the question – this may be a concentration, a
Number of moles (n) in sample = V volume, a mass, a % purity etc. In general this will be done
24 using the relationships from (1), (2), (3a) or (3b).

Volume in dm3 = 856 ÷ 1000 = 0.856 Note in this general scheme, and in the examples that follow,
0.856 how one step in a calculation is always connected to the previous
Î Number of moles in sample = 24 = 3.57 × 10-2
step.

1
103 Let EMMA Do Your Mole Calculations For You Chem Factsheet

All that remains is to go through some worked examples and then

Example 4
try some examples for yourself.
A sample of impure magnesium metal weighing 1.238g was
Example 1 was dissolved in excess hydrochloric acid. 1167cm 3 of
25.0 cm3 of 0.100M potassium hydroxide (KOH) reacts with hydrogen gas was produced (a) at 98 kPa and 200C or (b) at
21.4 cm3 of hydrochloric acid (HCl) to form potassium chloride room temperature and pressure.
(KCl) and water. Calculate the concentration of the
hydrochloric acid in (a) mol dm-3 (b) g dm-3. NB 1167cm3 = 1.167dm3 = 0.000167m3
Equation: Mg(s) + 2HCI(aq) → MgCI2(aq) + H2(g)
Equation: KOH(aq) + HCl(aq) Æ KCl(aq) + H2O(l) PV
CV 0.100 × 25.0 (a) Moles of hydrogen =
RT
Moles of KOH = = = 0.0025
1000 1000 98000 × 0.001167
= = 0.04697
Moles of HCl = 0.0025 because the equation shows a 1:1 reaction 8.31 × 293
Moles of magnesium = 0.0497 because the equation shows one
n × 1000 mole of H2 is produced from one mole of Mg
Answer (a): Concentration of HCl = V
0.0025 × 1000 Answer: Mass of Mg in sample = n × Mr(Mg)
= = 0.117 mol dm-3
21.4 = 0.0497 × 24.1 = 1.132g
Answer (b): Concentration of HCl = C × Mr(HCl) = 0.117 × 36.5 Mass of pure Mg in sample
% purity of Mg = × 100
= 4.26 g dm-3 Mass of impure Mg sample
1.132 × 100
= = 91.4
1.238
Example 2 V 1.167
(b) Moles of hydrogen = = = 0.0486
When barium nitrate is heated it decomposes as follows: 24 24
Ba(N03)2(s) → BaO(s) + 2NO2(g) + ½O2(g) Moles of magnesium = 0. 0486 because the equation shows one
Calculate the total volume, measured at (a) 298 K and 100 kPa mole of H2 is produced from one mole of Mg
or (b) room temperature and pressure, of gas which is produced Answer: Mass of Mg in sample = n × Mr(Mg)
by decomposing 5.00 g of barium nitrate. = 0.0486 × 24.1 = 1.171g
Mass of pure Mg in sample
% purity of Mg = × 100
Equation: Ba(NO3)2(s) → BaO(s) + 2NO2(g) + ½O2(g) Mass of impure Mg sample
w 5.00 1.171 × 100
Moles of Ba(NO3)2 = = = 0.01916 = = 94.6
Mr 137 + 2( 14 + 3(16)) 1.238
Moles of gas = 0.01916 × 2½
= 0.04789 Example 5
because the equation shows that 1 mole of Ba(NO3)2 produces 2 Calculate the volume of 0.0200 mol dm -3 potassium
+ ½ moles of gas in total
manganate(VII) solution, KMnO4, that will react with 25.0cm3
nRT 0.04789 × 8.31 × 298
Answer (a): Volume of gas = = of acidified hydrogen peroxide, H2O2, which contains 1.92 gdm-3.
P 100000
= 0.00119m3 = 1.19dm3 The reaction equation is:
2MnO4- + 5H2O2 + 6H+ → 2Mn2+ + 8H2O + 5O2
Answer (b): Volume of gas = n × 24 = 0.04789 × 24 = 1.15 dm3

Equation: 2MnO4- + 5H2O2 + 6H+ → 2Mn2+ + 8H2O + 5O2

Example 3 C × V (1.92 ÷ Mr(H2O2) × 25.0
Moles of H2O2 = 1000 = 1000
A sample of titanium(IV) chloride was reacted with water as
shown in the following equation. (1.92 ÷ 34.0) × 25.0
= = 0.001412
TiCl4(l) + 2H2O(l) → 4HCl(aq) + TiO2(s) 1000
The reaction produced 250 cm 3 of a 1.50 M solution of 0.001412 × 2
Moles of KMnO4 = = 0.0005647
hydrochloric acid. Calculate the mass of TiCI4 used. 5
because the equation shows 5 moles of H2O2 react with only 2
Equation: TiCl4(l) + 2H2O(l) → 4HCl(aq) + TiO2(s) moles of MnO4-
CV 1.50 × 250
Moles of HCl = = = 0.375
1000 1000 Answer:
0.375 n 0.0005647 × 1000
Moles of TiCl4 = = 0.09375 Volume of 0.02 mol dm-3 KMnO4 = × 1000 =
4 C 0.0200
because the equation shows 4 moles of HCl are produced from = 28.2 cm3
only one mole of TiCl4.
Answer: Mass of TiCl4 = n × Mr(TiCl4) = 0.09375 × (45 + 4(35.5))
= 17.5 g

2
103 Let EMMA Do Your Mole Calculations For You Chem Factsheet

Practice Questions 5. The concentration of concentrated sulphuric acid can, after

Note : Hints are given for the first three examples but then you are accurate dilution, be checked by titration. A sample of the
on your own! Don’t be put off if the examples seem unfamiliar – concentrated sulphuric acid was analysed as follows:
EMMA helps you do ANY such calculation. (a) 10.0 cm3 of sulphuric acid was diluted with water to make 500
cm3 of solution.
(b) The diluted sulphuric acid was then titrated with aqueous
1. The mineral dolomite is a double carbonate of magnesium and sodium hydroxide, NaOH.
calcium, with the formula CaMg(CO3)2. When 1.200 g of an impure (c) In the titration, 25.0 cm3 of 0.100 mol dm-3 aqueous sodium
sample of dolomite was completely dissolved in an excess of hydroxide required 21.4 cm3 of diluted sulphuric acid for
hydrochloric acid, 0.450 g of carbon dioxide was given off. neutralisation.
Calculate the percentage purity of the dolomite.
Calculate the concentration, in mol dm-3, of the original conc.
sulphuric acid.
Equation: CaMg(CO3)2 + 4HCl → CaCl2 + MgCl2 + 2CO2 + 2H2O
6 A student reacted 1.45g of pure barium with 500cm3 of water.
Moles of CO2 =
Calculate the concentration of the barium hydroxide solution
produced and the volume of hydrogen gas measured at (a) room
Moles of CaMg(CO3)2 =
temperature and pressure or (b) 20°C and 100kPa.
Answer: Mass of CaMg(CO3)2 in sample =
7 Pure copper is needed for electrical purposes. The purity of a
sample of copper can be found by reacting it with concentrated
% purity of CaMg(CO3)2 =
nitric acid, neutralising the resulting solution and treating it
with excess potassium iodide. Iodine is liberated and this can be
titrated with standard sodium thiosulphate solution. The
2. When copper reacts with dilute nitric acid, gaseous nitrogen
sequence of reactions is:
monoxide is formed as shown by the following equation:
3Cu + 8HNO3 → 3Cu(NO3)2 + 4H2O + 2NO
Cu (s) + 4H+(aq) + 2NO3-(aq) Æ Cu2+(aq) + 2NO2(g) + 2H2O(l)
Calculate the volume in cm3 of nitrogen monoxide, measured at
2Cu2+(aq) + 4I-(aq) Æ 2CuI(s) + I2(aq)
(a) 330 K and 98.0 kPa or (b) room temperature and pressure,
which is formed when 1.25g of pure copper metal reacts
I2(aq) + 2Na2S2O3(aq) Æ 2NaI(aq) + Na2S4O6(aq)
completely with an excess of dilute nitric acid.
A copper foil electrode from an electric cell weighs 1.75 g. It was
Equation: 3Cu + 8HNO3 → 3Cu(NO3)2 + 4H2O + 2NO
made into 250 cm3 of a solution of copper(II) ions. To 25.0 cm3 of
this solution excess iodide ions were added, and the mixture
Moles of Cu =
titrated with 0.100 mol dm-3 sodium thiosulphate solution ; 26.8
cm3 was required. Calculate the percentage purity of the copper
Moles of NO =
foil.
Answer: (a) Vol of NO =
(b) Vol of NO = Answers
1. 78.5%
2. (a) 367cm3 or (b) 315 cm3
3. A 1.40g sample of 90.0% pure iron was reacted with an excess of 3. Your answer should be 18.82 cm3. If not, have you allowed for
dilute sulphuric acid. All of the iron in the sample was converted the % purity and / or the sample size?
into aqueous iron(II) ions and hydrogen was evolved. The 4. 3.49 gdm-3
solution formed was made up to 250cm3. A 25.0cm3 sample of 5. 2.92 moldm-3
this solution would react completely with how many cm3 of a 6. 0.0211 moldm-3 ; (a) 253cm3 (b) 257cm3
0.0200 moldm–3 solution of potassium dichromate(VI)). 7. 97.2%

Equations: Fe + 2H+ → Fe2+ + H2 then

Cr2O72- + 6Fe2+ + 14H+ → 2Cr3+ + 6Fe3+ + 7H2O

Moles of Fe =
Moles of Cr2O72- =
Acknowledgements: This Factsheet was researched and written by Mike Hughes
Answer: Vol of 0.02M Cr2O72- = Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire, TF1
1NU. ChemistryFactsheets may be copied free of charge by teaching staff or
4. A 25.0cm3 sample of a solution of phosphoric acid [H3PO4] was students, provided that their school is a registered subscriber. No part of these
found to react with exactly 19.8 cm3 of a 0.135 mol dm-3 solution Factsheets may be reproduced, stored in a retrieval system, or transmitted, in
any other form or by any other means, without the prior permission of the
of potassium hydroxide. Calculate the concentration of the publisher. ISSN 1351-5136
phosphoric acid solution in gdm-3.

3
 Chem Factsheet
www.curriculum-press.co.uk Number 104
A FEW H’s Will Produce Any Half-Equation
After studying and working your way through this Factsheet you
Remember: There is a hierarchy of rules, descending in
should be confident that you can write any half-equation that is
priority from 1 to 6.. Hence the “exceptions” in rules 5 and 6
required.
because earlier rules must be given priority.
Before proceeding with this, let’s summarise the important background
information, definitions and ideas which you will need to achieve It is vital that half-equations are balanced both for atoms and overall
this. electrical charge. The most common error is to forget the charge
balance. For example,
Definitions NO3- + 4H+ + e- → NO + 2H2O
Redox reactions involve both reduction and oxidation processes
Oxidation is loss of electrons represents the reduction (electron gain) of nitrate (NO3- ) to nitrogen
Reduction is gain of electrons monoxide (NO). It balances in terms of atoms but not in terms of
Oxidation involves an increase in oxidation state (number) charges. Check it. The FEW H’s method for constructing half-
Reduction involves an decrease in oxidation state (number) equations will automatically balance both atoms and charges.
An oxidising agent (or oxidant) is an electron acceptor
A reducing agent (or reductant) is an electron donor The FEW H’s Method
This is merely a way of remembering the steps, and the order of those
Note: These definitions mean that, during the course of a redox steps, required to form a balanced half-equation. There are up to four
reaction, the oxidant will be reduced and the reductant will be steps in every case ; these are prompted by the acronym “FEWH”
oxidised where “F”, “E”, “W” and “H” represent the steps shown below.

Any redox reaction must involve a reduction (electron gain) part and F Write the Formulas of the reduced or oxidised particle
an oxidation (electron loss) part. A half-equation shows either the and the particle produced, on opposite sides of an
reduction or the oxidation process separately. A reduction half- equation
equation will contain electrons on the left-hand side (accepting) whilst e.g. NO3- Æ NO
an oxidation half-equation will contain electrons on the right-hand
E Insert the appropriate number of Electrons into the
side (losing).
equation. This is given by the change in oxidation
e.g. A reduction half-equation : Cu2+ + 2e- → Cu number of the particles shown above. Electrons go on
e.g. An oxidation half-equation : Zn → Zn2+ + 2e- the left for a reduction and on the right for an
oxidation.
Remember: If you reverse a reduction half equation, it becomes
NO3- Æ NO involves N(+5) changing to N(+2) oxidation
an oxidation half-equation, and vice-versa.
state. This shows the process is a reduction and that 3
e.g. 2H+ + 2e- Æ H2 represents a reduction but H2 Æ 2H+ + 2e- electrons must be involved in the final half-equation.
represents an oxidation e.g. NO3- + 3e- Æ NO
W Insert the appropriate number of Water molecules
Oxidation states (numbers) provide a quick way to work out if
into the equation so that oxygen atoms are made to
oxidation and reduction has taken place before attempting to write a
balance.
half-equation. Each atom in a reaction is assigned an oxidation number
by using a set of arithmetic rules which are shown below ; if this NO3- + 3e- Æ NO shows a shortage of 2 O atoms on
number increases (oxidation) or decreases (reduction) during the the right. Hence, 2H2O is inserted on the right.
reaction then redox processes are easily spotted. e.g. NO3- + 3e- Æ NO + 2H2O
Rules: H Insert the appropriate number of Hydrogen ion into
1. In all uncombined ELEMENTS, an atom’s oxidation number = 0 . the equation so that hydrogen atoms are made to
2. In all COMPOUNDS, the sum of all the oxidation numbers of all the balance
atoms equals zero. NO3- + 3e- Æ NO + 2H2O shows a shortage of 4 H
3. In all IONS, the sum of all the oxidation numbers of all the atoms atoms on the left. Hence, 4H+ are inserted on the left
equals the charge on the ion. e.g. NO3- + 4H+ + 3e- Æ NO + 2H2O This automatically
4. In all COMPOUNDS, group 1 elements have oxidation number +1, completes the fully balanced half-equation.
group 2 elements have oxidation number +2, group 3 elements
have oxidation number +3 and fluorine (F) has oxidation number -1.
5. In most COMPOUNDS hydrogen has an oxidation state of +1 except
Simple half-equations such as Cu2+ + 2e- Æ Cu and Zn Æ
in MHn where the metal M will have the positive oxidation number
Zn2+ + 2e- do not need the “W”and”H” steps but “F” and “E”
(+n) and and H will be -1.
still apply. In fact, such examples can usually be done simply by
6. In most COMPOUNDS oxygen has an oxidation state of -2 except
inspection! In general, 2 or 4 of the FEWH steps will be needed
in F2O where F must be -1 (rule 4) causing O to be +2 and peroxides
but never 1 or 3.
(O22-) where the oxidation number is -1 (rule 3)
1
104. A FEW H’s Will Produce Any Half-Equation Chem Factsheet

Half-equations involving H + imply acidic conditions. The 4. F MnO4- → Mn2+

corresponding half-equation in alkaline conditions can be formed E MnO4- → Mn2+ involves Mn(+7) changing to Mn(+2)
by adding the corresponding number of OH- ions to each side of oxidation state. This shows the process is a reduction and
the “acidic” half-equation and then cancelling the water that 5 electrons must be involved on the left in the final
molecules. half-equation.
NO3- + 4H+ + 3e- → NO + 2H2O becomes MnO4- + 5e- → Mn2+
NO3- + 4H+ + 4OH- + 3e- → NO + 2H2O + 4OH- W MnO4- + 6e- → Mn2+ shows a shortage of 4 O atoms on
Î NO3- + 4H2O + 3e- → NO + 2H2O + 4OH- the right. Hence, 4H2O is inserted on the right.
Î NO3- + 2 H2O + 3e- → NO + 4OH- MnO4- + 5e- → Mn2+ + 4H2O

Some Further Examples H MnO4- + 5e- → Mn2+ + 4H2O shows a shortage of 8 H

Construct fully balanced half-equations for each of the following atoms on the left. Hence, 8H+ are inserted on the left
changes MnO4- + 8H+ + 5e- → Mn2+ + 4H2O
1. Cl2 to ClO- in alkaline solution
2. BrO3- to Br- in acid solution 5. F Cr2O72- → 2Cr3+ (note how 2 moles of Cr3+ must be
3. Sn to SnO2 in alkaline solution formed)
4. MnO4- to Mn2+ in acid soution
5. Cr2O72- to Cr3+ in acid solution. E Cr2O72- → 2Cr3+ involves 2Cr(+6) changing to 2Cr(+3)
oxidation state. This shows the process is a reduction and
1. F Cl2 → 2ClO- (note how 2 moles of ClO- must be formed) that 6 electrons electrons must be involved on the left in
E Cl2 → 2ClO- involves 2Cl(0) changing to 2Cl(+1) oxidation the final half-equation. Cr2O72- + 6e- → 2Cr3+
state. This shows the process is an oxidation and that 2 W Cr2O72- + 6e- → 2Cr3+ shows a shortage of 7 O atoms on
electrons must be involved on the right in the final half- the right. Hence, 7H2O is inserted on the right.
equation. Cl2 → 2ClO- + 2e- Cr2O72- + 6e- → 2Cr3+ + 7H2O
W Cl2 → 2ClO- + 2e- shows a shortage of 2 O atoms on the H Cr2O72- + 6e- → 2Cr3+ + 7H2O shows a shortage of 14
left. Hence, 2H2O is inserted on the left. Cl2 + 2H2O → H atoms on the left. Hence, 14 H+ are inserted on the left
2ClO- + 2e- Cr2O72- + 14H+ + 6e- → 2Cr3+ + 7H2O

H Cl2 + 2H2O → 2ClO- + 2e- shows a shortage of 4 H atoms Now try a few examples for your self:
on the right. Hence, 4H+ are inserted on the right.
Cl2 + 2H2O → 2ClO- + 4H+ + 2e- Practice Questions
Î Cl2 + 4OH- + 2H2O Æ 2ClO- + 4H+ + 4OH- + 2e- 1. I2 to IO4- in alkaline solution
Î Cl2 + 4OH- → 2ClO- + 2H2O + 2e- 2. H2SO4 to H2S in acid solution
3. NO2 to NO3- in alkaline solution
2. F BrO3- → Br- 4. VO3- to V2+ in acid soution
5. RCHO (an aldehyde) to RCOOH (an acid) in alkaline solution.
E BrO3- → Br- involves Br(+5) changing to Br(-1) oxidation [Hint ; assign oxidation state 0 to the R group since it remains
state. This shows the process is a reduction and that 6 unchanged]
electrons must be involved on the left in the final half-
equation. BrO3- + 6e- → Br- Answers
W BrO3- + 6e- → Br- shows a shortage of 3 O atoms on the 1. I2 + 16OH- → 2IO4- + 8H2O + 14e-
right. Hence, 3H2O is inserted on the right. 2. H2SO4 + 8H+ + 8e- → H2S + 4H2O
BrO3- + 6e- → Br- + 3H2O 3. NO2 + 2OH- → NO3- + H2O + e-
4. VO3- + 6H+ + 3e- → V2+ + 3H2O
H BrO3- + 6e- → Br- + 3H2O shows a shortage of 6 H
5. RCHO + 2OH- → RCOOH + H2O + 2e-
atoms on the left. Hence, 6H+ are inserted on the left
BrO3- + 6H+ + 6e- → Br- + 3H2O

3. F Sn → SnO2
E Sn → SnO2 involves Sn(0) changing to Sn(+4) oxidation
state. This shows the process is an oxidation and that 4
electrons must be involved on the right in the final half-
equation. Sn → SnO2 + 4e-
W Sn → SnO2 + 4e- shows a shortage of 2 O atoms on the
left. Hence, 2H2O is inserted on the left.
Sn + 2H2O → SnO2 + 4e- Acknowledgements: This Factsheet was researched and written by Mike Hughes
Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire, TF1
H Sn + 2H2O → SnO2 + 4e- shows a shortage of 4 H atoms 1NU. ChemistryFactsheets may be copied free of charge by teaching staff or
on the rightt. Hence, 4H+ are inserted on the right students, provided that their school is a registered subscriber. No part of these
Sn + 2H2O → SnO2 + 4H+ + 4e- Factsheets may be reproduced, stored in a retrieval system, or transmitted, in
any other form or by any other means, without the prior permission of the
Î Sn + 4OH- + 2H2O → SnO2 + 4H+ + 4OH- + 4e-
publisher. ISSN 1351-5136
Î Sn + 4OH- → SnO2 + 2H2O + 4e-
2
 Chem Factsheet
www.curriculum-press.co.uk Number 105

Logs and Powers in Chemistry

Logs (short for logarithms) and powers are closely related. Logs Logarithms
arise in chemistry in the calculation of pH and powers are encountered
in expressions for equilibrium constants and rate equations. This The logarithm or log (to the base of 10) of a number is
Factsheet is concerned with explaining what logs and powers are defined as the power to which we have to raise 10 to give us
and how to calculate with them. It is not a sheet on pH calculations that number.
or rate equations - these are dealt with elsewhere.
If we look at the table of powers of 10:
Powers of 10
Number (n) Number in power form log10 n
Consider the following numbers:
100 1000 103 3
1000 100 102 2
10000 10 101 1
These can of course be written as follows: 1 100 0
100 = 10 × 10 0.1 10-1 -1
1000 = 10 × 10 × 10 0.01 10-2 -2
10000 = 10 × 10 × 10 × 10 0.001 10-3 -3

And these can be written as powers of 10: The entry in the third column is simply the power of the number in
100 = 10 ×10 = 102 the second column and it is the number in the third column which
1000 = 10 × 10 × 10 = 103 is called the log. 10 is referred to as the base of the log. We can
10000 = 10 × 10 ×10 × 10 = 104 use other numbers as the base but for working out pH calculations
where 102 means two tens multiplied together (10 × 10), 103 means we always use base 10.
three tens multiplied together (10 × 10 × 10) and so on.
Question 1. (a) What is log10 of 10000? (b) What is log10 0.00001?
We can extend this sequence of number upwards as far as we like by
continuing to multiply by ten. Each time we multiply by ten we add So it is quite easy to find the log of a number to the base of 10 so
one to the power, 100000 = 105 and so on. long as the number is a whole number power of 10. What happens
if we need to find the log of a number such as, say, 500 or 0.0027
However, what happens if we extend the sequence in the other
which is between the numbers in the table above? It is actually
direction? If we go from 1000 to 100 we are dividing by 10 and the
quite difficult to work out these logs but fortunately it can be
number in power form goes from 103 to 102. Each time we divide by 10
done on a scientific calculator.
we subtract 1 from the power. So the sequence goes like this (going
downwards):
For example, a calculator shows that the log10 of 500 is 2.699 ( to 3
decimal places). If we were to put this number in the table it would
Number Number in Power Form
be between 100 and 1000 and so the log would be between 2 and 3:
1000 = 103
100 = (1000 ÷ 10) = 102 Number(n) Number in power form log10 n
10 = (100 ÷ 10) = 101 3
1000 10 3
1 = (10 ÷ 10) = 100
500 102.699 2.699
0.1 = (1 ÷ 10) = 10-1
100 102 2
0.01 = (0.1 ÷ 10) = 10-2
0.001 = (0.01 ÷ 10) = 10-3
Similarly, a calculator shows that the log10 of 0.0027 is -2.569 (to 3
decimal places). Putting this number in the table would give:
There are several things we can see from this table.
1. 101 is just 10. This is true for any number - any number raised to
Number(n) Number in power form log 10 n
the power of 1 is just itself.
2. 100 is just 1. Again this is true for any number. Any number to the 0.01 10 −2
−2
power of 0 is 1. 0.0027 10−2.569 −2.569
3. 10 to the power of a negative number is 1 divided by 10 to the 0.001 10−3 −3
positive power (sometimes called the reciprocal). So
Notice that the logs of numbers less than 1 are always
10-1 = 1/101 = 1/10 = 0.1 negative. Notice also that we cannot have a log of a negative
10-2 = 1/102 = 1/100 = 0.01 number. If you try it on your calculator you will get an error
10-3 = 1/103 = 1/1000 = 0.001 meassage.

1
105. Logs and Powers in Chemistry Chem Factsheet

Using a calculator to find logs Example (1): Calculate the pH of a solution of hydrochloric acid
Virtually all scientific calculators can be used to find logs. On whose hydrogen ion concentration is 0.010 mol dm-3.
modern calculators it is simply a matter of pressing the “log” key,
Answer:
typing in the number and pressing “=”. (On older scientific
The concentration of hydrogen ions is represented as [H+]
calculators it was necessary to type in the number first and then
[H+] = 0.010
press the log key. Check in the instructions for your calculator
pH = -log10[H+]
which way to do it.)
= -log10 0.010
= 2.00
NB Be sure to press the key marked “log” and not the key (using a calculator or using the table on previous page. Don’t forget
marked “ln”. The “ln” key gives logs to a different base and to change the sign.)
would give the wrong answers in pH calculations.
Example (2): Calculate the pH of a solution of nitric acid whose
hydrogen ion concentration is 0.0050 mol dm-3.
Question 2 Use your calculator to find :
Answer: [H+] = 0.0050
(a) log10 12.345? (b) log10 0.012345 (give your answers to 3 d.p.)
pH = -log10[H+]
Inverse logs = -log10 0.0050
In calculations on pH we often need to take the inverse log of a = 2.30 (using a calculator)
number. In other words, find a number whose log is given.
Example (3): Calculate the pH of a solution of sulphuric acid whose
For example, find the inverse log of 0.301. hydrogen ion concentration is 1.00 mol dm-3.
What this means is, “find the number whose log is 0.301”, or to put Answer: [H+] = 1.00
it algebraically, “if log10 x = 0.3010, what is x?” pH = -log10[H+]
= -log10 1.00
From the definition of logs we know that the log of a number is the = 0.00
power to which we have to raise 10 to give us that number. So if the
log of the number is 0.301 then the number itself must be 100.301. Example (4): Calculate the pH of a solution of sodium hydroxide
whose hydrogen ion concentration is 3.00 × 10−11 mol dm−3.
We can again find inverse logs on a scientific calculator. On modern
calculators press the “shift” key and then the “log” key. (It is Answer: [H+] = 3.00 × 10−11
usually marked as 10x). Then enter the number and press “=”. pH = -log10[H+]
= -log10 (3.00 × 10−11) (enter as (-)/log/3/EXP/(-)/11.
In this case, the inverse log of 0.301 is 100.301 = 1.9999 (= 2.00 to 3 You don’t need to put the 10
significant figures). = 10.52 in – the calculator does it for you)
In general if n = log10 x, then x = 10n. Inverse logs are also sometimes
called antilogs. Example (5): A solution has a pH of 2.50. What is the concentration
of hydrogen ions in the solution?
Question 3. Using your calculator:
Answer: To do this we need to find the inverse log of -2.50
(a) What is the inverse log of 4?
(b) What is the antilog of 2.35 pH = 2.50
(c) What is the number whose log is -2.5? -log10[H+] = 2.50 (from the definition of pH)
(d) Calculate 100.35 log10[H+] = -2.50 (change the signs)
(e) If log10 x = −1.65 what is x? [H+] = 10−2..5 (don’t forget the minus sign)
(Give your answers to 3 significant figures) [H+] = 3.16 × 10−3 (find the inverse log using a calculator)

Using logs in pH calculations i.e. the hydrogen ion concentration of a solution whose pH is 2.5 is
pH is a measure of the concentration of hydrogen ions in a solution. 3.16 × 10−3 mol dm-3
Logs are used in pH calculations to make the numbers used for
small concentrations of hydrogen ions easier to handle. Since most Example (6): A solution has a pH of 7.00. What is the concentration
(though not all) of the concentrations of hydrogen ions that we of hydrogen ions in the solution?
come across in chemistry are less than one, the log of the hydrogen Answer: pH = 7.00
ion concentration would be a negative number. So, again, to give [H+] = 1.00 × 10−7
us easier numbers, the pH is taken to be the negative log of the
hydrogen ion concentration. i.e. the hydrogen ion concentration of a solution whose pH is 7 is
1.00 × 10−7 mol dm-3
pH is defined as the negative logarithm to the base 10
Example (7): A solution has a pH of 12.30. What is the concentration
of the hydrogen ion concentration or in symbols:
of hydrogen ions in the solution?
pH = -log10[H+]
Answer: pH = 12.30
where [H+] is the hydrogen ion concentration of a solution in [H+] = 10−12.5
mol dm-3 [H+] = 5.01 × 10−13
i.e. the hydrogen ion concentration of a solution whose pH is 12.30
is 5.01 × 10−13 mol dm-3

2
105. Logs and Powers in Chemistry Chem Factsheet

Logs to other bases Example (8) A reaction is first order with respect to a reactant P
Although pH calculations always use 10 as the base for logs, in and first order with respect to a reactant Q. It has the rate equation
other areas of chemistry logs to the base e are used. (e is a number rate = k[P][Q] The concentrations of P and Q are measured in
which has some special mathematical properties and has a value of mol dm−3. and the reaction rate is measured in mol dm−3 s−1
approximately 2.718.) These logs are sometimes called natural logs
and are often given the symbol ln or loge. Although you may see (a) What is the overall order of the reaction? (b) What are the
these logs in your reading and on calculators, you will not be required units for the rate constant?
to use them in current A level examinations.
Answer:
Powers (a) The overall order of the reaction is the sum of the orders with
respect to each of the reactants which in this case is 2.
When the same number is multiplied together several times we can
express this by writing it as a power. (b) The units must be equal on each side of the rate equation.
For example, 2×2 = 22 = 4,
mol dm-3 s-1 = units for k × mol dm-3 × mol dm-3
10 × 10 × 10 × 10 = 104 = 10000,
1.5 × 1.5 × 1.5 = 1.53 = 3.375 The units for k are found by rearranging the equation to give
mol dm-3 s-1
As we saw earlier any number raised to the power of 1 is itself. e.g. units for k =
(mol dm-3 × mol dm-3)
31 = 3
Any number raised to the power of 0 is 1. e.g. 50 = 1 This can be simplified to give:
Any number raised to a negative power is 1 divided by (or the
reciprocal of) the number raised to the positive power. e.g. 3-2 = 1/32. mol dm-3 s-1
units for k = (multiply by adding powers)
(mol2 dm-6)
Numbers expressed as powers can be multiplied by units for k = mol-1 dm3 s-1 (divide by subtracting powers)
adding their powers.
Finally, for reference, here is a summary of some important equations
used for handling powers.
e.g. 2 × 2 = 2
3 2 5
(adding the powers 2 + 3)
We can see that this is so because 23 = 2 × 2 × 2 and 22 = 2 × 2
and so 23 × 22 = (2 × 2 × 2) × (2 × 2 ) = 25
Multiplication of powers am × an = am+n
Numbers expressed as powers can be divided by
subtracting their powers. Division of powers am ÷ an = am-n
Powers of powers (am)n = amn
e.g. 26 ÷ 24 = 22
We can see that this is so because 26 = 2 × 2 × 2 × 2 × 2 × 2 and Roots of powers n
√(am) = am/n
24 = 2 × 2 × 2 × 2 Also remember a0 = 1
and so 26 ÷ 24 = (2 × 2 × 2 × 2 × 2 × 2 ) ÷ (2 × 2 × 2 × 2) = 2 × 2 = 22 a1 = a
a-n = 1/an
NB 26 ÷ 24 could also be written as 26 × 1/(24) or 26 × 2-4
These rules are also true for powers which are not whole numbers.
e.g. 43.7 ÷ 41.7 = 42 (you would have to use a calculator to check this) Answers to questions in text

Numbers expressed as powers can be raised to a power 1. (a) 4.00

by multiplying the powers together. (b) -5.00

e.g. (22)3 = 26 (the powers 2 and 3 are multiplied to give 6) 2. (a) 1.091
(b) -1.909
We can see that this is so because 22 = 2 × 2 and (22)3
= (22) × (22) × (22) 3. (a) 104 or 10000
and so (2 ) = (2 × 2) × (2 × 2) × (2 × 2) = 26
2 3
(b) 224
(c) 3.16 × 10-3
We can take roots of a number expressed as a power (d) 2.24
by dividing the powers. (e) 0.0224

e.g. √(26) = 23 (divide the power 6 by the root 2)

We can check this because 26 = 2 × 2 × 2 × 2 × 2 × 2 = 64 and the

square root of 64 is 8 which is 23.
Roots can also be written as a number raised to a fraction so √10
could be written as 101/2, the cube root of 8 could be written as 81/3

3
105. Logs and Powers in Chemistry Chem Factsheet

Practice Questions
1. Find the log to the base 10 to the following numbers. Give your answer to 3 decimal places.
(a) 100
(b) 0.01
(c) 5
(d) 0.05
(e) 500
(f) 0.00135
(g) 10-3
(h) 2.35 × 10-5
(i) 2.35 × 105
(k) 6.02 × 10-14

2. Find the inverse log of the following. Give your answer to three significant figures.
(a) 3
(b) -2
(c) 3.25
(d) -2.73
(e) 0

3. Calculate the pH of the following solutions. Give your answer to 2 decimal places.
(a) A solution of hydrochloric acid whose hydrogen ion concentration 0.0010
(b) A solution of nitric acid whose hydrogen ion concentration 0.0025
(c) A solution of propanoic acid whose hydrogen ion concentration 1.20 × 10-3
(d) A solution of sodium hydroxide whose hydrogen ion concentration 1.00 × 10-13
(e) A solution of potassium hydroxide acid whose hydrogen ion concentration 2.35 × 10-14

4. Calculate the hydrogen ion concentration of the following solutions. Give your answer to three significant figures.
(a) A solution of hydrochloric acid whose pH is 2.00
(b) A solution of ethanoic acid whose pH is 3.50
(c) A solution of iron(II) sulphate whose pH is 6.10
(d) A solution of sodium hydroxide whose pH is 14.00
(e) A solution of ammonia whose pH is 11.50

5. Simplify the following expression:

(a) mol dm-3 × mol dm-3
(b) mol2 dm-6 × mol dm-3
(c) mol dm-3 ÷ mol2 sm-6
(d) (mol dm-3 × mol2 dm-6) ÷ mol dm-3
(e) (mol dm-3)2

Answers
1. (a) 2 (b) -2 (c) 0.699 (d) -1.301 (e) 2.699
(f) -2.870 (g) -3 (h) -4.629 (i) 5.371 (k) -13.221
2. (a) 103 or 1000 (b) 10-2 or 0.01 (c) 1780 (d) 1.86 × 10-3 (e) 1
3. (a) 3.00 (b) 2.60 (c) 2.92 (d) 13.00 (e) 13.63
(If you use a calculator to work out 3(d) be sure to enter ”log 1 EXP -13” and not ”log 10 EXP -13”. The calculator interprets 10 EXP -13 as
10 × 10-13 = 10-12. But you shouldn’t need a calculator for this anyway!)
4. (a) 1.00 × 10-2 (b) 3.16 × 10-4 (c) 7.94 × 10-7 (d) 1.00 × 10-14 (e) 3.16 × 10-12
5. (a) mol2 dm-6 (b) mol3 dm-9 (c) mol-1 dm+3 (d) mol2 dm-6 (e) mol2 dm-6

Acknowledgements: This Factsheet was researched and written by Mike Hughes.Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire, TF1
1NU. ChemistryFactsheets may be copied free of charge by teaching staff or students, provided that their school is a registered subscriber. No part of these
Factsheets may be reproduced, stored in a retrieval system, or transmitted, in any other form or by any other means, without the prior permission of the
publisher. ISSN 1351-5136

4
 Chem Factsheet
www.curriculum-press.co.uk Number 106
AS Chemical bonding: Intermolecular bonds
This Fact sheet is designed to help develop your understanding of “Intermolecular” bonds are found between atoms and molecules.
intermolecular bonding – bonds that form between particles. After To start, check your understanding by answering these two
a brief word about terminology, the areas covered are:- questions.
• Check your understanding about intermolecular bonds
Check your understanding about intermolecular bonds
• Hydrogen bonds
• Permanent dipole- permanent dipole (PDPD) bonds Boiling Chlorides
• Instantaneous dipole – induced dipole bonds (IDID) bonds When water boils, bubbles The bonding in magnesium
(“van der Waals forces”) appear in the liquid. chloride (MgCl ) is ionic. The
• Exam questions and answers on intermolecular bonds 2
bonding in titanium(IV)
What is in the bubbles? chloride is covalent.
Exam questions and answers are included. Don’t forget to complete
A mixture of the two chlorides
your knowledge of chemical bonding by reading Chem Factsheet
is heated to 1000oC.
107 on intramolecular bonds.
Explain why the vapour
A word about terminology – what are “they” called? above the heated mixture
Chemists are inconsistent about the names for bonds between consists only of titanium(IV)
particles. The terms “forces”, “attractions” and “forces of attraction” chloride.
are used to describe them. Some are given specific names - you
may (or may not) have heard of “van der Waals forces”, “London Full answers are given at the end of the fact sheet.
forces” and “dipole-dipole attractions”. To be consistent, this
FactSheet calls them “bonds” and uses names that say exactly Intermolecular bonds are responsible for many physical properties
what they are. Our view is that this is most helpful for you, as these we observe. In water (see the “Boiling” question above),
names make the origins of the bond types clear and so are easier to intermolecular bonds break when water boils, creating water vapour.
remember. The names we have used will also help you realise that The molecules themselves stay as H 2 O. In “Chlorides”
all bonds involve attractions between positively and negatively intermolecular bonds between titanium(IV) chloride molecules break,
charged particles – its just the particles and the origins of the positive creating the vapour. Again the molecules stay intact as TiCl4. The
and negative charges that differ. Examiners, as chemists, are aware strong ionic lattice of magnesium chloride does not break up at this
of alternative names and credit accordingly. temperature.

Hydrogen bonds
Hydrogen bonds arise when hydrogen atoms are covalently bonded to a highly electronegative atom, namely nitrogen, oxygen or
fluorine. For similar size molecules they are the strongest of all intermolecular bonds. The strength arises because the hydrogen atom has
no other electrons to shield the nucleus, so when distortion of the electron cloud occurs the nucleus is left very exposed, creating a large
permanent dipole. The other, negatively charged atom always has one or more lone pairs of electrons. When opposite ends of two
molecules approach each other a bond is formed between the hydrogen atom on one molecule and the nitrogen, oxygen or fluorine atom
on the other molecule that is 90% ionic and 10% covalent. In water, this requires typically about 25 kJmol-1 to break.

Simple molecular compounds with hydrogen bonds: Ammonia, NH3; water, H2O; hydrogen fluoride, HF.
Giant molecular compounds with hydrogen bonds: the polymers DNA, nylon and Kevlar®, also proteins
Drawing hydrogen bonds between particles is a common exam question. Here are two examples.

What the diagram shows Hydrogen bonding in… What to do in an exam

Permanent dipoles exist in water molecules due Water Hydrogen bond Show at least two water molecules
to the large difference in electronegativity δ+ δ+
Draw 2 lone pairs on each oxygen atom
between hydrogen and oxygen. H H
.. .. Show the dipoles clearly
The hydrogen bond forms between the O δ− O δ−
hydrogen atom on one molecule and an oxygen
.. .. Show the hydrogen bond clearly
H H
atom in another. δ+ δ+
A permanent dipole exists in hydrogen fluoride Hydrogen Fluoride Show at least two hydrogen fluoride
molecules due to the large difference in molecules.
electronegativity between hydrogen and Hydrogen bond
.. δ− δ+
.. δ−
Draw 3 lone pairs on each fluorine
fluorine. δ+

H F .. H F .. atom.
The hydrogen bond forms between the ..
hydrogen atom on one molecule and the .. Show the dipoles clearly!
fluorine atom in another. Show the hydrogen bond.

1
106. AS Chemical bonding: Intermolecular bonds Chem Factsheet

Permanent dipole – permanent dipole bonds (PDPD bonds) The opposites attract, creating a short-lived IDID bond. When the
PDPD bonds arise between molecules with permanent dipoles. electron clouds rearrange, an IDID bond will form between two
When “opposite” ends of two molecules meet, a bond forms between other atoms. IDID bonds also form between molecules. Although
them. These bonds require about 5kJmol-1 to break. any one IDID bond has a very small dissociation enthalpy, when
there are millions of IDID bonds their effects can be extreme.
• Simple molecular compounds with PDPD bonds: hydrogen
chloride, HCl; chloromethane, CH3Cl; hydrogen sulphide, H2S • Typical examples of simple compounds or elements with IDID
• Giant molecular compounds with PDPD bonds: polyvinylchloride bonds: liquified inert gas atoms; halogen molecules; low carbon
(PVC); some proteins alkanes
• Giant structures with IDID bonds: all polymers; long chain fat
Instantaneous dipole – induced dipole bonds (IDID bonds) molecules; high carbon alkanes; iodine; graphite (between layers)
These are often rather confusingly called “Van der Waals forces”
after the chemist who proposed their existence. IDID bonds arise Remember: IDID bonds are found in every substance – they
because the electron cloud around, for example, an atom is not are universal. Instantaneous dipoles arise around any atom and
always evenly distributed. At any instant, a dipole may exist across can induce a dipole in any neighbouring atom or molecule.
the two sides of the atom. If a second atom gets close enough, its
electron cloud will be distorted by the dipole on the first atom,
creating an “induced” dipole.

Exam questions and answers on intermolecular bonds

These are questions examiners have asked specifically about intermolecular bonding in recent AS exams. Make the most of this section by
covering up the “Answer” column and writing your own answers, taking note of the number of marks available. All the answers can be
found in this Factsheet.

Question Marks Answer

Iodine and diamond are both crystalline solids at 4 Both have covalent bonding.(1)
room temperature. Identify one similarity in the IDID bonds exist between iodine molecules requiring relatively little
bonding. Explain why they have very different energy to break (1)
melting points. Covalent bonds exist between carbon atoms in diamond (1)
requiring much more energy to break (1)
(part question)
Name the strongest type of intermolecular “force” 3 Hydrogen bonding (1)
between hydrogen fluoride molecules.
Suggest why these bonds are not present
between HI molecules. Fluorine is more electronegative than iodine (1)
So the dipole is weaker in HI creating less strong intermolecular bonds
(part question) (1)
The halogens all have van der Waals forces. 3 Uneven distribution of electrons around an atom/molecule creates an
Explain how van der Waals forces are formed. instantaneous dipole. (1)
This induces a dipole (1)
(part question) to form on a neighbouring atom/molecule. (1)
H2O, HCl, and Ar all have van der Waals forces. 2 An uneven distribution of electrons around an atom creates an
Outline how these arise between molecules instantaneous dipole. (1)
This induces a dipole to form on a neighbouring molecule. (1)
Describe the nature of hydrogen bonding in 3 An oxygen atom of one molecule bonds to the hydrogen atom (can be a
water. diagram) (1)
(part question) Dipole exists in the H-O bond: δ+H - Oδ− (1)
Explain with the aid of a diagram how hydrogen 5 H2O molecules are polar (1)
bonds arise between molecules of H2O(l) Dipole in water molecule shown correctly (1)
H-bond between hydrogen and oxygen in another H2O molecule (1)
Oxygen is very electronegative (1)
Oxygen has lone pairs (1) (see diagram on page 1)
Draw a diagram to show how two molecules of 3 At least one ? + H and at least one ? -F shown (1)
HF are attracted to each other. 3 lone pairs shown on at least one fluorine atom (1)
H bond shown between H and a lone pair on F in a different molecule (1)

2
106. AS Chemical bonding: Intermolecular bonds Chem Factsheet

Answers to introductory questions

Boiling
Boiling is a change of state. Water molecules change from the liquid state to the gaseous state. Hydrogen bonds between molecules are
broken in the process. Gaseous water is called “steam”. The bubbles contain steam, since the hydrogen bonds between water molecules
break when water boils.

Correct answers: Steam, water vapour, gaseous water

Possible incorrect answers: Oxygen; dissolved gas; Heat, energy; Carbon dioxide; Hydrogen; Oxygen; and /or hydrogen; Nothing /
vacuum

Chlorides
Small induced dipole- dipole bonds between covalent molecules require much less energy to break than the bonds present in an ionic
lattice. Intermolecular bonds between TiCl4 molecules require relatively little energy to break them compared to that required to break up
the ionic lattice.

Correct answer: Intermolecular bonds between TiCl4 molecules break. Intermolecular bonds in ionic solids are much stronger.

Possible incorrect answers: Covalent substances have lower boiling points; Ionic bonds can’t be broken by heating; MgCl2 ionises;
Covalent bonds are weaker than ionic ones so break; Covalent bonds are stronger than ionic ones of MgCl2

Acknowledgements: This Factsheet was researched and written by Vanessa Kind. Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire, TF1
1NU. ChemistryFactsheets may be copied free of charge by teaching staff or students, provided that their school is a registered subscriber. No part of these
Factsheets may be reproduced, stored in a retrieval system, or transmitted, in any other form or by any other means, without the prior permission of the
publisher. ISSN 1351-5136

3
 Chem Factsheet
www.curriculum-press.co.uk Number 107
AS Chemical bonding: Intramolecular bonds
This fact sheet is designed to help you check your understanding about intramolecular bonding – bonds that form within molecules. The
areas covered are:-
• Bonding: why do bonds form?
• Intramolecular bonds: the extremes and “in-betweens” –e.g. ionic, covalent, polar covalent
• Bonding in metals – a special case
• Drawing “dot-and-cross” diagrams for ionic and covalent bonds
• Exam questions and answers on intramolecular bonds
Exam questions and answers are included. Don’t forget to complete your understanding of chemical bonding by reading Chem Factsheet
106 on intermolecular bonds.

Bonding: why do bonds form?

Check your understanding by trying this question.

Methane
Natural gas is mainly methane, CH4.
Explain as clearly as you can why carbon and hydrogen form molecules with the formula CH4 rather than CH3, CH2 or CH.

The full answer is given at the end of the FactSheet.

Bonds form because making bonds lowers the overall energy of the particles involved. For example, methane molecules exist as CH4
because this is the most energetically favoured arrangement for 1 carbon atom bonding with hydrogen atoms. So, a molecule with the
formula CH4 has less potential energy than any other suggested combination. Bonds don’t form because atoms “want” to form bonds, or
because, in this case “carbon needs 4 more electrons” or to “satisfy the Octet Rule”.

Intramolecular bonds
The extremes: ionic and covalent
There are two “extreme” types of chemical bond: ionic and covalent, as shown in the table below:

An ionic bond A covalent bond

Forms when.. transfer of one or more electrons between atoms is electron transfer is not energetically favourable
energetically favourable
Is attraction between… ions of opposite charge: cation +ve and anion –ve a shared electron pair and two atomic nuclei
Examples Compounds of Group I and Group II metals, e.g. Compounds of ‘p’ block elements, e.g.
Carbon dioxide CO2
sodium chloride NaCl Boron trichloride BCl3
lithium fluoride LiF Methane CH4
calcium chloride CaCl2 Atoms of ‘p’ block elements, e.g.
magnesium oxide MgO Carbon C(n)
Nitrogen N2
Oxygen O2
Sulfur S8
Chlorine Cl2
Examiners dislike… • Sodium chloride exists as “molecules”. • Covalent bonds can be “disturbed” or “weakened”.
• Covalent bonds are “weaker” than ionic bonds.
Examiners like… • (For example) “NaCl” represents the ratio of sodium • Covalent bonds can be broken.
to chloride ions in the ionic lattice, i.e. 1:1. • Covalent bonds exist in simple molecules such
• The ions are packed alternately in as energetically as iodine and water and in giant structures such
favourable way as possible. as diamond, graphite and silicon dioxide.
• Ionic bonds are multi-directional. • Covalent bonds are linear.
• Ionic bonds are strong. • Covalent bonds are strong.

The “in-betweens”: polar covalent and ionic bonds with covalent character
In most bonds distortion of electron charge clouds surrounding atomic nuclei occurs. Hence, bonds are neither 100% covalent or ionic, but
in-between, having a degree of “ionic” or “covalent” character.
1
107. AS Chemical bonding: Intramolecular bonds Chem Factsheet

Polar covalent bonds

In a covalent bond, electrons may spend more time around the nucleus of one atom in the pair. This leaves the other nucleus more
exposed creating a partial positive charge labelled “δ+”. The “other side”, where there is a greater chance of finding electrons, is labelled
“δ−“. The bond has a “permanent dipole” (PD) and is described as “polar covalent”.

δ+
Examples H-Cl bond in hydrogen chloride H - Clδ−
δ+
H-F bond in hydrogen fluoride H - Fδ−
δ+
H-O bond in water (H2O) H - Oδ−
δ+
C=O bond in carbon dioxide (CO2 C = Oδ−
δ+
N-H bond in ammonia (NH3) N - Hδ+

Atoms of nitrogen, oxygen and fluorine attract the bonding electrons in a covalent bond significantly. These elements are highly
“electronegative”.

• Polar covalent bonds are favoured when there is a large difference in electronegativity between the atoms in the bond. The most
electronegative elements are nitrogen, oxygen and fluorine.
• Electronegativity increases across a period due to more protons being present in the nucleus while the corresponding electrons go
into the same shell.
• This means the distortion power increases left to right.
• Electronegativity decreases down a group due to the increased number of electron shells which shield the atomic nucleus.

Permanent dipoles in bonds do not always create molecules with an overall dipole. When the molecule is symmetrical the dipoles
effectively cancel each other out. BCl3 is an example – the B-Cl bond has a dipole, but the molecule overall does not.

Ionic bonds with covalent character

The charge clouds surrounding ions in an ionic lattice may be distorted when the cation is small and highly positive – it has high charge
density while the anion has low charge density in comparison. The electron charge cloud surrounding the anion is drawn towards the
cation, so that electrons stand some chance of being found close to the cation nucleus. The bond is not completely ionic, but has
“covalent character”, as the two electrons are partially shared between the two nuclei. The bond can be so “covalent” that it is referred
to as a covalent bond, as in:-

Beryllium iodide BeI2

Aluminium chloride AlCl3

Cations have high polarising power if they are small and highly charged.

You can spot ionic bonds with covalent character by looking for ions like Al3+, B3+, Be2+ and Fe3+, especially when combined with
relatively large anions like Cl- and I-.

Bonding in metals – a special case

In metals, each atom shares one or more electrons between many others – the electrons are delocalised. The “atoms” have lost these
electrons, so strictly are positively charged ions, bonded together by the delocalised “electron sea”. The metallic bond is the attraction
between electrons and ions. The electrons are mobile, which means metals can conduct electricity. The positive ions are packed as
energetically favourably as possible in a lattice structure.

Drawing “dot-and-cross” diagrams for ionic and covalent bonds

Examiners ask you to draw ionic and covalent bonds using “dot-and-cross” diagrams. These show the locations of electrons in the
bonds. Each dot or cross represents one electron. The dot-and-cross system enables us to see the origin of each electron in the bond.
The “rules” for drawing these are:-

• Use dots for electrons from one atom and crosses for the other atom
• Different symbols to . and + are allowed, but be consistent and sensible in your choices
• When three different atoms are involved, a third symbol, e.g. Ä or can be used for the third atom
• Show the outermost electrons because only these are involved in bonding, but label the diagram “highest energy level electrons
shown only”
• Circles are not essential – here we show one with circles and the other without.
• The diagrams score only 1 or 2 marks – so don’t spend ages getting circles perfect

2
107. AS Chemical bonding: Intramolecular bonds Chem Factsheet

Exam questions and answers on intramolecular bonds

These are questions examiners have asked about bonding in recent AS exams. Make the most of this section by covering up the “Answer”
column and writing your own answers, taking note of the number of marks available. All the answers can be found in this Factsheet.

Question Marks Answer

Explain how the ions in MgCl2 are formed. 2 Two electrons transfer from each magnesium atom (1)
Each chlorine atom gains one electron (1)
State what is meant by an “ionic bond”. 1 Electrostatic attraction between (1) oppositely charged ions (1)
State what is meant by a “covalent bond”. 2 A pair of electrons shared (1) between two atoms (1)
Define “electronegativity”. 2 Power of an atom in a covalent bond (1) to attract the bonding
electrons (1)
Explain why electronegativity increases across a period in 2 The nuclear charge increases (1)
the Periodic Table. Shielding stays the same (1)
Explain why electronegativity values decrease down group 1 The number of electron shells increases(1)
II (Be-Ba). OR The shielding of the nucleus increases (1)
What is meant by “polarised”? 2 Electron cloud (1) around an anion is distorted (1)
Why is a chloride ion polarised more by an aluminium ion 2 Al3+ is smaller (1) and has a higher charge (1)
than a magnesium ion?
The B-Cl bond is polar. Explain why BCl3 is not a polar 2 The molecule is symmetrical (1) so the bond polarities cancel (1)
molecule.
State and explain the effect a single Be2+ ion would have 2 Be2+ ion has high charge density (1)
on a Cl- ion. The Be2+ ion polarises the chloride ion (1)
Explain how this effect would lead to formation of a 1 Electrons from a chloride ion are shared by Be2+ to form each
covalent bond. covalent bond (1)
The bonding in aluminium oxide is intermediate between 4 max 3 Al3+ ions are small (1) highly charged (1)
ionic and covalent bonding. Explain why. O2- ions are large (1)
O2- ions are polarised / distorted (1)
δ+
Show the polarity of the bonds: 2 H-Nδ−, δ−F-Bδ+ and δ+H-Iδ− 3 correct scores 2, 2 correct scores 1
H-N, F-B and H-I
State what is meant by “metallic bonding”. 3 The attraction (1) between positive ions (1) and a “sea” of
delocalised electrons (1)
Draw a “dot-and-cross” diagram of a molecule of HOCl 2 Covalent bonds shown correctly (1)
All lone pairs shown on chlorine and oxygen atoms (1)

H O Cl

Draw a “dot-and-cross” diagram of calcium chloride. 2 Ca 2+ ion shown correctly – either 8 or no electrons with no
overlap (1)
2Cl- ions shown correctly – dot and crosses required (1)

Cl− Ca2+ Cl−

Answer to introductory question

Methane
Stability is associated with the formation of covalent bonds by which electron orbitals are filled by sharing a pair of electrons between two
atoms. CH4 is the most stable formula of those listed. This formula confers the greatest stability on all atoms as their outer electron shells
are filled by sharing electrons.

Possible incorrect responses: Carbon needs four bonds / 4 more electrons; Carbon has 4 bonding pairs; Carbon wants to form 4 bonds;
Because there are 4Hs and 1C.

3
107. AS Chemical bonding: Intramolecular bonds Chem Factsheet

What the diagram shows Dot-and-cross diagram for sodium chloride, NaCl What to do in an exam
The outermost electron (3s) of a Only show the atoms in this first stage if
sodium atom transfers to a chlorine the question asks for them. Check the
atom. question and the number of marks
Na Cl
available. e.g.
The sodium atom is ionised,
becoming a positively charged “Show how an ionic bond forms
sodium ion, as the nucleus has 11 between X and Y” (4 marks)
protons and only 10 electrons Sodium atom 2,8,1 Chlorine atom 2,8,7
remain. implies draw the atoms and the ions,
giving the commentary shown left.
Each chlorine atom accepts an
electron, creating a negative charge + − “Draw a dot-and-cross diagram of
as the nuclei have 17 protons each, XYide” (2 marks)
but 18 electrons. Na Cl
The atom becomes a chloride ion. implies draw the ions only, showing all
electrons in the outermost shells. No
An ionic bond forms due to commentary is needed. Vital components
electrostatic attraction between the Sodium ion 2,8 Chloride ion 2,8,8 are:-
two oppositely charged ions. • the correct number of ions
• the correct charges on the ions
This process is repeated millions of • all outermost electrons shown
times to create a giant ionic lattice of So, check the formula of the compound!
sodium and chloride ions in a 1:1 ratio.

Four bonding pairs are created Make sure the dots and crosses are
between the carbon atom and the aligned neatly.
chlorine atoms. Cl
Check the formula of the molecule – make
The chlorine atom electrons are sure you have included all atoms.
shared in the outermost shell of the
carbon atom. Cl C Cl Check you have got the right number of
electrons in all orbitals – here it is easy
All atoms in the molecule have an to forget the other 3 electron pairs in the
noble gas electron configuration. Cl outermost shells of the chlorine atoms!

The molecule is symmetrical.

Acknowledgements: This Factsheet was researched and written by Vanessa Kind. Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire, TF1
1NU. ChemistryFactsheets may be copied free of charge by teaching staff or students, provided that their school is a registered subscriber. No part of these
Factsheets may be reproduced, stored in a retrieval system, or transmitted, in any other form or by any other means, without the prior permission of the
publisher. ISSN 1351-5136

4
 Chem Factsheet
www.curriculum-press.co.uk Number 108

Amino Acids and Polypeptides

Decide which of the following statements are true and which are false?

Statement True False

Amino acids all have the amino and carboxylic acid functional groups
Amino acids have the general formula NH2CH2(R)COOH
Amino acids can show acidic and basic properties
Amino acids can exist as twitterions
In the solid state amino acids display the physical properties of ionic compounds
Amino acids are insoluble in water
Polypeptides result from the combination of two or more amino acids
Amino acids are proteins

If you answered “true” then “false” alternately throughout, then

Typical Exam Question
you are an A student! Why not try the questions at the end of this
Name the amino acid whose structure is represented below
Factsheet? If you answered in any other way, then read on.
CH 3 H
After you have worked through this Factsheet you will know about:
1. the structure and properties of amino acids HO C C N:
2. how they join together to form peptides and polypeptides. H
O H
You will also have worked through typical examination questions, Credit worthy answer is 2-aminopropanoic acid (1 mark)
and be ready to answer questions on this topic. (No marks for alanine)

Proteins, peptides and amino acids are a very closely related group. 2) Amino acids are amphoteric since they show both the
All living matter has protein as an essential constituent. Complete properties of an acid and of a base. Consequently :
hydrolysis of a protein will yield α-amino acids, which contain both (a) In alkaline solution (excess OH- ions present) the carboxy-
the primary amino group (-NH 2) and the carboxylic acid group lic acid group can lose a proton:-
(-COOH) attached to the same carbon.
R H
Key Facts HO C C N: + OH−
1) The amino acids included in your syllabus can be represented by
H
the general formula: O H
R H
R H
HO C C N:
H −
O C C N: + H2O
O H
H
O H
They are called α–amino acids because the amino (–NH2) and
carboxylic acid (–COOH) groups are both attached to the second b) In acid solution (excess H+ ions present) the basic amino
or α–carbon atom. group can accept a proton via the lone pair of the nitrogen:-
R H
The 20 or so different amino acids occurring in nature are the
result of the different groups generally denoted by “R” above. HO C C N: + H+
Students are expected to be able to give the systematic name of a H
given amino acid, and give the formula for a named amino acid. O H
However, they are not expected to recall trivial names or write
down the formulae corresponding to these. For example: if –R is R H
–H then the resultant amino acid is aminoethanoic acid. The trivial +
name is glycine; biologists tend to use the trivial names, whereas HO C C N H
chemists prefer to use systematic nomenclature. H
O H
1
108 Amino Acids And Polypeptides Chem Factsheet

Typical Exam Question 4) The combination of two amino acids via a condensation reaction
The structural formula of an amino acid is given as : (with the elimination of water) resulting in them being joined
together by a peptide link, – NH.CO –, forming a dipeptide.
CH(CH3)2
R1 H R2 H
H 2N C COOH H C C N: + HO C C N:
H H H
O H O H
Draw the structure of the amino acid species present in a R1 R2
solution at pH 13 H
H2O + H C C N C C N:
pH 13 is very alkaline resulting in the removal of a proton from
the COOH group. H
O H H O H
Correct answer is shown below and is worth 1 mark.
If more than two amino acids combine in this way then a
CH(CH3)2
polypeptide is formed.
H 2N C COO−
Typical Exam Question
H Draw the organic product formed by the condensation of two
molecules of aminoethanoic acid
Note : the other parts of the molecule remain the same but
look out for a second COOH group contained in the The correct answer is shown below and is worth 2 marks.
R group. This too would be deprotonated. Similarly,
H H H
a second NH group may be present in the R group
2
and this too would be protonated to NH3+ at low pH.
H C C N C C N:
H
O H H O H
3) As a result of an internal proton transfer from the COOH group
to the NH2 group, amino acids often exist as dipolar ions called
zwitterions: Note : Had the R group not been the same (ie H), TWO possible
R H dipeptides can be formed with R1 left and R2 right or vice
−
+ versa. Try this for yourself by condensing 2-aminoethanoic
O C C N H
acid with 2-aminopropanoic acid.
H
O H
This can occur: 5) As the dipeptide formed between any two amino acids has a
(a) in solution at about pH 7 or b) in the solid state free amino, – NH2 and a free carboxylic acid, – COOH functional
Thus amino acids show important physical properties typical group at opposite ends of the molecule, the dipeptide can enter
of ionic compounds: into further combination with amino acids (by similar
(i) they are white solids which melt or decompose at relatively condensation reactions) to form polypeptides.
high temperatures, around 300ºC
R
(ii) they are soluble in water, but mostly insoluble in organic
solvents. HO C C N H

Typical Exam Question O H H n

Milk proteins can be broken down by enzymes to give á-amino
acids such as 2-aminopropanoic acid, existing mainly in their The region enclosed by the brackets is referred to as the
zwitterion forms. Give the structural formula of the zwitterion repeating unit of the polypeptide.
form of 2-aminopropanoic acid. Typical Exam Question
Correct answer shown below is worth 1 mark Give the repeating unit of the polypeptide formed when 2-
aminopropanoic acid molecules are reacted together.
CH3 H The correct answer is below and is worth 1 mark
−
+
O C C N H CH3
H
O H C C N

Note: It is important to ensure that the bonds are shown O H H

going to the nitrogen and carbon atoms from the
α-carbon Name the type of polymerisation involved when the polypeptide
is formed.
The correct answer is condensation or (nucleophilic addition-
elimination) polymerisation and is also worth 1 mark.

2
108 Amino Acids And Polypeptides Chem Factsheet

6. Proteins are polypeptide chains which result from the peptide 4. (a) Draw the structure of aminoethanoic acid in the solid state.
linking of many amino acids. 20 different α-amino acids are (1 mark)
found to take part in protein structure. Small proteins contain (b) State the type of bonding involved between adjacent amino
50 to 100 amino acid residues, large proteins may contain acid particles (1 mark)
several thousand. (c) Compare the strength of this bonding with the bonding
present between molecules of hydroxyethanoic acid (1 mark)
7. Proteins have a three dimensional structure which may be
considered as follows. Answers
(a) Primary structure (as discussed above) which is dependant 1. (a) H H
on the number and sequence of amino acids in the chain.
b) Secondary structure which describes the coiling or zig- HO C C N:
zagging of a polypeptide chain (e.g. a helix). This results H
O H
from hydrogen bonding between the peptide bonds. (For
more details of the hydrogen bonding mechanism in general
(b) CH3 H
– Factsheet 77 is useful.) H
(c) Tertiary structure which results when the chains twist in a H C C N C C N:
regular or irregular fashion on themselves. This is caused
H
by interactions between amino acid side chains. For example O H H O H
hydrogen bonding or the formation of disulphide bridges
may occur. N.B. the actual peptide link (highlighted above) does not
(d) Quaternary structure occurs only when two or more chains depend on which two amino acids are reacting. However, if
assemble to form a final protein, and concerns the way in the full structure is given by a candidate, then it must all be
which these protein chains come together. correct. Also, the CH3 group could be on either the first or
second amino acid redidue.
8. Some proteins act as biocatalysts or enzymes. The three CH2CH2SCH3
dimensional shape of the protein results in the formation of
2.
a unique active site on which a specific reaction can occur. −
OOC C NH 3 +
If the protein is subjected to changes in temperature or pH,
certain metal ions, the addition of a small polar molecule H
(such as urea) or a mild reducing agent, then the unique
three dimensional shape of the protein may be lost and the 3. (a) CH2 C6H 5
active site destroyed – this is termed denaturation.
Denaturation may be temporary or permanent. HOOC C NH 3 +

Practice Questions H
1. Write down the full structural formula of: (b) The amino group has a lone pair of electrons on the N atom.
(a) aminoethanoic acid (1 mark) Thus it can accept a proton and show the properties of a base.
(b) the peptide link which forms when an aminoethanoic acid
and a 2-aminopropanoic acid molecule react (1 mark) H CH2 C6H 5 H
(c)
2. Draw the structural formula for the zwitterion form of the H C C N C C N:
á-amino acid shown below (1 mark) H
CH2CH2SCH3 O H H O H

HOOC C NH 2 CH 2C 6H 5 H H
H H C C N C C N:
3. The structure of an amino acid is given below H
CH 2C 6H 5 O H H O H
(d) Water
HOOC C NH 2 (e) Hydrogen bonding
H H H
4. (a)
+
(a) Draw the structure of the amino acid species present in −
O C C N H
solution at pH3 (1 mark)
H
(b) What feature of the amino group means that it can accept a O H
proton (H+ ion) under certain conditions? (1 mark) (b) Ionic
(c) Draw the structures of the dipeptides formed when a molecule (c) The electrostatic interactions involved in the ionic bonding
of this amino acid combines with a molecule of aminoethanoic between the glycine ions is much stronger than the hydrogen
acid. (2 marks) bonding present between molecules of hydroxyethanoic acid
(d) Name the non-organic product of this reaction. (1 mark)
(e) A protein chain is arranged in the shape of a helix. Name the Acknowledgements: This Factsheet was researched and written by Christine
type of bonding involved in forming and holding this shape. Collier. Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire,
TF1 1NU. ISSN 1351-5136
(1 mark)
3
 Chem Factsheet
www.curriculum-press.co.uk Number 109

Cracking, Reforming and Isomerisation

You have already studied the separation of crude oil into its For the refinery operator, cracking is a two-win process. He gets
components by fractional distillation. This method of separation is both a more valuable compound for use in petrol blends and also
dependant on the different boiling points of the various fractions. an alkene which, being more reactive, can be used as an
But this is only the first stage in petroleum refining. To maximise the intermediate in the synthesis of other compounds such as
economics of the process, the production of the most valuable poly(ethene) and ethanol. Before going onto the next two sections,
fraction needs to be enhanced. Obviously demand and income from we need to consider combustion a little more – particularly what
petrol (gasoline) is very high and so the refinery conditions are geared happens to the fuel inside a petrol engine.
to maximise the production of this fraction.
You have probably been to a garage and seen numbers on the
One of the fractions, the naphtha fraction, does not have very many petrol pumps e.g. ‘95 Ron‘ - this is the octane number of the
uses. It is too volatile to be used as a lubricant and it does not have petrol. But what does number this mean?
very good burning qualities. Naphtha does not make a very good
fuel so, to the refinery operator, producing lots of naphtha is not a Petrol engines basically work by compressing an air/petrol mixture
very good thing. Different processes are applied to this fraction in and then igniting it with a spark from a spark plug. The fuel then
particular to produce much more valuable compounds. burns and the hot gases produced push down a piston. This
downward push is then converted to kinetic energy that finally
arrives at the wheels of the car making it move. However, conditions
1. Cracking can arise by which the fuel can ignite before the spark occurs.
Cracking involves the breaking up of large alkane molecules to This is called auto-ignition. When auto-ignition occurs, instead
form smaller ones. There are two types. of having a smooth burn, the fuel literally detonates and is heard
(a) Thermal cracking uses high temperatures (800oC) and so is as a loud rattle. This is called ‘knocking‘ (or pinking‘). Knocking
energy intensive. It is used on the residue (tar) obtained at the is not good. At worst, it can lead to a hole forming in the top of the
bottom of the tower. piston (very expensive!) ; at best, a fall off in performance and
poor fuel consumption (very expensive!). If allowed to continue,
(b) Catalytic cracking uses a catalyst and is used on some of the both malfunctions will occur (very, very expensive!!). Most cars
distillates obtained further up the tower. The catalyst used is these days have an anti-knock sensor connected to a computer
called a zeolite catalyst. These are compounds of complex that, when it detects knocking in the engine, will induce a change
aluminosilicates that occur both naturally and are made in engine conditions and stop the knocking. But the engine can
synthetically. Due to the presence of the catalyst lower only be adjusted within a small range and so it is important that
temperatures are used and so a saving is made on energy the right fuel is put into the petrol tank.
usage.
Some fuels have a very low ability to resist knocking - such a fuel
During cracking an unsaturated compound is always formed. Below is heptane. This alkane is given an octane rating of 0. Now, this is
is an example of a cracking reaction when things get confusing! The compound 2,2,4-trimethylpentane
is not octane - but it does contain eight carbon atoms. It used to
be called iso-octane and so the label ‘octane‘ has stuck. This
CH3CH2CH2CH2CH2CH2CH2CH2CH2CH3 compound has a very high ability to resist knocking and so is
given an octane rating of 100. A fuel rated with an octane rating of
This is decane (an alkane) - one of the 95 will perform as if it was composed of 95% 2,2,4-trimethylpentane
molecules that might be in the naphtha and 5% heptane. The fuel may not actually contain these amounts
fraction. It is not a good fuel for petrol as other substances are blended in, but the fuel will behave as if it
engines does. It is possible to obtain fuels with octane ratings greater than
100.

Lead compounds particularly ‘tetraethyl lead, [Pb(C2H5)4]‘ were

CH3CH2CH2CH2CH2CH2CH3 + CH 2=CH2 found to significantly increase the octane rating of fuels (If a fuel
has a very high octane rating it means that higher compressions
This is octane. It is a good This is ethene. It is
can be used and more power obtained from the engine.) but because
fuel for petrol engines. It is unsaturated. It is
of environmental issues lead petrol is not used today.
saturated. more reactive than
an alkane and a
valuable raw
material

1
109 Cracking, Reforming and Isomerisation Chem Factsheet

2. Reforming
Reforming is important because many useful intermediates are produced. Platinum or platinum/rhodium catalysts are used. Very
often cyclic or aromatic compounds are formed.
CH2 CH
Pt/5000C Pt/5000C HC
H2C CH2 CH
CH3CH2CH2CH2CH2CH3
H2C CH2 HC CH
This is hexane. It is a
CH2 CH
straight chain alkane
This is cyclohexane. This is benzene. It is an
It is a cyclic alkane. aromatic compound.

Note that during reforming, the number of carbon atoms does not change; the number of hydrogen atoms does change. Very often
hydrogen is given off as a by-product. The change from hexane to cyclohexane gives 1 mole of hydrogen gas and the change from
cyclohexane produces 3 moles of hydrogen gas. This amount of hydrogen is significant and can be sold as a product; for instance, to
manufacture ammonia.

3. Isomerisation
Isomers are compounds with the same molecular formula but with different structural formula. In this process then, the number
hydrogen and carbon atoms are the same in both reactant and product. In terms of refining practice, isomerisation is used to induce
branching into hydrocarbon chains because branching has been found to produce better burning characteristics than hydrocarbons
with straight chains.

Isomerisation involves a platinum catalyst, temperatures of about 250oC and pressures of about 20atm. The process is usually applied
to C-4 and C-5 straight chain alkanes.

CH3CH2CHCH3 methylbutane
CH3
CH3CH2CH2CH2CH3 0
pt/250 C 20 atm
pentane CH3

CH3CCH3 dimethylpropane

CH3

Practice Questions
1. Complete the following equations which represent cracking 2,2,3-trimethylbutane; CH3CH(CH3)CH(CH3)2CH3
reactions. 3,3-dimethylpentane; CH3CH2CH(CH3)2CH2CH3
2,4-dimethylpentane; CH3CH(CH3)CH2CH(CH3)CH3
(a) C15H32 Æ C4H8 + 2,3-dimethylpentane; CH3CH2CH(CH3)CH(CH3)CH3
2,2,-dimethylpentane; CH3CH2CH2CH(CH3)2CH3
(b) C10H22 Æ C8H18 + 3-methylhexane; CH3CH2CH2CH(CH3)CH2CH3
(b) 2-methylhexane; CH3CH2CH2CH2CH2CH(CH3)CH3
(c) Æ C3H6 + C9H20 2,3-dimethylbutane; CH3CH(CH3)CH(CH3)CH3
2,2-dimethylbutane; CH3CH2C(CH3)2CH3
2. What alkanes would you need to form…? 3-methylpentane; CH3CH2CH(CH3)CH2CH3
(a) Cyclopropane 3. (a) 2-methylpentane; CH3CH2CH2CH(CH3)CH3
(b) Cycloheptane
2. (a) Propane (b) heptane
3. What are the possible structures and names for the isomerisation
(c) C12H26 1. (a) C11H24 (b) C2H4
products of (a) hexane and (b) heptane?
Answers

Acknowledgements: This Factsheet was researched and written by Jeff Cole. Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire, TF1 1NU.
ChemistryFactsheets may be copied free of charge by teaching staff or students, provided that their school is a registered subscriber. No part of these Factsheets
may be reproduced, stored in a retrieval system, or transmitted, in any other form or by any other means, without the prior permission of the publisher. ISSN
1351-5136
2
 Chem Factsheet
www.curriculum-press.co.uk Number 110

∆G = ∆H - T∆
∆S
The study of Free Energy and Entropy is concerned with the factors Calculating Standard Entropy Changes, ∆ S ê from
which make reactions occur spontaneously – this means they occur Standard Entropies, Sê
without having to input energy but it does not mean they are Entropy changes for reactions can be calculated in the same way
necessarily fast. as enthalpy changes. The entropy change for a reaction is the
difference between the total (Σ) entropies of the products and the
Consider the following two reactions: total entropies of the reactants.

1. Some dilute hydrochloric acid is added to magnesium ribbon. i.e. ∆Sê = ΣSêproducts - ΣSêreactants
There is some effervescence as hydrogen is given off and the
reaction vessel gets quite warm.
Example 1. Calculate the standard entropy change for the
Mg + 2HCl MgCl2 + H2 ∆H -ve following reaction using the given standard entropies:

2. Some dilute hydrochloric acid is added to sodium CaCO3(s) CaO(s) + CO2(g)

hydrogencarbonate. There is again some effervescence but this
time the temperature of the reaction vessel decreases. Sêê (298 K)/J K-1 mol-1
CaCO3(s) 92·9
HCl + NaHCO3 NaCl + H2O + CO2 ∆H +ve CaO(s) 39·7
CO2(g) 213·6
Both reactions are spontaneous but while one reaction gives out
heat the other takes heat in.
CaCO3(s) CaO(s) + CO2(g)
To explain why some reactions are spontaneous even though they ∆Sê/ J K-1 mol-1 +92·9 +39·7 +213·6
have a positive enthalpy change we need to take into account another
factor called entropy. ∆Sê = ΣSêproducts - ΣSêreactants

Entropy ∆S = (39·7 + 213·6) - 92·9 = +160·4 J K-1 mol-1

Entropy is often thought of as being a measure of the disorder of a
system. For example, a gas in which the molecules are moving more Free Energy
or less completely freely and randomly throughout the system has a Entropy (in the universe as a whole) tends to increase. However,
high degree of disorder. On the other hand a regular crystal, such as this does not mean that there must be an increase in entropy in
sodium chloride in which all the particles are vibrating about fixed any given reaction. A reaction can show a decrease in entropy
positions, is highly ordered. Systems which have a high degree of provided that the surroundings show an appropriate increase in
disorder are said to have a high entropy; systems which are highly entropy. Entropy and enthalpy by themselves do not help us to
ordered (or have a low degree of disorder) are said to have a low decide whether a reaction is spontaneous or not.
entropy.
A better indication of the feasibility of a reaction is the free energy
Entropy is measured in J K-1 mol-1 and is given the symbol S. A change, ∆G. ∆G is related to the enthalpy change and the entropy
change in entropy is given the symbol ∆S. Entropy change which is change in a reaction by the following equation.
measured under standard conditions is referred to as standard
entropy change and is given the symbol ∆Sê. Entropies change with
temperature and so the temperature at which they are measured must ∆G = ∆H - T ∆S
be specified. Free energy Enthalpy Temperature Entropy
change change change
Table 1. Some Examples of Entropy Values

C(diamond) +5.7 J K-1 mol-1 A relative small value because it is a regular crystalline solid
Increasing
entropy

-1 -1
H2O(l) +69.9 J K mol A liquid so it has a higher entropy

Ne(g) +146.2 J K-1 mol-1 A gas and so is highly disordered. It has a relatively high entropy

The standard entropies of elements and many compounds can be found in data books.

1
110 ∆G = ∆H - T∆S Chem Factsheet

Free Energy Changes and Temperature

The change in free energy does enable us to say whether a By changing the temperature at which a reaction is carried out it is
reaction is or is not spontaneous: sometimes possible to change the factor TÄS to such an extent that
the feasibility of a reaction is changed.
If the free energy change for a reaction is
negative, the reaction is spontaneous. Example 3
(a) Is the following reaction spontaneous at 25oC?
If the free energy change for a reaction is (b) Is it spontaneous at 1000oC?
positive, the reaction is not spontaneous. (c) What is the temperature at which it becomes spontaneous?

CaCO3(s) CaO(s) + CO2(g)

For example,
∆Sê= +165 J mol-1 K-1
CaCO3 CaO + CO2 ∆G = +130 kJ mol-1 at 298K ∆Hê= +178 kJ mol-1
Not spontaneous at 298K because ∆G is positive.
Solution
H2(g) + Cl2(g) 2HCl(g) ∆G = -190 kJ mol-1 at 298K (a) At 25oC,
Spontaneous at 298K because ∆G is negative. ∆Gê= ∆Hê- T∆Sê
As seen above, free energy is usually measured, like enthalpy, in = 178 – 298 × 165/1000
kJ mol-1. This means you must remember to convert S values from = +128.8 kJ mol-1
J mol-1 K-1 to kJ mol-1 K-1 by dividing by 1000. This value for ∆G is positive and so the reaction is not
spontaneous at 25oC
Example 2 Calculate the standard free energy change for the
following reaction at 500 K and hence determine whether the (b) At 1000oC
reaction is spontaneous at 500K:
∆Gê = ∆Hê - T∆Sê
CuO(s) + H2(g) Cu(s) + H2O(g) = 178 – 1273 × 165/1000
= -32 kJ mol-1
∆Hêf /kJ mol-1 Sê/J mol-1 K-1
CuO(s) -155 +44 This value for ∆G is negative and so the reaction is spontaneous
H2(g) 0 +131 at 1000oC
Cu(s) 0 +33
H2O(g) -242 +189 (c) To find the temperature at which the reaction becomes
spontaneous we find the temperature at which the value of ∆G
Solution is changing from positive to negative, i.e. ∆G = 0
1. Calculate the enthalpy change for the reaction using the given
data ∆Gê = ∆Hê - T∆Sê
∆Hêf = Σ∆Hêf, prods – Σ∆Hêf, reactants 165
= (0 + (-242) – ((-155) -0) 0 = 178 – T ×
1000
= -87 kJ mol-1 1000
T = 178 × (rearranging the equation to give T)
165
2. Calculate the entropy change for the reaction using the given
data = 1079 K
∆Sê = ΣSêprods – ΣSêreactants
= (33 + 189) - (44 + 131) i.e. The reaction becomes spontaneous at temperatures above
= 47 J K-1 mol-1 1079K (806 oC)
= 0.047 kJ K-1 mol-1
In other words calcium carbonate does not decompose at room
3. Use the enthalpy and entropy changes calculated in 1. and 2. temperature but if it is heated to a temperature above 1079 K then
and the equation for free energy to find ∆G at 500K. it does decompose. This, of course, agrees with what we know
about the stability of calcium carbonate.
∆Gê = ∆Hê- T∆S
= -87 - 500 × 47/1000
= -110.5 kJ mol-1
∆G is negative therefore the reaction is spontaneous.

2
110 ∆G = ∆H - T∆S Chem Factsheet

∆Gê, becomes more positive.

Practice Questions
makes the reaction less spontaneous because –T∆Sê, and hence
1. Would you expect that the entropy change for the following
If the sign of ∆Sê is negative then increasing the temperature
reactions is positive, negative or approximately zero?

Mg(s) + 2HCl(aq) → MgCl2(aq) + H2(g)

hence ∆Gê, becomes more negative.
(a)
2Ca(s) + O2(g) → 2CaO(s)
makes the reaction more spontaneous because –T∆Sê, and
(b)
N2(g) + O2(g) → 2NO(g)
If the sign of ∆S is positive then increasing the temperature
(c)
(d) C2H6(g) + 3½O2(g) →2CO2(g) + 3H2O(g)
(∆Gê= 4.1 kJ mol-1)
At 1000 K the second reaction is not spontaneous
2. Calculate the standard entropy change for the following reaction:
At 1000 K the first reaction is spontaneous (∆Gê= -5 kJ mol-1)
BaCO3(s) → BaO(s) + CO2(g)
At 500 K the second reaction is spontaneous (∆Gê= -3.5 kJ mol-1)
5. At 500 K the first reaction is not spontaneous (∆Gê= +81.1 kJ mol-1)
Sê (298 K)/J K-1 mol-1
BaCO3(s) 112.1 spontaneous at temperatures above 978 K
BaO(s) 70.4 4. The reaction is not spontaneous at 25oC. The reaction becomes
CO2(g) 213.6
3. -237 kJ mol-1
3. Calculate the free energy change for the following reaction at
298 K: 2. 172 J K-1 mol-1

H2(g) + ½O2(g) → H2O(g) moles of equally disordered gases.

(d) positive because 4½ moles of disordered gases produce 5
∆Hê = -286 kJ mol-1 ; ∆Sê = -164 J K-1 mol-1
produce 2 moles of equally disordered gases.
4. Decide whether the following reaction is spontaneous at 25oC. (c) approximately zero because 2 moles of disordered gases
If it is spontaneous, decide at what temperature it would cease
to be spontaneous. If it is not spontaneous, decide at what (b) negative because a highly disordered gas is consumed
temperature it would become spontaneous.
C(s) + H2O(g) → CO(g) + H2(g)
1. (a) positive because a highly disordered gas is produced
Answers
∆Hê = + 131 kJ mol-1 ; ∆Sê = +134 J K-1 mol-1

5. Calculate the free energy change at 500K and 1000K for each of
the following reactions:
FeO(s) + C(s) → Fe(s) + CO(g)
FeO(s) + CO(g)→ Fe(s) + CO2 (g)
(Assume that ∆Sê and ∆Hê at 500 K and 1000 K are the same as
at 298K.)
FeO(s) Fe(s) C (s) CO(g) CO2(g)
∆Hê/kJ mol-1 –271.9 0 0 –110.5 -393.5
∆Sê/J K-1 mol-1 57.5 27.3 5.7 197.6 213.6

Which of the reactions is spontaneous at 500 K? Which is

spontaneous at 1000 K? How does the sign of ∆Sêaffect the
way in which feasibility changes with temperature?

Acknowledgements: This Factsheet was researched and written by Chris

Senior. Curriculum Press, Bank House, 105 King Street, Wellington,
Shropshire, TF1 1NU. ChemistryFactsheets may be copied free of charge
by teaching staff or students, provided that their school is a registered
subscriber. No part of these Factsheets may be reproduced, stored in a
retrieval system, or transmitted, in any other form or by any other means,
without the prior permission of the publisher. ISSN 1351-5136

3
 Chem Factsheet
www.curriculum-press.co.uk Number 111

OXYACIDS
Which of the following statements are true and which are false?
Background Understanding
Statement True False It is important to understand how the atom(s) or group(s) bonded
to the OH determines whether the compound behaves as an acid
Oxyacids contain the OH− group
rather than a base.
Oxyacids contain oxygen
The electronegativity of an element is a measure of its tendency
Oxyacids are always weak acids
to attract electrons from a covalent bond.
Chlorine exhibits an anionic electrovalency
in hyperchlorous acid a) An atom of an element of low electronegativity will tend to
The Group 7 elements may exhibit their lose electrons, so the average position of the electrons in the
ionic valency when forming an oxyacid bond will be shifted away from the atom of that element, causing
the bond to become highly polar. The element of lower
Oxygen is bonded to an element of electronegativity will become a centre of higher positive charge.
high electronegativity in an oxyacid The degree to which this occurs is dependent also on the
electronegativities of the other atoms to which the atom is
On descending Group 7 the higher
bonded.
oxidation states become more oxidising
b) An atom of an element of high electronegativity will tend to
If you answered alternately false then true throughout, then you
gain electrons, so the average position of the electrons in the
already have a good understanding of the principles involved in the
bond will be shifted towards that atom, again causing the bond
formation and reactions of oxyacids. Why not try the questions at
to become highly polar. The high electronegativity element
the end first?
becomes a centre of higher negative charge. Again the degree
to which this occurs is dependent on the electronegativities
If you found the statements problematic or had to guess, then this
of the other atoms to which the atom is bonded.
Factsheet aims to cure your misconceptions.
c) When the shift of charge is high enough, the electrons in the
Key Fact 1 bond spend all of their time on one of the atoms, and ion
Oxyacids contain one or more O – H bonds. formation results.
For example, H2SO4 contains two such bonds:
We can now see how this can result in the O–H group forming
either OH¯ ions and the compound behaving as a base, or H+
:

:O:
ions and the compound behaving as an acid.
: :

: :

H O S O H
:O : If X is a metal such as Na, K, or Ca, the low electronegativity
of X results in the complete transfer of the bonding pair of
electrons between X and O to the oxygen and an ionic
Key Fact 2 compound involving OH¯ is formed. Thus such compounds
The electronegativity of the atom (X) directly attached to the OH are sources of OH¯ ions and behave as bases.
determines whether an OH group will form an OH¯ ion and so
produce an alkaline solution, or lose an H+ ion and so produce an If X is a non-metal, the X–O bond is covalent and the
acidic solution. compound will not readily lose an OH¯ ion. These compounds
will be either neutral or acidic in character.
This is also true if X has other groups attached to it.

X O H Key Fact 3
As a general rule, the greater the electronegativity of X, the
greater the acidity of the compound.

1
111. OXYACIDS Chem Factsheet

Background Understanding
Extract from examiners report: “A number of candidates could
The increasing acidity with increasing electronegativity of X is
not distinguish between an anion and a cation” – make sure
because:
you can
1) The O–H bond becomes more polar as substantial drift of
electrons towards the electronegative atom occurs. (The electron Note: Remember anions are negative and so are attracted by and
loving electronegative atom attracts the electrons.) This leaves go to a positive anode.
the hydrogen atom with a positive charge.
The more positive the potential for the process, the more oxidising
For example: the Hal2 species and the less reducing the Hal- species.
Cl – O – H Ù Cl – O− + H+
Å Å F2 → 2F¯ Cl2 → 2Cl¯ Br2 → 2Br¯ I2 → 2I¯

where Å represents the electron drift Eê in volts + 2.87 + 1.36 + 1.07 + 0.54

Ka for HClO = 3.0 × 10-8 mol dm-3 [If you would like to revise Electrode Potentials and Feasibility of
Reactions Factsheet Number 45 will be helpful to you.]
I – O – H Ù I – O− + H+
Å Å Remember oxidation is loss of electrons and so an oxidising
agent will have a high positive potential for gaining electrons.
Ka for HIO = 2.3 × 10-11 mol dm-3

Chlorine is more electronegative than iodine, thus the chlorine atom Key Fact 6
will cause the electrons to move more towards itself, and the bond The halogens thus exhibit an anionic electrovalency. The
will become more polar. This results in HClO being a stronger acid halogens also exhibit a range of positive oxidation states, which
than HIO, as reflected in the decreasing values for Ka. do not correspond to the ionic valencies. Oxidation states ranging
from +1 to +7 are exhibited by Cl, Br and I.
[If you are not sure of the significance of Ka values and your
Bronsted-Lowry Theory has not been used for a while, then The oxoanions formed by oxyacids are examples where Cl, Br and I
Factsheet Number 25 will help you revise!] have these oxidation states. The following examples should be
remembered specifically

Acid Electronegativity of X Ka / mol dm-3 Chlorine has the oxidation state +1 in OCl− [chlorate(I)]
the oxidation state +5 in ClO3− [chlorate(V)]
HClO 3.0 3.0 × 10-8 the oxidation state +7 in ClO4− [chlorate(VII)]
HBrO 2.8 2.5 × 10-9
Iodine has the oxidation state +7 in IO4− [iodate(VII)]
HIO 2.5 2.3 × 10-11

Key Fact 7
Although they are behaving as anions and form salts with the
Key Fact 4
alkali metals of Group I, the bonds between the halogen and
If oxygen atoms are attached to X, the electron withdrawing
oxygen(s) are covalent, due to the comparability of the
power of X is increased and thus the acidity of the oxyacids
electronegativity values of oxygen and the halogens.
increases.

Thus the strength of the oxyacids of chlorine increases from

Key Fact 8
hypochlorous or chloric(I) acid, HClO to perchloric or chloric(VII)
The higher oxidation states are highly oxidising
acid, HClO4. As the oxidation number of X increases as the number
of oxygen atoms attached increases, this may be restated:
e.g. chlorate (V), ClO3− and chlorate (VII), ClO4−, tend to be reduced
to Cl−.
Key Fact 5
In a series of oxyacids the acidity increases as the oxidation
However, as Group 7 is descended and the electronegativity of the
number of the central atom (X) increases.
halogen decreases, the higher oxidation states become more stable
and less strongly oxidising.
The Formation of Oxoanions and Electrovalency e.g. the tendency of IO3− to become I− is less than the tendency for
The formation of oxoanions may also be considered in terms of the ClO3− to become Cl−.
Eê values relating to the process:

Hal2 + 2e− → 2Hal−

where Hal represents any halogen and Hal- corresponding halide

anion

2
111. OXYACIDS Chem Factsheet

Formation of the oxoanion ClO−

Question2:
ClO− is formed by the redox disproportionation reaction between
What is the change in oxidation number for a) bromine b) sulphur
chlorine gas and cold, dilute sodium hydroxide solution:-
in the reaction above?
Cl2 + 2OH− → Cl− + ClO− + H2O 2HI + H2SO4 → I2 + SO2 + 2 H2 O
Oxidation state of chlorine 0 -1 +1 6HI + H2SO4 → 3I2 + S + 4 H2O

If chlorine is passed into hot concentrated sodium hydroxide 8HI + H2SO4 → 4I2 + H2S + 4 H 2O
solution, the following reaction occurs:-
The reducing power of the hydrogen halide becomes greater as one
3Cl2 + 6OH− → 5Cl− + ClO3− + H2O goes further down Group 7. This is to be expected as the E? values
Oxidation state of chlorine 0 -1 +5 for Hal 2 → 2Hal − become less positive, thus reflecting the
decreasing oxidising power of the free halogen and increasing
Disproportionation of the oxoanion ClO− reducing power of the hydrogen halides.
Warming of a solution containing ClO− results in the following
disproportionation: Question3:
What is the change in oxidation number for a) iodine b) sulphur
3ClO− → 2Cl− + ClO3− in each of the reactions above?
Oxidation state of chlorine +1 -1 +5
Practice Questions
1. Arrange the following compounds in order of increasing acid
Oxidising Properties of ClO− strength: H2SeO3, H2SeO4, H2O
The chlorate anion behaves in a similar way to chlorine, having
substantial oxidising power and displaying bleaching and 2. Which of the following pairs of oxyacids will be the stronger?
bactericidal action. a) HNO2 HNO3 b) H2SO3 H2SeO3
c) HIO HBrO d) HClO3 HClO2
This type of oxidation reaction results in chlorine (+1) in ClO− being
3. Give the oxidation state of:
reduced to chlorine (-I) in Cl−.
a) Iodine in IO3− b) Bromine in BrO2− c) Chlorine in ClO−
Key Fact 9 4. Name the gas produced when solid sodium chloride is reacted
The decrease in electronegativity as one goes down Group 7 with concentrated sulphuric acid.
results in the elements becoming less oxidising and thus the 5. Name the two gases produced when solid sodium bromide reacts
higher oxidation states are more stable. with concentrated sulphuric acid and give their appearance.
For example iodate (V) IO3− is less oxidising than chlorate (V), 6. Give the equation for the reaction of chlorine with dilute aqueous
ClO3−, and thus more stable. sodium hydroxide at room temperature. Explain, using oxidation
numbers why this may be regarded as a disproportionation
Reactions of sodium halides when heated with reaction.
concentrated sulphuric acid Answers to Questions from Text
Q1 a) 0 (-1 → -1) b) 0 (+6 →+6)]
At first, the sodium halides react to form the corresponding Q2 a) +1 (-1 → 0) b) -2 (+6 →+4)]
hydrogen halides: Q3 a) +1 ( -1 → 0) in all reactions
b) -2 (+6 → +4); -6 (+6 → 0); -8(+6 → -2).]
NaHal + H2SO4 → NaHSO4 + HHal
and reduced from oxidation state 0 to -1 and +1
Disproportionation because the chlorine is simultaneously oxidised
where Hal = F, Cl, Br or I
6. Cl2 + 2NaOH → NaCl + NaClO + H2O
5. Bromine gas – brown ; sulphur dioxide gas - colourless
These are not redox reactions. 4. Hydrogen chloride gas
3. a) +5 b) +3 c) +1
Question1: greater.
What is the change in oxidation number for a) the halogen b) d) HClO3 as the number of oxygen atoms bonded to chlorine atom is
sulphur in the reaction above? c) HBrO as bromine is more electronegative than iodine.
selenium (sulphur is higher up group six).
b) H2SO3 as the electronegativity of sulphur is greater than that of
However, HBr and HI are then oxidised by the oxyacid H2SO4 to 2. a) HNO3 as the number of oxygen atoms bonded to the nitrogen is greater.
form the free halogen. stronger acid than H2SeO3.
bonded to the central atom increases. This means that H2SeO4 will be a
2HBr + H2SO4 → Br2 + SO2 + 2 H2O acid . The acidity of oxyacids increases as the number of oxygen atoms
element of higher electronegativity than hydrogen and forms a stronger
Extract from examiners’ report: Many candidates recognised Explanation: Selenium is a non-metal (similar to sulphur) and thus is an
the brown gas as bromine, but failed to state that bromine was 1. The correct order is H2O (weakest) - H2SeO3 - H2SeO4 (strongest)
an oxidation product Answers
Acknowledgements: This Factsheet was researched and written by Christine Collier.
Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire, TF1 1NU.
3
 Chem Factsheet
www.curriculum-press.co.uk Number 112

Acid Base Reactions of Transition

Metal Complexes
It is perhaps surprising at first sight that, whereas many common salts such as sodium chloride are neutral, solutions of transition metal
ions are usually acidic. Like other acids, solutions of transition metal ion solutions contain H+ ions and may react with bases, with
carbonates to give carbon dioxide and even with reactive metals such as magnesium to give hydrogen.

Why are complexes of transition metals acidic?

Recall that complex ions are formed by a central metal ion surrounded This process can be represented by the following sequence of
by several ligands. The ligands bind to the central metal ion by equations. The hexaaquairon(III) ion,[Fe(H2O)6]3+, donates a proton
dative (co-ordinate) bonds. The lone pairs of electrons from the to a water molecule to form the hydrated proton H3O+.
ligands are donated into the empty orbitals of the metal ion.
e.g. [Fe(H2O)6]3+ + H2O → [Fe(H2O)5OH]2+ + H3O+
Ligands are molecules or ions which have one or more lone pairs of acid base
electrons which they can donate to a transition metal ion to form proton donor proton acceptor
the dative bond. They are electron pair donors or Lewis bases.
Water is a common ligand. The [Fe(H2O)6]3+ ion is behaving as an acid in the Lowry Bronsted
sense of being a proton donor and the solvent water molecules
When transition metals ions are dissolved in water they form complex behave as the base, the proton acceptor.
ions in which water is the ligand. For example, solutions of iron(III)
salts contain the hexaaquairon(III) ion, [Fe(H2O)6]3+ Notice that the Fe containing ion which is formed has one fewer
positive charges because it has lost a proton. (This does not mean,
of course, that its oxidation state has changed)
3+
H2O: The reaction sequence continues with the ion [Fe(H 2O)5OH] 2+
behaving as an acid and donating a proton to the solvent water
:OH2 molecule. However this process takes place to a much lesser extent
than the first reaction.
H2O: Fe :OH2
[Fe(H2O)5OH]2+ + H2O → [Fe(H2O)4(OH)2]+ + H3O+ etc.
H2O: The extent to which hexaaqua ions are hydrolysed depends on the
charge on the ion and on its size.
:OH2
• Ions with a higher charge are more polarising than those with a
smaller charge.
Hexaaqua complexes of transition metal ions are hydrolysed in
aqueous solution. This means that the co-ordinated water molecule • Smaller ions are more polarising than larger ions.
ligands split up and donate protons to the solvent. This occurs
because the central metal atom is small and highly charged. It Hexaaqua ions are therefore acidic in aqueous solution since they
polarises the co-ordinated water molecules and weakens the oxygen are acting as proton donors. The pH of the solution is related to the
to hydrogen bond. charge and size of the ion. As a rough guide, hexaaqua ions with a
charge of 2+ have a pH of about 6; hexaaqua ions with a charge of
3+ have a pH of about 3.

H
δ+ [M(H2O)6]2+(aq) → ≅ pH 6
[M(H2O)6]3+ → pH ≅ 3
Fe3+ O δ− the proton can be
donated to a base
this bond is H δ+
weakened

1
112 Acid Base Reactions of Transition Metal Complexes Chem Factsheet

Reaction of Transition Metal Complexes with Strong Reaction of Transition Metal Complexes with Weak
Bases Bases
Ammonia
Hydroxide Ions Ammonia is a weak base. It removes protons from hexaaqua
Hydroxide ions are strongly basic and so have a strong tendency metal ions but to a lesser extent than the hydroxide ion. It always
to remove protons from the acidic hexaaqua ions. All solutions reacts with transition metal ions to give a precipitate of the
of transition metal ions (2+ and 3+) react with hydroxide ions to hydroxide but it is not sufficiently basic to cause the precipitate
give a precipitate of the hydroxide; some transition metal ions to re-dissolve to form a soluble hydroxy complex. (However, it
form a precipitate which re-dissolves in excess of the hydroxide. may react by a ligand exchange reaction to form a soluble
complex.)
Ions in oxidation state 2
[Fe(H2O)6]2+ + 2OH- → Fe(H2O)4(OH)2 + 2H2O Ions in oxidation state 2
pale green solution green precipitate [Fe(H2O)6]2+ + 2NH3 → Fe(H2O)4(OH)2 + 2NH4+
pale green solution green precipitate
[Co(H2O)6]2+ + 2OH- → Co(H2O)4(OH)2 + 2H2O
pink solution blue precipitate [Co(H2O)6]2+ + 2NH3 → Co(H2O)4(OH)2 + 2NH4+
(turns pink on standing) pink solution blue precipitate

[Cu(H2O)6]2+ + 2OH- → Cu(H2O)4(OH)2 + 2H2O This blue precipitate then redissolves. This is because a ligand
blue solution blue precipitate exchange reaction occurs to give the hexaammine cobalt(II)
ion. This is not related to the acidity of the ion.
Mn2+ and Ni2+ behave in a similar way. Mn2+ give a buff coloured
precipitate which darkens on standing due to oxidation; Ni2+ [Co(H2O)6]2+ + 6NH3 → [Co(NH3)6]2+ + 6H2O
gives a green precipitate. pink solution straw solution

Ions in oxidation state 3 This is then readily oxidised by oxygen from the air to
[Cr(H2O)6]3+ + 3OH- → Cr(H2O)3(OH)3 + 3H2O hexaammine cobalt(III) ion
ruby solution green precipitate
[Co(NH 3) 6] 2+ → [Co(NH3)6]3+ + e
straw solution orange solution
The precipitate dissolves in excess OH- to give the hexahydroxy
complex: [Cu(H2O)6]2+ + 2NH3 → Cu(H2O)4(OH)2 + 2NH4+
blue solution blue precipitate
Cr(H2O)3(OH)3 + 3OH- → [Cr(OH)6]3- + 3H2O
green precipitate deep green solution The precipitate again dissolves because a ligand exchange
reaction occurs to give the tetraamminecopper(II) ion
[Fe(H2O)6]3+ + 3OH- → Fe(H2O)3(OH)3 + 3H2O
[Cu(H2O)6]2+ + 4NH3 → [Cu(NH3)4(H2O)2]2+ + 4H2O
violet orange/brown
pale blue solution deep blue solution
precipitate
This precipitate does not re-dissolve Mn2+ and Ni2+ behave in a similar way. Mn2+ gives a buff coloured
Aluminium, although not a transition metal, behaves like precipitate which darkens on standing due to oxidation; Ni2+
chromium: gives a green precipitate which dissolves in excess ammonia to
give a blue solution. This is due to a ligand exchange reaction.
[Al(H2O)6]3+ + 3OH- → Al(H2O)3(OH)3 + 3H2O
colourless solution white precipitate Ions in oxidation state 3
[Cr(H2O)6]3+ + 3NH3 → Cr(H2O)3(OH)3 + 3NH4+
Al(H2O)3(OH)3 + 3OH- → [Al(OH)6]3- + 3H2O ruby solution green precipitate
white precipitate colourless solution
The precipitate dissolves slowly in excess conc. NH3 to give the
Aluminium hydroxide and chromium hydroxide are said to be hexaamine complex. This is again a ligand exchange reaction.
amphoteric since they will react both with acid (to give the
hexaaqua ion) and strong base (to give the hexahydroxy [Cr(H 2O) 6] 3+ + 6NH3 → [Cr(NH3)6]3+ + 6H2O
chromium(III) ion or hexahydroxyaluminium(III) ion). green solution purple solution
[Fe(H2O)6]3+ + 3NH3 → Fe(H2O)3(OH)3 + 3NH4+
violet solution orange/brown precipitate

[Al(H2O)6]3+ + 3NH3 → Al(H2O)3(OH)3 + 3NH4+

colourless solution white precipitate

2
112 Acid Base Reactions of Transition Metal Complexes Chem Factsheet

Reaction of Transition Metal Complexes with Weak Bases

Carbonate Ions
Carbonate ions are weakly basic.
Ions in oxidation state 2 Ions in oxidation state 3
Hexaaqua ions of transition metal ions in oxidation state 2 react Hexaaqua ions of transition metal ions in oxidation state 3 are
with carbonate ions to give a precipitate of the carbonate. The more acidic than those in oxidation state 2. They are sufficiently
carbonates do not redissolve in excess. acidic to decompose the carbonate to carbon dioxide and water
and they give a precipitate of the metal hydroxide.
[Fe(H2O)6]2+ + CO32- → FeCO3 + 6H2O
green solution green precipitate 2[Fe(H2O)6]3+ + 3CO32- → 2Fe(H2O)3(OH)3 + 3CO2 + 3H2O
[Co(H2O)6] 2+
+ CO 2-
→ CoCO3 + 6H2O violet solution orange brown
3
pink solution pink precipitate precipitate
[Cu(H2O)6]2+ + CO32- → CuCO3 + 6H2O 2[Cr(H2O)6]3+ + 3CO32- → 2Cr(H2O)3(OH)3 + 3CO2 + 3H2O
blue solution green precipitate ruby solution green precipitate
The hexaaqua 2+ ion solutions are not sufficiently acidic to 2[Al(H2O)6]3+ + 3CO32- → 2Al(H2O)3(OH)3 + 3CO2 + 3H2O
displace carbon dioxide. colourless solution white precipitate

Questions
1. Give an approximate value for the pH of the following solutions. colourless solution white precipitate
Select your answer from the following choices: approximately 6, [Al(H2O)6]3+ Al(H2O)3(OH)3 + 3H+ Æ
approximately 3 or approximately neutral. Assume that all the
give the hexaaquaaluminium ion.
solutions are 1M.
The aluminium hydroxide redissolves in excess of the acid to
(a) chromium(III) sulphate (b) iron(II) chloride
(c) potassium chloride (d) copper(II) sulphate colourless solution white precipitate
(e) cobalt(II) sulphate (f) iron(III) chloride [Al(OH)4]- + H+ + 2H2O → Al(H2O)3(OH)3
aluminium hydroxide:
2. A solution containing nickel(II) ions (such as nickel(II) sulphate) The aluminate ion reacts with the acid to give a precipitate of
reacts with a solution of sodium hydroxide to give a green
precipitate of nickel(II) hydroxide. Write an equation for this On addition of dilute acid, these reactions are reversed:
reaction using [Ni(H2O)6]2+ for the nickel(II) ion. white precipitate colourless solution
Al(H2O)3(OH)3 + OH- → [Al(OH)4]- + 3H2O
3. A solution containing manganese(II) ions (such as
the aluminate ion:
manganese(II) sulphate) reacts with a solution of ammonia to
The precipitate redissolves in excess sodium hydroxide to give
give a buff coloured precipitate of manganese(II) hydroxide.
Write an equation for this reaction using [Mn(H2O)6]2+ for the colourless solution white precipitate
manganese(II) ion. [Al(H2O)6]3+ + 3OH- → Al(H2O)3(OH)3 + 3H2O
4. When iron(III) chloride reacts with sodium carbonate an orange/ aluminium hydroxide:
brown precipitate is seen and bubbles of gas are evolved. Explain 5. Addition of sodium hydroxide forms a white precipitate of
these observations and write an equation for the reaction.
2[Fe(H2O)6]3+ + 3CO32- → 2Fe(H2O)3(OH)3 + 3CO2 + 3H2O
5. If sodium hydroxide is added slowly to a solution of aluminium
hexaaquairon(III) ion to give iron(III) hydroxide Fe(H2O)3(OH)3
sulphate, a white precipitate is formed which redissolves in
ion behaves as a base and removes protons from the
excess sodium hydroxide to give a colourless solution. Explain
the carbonate ion to give carbon dioxide gas. The carbonate
these observations and write equations for the reactions. What
4. The hexaaquairon(III) ion is sufficiently acidic to decompose
would you expect to see if dilute hydrochloric acid were slowly
added to the resulting solution? Write equations to explain the + 2NH3 → Mn(H2O)4(OH)2 + 2NH4+ 3. [Mn(H2O)6]2+
expected observations.
2. [Ni(H2O)6]2+ + 2OH- → Ni(H2O)4(OH)2 + 2H2O

(f) approx. 3 (d) approx. 6 (e) approx. 6

(c) approx. neutral 1. (a) approx. 3 (b) approx. 6
Answers
Acknowledgements: This Factsheet was researched and written by Chris Senior.
Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire, TF1
1NU. ChemistryFactsheets may be copied free of charge by teaching staff or
students, provided that their school is a registered subscriber. No part of these
Factsheets may be reproduced, stored in a retrieval system, or transmitted, in
any other form or by any other means, without the prior permission of the
publisher. ISSN 1351-5136

3
 Chem Factsheet
www.curriculum-press.co.uk Number 113
High Resolution NMR Spectroscopy
To succeed in this topic you need to understand: The exact amount of energy required depends on the chemical
• the structure of atoms environment of the hydrogen nuclei. Nuclei with a high electron
• the functional groups of the organic compounds studied at AS density surrounding them are shielded from the effects of the
and A2 magnetic field, so require more energy, while nuclei near to an
• that chemists need to analyse compounds (for example through electron-withdrawing group like chlorine or oxygen are deshielded
mass spectrometry and infra-red) and need less energy. The NMR machine detects the amount of
energy needed and scans through a range of energies until all the
After working through this Factsheet you will be able to: hydrogen nuclei have flipped.
• understand the importance of NMR as an analytical technique
• predict and interpret high resolution proton NMR spectra How is an NMR carried out?
To carry out an NMR spectrum, the sample is first dissolved in a
What is NMR? solvent. The solvent must not contain any hydrogen atoms, since
NMR stands for nuclear magnetic resonance. It is a powerful these would interfere with the resonance of the sample. The solvents
technique which gives us detailed information about the structure normally used are tetrachloromethane (CCl4), or deuterated solvents
of compounds. NMR can be used to analyse a number of elements like CDCl 3, where the hydrogen atoms have been replaced by
in compounds provided they have an odd mass number; these deuterium atoms (the 2H isotope of hydrogen), which do not
include 13 C, 19F and 31P, but is most commonly used to study interfere with the magnetic resonance.Spectra are calibrated using
hydrogen atoms, 1H. Remember that the nucleus of a hydrogen tetramethylsilane (TMS) (Fig 3).
atom contains a single proton, so we often refer to hydrogen NMR
as proton NMR. NMR is always used in conjunction with other Fig 3 Tetramethylsilane
techniques, like mass spectrometry and infra-red, but is arguably CH 3
the most powerful method of analysis available to organic chemists.
H 3C Si CH 3
How does NMR work?
CH 3
Hydrogen nuclei have a property called spin, which makes them
behave like tiny magnets. When you hold the nuclei in a magnetic All the hydrogen atoms in TMS are in the same, highly shielded,
field, they align themselves with the field, like compass needles all environment and so will produce a single peak in the NMR spectrum.
pointing north (Fig 1). The horizontal axis of the spectrum is called the chemical shift (δ),
which is measured in parts per million (ppm). It indicates the
Fig 1 Hydrogen nuclei without and with a magnetic field applied difference in absorbed energy between the TMS protons and the
sample protons. The peak for TMS at 0 ppm does not always appear
in the spectra, since machines are often internally calibrated, but if
Direction of applied

there is a peak at 0 ppm, it will be due to the TMS protons.

What does an NMR spectrum tell us?
Fig 4 shows the proton NMR spectrum of 1,2-dichloro-2-
magnetic field

methylpropane. In the spectrum there are two peaks, at 1.6 and 3.7
ppm. There are four pieces of information we can gather from these
peaks.
No magnetic field applied
Fig 4 The proton NMR spectrum of 1,2-dichloro-2-methylpropane
If exactly the right amount of energy is absorbed by the nuclei, they
will flip and point in the other direction (Fig 2). This is called nuclear
magnetic resonance. H

Fig 2 Hydrogen nuclei absorb energy and their spin flips H C H

H H
Direction of applied

H C C C H
Cl Cl H
magnetic field

10 9 8 7 6 5 4 3 2 1 0
δ (ppm)
1
113 High Resolution NMR Spectroscopy Chem Factsheet

1. The number of different chemical environments in the compound 4. How many neighbours each hydrogen atom has
Firstly, the NMR shows us that there are two different chemical Finally, the spectrum gives us information about the
environments for hydrogen atoms in this compound (Figure 5). neighbouring hydrogen atoms of the nuclei. This comes from
The six hydrogens in the methyl (CH3) groups are in the same the splitting pattern, where the peaks in the spectrum are split
environment since they are the same distance from the chlorine into groups of sub-peaks (Table 2). The splitting pattern depends
atoms and from the central carbon atom. The two hydrogens in on how many non-equivalent hydrogen nuclei are on the
Environment 2 are closer to one of the chlorine atoms and adjacent carbon atoms. Splitting occurs because the magnetic
therefore chemically different from Environment 1. fields of different hydrogen nuclei interact with each other, and
the number of sub-peaks is always one more (n+1) than the
Fig 5 The two hydrogen environments in 1,2-dichloro-2- number of hydrogens (n) on the adjacent carbon atom. You
methylpropane won’t need to explain how this happens, but you do need to
H understand its effects.
H C H environment 1
Table 2 Splitting patterns
H H
environment 2
H C C C H Number of Splitting How it looks Typical
Cl Cl H hydrogen atoms pattern structure
on the adjacent (n+1)
2. The relative number of hydrogens in each environment carbon atom (n)
The second piece of information comes from the integration
curve, the line above each peak. The height of this line
corresponds to the area under the curve and therefore tells us
the relative numbers of hydrogen atoms in the different 0 Singlet R3CCH
environments. If you measure the height of the two integration
curves in Fig 4 you will find that they are in a ratio of 1:3. This
matches the structure of the compound, with two hydrogen
nuclei in Environment 2 and six in Environment 1.
3. The electron density around the hydrogen atoms 1 Doublet R2CH-CH
The third piece of information is about the nature of each
environment. This information is given by the chemical shifts
(Table 1). In the exam, you will be given the chemical shifts that
you need, so don’t try to memorise them.
Looking at Fig 4 again, the peaks at 1.6 and 3.7 ppm correspond
respectively to the methyl hydrogens (Environment 1) and the
CH2Cl hydrogens (Environment 2), which are deshielded by the
closer electron-withdrawing chlorine atom. 2 Triplet RCH2-CH

Table 1 Typical chemical shifts of a range of hydrogen nuclei

Proton Chemical shift (ppm)
R-CH3 0.8-1.2
R2-CH2 1.1-1.5
R3-CH 1.5 3 Quartet CH3-CH
R3-OH 1.0-6.0

Note that the OH hydrogen

atom can appear almost In the NMR of 1,2-dichloro-2-methylpropane (Fig 4), both peaks are
anywhere along the chemical singlets. This means that none of the hydrogens are adjacent to
shift scale non-equivalent hydrogen nuclei (Fig 6).
O
1.0-6.0 Fig 6 No adjacent hydrogen atoms to either environment
C
R CH2R H
R-CH2-Cl 2.5-4.3 environment 1
H C H
R-CH2-OH 3.3-4.0 H H
R H environment 2
4.4-6.9 H C C C H
C C
R R Cl Cl H
O
C 9.2-9.8
R H This carbon atom is adjacent to both environments. It has no hydrogen
O atoms so both peaks are singlets
C 10.0-12.0
R OH
2
113 High Resolution NMR Spectroscopy Chem Factsheet

Fig 7 shows the proton NMR spectrum of ethyl ethanoate. The Answer
three peaks show that there are three different environments for the The displayed formula and NMR spectrum of chloroethane are
hydrogen atoms. The integration curves give us a ratio of 2:1:3, shown in Fig 9. There are two hydrogen environments: the methyl
and analysis of the splitting patterns (Table 3) leads to a full hydrogens (a) and the CH2Cl hydrogens (b). Using Table 1 the
assignment of peaks (Fig 8). approximate chemical shifts are 1.1-1.5 and 2.5-4.3 ppm respectively.
The peak at about 1.4 ppm (corresponding to the CH3) is split into a
Fig 7 The proton NMR spectrum of ethyl ethanoate triplet by the neighbouring CH2Cl hydrogens, while the peak at 3.5
ppm (corresponding to the CH2Cl) is split into a quartet by the
H methyl group.
O
H H
H C C
Fig 9 Chloroethane and its NMR spectrum
O C C H
H
H H -CH3(a)
b
a H H

H C C Cl -CH2Cl(b)

H H

11 10 9 8 7 6 5 4 3 2 1 0
δ (ppm)

Table 3 Assigning the peaks in the NMR of ethyl ethanoate

10 9 8 7 6 5 4 3 2 1 0
Chemical Relative Splitting Number of Assigned δ (ppm)
shift number pattern adjacent to proton
of hydrogen hydrogens group An unusual case: Alcohol OH groups
atoms The hydrogen atom in alcohol OH groups is unusual in two ways.
4.1 2 Quartet 3 b Firstly, as it says in Table 1, this proton can have almost any chemical
shift. The actual shift depends on, among other things, the solvent
2.0 3 Singlet 0 a that the compound is dissolved in. Secondly, at room temperature
OH proton peaks do not get split like others, no matter how many
1.2 3 Triplet 2 c
adjacent hydrogen nuclei there are. This helps you, therefore, to
identify them in the spectra since they are always singlet peaks.
Fig 8 Assigned peaks in ethyl ethanoate
Practice Questions
a H 1. For each of the following compounds, draw the displayed
b c
O formula, label the different hydrogen environments and predict
H H
H C C
approximate chemical shifts for each peak in the proton NMR
spectrum:
O C C H
(a) 2-chloropropane
H
(b) 1-chloropropane
H H (c) ethanol
(d) ethanoic acid
(e) 2-chloropentane
Worked example (f) 3-chloropentane
1. Draw the displayed formula of chloroethane.
2. State the number of different hydrogen environments found 2. Sketch the proton NMR spectra you would expect for the
in chloroethane. following compounds:
3. Predict approximate chemical shifts for the different (a) ethanoic acid
environments. (b) propanone
4. Predict the splitting pattern of the NMR peaks. (c) ethanal
5. Sketch the NMR spectrum of chloroethane, including (d) ethanol
integration curves to show the relative numbers of hydrogen
atoms in each environment.

3
113 High Resolution NMR Spectroscopy Chem Factsheet

(b)
Answers

Question 1 O
(a) Environment 2 C
Cl H3C CH3
Environment 1 = 2.5-4.3 ppm
H 3C C CH3 Environment 2 = 0.8-1.2 ppm
H
Environment 1

H H
(b) Environment 1 = 0.8-1.2 ppm
H 3C C C Cl
Environment 2 = 1.1-1.5 ppm
1 H H Environment 3 = 2.5-4.3 ppm
2 3
10 9 8 7 6 5 4 3 2 1 0
H H
(c) Environment 1 = 0.8-1.2 ppm δ (ppm)
H C C O Environment 2 = 3.3-4.0 ppm
H H H Environment 3 = 1.0-6.0 ppm (c)
1 2 3
O

O C
(d) H H 3C H
H C C O Environment 1 = 2.0-3.0 ppm
H H Environment 2 = 10.0-12.0 ppm
1 2

Cl H H Environment 1 = 0.8-1.2 ppm

Environment 2 = 2.5-4.3 ppm
(e) H 3C C C C CH3
Environment 3 = 1.1-1.5 ppm
1 H H H 5 Environment 4 = 1.1-1.5 ppm
2 3 4 Environment 5 = 0.8-1.2 ppm

(f) Environment 1 = 0.8-1.2 ppm 10 9 8 7 6 5 4 3 2 1 0

H Cl H Environment 2 = 1.1-1.5 ppm δ (ppm)
H3C C C C CH 3 Environment 3 = 2.5-4.3 ppm
1 Note that this molecule is (d)
H H H 1
symmetrical so has only three
2 3 2
different hydrogen environments H H
H C C O
H
Question 2 H H
(a)

O
C
H 3C OH

11 10 9 8 7 6 5 4 3 2 1 0
δ (ppm)
Acknowledgements: This Factsheet was researched and written by Emily Perry.
Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire, TF1
12 10 8 6 4 2 0 -2 1NU. ChemistryFactsheets may be copied free of charge by teaching staff or
δ (ppm) students, provided that their school is a registered subscriber. No part of these
Factsheets may be reproduced, stored in a retrieval system, or transmitted, in
any other form or by any other means, without the prior permission of the
publisher. ISSN 1351-5136
4
 Chem Factsheet
www.curriculum-press.co.uk Number 114

Buffers: Action and Calculations

To succeed in this topic you need to: Note that we can use HA to represent any weak acid, which
• understand definitions of BrØnsted-Lowry acids and bases gives these general equations:
• understand definitions of strong and weak acids and bases
• be able to calculate the pH of strong and weak acids and bases HA (aq) + H2O (l) H3O+ (aq) + A- (aq)
• understand Le Chatelier’s Principle
NaA (aq) Na+ (aq) + A- (aq)
• be able to use the equation pKa = -log10Ka

After working through this Factsheet you will:

• understand what a buffer solution does and how it does it If an acid is added to the buffer, the concentration of H+ ions
• be able to explain how to make a buffer solution increases. These extra H+ ions combine with CH3COO- ions to
• be able to calculate the pH of buffer solutions make undissociated CH 3 COOH (Equation 3), shifting the
equilibrium in Equation 1 to the left. The concentration of H+ ions
(and therefore the pH) remains constant.
What does a buffer solution do?
Definition: A buffer solution is a solution that resists changes in Equation 3
pH when small amounts of acid or base are added to it. CH3COO- (aq) + H+ (aq) CH3COOH (aq)
If an alkali is added, the solution has to remove the extra OH- ions.
These combine with H+ ions to make water (Equation 4). The
What this means is that, by adding a buffer solution to a mixture, the equilibrium in Equation 1 will shift to the right to replace these
pH will stay roughly constant even when some acid or alkali is added used H+ ions and again the pH will remain constant.
to the mixture. This is useful in many experiments, especially many
biological systems, where it can be vital to control the pH of an Equation 4
enzyme, for example. OH- (aq) + H+ (aq) H2O (l)

What is a buffer solution made of? Alkali buffers

Buffers can be acidic or alkaline. Acid buffers are made from a solution Alkali buffers behave in similar ways to acid buffers, but there are
of a weak acid with a salt of same the weak acid. For example, an acid subtle differences.
buffer could be made by mixing solutions of ethanoic acid (CH3COOH,
the weak acid) and sodium ethanoate (CH3COONa, the salt). The pH As with the acid buffer, the weak base (ammonia, NH3, in this
of this solution would be below 7 (see below for how to calculate the example) reacts with water to release ammonium ions (NH4+) and
pH of buffer solutions), so the buffer is acidic. Alkali buffers are hydroxide ions (OH-) (Equation 5), but the equilibrium lies a long
made from a solution of a weak base with the salt of the same base. way to the left because only a small percentage of ammonia
For example, you could mix ammonia solution (NH3, the weak base) dissociates:
with ammonium chloride (NH4Cl, the salt), and the pH of the resulting
buffer solution would be above 7. Equation 5
NH3 (aq) + H2O (l) NH4+ (aq) + OH- (aq)
How do buffer solutions work? Similarly, the salt (ammonium chloride, NH 4Cl) dissociates
Buffers work because they can absorb and release H+ ions to maintain completely in solution (Equation 6):
their pH. They do this by changing the position of equilibrium of the
substances in solution. Equation 6
NH4Cl (aq) NH4+ (aq) + Cl- (aq)
Acid buffers This means that this buffer solution contains relatively high
The weak acid (ethanoic acid, CH3COOH) partially dissociates in concentrations of both NH3 molecules and NH4+ ions.
solution (Equation 1), but the equilibrium lies a long way to the left
because only a tiny percentage of acid dissociates:
Note that we can use B to represent any weak base, which
Equation 1 gives these general equations:
CH3COOH (aq) H+ (aq) + CH3COO- (aq)
The salt (sodium ethanoate, CH3COONa) dissociates completely in B (aq) + H2O (l) BH+ (aq) + OH- (aq)
solution (Equation 2): BH+Cl- (aq) BH+ (aq) + Cl- (aq)

Equation 2
CH3COONa (aq) Na+ (aq) + CH3COO- (aq) If acid is added, the concentration of H+ ions will increase. These
This means that this buffer solution contains relatively high extra H+ ions will combine with OH- ions to make undissociated
concentrations of both CH3COOH molecules and CH3COO- ions. water (Equation 7). The equilibrium in Equation 5 will subsequently
shift to the right to replace the OH- ions.
1
114 Buffers: Action and Calculations Chem Factsheet

Equation 7
Example 2
H+ (aq) + OH- (aq) H2O (l)
A buffer solution was made by mixing 30.0 cm3 of 2.0 moldm-3
If alkali is added, the solution has to remove the added OH- ions. ethanoic acid (Ka = 1.76 x 10-5 moldm-3) with 35.0 cm3 of 1.5
These react with NH4+ ions to make ammonia and water (Equation 8) moldm-3 sodium ethanoate. What is its pH?
and so the equilibrium in Equation 5 will shift to the left. Again the
pH will remain constant. The first steps this time involve calculating the concentrations of
the two liquids in the buffer solution.
Equation 8
OH- (aq) + NH4+ (aq) NH3 (aq) + H2O (l) Step 1. Calculate the number of moles of ethanoic acid in the
solution:
Remember : Don’t forget that, with all buffer solutions, if a
large amount of acid or alkali is added, then the pH will moles = concentration × volume
30.0
eventually change. = 2.0 × = 0.060 moles ethanoic acid
1000
Step 2. Calculate the number of moles of ethanoate ions in the
Buffer Range solution:
Buffers work effectively within a range of ±1 pH value of the pKa of moles = concentration × volume
the weak acid (or the pKb of the weak base). For example, ethanoic 35.0
acid, the weak acid used in the example above, has a K a of = 1.5 × = 0.053 moles ethanoate ions
1000
1.76 x 10-5 moldm-3. Its pKa is therefore 4.75 (remember that pKa = - The rest of the calculation follows the same route as Example 1:
log10Ka). The range of an ethanoic acid buffer is therefore from a pH
of around 3.7 up to a pH of about 5.7. [CH3COOH] 0.060/Vtot
[H3O+] = Ka × = 1.76 × 10-5 ×
[CH3COO-] 0.053/Vtot
Calculating the pH of a buffer solution [H3O+] = 2.00 × 10-5 moldm-3
To calculate the pH of buffer solutions, you need to know:
ƒ the amounts and concentrations of the weak acid (or base) and pH = -log10[H+] = -log10(2.00 × 10-5) = 4.70
the salt in the buffer Note: You don’t need to calculate the actual concentrations
ƒ the Ka of the weak acid (or Kb of the weak base) – remember that of ethanoic acid and ethanoate ions, because the total volume
this is a constant at a given temperature. of the solution (Vtot) cancels itself out in the equation.

Example 1 Example 3
A buffer solution was made containing 0.20 moldm-3 ethanoic 10.0 cm3 of 0.10 moldm-3 hydrochloric acid was added to the
acid and 0.25 moldm-3 sodium ethanoate. What is its pH? The buffer solution in Example 2. What is its new pH?
Ka of ethanoic acid is 1.76 x 10-5 moldm-3.
Adding hydrochloric acid to the buffer involves adding H+ ions.
Step 1. Write an expression for Ka: The first step is to calculate how many moles of H+ ions are added.
[CH3COO-][H3O+] moles = concentration × volume
Ka = [CH3COOH] 10
= 0.10 × = 0.001 moles H+ ions.
1000
Step 2. Rearrange to give an expression for [H3O+]: These H+ ions will react with 0.001 moles of CH3COO- ions to form
0.001 moles of CH3COOH as shown in equation 9.
[CH3COOH]
[H3O+] = Ka ×
[CH3COO-]
Equation 9
CH3CHOO- (aq) + H+ (aq) CH3COOH (aq)
Step 3. The salt is fully ionised in solution, so we can assume
that [CH3COO-] is equal to the concentration of the salt solution. We need, therefore, to calculate new values of [CH3COO-] and
So in this case [CH3COO-] = 0.25 moldm-3. [CH3COOH].
New moles of CH3COO- ions = 0.053 – 0.001 = 0.052 moles.
Step 4. The weak acid is very slightly dissociated in solution, so we
assume that [CH3COOH] is, in fact, equal to the concentration of New moles of CH3COOH = 0.060 + 0.001 = 0.061 moles.
acid in the buffer. In this case, then, [CH3COOH] = 0.20 moldm-3.
The rest of the calculation now follows the same route as before:
Step 5. Substitute the values into the equation: [CH3COOH] 0.061/Vtot
[H3O+] = Ka × = 1.76 × 10-5 ×
[CH3COOH] 0.20 [CH3COO-] 0.052/Vtot
[H3O ] = Ka ×
+
= 1.76 × 10-5 ×
[CH3COO-] 0.25
[H3O+] = 2.07 × 10-5 moldm-3
[H3O ] = 1.41 × 10 moldm
+ -5 -3

pH = -log10[H+] = -log10(2.00 × 10-5) = 4.68

Step 6. Calculate the pH:
You can see that, as expected, the addition of hydrochloric acid
pH = -log10[H+] = -log10(1.41 × 10-5) = 4.85
to this buffer solution has changed the pH only slightly.

2
114 Buffers: Action and Calculations Chem Factsheet

Exam Hints:
1. Learn the definition of a buffer solution.
2. Practice writing equations to show how buffers work.
3. Remember that for a weak acid, [acid] is not equal to [H+].
4. Practice and take great care with the calculations; many students make mistakes with them.

Practice Questions Answers

1. Given samples of the following solutions (all 0.20 moldm ), pick-3 1. (a) acidic buffer: ethanoic acid and sodium ethanoate
(a) a pair which could be mixed to make an acidic buffer, and (b) alkali buffer: ammonia and ammonium nitrate
(b) a pair which could be mixed to make an alkali buffer.
2. Propanoic acid is weak, so it only partially dissociates in
Ammonia Sodium hydroxide solution. The equilibrium lies a long way to the left:
Ammonium nitrate Sodium ethanoate
Ethanoic acid Sodium nitrate CH3CH2COOH (aq) H+ (aq) + CH3CH2COO- (aq)
Nitric acid Sulphuric acid
The sodium propanoate salt ionises fully in solution:
2. A buffer solution can be made by mixing solutions of propanoic
CH3CH2COONa (aq) Na+ (aq) + CH3CH2COO- (aq)
acid (CH3CH2COOH) with sodium propanoate (CH3CH2COONa).
Explain how this buffer maintains a constant pH when a small This buffer solution therefore contains relatively high
amount of hydrochloric acid is added. concentrations of both CH 3 CH 2 COOH molecules and
CH3CH2COO- ions.
3. Three buffer solutions contain ethanoic acid (Ka = 1.76 × 10-5 mol dm-3)
When hydrochloric acid is added, the additional H+ ions combine
at a concentration of 0.15 moldm-3. They also contain sodium
with CH3CH2COO- ions to make undissociated propanoic acid:
ethanoate at concentrations of :
(a) 0.10 moldm-3 CH3CH2COO- (aq) + H+ (aq) CH3CH2COOH (aq)
(b) 0.25 moldm-3 and
The equilibrium shifts to the left and the concentration of H+
(c) 0.50 moldm-3.
Calculate the pH values of the three solutions. ions (and therefore the pH) remains constant.

4. What is the pH of the buffer solution formed by mixing 25.0 cm3 3. (a) 4.58, (b) 4.98, (c) 5.28.
of 0.20 moldm-3 sodium hydroxide with 25.0 cm3 of 0.40 moldm-3
ethanoic acid (Ka = 1.76 × 10-5 moldm-3)? 4. 4.75. You first need to calculate the number of moles of NaOH
= 0.20 × (25/1000) = 0.005.
5. A buffer solution was made by mixing 10.0 cm3 of 0.025 mol dm-3 Next, calculate the number of moles of CH3COOH
ethanoic acid (Ka = 1.76 × 10-5 mold m-3) with 15.0 cm3 of 0.025 mol dm-3 = 0.4 × (25/1000) = 0.010.
sodium ethanoate. NaOH reacts with CH3COOH to make sodium ethanoate and
water:
A sample of 15 cm3 0.010 moldm-3 hydrochloric acid was added.
Calculate the pH of the buffer solution (a) before, and (b) after NaOH (aq) + CH3COOH (aq) → CH3CH2COONa (aq) + H2O (l)
the addition of the hydrochloric acid. 0.005 moles of NaOH will make 0.005 moles of sodium ethanoate,
leaving (0.010-0.005) = 0.005 moles of ethanoic acid unreacted.

[CH3COOH] 0.005
[H3O+] = Ka × = 1.76 × 10-5 ×
[CH3COO-] 0.005
[H3O+] = 1.76 × 10-5 moldm-3
pH = -log10[H+] = 4.75

5. (a) 4.93, (b) 4.50.

Acknowledgements: This Factsheet was researched and written by Emily Perry. Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire,
TF1 1NU. ChemistryFactsheets may be copied free of charge by teaching staff or students, provided that their school is a registered subscriber. No part
of these Factsheets may be reproduced, stored in a retrieval system, or transmitted, in any other form or by any other means, without the prior permission
of the publisher. ISSN 1351-5136

3
 Chem Factsheet
www.curriculum-press.co.uk Number 115

Polarimetry
Which of the following statements are true and which are false?
Plane-polarised light results from the superposition of equal
intensities of left- and right-circularly polarised light. When
Statement True False
plane-polarised light travels through an optically active sample
1 Polarimetry determines the degree of the left- and right- circularly polarised components travel at
polarity of a molecule different velocities and, as it exits, the sum of the two
2 A polarimeter can be used to follow the components is still plane-polarised but at a different orientation
progress of some reactions from the light entering the sample. Even if you do not understand
all of this, as it is somewhat outside the scope of the specification,
3 A chiral molecule gives rise to optical do be careful to use correct terms: “Some candidates used
isomers which are mirror images of each other ‘polarised light’ as a synonym for plane-polarised light” –
4 Optical isomers result from the fact that carbon critical extract from Examiners Report
atoms on either side of a double bond cannot
rotate freely
Key Fact 2
5 Optical isomers have a chiral centre which can
A simple polarimeter consists of a monochromatic light source (e.g.
be a nitrogen atom
sodium lamp), a polariser (e.g. Nicol prism of calcite) which sends a
6 A racemic mixture has equal amounts of two beam of plane-polarised light through the sample cell, a second
enantiomers polariser called the analyser, and a light detector.
7 A chiral centre is a carbon atom with two
identical groups attached
8 An enantiomer can be dextrorotatory (d)
Sodium Polariser Sample Analyser Detector
or laevorotatory (l) or a combination of both
Lamp Cell
9 The polarised light from the polarimeter rotates
the molecules In the absence of the sample in the cell, the analyser is rotated until
the light reaching the detector is a minimum. Then, with the sample
If you answered true to questions 2, 3, 6 and false to all the others, in the cell the analyser is rotated to restore the light to minimum
then you are a star student! You may already have an excellent intensity. The direction and angle of rotation needed to restore the
grasp of the fundamental knowledge needed to succeed in this area light to minimum intensity is recorded. This is the angle through
of your specification, so why not go straight to the sample questions which the sample has rotated the plane of polarisation of the plane-
at the end and try your knowledge further? Otherwise read on polarised light.
……..
Key Fact 3
If you feel that this topic is a minefield of new terms and ideas which (a) A chiral centre may be identified or detected as a carbon atom
are difficult to express, then this Factsheet is structured to ensure with four different groups attached (also called an asymmetric
that you can explain these in the way which examiners like and give carbon atom).
marks for. It is designed to help you learn and understand: (b) The chiral centre results in the molecule being able to exist in
two forms which are object and non-super imposable mirror
(a) The fundamental principles of polarimetry and the use of a image (rather like left and right hands).
polarimeter. e.g. Lactic acid (systematic name 2-hydroxypropanoic acid)
(b) How to identify the molecular structure which results in optical
COOH
isomerism.
(c) The terms chirality and chiral centre, racemate or racemic mixture H C CH3
and enantiomer. OH
(d) The importance of chiral molecules in living systems.
The central carbon atom is asymmetric. This means that the
(e) The use of polarimetry in distinguishing between enantiomers
molecule can exist in two mirror image forms:
and determining their relative concentrations, and its importance
in relation to the synthesis of pharmaceuticals.
COOH HOOC
Key Fact 1
C C
Polarimetry is the measurement of the angle of rotation of the plane H 3C H CH 3
H
of polarisation of plane-polarised light. This rotation of the plane of
polarisation occurs when plane-polarised light passes through OH HO
certain transparent materials.
1
115. Polarimetry Chem Factsheet

It is important to include the idea of non-super imposable mirror Key Fact 8

images when explaining the term ‘chiral’ – “A large number of Many of the molecules found in living organisms exist as enantiomers
candidates gave a correct description of chiral, although there and usually only one of the enantiomers is biochemically active.
are still a few who just write that it is a carbon atom with four
different atoms or groups attached”. Detection involves looking For example, nearly all of the amino acids which make up proteins
for the four different groups - “chirality is best defined in terms are chiral molecules, but only one of the forms (the L-amino acids)
of non-super imposable mirror images, and many candidates is found in living systems.
used this idea and could say how chirality is detected” – extracts
from Examiners Reports. Example: An enzymes is shaped selective. Thus only one
enantiomer can act as its substrate.

Key Fact 4
The presence of a single asymmetric carbon atom (chiral centre) in Key Fact 9
a molecule results in the molecule being able to exist as two optical The optical isomers of a pharmaceutical compound which is chiral
isomers which are called enantiomers. must be isolated and tested separately as the isomers may have
very different effects on living organisms. Medicines having chiral
Key Fact 5 molecules often need to be administered as a pure enantiomer.
The only difference between enantiomers is that one form rotates Examples of this include:
the plane of plane-polarised light clockwise and is called the (+) or (a) The Thalidomide molecule is chiral; one optical isomer acts as a
dextrorotatory (d) isomer. The other rotates the plane of plane- non-addictive sedative but the other isomer has the potential to
polarised light anticlockwise and is called the (-) or laevorotatory (l) adversely affect foetal growth.
isomer.
Care is needed here when choosing words – “Many candidates (b) Morphine is a chiral compound but only one isomer acts as an
knew how to distinguish optical isomers, but some were still efficient (but addictive) painkiller.
using words like reflect or deflect instead of rotate and there
were some candidates who thought that the polarised light (c) One optical isomer of DOPA, called L-DOPA, is effective in the
rotates the molecules” – extract from Examiners Report treatment of Parkinson’s disease but the other isomer is of no
use.]

Key Fact 6 Key Fact 10

An equimolar mixture of the dextrorotatory (+) and laevorotatory (-) Synthetic organic reactions often result in a mixture containing both
isomers is called a racemic mixture or racemate. A racemic mixture isomers in equal amounts (racemic mixture).
does not rotate the plane of plane-polarised light because the effect
of the two isomers cancel one another out. The isomers may be separated by crystallisation with a chiral
acid or base or by chiral high performance liquid chromatography.
Key Fact 7 Processes have also been developed which produce pure
Many natural products are chiral (for example sugars, amino acids, enantiomers, making separation unnecessary
proteins and nucleic acids). A polarimeter may be used to monitor
reaction rates where these compounds are involved. The synthesis of pharmaceuticals often requires the production of
chiral drugs containing a single optical isomer. The advantages
e.g. the hydrolysis of sucrose in acid solution using enzymes
are:
(a) Smaller doses (only half the drug is needed)
C12H22O11 + H2O → C6H12O6 + C6H12O6
(b) Reduced side effects
Sucrose Glucose Fructose
Dextrorotatory Dextrorotatory Laevorotatory (c) Improved pharmacological activity
(+) (+) (–)

Note that glucose and fructose are enantiomers. Although the

reactants and products are all optically active, the extent and
direction of rotation of the plane of plane-polarised light is different
for each.

As the reaction proceeds, the formation of fructose with it’s strongly

(–) rotation dominates over the weaker (+) rotation of glucose, thus
an inversion of rotation occurs. The progress of the hydrolysis can
be determined by measuring changes in the optical rotation of the Acknowledgements: This Factsheet was researched and written by Christine
reaction solution. Collier. Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire,
TF1 1NU. ChemistryFactsheets may be copied free of charge by teaching
staff or students, provided that their school is a registered subscriber. No part
of these Factsheets may be reproduced, stored in a retrieval system, or
transmitted, in any other form or by any other means, without the prior
permission of the publisher. ISSN 1351-5136

2
115. Polarimetry Chem Factsheet

Answers
Practice Questions 1. OH
1. There are four isomeric alcohols with the molecular formula
C4H9OH. Only one of the isomers is optically active. Draw the H 3C CH 2 CH CH 3
structure of this isomer, and place an asterisk * next to the carbon 2. *
H
which is a chiral centre.
H 2N C* COOH
2. The amino acid isoleucine (structure shown below) has more *
than one chiral centre. Mark the chiral centres with asterisks. CHCH 2
CH 3
H CH3

H 2N C COOH 3. A carbon atom bonded to four different groups. This gives two
possible optical isomers which are non-super imposable mirror
CHCH2CH3
images of each other.
CH 3
3. Explain the meaning of the term chiral centre 4. (a) CH3
C * CH3
. H 2C
4. (a) Carvone is a chiral molecule, which exists in two forms in O
nature. One enantiomer gives the odour of spearmint and (b) Enantiomers have the same molecular formula but the
the other is the principal odour in caraway seed. Identify the molecule has an asymmetric carbon atom so can exist in two
chiral centre in the carvone molecule shown below: forms (enantiomers) which are non identical mirror images
CH 3 of each other. They rotate the plane of plane-polarised
C CH 3 monochromatic light in opposite directions.
H2C
CH3
O 5.
(b) Explain the term enantiomer. CH 3 C * * CH3
5. Menthol has more than one chiral centre. Mark the chiral centres H
OH
*
with asterisks in the diagram below.
H H CH3
H
CH3 6.
H C C C* N
CH 3 C CH3
H
H H H
H
OH
The asymmetric carbon atom has four different groups
attached, which results in the two enantiomers (optical
6. One isomer of C4H9NH 2 is optically active. Draw the full isomers) which are non identical mirror images of each other.
structural formula of this isomer and identify with an asterisk
the feature which gives it its optical activity. Explain how this 7. (a) By using a polarimeter, and measuring the rotation of the
feature results in two enantiomers. plane of plane-polarised monochromatic light. The light will
be rotated anti-clockwise by one enantiomer and clockwise
7. (a) How might you distinguish between two enantiomers. by the other.
(b) A racemic mixture is formed (which has equimolar amounts
(b) A chemical reaction produces two enantiomers. The mixture of each enantiomer). The plane of plane-polarised light is
formed is not optically active. Explain this. rotated anti-clockwise by one enantiomer and clockwise by
the other enantiomer by an equal amount and so the two
(c) What property of two enantiomers might be used as the rotational effects cancel out.
basis for separation of a racemate? (c) The two enantiomers react differently with other chiral
molecules.
8. When the following reaction was performed on a single
enantiomer, the resulting mixture was found to be no longer 8. The single enantiomer contains an asymmetric carbon atom,
optically active. Explain this by considering the mechanism which has four different groups attached and thus is optically
involved. active. The mechanism of the reaction is nucleophilic
substitution.
CH3 CH3
The C-Br bond breaks to form a planar carbocation. The attack
CH 3CH2 C Br + OH− → CH 3CH2 C OH + Br by the OH− can occur from either above or below this plannar
carbocation and is equally likely in any direction, and thus two
CH 2CH2 CH3 CH2CH 2CH 3
enantiomers are formed in equal amounts. This gives a racemic
mixture or racemate of (+) and (-) forms, which is optically inactive.
(The effect of the (+) form on the plane of plane-polarised light
is equal and opposite to the effect of the (-) form and thus the
two effects cancel out.)
(This type of question is worth seven or eight marks so a careful,
detailed explanation is needed.)
Note similar effects occur for planar alkenes and carbonyl
compounds.
3
 Chem Factsheet
www.curriculum-press.co.uk Number 116
The Application of Organic Reactions To
Unfamiliar Molecules (AS)
(1) The objective of this Factsheet is to test your understanding of 2. When propane reacts with chlorine in the presence of ultra
AS level organic chemistry by applying your knowledge of violet light, two isomers containing one chlorine atom per
familiar reactions to unusual molecules and unfamiliar situations. molecule, four isomers containing two chorine atoms per
This type of exercise is an excellent way of revising organic molecule and five isomers containing three chlorine atoms per
chemistry. molecule are formed.
(2) You should learn the basic chemical reactions of each of the (a) Draw abbreviated structural formula (i.e. CH3CH2- etc) for
functional groups and make sure you understand concepts such all eleven compounds and systematically name all of them.
as isomerism and spectroscopy. (b) When the chlorinated compounds above are reacted with
aqueous sodium hydroxide, the chlorine atom in the
(3) The main point to remember is that, although the problems may molecule is replaced by a hydroxy group forming an alcohol.
appear to be daunting, as far as the examination is concerned, (i) Which of the chlorinated compounds in (a) would give
the functional groups, provided they are not too close to each propane-1,3- diol in this reaction.
other, behave chemically independently of each other. (ii) If the chlorine atom in 1-chloropropane was replaced
by an iodine atom, would the iodo compound be more
(4) In problems of the type ‘A reacts and gives B' etc., it is best to or less reactive? (Bond energies C-Cl = 338 and C-I =
draw a flow chart. On many exam papers the problem is presented 238 (kJmol-1))
in a flow chart anyway. (c) What type of reaction is occurring between propane and
chlorine in the presence of ultra-violet light?
Exam Hint: Examiners may set questions on molecules that (d) Give the initiation step for this type of reaction.
you have not studied! But if they do this will be because (e) Pentane (Bpt. = 36oC), 1-choropropane (Bpt. = 47oC), and
molecules which behave in a similar way are on your
butan-1-ol (Bpt. = 117oC) all have similar molecular masses.
specification and they expect you to be able to apply your
Explain the trend in boiling points for these three
knowledge to these unfamiliar situations.
compounds.
Note : Some parts of the problems that follow may not apply to (f) Why are there no chain isomers for any of the compounds
your particular specification. If you know your stuff thoroughly, in (a)?
you will recognise these parts! You can also reinterpret the (g) Why does the mass spectrum of 1,3-dichloropropane give
question e.g. when asked for a skeletal formula it may be more three peaks at 112, 114 and 116? What might be the formula
appropriate to you to give a full structural formula. of the peak at m/z = 49?
Problems
1. Ocimene is an unsaturated hydrocarbon that belongs to a 3. There are five alkanes with the formula C6H14.
group of compounds called terpenes. Ocimene is found (a) Systematically name all five.
naturally in some well known cooking herbs and has the (b) Name the isomers with the lowest and highest boiling
structure shown below. points. Explain your reasons.
(c) Give the name of the isomer that gives only two isomeric
H2C C CH2 CH 2 CH C CH CH2 compounds containing only one chlorine atom per
molecule.
CH 3 CH 3 (d) Hexane can be cracked to give propene and propane. Give
(a) What is the molecular formula of ocimene? an equation showing this reaction.
(b) How many moles of hydrogen would be needed to fully (e) What type of mechanism is undergone by alkenes when
hydrogenate one mole of ocimene? they react?
(c) Draw the skeletal structure, and give the systematic name (f) What type of mechanism is undergone by alkanes when
of the compound formed when ocimene is fully they react?
hydrogenated. (g) Give an equation showing the complete combustion of
(d) Ocimene exists as a pair of geometric isomers. Specifically, hexane in air.
what is the feature that causes geometric isomerism in this (h) Explain how, when hexane reacts with chlorine in the
molecule? Draw the full structural formula of one of the presence of ultra violet light, there are traces of C12H26 in
two geometric isomers. the reaction mixture.
(e) The systematic name for ocimene is 3,7-dimethylocta-1,3,7-
triene. Explain the formation of this name.
(f) Explain whether this ocimene would have a higher or lower
boiling point than 2,6-dimethyloctan-1-ol.
(g) Draw a skeletal structural formula for ocimene.

1
116 The Application of Organic Reactions To Unfamiliar Molecules (AS) Chem Factsheet

4. There are five alkenes with the molecular formula C5H10. 8. The compound below has been used as an insect repellent.
(a) Draw abbreviated structural formulae for each of the five CH3 CH2 CH 2 CH CH CH2 OH
compounds.
(b) Identify which of the five structures, if any, will exist as a OH CH 2
pair of geometric isomers.
(c) When all five compounds are reacted in the presence of a CH 3
nickel catalyst, only two products are formed. Name these (a) What is the systematic name for this compound?
compounds. (b) The boiling point of the above compound is 245oC while that
(d) Explain why 2,2-dimethylpropane cannot be a product of of decane (which has a similar molecular mass) is only 174oC.
the reaction between hydrogen and any of the five Why is the boiling point of decane so much lower?
compounds with the formula C5H10. (c) When the compound is oxidised, two compounds are formed
(e) What process is used in industry to produce alkenes from depending on the conditions. Draw abbreviated structures
alkanes? for both compounds. Name a suitable oxidising agent.

H2C CH 3 5. This is the structure of limonene, a 9. Halothane, a well known general anaesthetic, has the structural
C compound found in lemons. formula shown below.
H (a) What is the molecular formula of
C limonene? Cl F (a) What is the systematic name of
H2C CH 2 (b) What is the empirical formula of H C C F halothane?
limonene? (b) Draw the structural for its isomer
HC CH 2 (c) Draw the skeletal structure of limonene. Br F 1-bromo-2-chloro-1,1,2- trifluoroethane.
C (d) Draw the skeletal structure of the
compound formed when limonene (c) A related compound, bromochlorodifluoromethane is sold
CH3 reacts with bromine. What would you under the name Halon which is used in automatic fire
observe? extinguisher systems. Draw the structural isomer for Halon.
(e) Draw the skeletal structure of the compound formed when (d) State, with an explanation whether halon, or halothane,
limonene reacts with hydrogen in the presence of a catalyst. has the highest boiling point.
(f) When the compound formed in (d) is treated with sodium (e) Considering the uses that both these compounds are put
hydroxide, all the bromine atoms in the molecule are replaced to, do you think that these compounds are very reactive?
by hydroxy groups. Draw the structure of this compound and (f ) Both these compounds are related to ‘CFC‘s. Why might
label each hydroxy group as primary, secondary, or tertiary. it not be a good idea to release large quantities of these
compounds into the upper atmosphere?

6. The compound below, eugenol, is found in clove oil and has,

in the past, been used to relieve toothache. 10. Compound A has the following composition; 60%C; 13.3%H;
26.7%O. The empirical and molecular formulas of A are the
OH (a) What is the molecular formula of same. When A is oxidised, two products (B) and (C) are possible
eugenol? depending on the conditions of the reaction. Compound B
OCH 3 (b) Draw the skeletal structure of the will release carbon dioxide from sodium carbonate solution
compound formed when eugenol is but compound C will not do this. Compound C also has a
completely hydrogenated. much lower boiling point than B. A is capable of being
(c) Can eugenol exist as a pair of geometric dehydrated to an alkene (D). When D is reacted with hydrogen
isomers? bromide, E is produced as a major product (95%) whilst F, the
(d) What type of alcohol is the compound minor product is only produced in small amounts (5%). When
formed in b) E is refluxed with sodium hydroxide solution G is formed. G is
an isomer of A.

(a) Calculate the empirical formula of A.

7. The elemental composition of substance X is; 64.9%C; (b) What are the two possible structures of A that are alcohols.
13.5%H; 21.6%O. (c) Deduce the identities of compounds A to G.
(a) Calculate the empirical formula of X. (d) Why does B have a much higher boiling point than C?
(b) The mass spectrum of X shows a molecular ion peak at (e) What type of mechanism occurs when D reacts with HBr?
m/z = 74. What is the molecular formula of X? (f) What does ‘reflux‘ mean?
(c) There are four alcohols with this molecular formula. Draw (g) Draw the repeat unit for the polymer formed from D.
and name all four.
(d) Alcohols can be dehydrated to give alkenes. X is the only
alcohol that can be dehydrated to give a mixture of two
alkenes, Y and Z. Y can exist as a pair of geometric isomers
whilst Z does not exhibit geometric isomerism. Deduce the
structures of X, Y, and Z.

2
116 The Application of Organic Reactions To Unfamiliar Molecules (AS) Chem Factsheet

Answers 3. (a) hexane, 2-methylpentane, 3-methylpentane,

1. (a) C10H16 2,3-dimethylbutane and 2,2-dimethylbutane
(b) 3 (b) Hexane (highest); 2,2-dimethylbutane (lowest) Surface area
(c) is maximised in the linear hexane molecule and so
intermolecular forces are also maximised.
(c) 2,3-dimethylbutane (d) C6H14 Æ C3H6 + C3H8
or CH3CH(CH3)CH2CH2CH2CH(CH3)CH2CH3 (e) Electrophilic addition(f) Free radical substitution
2,6-dimethyloctante (g) 2C6H14 + 19O2 Æ 12CO2 + 14H2O
(h) During the propagation steps in the reaction mechanism,
(d) The non-rotating double bond between carbon atoms 3 and the C6H13. ;radical is formed. Two of these can combine in
4 gives rise to geometric isomerism. the termination step to form C12H26.

H2C C CH2 CH 2 CH CH 2

CH 3 C C 4. (a) CH 3 CH2 CH 2 CH CH2 (pent-1-ene)

H CH 3 CH 3 CH2 CH CH CH2 (pent-2-ene)
(e) The double bonds take precedence in the numbering system. CH 3 CH2 C CH2 CH 3 CH C CH 3
They are labelled with the lowest carbon atom they are
attached to hence ‘1,3,7 triene‘. This makes the carbon atoms CH 3 CH 3
that the methyl groups are attached to numbers 3 and 7. 2-methylbut-1-ene 2-methylbut-2-ene
(f) 2,6-dimethyloctan-1-ol would exhibit hydrogen bonding CH2 CH C CH 3
whereas ocimene being a hydrocarbon would not. Hence
the alcohol would have the higher boiling point. CH3
(g) 3-methylbut-1-ene
(b) Only pent-2-ene would exist as geometric isomers.
(c) Pentane and methylbutane.
or CH2=CH(CH3)CH2CH2CH=CH(CH3)CH=CH2 (d) It is impossible to produce 2,2-dimethylbutane because the
central carbon atom in the alkene molecule would then have
2. (a) 1-chloropropane CH3CH2CH2Cl five covalent bonds.
2-chloropropane CH3CHClCH3 (e) Cracking
1,1-dichloropropane CH3CH2CHCl2
1,2-dichloropropane CH3CHClCH2Cl 5. (a) C10H16
2,2-dichlropropane CH3CHCl2CH3 (b) C5H8
1,3-dichlropropane CH2ClCH2CH2Cl 1o
(c) (d) (e) (f) HO
1,1,1-trichloropropane CH3CH2CHCl3 Br
Br 3 o HO
1,1,2-trichloropropane CH3CHClCHCl2
1,2,3-trichloropropane CH2ClCHClCH2Cl Br 2 o HO
1,2,2-trichloropropane CH3CHCl2CH2Cl
1,1,3-trichloropropane CH2ClCH2CH2Cl Br 3 o HO
(b) (i) 1,3 –dichloropropane Obs: Decolourisation
(ii) The iodo compound would be more reactive because the 6. (a) C9H10O2
C-I bond is easier to break (lower energy needed). (b)
(c) Free radical substitution. OH
(d) Homolytic fission : Cl2Æ 2Cl. OCH 3
(e) Pentane is essentially a non-polar molecule hence
intermolecular attractions are minimised and only temporary
van der Waals forces act between the molecules.
1-chloropropane has a permanent dipole so attractions are
greater and thus the boiling point is higher. Butan-1-ol like (c) No, none of the double bonds within the ring system can
all alcohols exhibits hydrogen bonding and since this is the give rise to geometric isomerism since they are delocalised
strongest force between molecules the boiling point is higher and the terminal double bond at the bottom of the structure
than the other two compounds. has two hydrogen atoms attached to one of the carbon atoms
(f) It is impossible to make another chain out of just three carbon that make up the double bond.
atoms. (d) Tertiary.
(g) Chlorine exists as two isotopes 35Cl and 37Cl. This gives
three possible masses for the dichloropropanes (ignoring
the presence of small amounts of any isotopes of carbon
and hydrogen) CH35ClCH2CH35Cl (112); CH35ClCH2CH37Cl
(114) and CH37ClCH2CH37Cl (116).
[CH235Cl]+

3
116 The Application of Organic Reactions To Unfamiliar Molecules (AS) Chem Factsheet

7. (a) C4H10O

(b) Mr = Er so molecular formula is C4H10O.

(c) CH3CH2CH2CH2OH (Butan-1-ol)
CH3CH2CH2(OH)CH3 (Butan-2-ol)
CH3CH(CH3)CH2OH (methylpropan-1-ol)
CH3C(CH3)(OH)CH3 (methylpropan-2-ol)

(d) Only butan-2-ol can be dehydrated to give two alkenes; but-1-ene and but-2-ene so X is butan-2-ol.
Only but-2-ene exists as two geometric isomers and so this is Y.
Thus Z is but-1-ene.

8. (a) 2-ethylhexan-1,3-diol

(b) Hydrogen bonding is present in the compound but absent in decane.

(c) OH H
CH3CH2CH2CCH(CH2CH3)C CH3CH2CH2CCH(CH2CH3)C
O O
O O
acidified dichromate
9. (a) 2-bromo-2-chloro-1,1,1-trifluoroethane
(b) (c)
F F F

H C C F Br C F

Cl Br Cl
(d) Halothane is a larger molecule with a greater molecular mass than halon hence the van der Waals forces will be greater and the
boiling point will be higher. Dipole-dipole forces also exist but will be similar.
(e) As an anaesthetic halothane must have a low toxicity and to extinguish fires, halon must not degrade easily to give toxic gases so
the reactivity of both these compounds must be very low.
(f) CFC‘s degrade in the upper atmosphere to deplete ozone. This depletion allows more uv light t reach the Earth’s surface and cause
a higher incidence of skin cancer.

10. (a) C3H8O

(b) CH3CH2CH2OH (propan-1-ol) and CH3CH(OH)CH3 (propan-2-ol)
(c) A = Propan-1-ol ; B = Propanoic acid ; C = Propanal ; D = Propene ;
E = 2-bromopropane ; F = 1-bromopropane ; G = Propan-2-ol
(d) Hydrogen bonding exists in carboxylic acids but not in aldehydes
(e) Electrophilic addition
(f) Condenser is vertically above reaction flask so that vapours run back into the reaction flask for prolonged reaction.
(g) H CH3

C C

H H

Acknowledgements: This Factsheet was researched and written by Jeff Cole. Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire, TF1 1NU.
ChemistryFactsheets may be copied free of charge by teaching staff or students, provided that their school is a registered subscriber. No part of these Factsheets
may be reproduced, stored in a retrieval system, or transmitted, in any other form or by any other means, without the prior permission of the publisher. ISSN
1351-5136

4
 Chem Factsheet
www.curriculum-press.co.uk Number 117
The Application of Organic Reactions To
Unfamiliar Molecules (A2)
(1) The objective of this Factsheet is to test your understanding of Problem 2.
A2 level organic chemistry by applying your knowledge of Look at the molecule below.
reactions you have studied in the course to unusual molecules O CH 3
and unfamiliar situations. This type of exercise is an excellent
way of revising organic chemistry. C CH2 CH2
H 2C C HC CH
(2) You should learn the basic chemical reactions of each of the
functional groups (including those from your AS course!) and H 2C C
make sure you understand concepts such isomerism and CH 3
spectroscopy.
This is the chemical structure of jasmone. It is secreted by
(3) The main point to remember is that, although the problems may
plants and attracts some insects and repels others. It is an
appear to be daunting, as far as the examination is concerned,
the functional groups, provided they are not too close to each important chemical in the perfumery industry
other, behave chemically independently of each other.
(a) What is the molecular formula and molecular mass of jasmone?
(4) In problems of the type ‘A reacts and gives B' etc., it is best to (b) Jasmone can exist as a pair of geometric isomers. What
draw a flow chart. On many exam papers the problem is presented molecular feature of the molecule allows jasmone to exhibit
in a flow chart anyway. this type of stereoisomerism?
(c) Draw the trans isomer of jasmone.
Exam Hint: Examiners may set questions on molecules that (d) What would you observe if some bromine water was added to
you have not studied! But if they do this will be because jasmone?
molecules which behave in a similar way are on your (e) Draw the structure of the compound formed when jasmone
specification and they expect you to be able to apply your reacts with bromine.
knowledge to these unfamiliar situations. (f) How many moles of bromine would react with 1.64g of jasmone?
Note : Some parts of the problems that follow may not apply to (g) There are four chiral centres in the structure you have drawn
your particular specification. If you know your stuff thoroughly, for (e). Mark with an asterisk all four chiral centres.
you will recognise these parts! You can also reinterpret the
question e.g. when asked for a skeletal formula it may be more
appropriate to you to give a full structural formula. Problem 3
H H H H O
Vigabatrin is used
Problem 1. C C C C C C in the treatment of
Look at the molecule below. epilepsy.
H H N H H O H
O OH This molecule is called
H H
gingerol, a compound
CH 2 C CH CH 2 CH 2 found in ginger, an (a) Identify the chiral centre in this structure.
CH 2 CH 2 CH 2 CH 2 CH3 ingredient often used in (b) Double bonds in compounds often give rise to geometric
HO cooking. isomerism. Explain why this is so and explain why, although
(a) Explain why the gingerol exists as two optical isomers. vigabatrin contains a double bond, it does not exist as geometric
(b) Explain why gingerol does not exist as a pair of geometric isomers.
isomers. (c) What would you observe when vigabatrin was treated was
(c) What is the molecular formula of gingerol? treated with
(d) Draw a dotted circle around the phenolic group in gingerol. (i) A cold solution of nitrous (nitric (III)) acid.
(e) Describe what you would see if gingerol was added to (ii) A solution of bromine
2,4-dinitrophenylhydrazine reagent. What functional group (iii) A solution of sodium hydrogen carbonate.
present in the molecule is reacting? (d) Give the structure of the compound formed when vigabatrin
(f) Describe what you would see, if anything, when gingerol is reacts with ethanol in the presence of sulphuric acid as a
added to Tollen‘s reagent and warmed. Explain your reasoning. catalyst.
(g) Explain why gingerol does not give a positive test with the
tri-iodomethane (iodoform) reaction.

1
117 The Application of Organic Reactions To Unfamiliar Molecules (A2) Chem Factsheet

Problem 4
HBr Compound C. This is the minor product
Compound A: 85.7%C; 14.3%H
m/z of molecular ion in mass spec = 42
HBr Compound B. This is the major product

NaOH

Compound E. The NMR Compound D. Soluble in water

spectrum consists of just K2Cr2O7/H+/Heat
one singlet

(a) Calculate the empirical and molecular formulas of A.

(b) Deduce the structures of compounds A to E
(c) Explain why there are ‘major‘ and ‘minor‘ products in the first reaction.
(d) Explain why compound E has only one singlet in its NMR spectrum.

Problem 5 Problem 6
Substance A has the molecular formula C4H10O. There are four A substance M has the following composition; 38.9%C; 5.4%H;
possible alcohols with this formula of which only A is optically 17.3%O; 38.4%Cl. Its molecular and empirical formulae are the
active. same. M has a vigorous reaction with water and steamy white
fumes are seen evolving. Compound N is formed in this reaction.
When A is treated with concentrated sulphuric acid, two
compounds are formed, B and C. B shows geometric isomerism When N is heated with soda lime, O is formed – a compound that
whilst C does not. contains only carbon and hydrogen. When O is reacted with
When B is treated with hydrogen bromide, only one product, D chlorine gas in the presence of UV light, P is formed which contains
is formed but, when C is treated with the same reagent, D is one chlorine atom per molecule and can react with aqueous sodium
formed as the major product and E is formed as a minor product. hydroxide to form Q, a compound that can itself undergo
dehydration to give R, a compound that will decolourise bromine
Treatment of D with aqueous sodium hydroxide under the water. R undergoes an industrially important reaction reacting as
appropriate conditions gives A while similar treatment of E gives a monomer to give S and reacts with hydrogen chloride to reform
F, an isomer of A. P. P reacts with potassium cyanide to give T which is hydrolysed
When F is gently heated with a solution of potassium when heated with a concentrated strong acid to reform N. T can
dichromate(VI) in sulphuric acid, G is formed. G gives a silver also react with a suitable reducing agent to give U. Finally, M and
mirror when treated with ammoniacal silver nitrate solution. U can react together to form V a compound that has a linkage
found in many biological molecules.
(a) Draw full graphical formulae for all the possible alcohols with
the molecular formula C4H10O. Give the systematic names for (a) Deduce the molecular formula of M and hence deduce the
each one. identities of molecules N-V.
(b) Which one the four compounds is optically active and hence (b) What are the ‘white steamy fumes‘ observed in the reaction
is the structure of A? between M and water?
(c) Which one of the structures gives only two singlets in its (c) What is the type of reaction between N and soda lime called?
NMR spectrum? (d) What is the type of mechanism occurring when O reacts with
(d) Deduce the structures of compounds B to G. chlorine in the presence of UV light?
(e) Explain why B is capable of geometric isomerism whilst C is (e) What type of compound is S? Give an advantage and
not. disadvantage of is presence in modern society.
(f) Give a chemical test that would distinguish between A and F (f) What type of reaction is undergone when R reacts with bromine
water?
(g) Name another reagent that would confirm the identity of the
functional group in G (g) What type of reaction occurs when P reacts with potassium
cyanide?
(h) Name a third reagent that would react with G but would not
distinguish it from a second different functional group. (h) What is the name of the molecular linkage found in V? What
type of biological molecule is this linkage found in? What
type of synthetic fibre is this type of linkage also found in?

2
117 The Application of Organic Reactions To Unfamiliar Molecules (A2) Chem Factsheet

Problem 7 Problem 8
*
OH H
O

C O CH3 HO C N
CH2 CH3
HC *CH
CH2 H
H3C N CH O C HO
CH2
HC CH2
O
The above structure is of adrenaline – the so-called ‘fight or
flight‘ hormone
The above is the structural formula of cocaine, a class A restricted (a) Draw the structure of the compound formed (A) when
drug. adrenaline is reacted with an oxidising agent such as acidified
(a) What is the molecular formula of cocaine? potassium dichromate (VI)
(b) What would you observe when molecule A is treated with
(b) Put a ring around the tertiary amine group in cocaine.
2,4-dinitrophenylhydrazine?
(c) The carbon atoms marked with an asterisk (*) can be described (c) What type of amine is adrenaline?
as chiral. What does this mean and what affect does the (d) How many phenolic groups are there in adrenaline?
presence of a chiral carbon have in a molecule? (e) If adrenaline is capable of reacting as a phenol, what would
you observe when adrenaline was added to iron (III) chloride
(d) How would you detect the presence of the chiral carbon
solution?
atom?
(f) Would compound A give a positive tri-iodoform test. Explain
(e) Draw the structures of the 3 organic molecules formed when your answer.
cocaine is treated with sodium hydroxide and then acidified. (g) If the alcohol group marked with an asterisk is dehydrated
compound B is formed and exists as two geometric isomers.
Draw both of these stereo isomers.

Answers
(e/g) Br
Problem 1 O H
(a) The carbon atom attached to the hydroxyl group has four CH2 C*
*C Br
C
different atoms groups attached to it. This is a chiral carbon
H 2C *C
atom and makes the molecule optically active. H CH2
(b) Gingerol does not contain a double bond. Br
H 2C *C
(c) C16H24O3 CH3
(d) Dotted circle around the hydroxyl group attached to the benzene CH 3
Br
ring.
(e) The carbonyl group (C=O) reacts to form an orange crystalline
precipitate. Problem 3
(f) There would be no reaction with Tollen‘s reagent because there
(a) The carbon atom bonded to the nitrogen atom is chiral.
is no aldehyde group in gingerol.
(b) Double bonds restrict internal rotation. Vigabatrin does not form
(g) The tri-iodoform tests for either a CH3C=O group or a CH3CHOH-
geometric isomers because there are two identical groups
group. Both of these are absent in gingerol.
attached to one of the carbon atoms forming the double bond.
Problem 2 (c) (i) Effervescence (N2 evolved)
(a) Molecular formula = C11H16O; Mr. = (164) (ii) Bromine is decolourised.
(b) All organic compounds that exist as geometric isomers (as far (iii) Effervescence (CO2 evolved)
as A level courses go) contain double bonds which restricts (d)
internal rotation about them. It is the double bond that is part of
the chain that causes geometric isomerism. H H H H O Reaction forms an
(c) O C C C C C C ester
C CH2 H H H O CH 2 CH 3
N H H
H 2C C C C Trans isomer of jasmone
H H
H CH2
H 2C C
CH 3 CH3

(d) The bromine water would change from orange/red to colourless Acknowledgements: This Factsheet was researched and written by Jeff Cole.
(f) 1.64g of jasmone = 1.64/164 = 0.01moles. There are two C=C Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire, TF1
bonds in one molecule of jasmone. Hence 0.02 moles of bromine 1NU. ChemistryFactsheets may be copied free of charge by teaching staff or
would react. students, provided that their school is a registered subscriber. No part of these
Factsheets may be reproduced, stored in a retrieval system, or transmitted, in
any other form or by any other means, without the prior permission of the
publisher. ISSN 1351-5136

3
117 The Application of Organic Reactions To Unfamiliar Molecules (A2) Chem Factsheet

Problem 4 Problem 6
(a) C = 85.7/12 = 7.15; H = 14.3/1 = 14.3 ; Empirical formula = CH2. (a) Molecular formula = empirical formula = C3H5OCl.
Empirical mass = 12+2 = 14; 42/14 = 3 Molecular formula = C3H6. M (from its vigorous reaction with water) is propanoyl chloride;
CH3CH2COCl. N is thus propanoic acid; CH3CH2COOH. When
(b) A is propene. Addition of hydrogen bromide to this molecule
this compound is reacted with soda lime the carboxyl group is
will give 2-bromopropane (CH3CHBrCH3) as the major product,
cleaved off forming ethane, C2H6 (O) and carbon dioxide. Reacting
(B) and 1-bromopropane (CH3CH2CH2Br) as the minor product,
ethane with chlorine gives chloroethane, CH 3 CH 2 Cl (P).
(C). D is propan-2-ol. This reaction is hydrolysis. Oxidation of D
Chloroethane reacts with sodium hydroxide to give ethanol,
gives propanone (E).
CH3CH 2OH (Q). This compound can be dehydrated to give
(c) The mechanism for the reaction is one of electrophilic addition. ethene, CH2=CH2 (R). Ethene can undergo polymerisation to
There are two carbocations possible; CH 3CH + CH 3 and poly(ethene), (S). When chloroethene (P) reacts with potassium
CH3CH2CH2+. The former is a secondary carbocation and is cyanide a nitrile is formed, in this case propanonitrile, CH3CH2CN
stabilised by two alkyl groups. The latter is a primary carbocation (T). Nitriles hydrolyse when heated with strong acids to yield
and is stabilised by only one alkyl group. Primary carbocations, carboxylic acids. Hence N, propanoic acid, is reformed. Nitriles
being less stable, are formed only in small amounts leading to are reduced to primary amines, so (U) is 1-aminopropane,
only small amounts of 1-bromopropane. Conversely, secondary CH3CH2CH2NH2. U and M react to give a substituted amide (V),
carbocations, being more stable, are formed in large amounts CH3CH2CH2NHCOCH2CH3.
leading to 2-bromopropane being the major product. (b) Hydrogen chloride
(c) Decarboxylation.
(d) Compound E is propanone CH3COCH3. All 6 hydrogen atoms (d) Free radical substitution
have the same molecular environment and so will give a singlet (e) S is a polymer (forms material is non-corrodible but is also non-
nmr absorption. biodegradable)
(f) Electrophilic addition
Problem 5 (g) Nucleophilic substitution
(a) (h) Linkage is amide (found in proteins and polyamides like nylon)
*
CH3 CH2 CH2 CH2OH CH3 CH2 CH CH3
Butan-1-ol
OH
Problem 7
Butan-2-ol (a) C17H21NO4
OH (b) Ring goes around the N atom.
CH3 CH CH2OH CH3 C CH3 (c) The chiral carbon atom destroys any symmetry in the molecule.
Essentially it is a carbon atom that has four different groups
CH3 CH3 attached to it. It renders the molecule optically active.
2-methylbutan-1-ol 2-methylbutan-2-ol (d) A single enantiomer will rotate the plane of plane-polarised light
in a polarimeter. This will not work if both enantiomers are present
(b) Only butan-2-ol has a chiral carbon atom (marked with a *) and in equimolar amounts because of the cancelling effect. These
so this compound is A. mixtures are called racemic mixtures.
(c) 2-methylbutan-2-ol. All the methyl hydrogen atoms are (e) The three structures are shown below.
equivalent and will give one peak. The hydroxy hydrogen atom
(i) CH3OH (ii) O
will give the second peak. There is no coupling (no H on adjacent COOH (iii)
carbon atoms) between these two sets of hydrogen atoms. C O H
Hence the peaks are singlets. HC CH
(d) When A is dehydrated, but-1-ene (CH3CH2CH=CH2) and but-2- CH2
ene (CH3CH=CHCH3) are formed. Only but-2-ene is capable of H3C N CHOH
CH
CH2
geometric isomerism so B is but-2-ene and C is but-1-ene. When HC CH2
both of these compounds are reacted with hydrogen bromide,
but-2-ene being a symmetrical alkene gives only one product, 2- Problem 8
O H
bromobutane (CH3CH2CHBrCH3) (D). However, but-1-ene will (a)
give D as the major product and 1-bromobutane HO C N
(CH3CH2CH2CH2Br) (E) as the minor product. Reaction of 2- CH2 CH3
bromobutane with sodium hydroxide solution will reform A HO
(butan-2-ol) while the reaction of 1-bromobutane with sodium (b) An orange crystalline precipitate of the hydrazone would be
hydroxide will give butan-1-ol, (CH2CH2CH2CH2OH) (F), which formed.
is isomeric with A. When F is gently oxidised the product is (c) Secondary
butanal, (CH3CH2CH2CHO) (G). (d) 2
(e) B, but-2-ene, has two different groups bonded to the carbon (e) Violet colouration produced.
atoms that form the double bond while C but-1-ene has two (f) No. The molecule does not contain the CH3CO- or CH3CHOH-
hydrogen atoms attached to one of these carbon atoms. groups.
(f) Butan-2-ol (A) will give a positive tri-iodomethane test while (g) H C H
butan-1-ol (F) will not. HO
C
(g) Fehling‘s solution will also give a positive reaction for an C N H
HO CH3 HO
aldehyde group. C N
(h) 2,4-dintrophenylhydrazine would give an orange crystalline HO H
H H CH3
precipitate with butanal but would also give a similar reaction
with a ketone. Cis isomer Trans isomer
4
 Chem Factsheet
September 2000 Titles 1 - 36 April 2002

VOLUME 1: 2000/2001 TITLES VOLUME 2: 2001/2002 TITLES

01. Atomic Structure 19. The Periodic Table - Period 3

02. Moles and Formulae 20. The Periodic Table - Group 4

03. Moles and Equations 21. Chemical Equilibria: Kc

04. Shapes of Molecules and Ions 22. Chemical Equilibria: Kp

05. Bonding 23. How To Answer Questions on Titration Calculations

06. Structure of Elements and Compounds 24. Laboratory Chemistry: Making Observations and Inferences

07. Moles and Volumetric Analysis 25. Acid-Base Equilibria I – pH, Kw and Ka
08. Energetics I – Hess’s Law 26. Acid Base Equilibria II – Buffer Solutions, Titrations & Indicators

09. Equilibrium and Le Châtelier’s Principle 27. Organic Chemistry 1 – Key concepts and Optical Isomerism

10. Kinetics I – Rates of Reaction 28. Energetics – Lattice Enthalpy and Born-Haber Cycle
11. Oxidation and Reduction 1 29. Answering Questions on Born-Haber Cycles

12. Periodicity – Trends in Period 3 30. Laboratory Chemistry – Separation & Purification Techniques

13. Groups 1 and 2 31. Organic Chemistry 2 – Halogeno-compounds & Grignard Reagents
14. Group 7 32. Organic Chemistry 3 – Carboxylic Acids, Esters & Acyl Chlorides

15. Organic Chemistry I - Nomenclature 33. Organic Chemistry 4 – Carbonyl Compounds

16. Organic Chemistry II – Reactions I 34. Organic Chemistry 5 – Compounds Containing Nitrogen
17. Organic Chemistry III – Reactions II 35. Answering Questions on Organic Pathways and Conversions

18. Applied Chemistry 36. Laboratory Chemistry – Continuous Practical Assessment

www.curriculumpress.co.uk
 Chem Factsheet
September 2002 January 2003 April 2003

37 Redox Equilibria 1: Standard Electrode Potentials & Cells

38 Transition Metals 1: Definitions & Properties
39 Reactions of Benzene & its Compounds
40 Organic Reaction Mechanisms
41 Answering Questions on Electrochemical Cells
42 Critical Analysis of Experimental Procedures & Accuracy
43 Rate Equations, Orders & Constants
44 Rate Expression Orders & Experimental Procedures
45 Standard Electrode Potentials & Feasibility of Reactions
46 Transition Metals 2 - Compounds & Reactions
47 Answering Questions on Transition Metals
48 Laboratory Chemistry - Organic Techniques
49 Rate Orders & Reaction Mechanisms
50 Redox Equilibria 3: Applications
51 Redox Equilibria 4: Redox Titrations
52 Reactions of Functional Groups: Revision Summary
53 Answering Questions on Organic Synthesis
54 Organic Analysis 1: Infrared Spectroscopy