8A.

Redox
oxidation is the process of electron loss: reduction is the process of electron gain:
Zn Zn2+ + 2e- Cl2 + 2e-  2Cl-
It involves an increase in oxidation number It involves a decrease in oxidation number

Rules for assigning oxidation numbers

1. All uncombined elements have an oxidation number of zero eg . Zn, Cl2, O2, Ar all have oxidation numbers of zero

2. The oxidation numbers of the elements in a compound add In NaCl Na= +1 Cl= -1
up to zero Sum = +1 -1 = 0

3. The oxidation number of a monoatomic ion is equal to the

e.g. Zn2+ = +2 Cl- = -1
ionic charge
4. In a polyatomic ion (CO32-) the sum of the individual e.g. in CO32- C = +4 and O = -2
oxidation numbers of the elements adds up to the charge
sum = +4 + (3 x -2) = -2
on the ion
5. Several elements have invariable oxidation numbers in their
common compounds.

Group 1 metals = +1
Group 2 metals = +2
Al = +3 We use these rules to
H = +1 (except in metal hydrides where it is –1 eg NaH) identify the oxidation
numbers of elements that
F = -1 have variable oxidation
Cl, Br, I = –1 except in compounds with oxygen and fluorine numbers.

O = -2 except in peroxides (H2O2 ) where it is –1 and in compounds with fluorine.

Note the oxidation number of Cl

What is the oxidation number of Fe in FeCl 3
in CaCl2 = -1 and not -2 because
Using rule 5, Cl has an O.N. of –1 there are two Cl’s
Using rule 2, the O.N. of the elements must add up to 0 Always work out the oxidation for
one atom of the element
Fe must have an O.N. of +3
in order to cancel out 3 x –1 = -3 of the Cl’s

Naming using oxidation number

If an element can have various oxidation numbers then the oxidation number of that element in a
compound can be given by writing the number in roman numerals

FeCl2: Iron (II) chloride

FeCl3 Iron (III) chloride
MnO2 Manganese (IV) Oxide

In IUPAC convention the various forms of sulfur,nitrogen and chlorine compounds where oxygen
is combined are all called sulfates, nitrates and chlorates with relevant oxidation number given in
roman numerals. If asked to name these compounds remember to add the oxidation number.

NaClO: sodium chlorate(I) NaNO3 sodium nitrate (V)

NaClO3: sodium chlorate(V) NaNO2 sodium nitrate (III)
K2SO4 potassium sulfate(VI)
K2SO3 potassium sulfate(IV)

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Redox equations and half equations

Br2 (aq) + 2I- (aq)  I2 (aq) + 2 Br- (aq)

Br2 (aq) + 2e-  + 2 Br- (aq) 2I- (aq)  I2 (aq) + 2 e-

Br has reduced as it has gained electrons I has oxidised as it has lost electrons

A reduction half equation only shows the parts An oxidation half equation only shows the reducing agents are
of a chemical equation involved in reduction parts of a chemical equation involved in electron donors
The electrons are on the left oxidation
The electrons are on the right
oxidising agents are
electron acceptors
The oxidising agent is Bromine The reducing agent is the Iodide
water . It is an electron acceptor ion. It is an electron donor
When naming oxidising
and reducing agents
An oxidising agent (or oxidant) is the A reducing agent (or reductant) is the
species that causes another element to species that causes another element always refer to full name
oxidise. It is itself reduced in the reaction reduce. It is itself oxidised in the reaction. of substance and not
just name of element

Redox Reactions

metals generally form ions by losing non-metals generally react by gaining

electrons with an increase in oxidation electrons with a decrease in oxidation
number to form positive ions: number to form negative ions
Zn Zn2+ + 2e- Cl2 + 2e-  2Cl-

Oxygen is reducing because Tungsten is reducing because

its oxidation number is its oxidation number is
decreasing from 0 to -2 decreasing from +6 to 0

0 -2 +6 0
4Li + O2  2Li2O WO3 + 3H2  W + 3H2O
0 +1 0 +1

Lithium is oxidising because its Hydrogen is oxidising

oxidation number is increasing from 0 because its oxidation number
to +1 is increasing from 0 to +1

Nitrogen is reducing because Chlorine is reducing because

its oxidation number is its oxidation number is
decreasing from +5 to+4 decreasing from +1 to -1

+5 +4 +1 -1
2Sr(NO3)2  2SrO + 4NO2 + O2 2 NH3 + NaClO  N2H4 + NaCl + H2O
-2 0 -3 -2

Oxygen is oxidising because its oxidation Nitrogen is oxidising because its oxidation
number is increasing from -2 to 0 number is increasing from -3 to -2

Note that not all the oxygen atoms are

changing oxidation number in this reaction

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 Redox Reactions of Metals and acid
ACID + METAL  SALT + HYDROGEN

Hydrogen is reducing Be able to write equations for reactions of

because its oxidation number metals with hydrochloric acid and sulphuric
is decreasing from +1 to 0 acid

+1 0 Fe + H2SO4  FeSO4 +H2

2HCl + Mg  MgCl2 +H2
0 +2
Observations: These reaction will
Magnesium is oxidising effervesce because H2 gas is evolved
because its oxidation number is and the metal will dissolve
increasing from 0 to +2

Disproportionation

Disproportionation is the name for a reaction where

an element in a single species simultaneously
oxidises and reduces.
Chlorine is both simultaneously reducing and
Cl2(aq) + H2O(l)  HClO(aq) + HCl (aq) oxidising changing its oxidation number from 0 to
-1 and 0 to +1

Copper(I) ions (+1) when reacting with sulphuric acid will

2Cu+  Cu + Cu2+
disproportionate to Cu2+ (+2) and Cu (0) metal

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Balancing Redox equations
Writing half equations
1. Work out oxidation numbers for element being oxidised/ reduced Zn  Zn2+ Zn changes from 0 to +2

2. Add electrons equal to the change in oxidation number

For reduction add e’s to reactants
Zn  Zn2+ + 2e-
For oxidation add e’s to products

3. check to see that the sum of the charges on the reactant side
equals the sum of the charges on the product side 0 +2 –2 =0

More complex Half equations

If the substance that is being oxidised or reduced contains a varying amount of O (eg In acidic conditions
MnO4-  Mn2+ ) then the half equations are balanced by adding H+, OH- ions and H2O. use H+ and H2O

Example: Write the half equation for the change MnO4-  Mn2+
Mn changes from +7 to +2
1. Balance the change in O.N. with electrons Add 5 electrons to reactants MnO4- + 5e-  Mn2+

2. Add H2O in products to balance O’s in MnO4- MnO4- + 5e-  Mn2+ + 4H2O

3. Add H+ in reactants to balance H’s in H2O MnO4- + 8H+ + 5e-  Mn2+ + 4H2O

4. check to see that the sum of the charges on the reactant side
equals the sum of the charges on the product side -1 + 8 -5 = +2 +2

Example: Write the half equation for the change SO42-  SO2
S changes from +6 to +4
1. Balance the change in O.N. with electrons Add 2 electrons to reactants SO42- + 2e-  SO2

2. Add H2O in products to balance O’s in SO42- SO42- + 2e-  SO2 + 2H2O

3. Add H+ in reactants to balance H’s in H2O SO42- + 4H+ + 2e-  SO2 + 2H2O

4. check to see that the sum of the charges on the reactant side
equals the sum of the charges on the product side -4 + 4 = 0 0

Combining half equations

To combine two half equations there must be
To make a full redox equation combine a reduction
equal numbers of electrons in the two half
half equation with a oxidation half equation
equations so that the electrons cancel out
Example 1

Reduction MnO4- + 8 H+ + 5 e-  Mn2+ + 4 H2O x2

Multiply the half equations to get
Oxidation C2O42-  2 CO2 + 2 e- x5 equal electrons

2MnO4- + 16 H+ + 5C2O42-  2Mn2+ + 10 CO2 + 8 H2O Add half equations together and cancel
electrons
Example 2

Reduction SO42- + 10H+ + 8e- H2S+ 4H2O Multiply the half equations to get
equal electrons
Oxidation 2I-  I2 + 2 e- x4
Add half equations together and
8I- + SO42- + 10H+  H2S+ 4I2 + 4H2O cancel electrons

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 8B: Group 1+2
Melting points
Down the group the melting points decrease. The metallic
bonding weakens as the atomic size increases. The distance
Atomic radius between the positive ions and delocalized electrons
Atomic radius increases down the groups. increases. Therefore the electrostatic attractive forces
As one goes down the groups, the atoms have more between the positive ions and the delocalized electrons
shells of electrons making the atom bigger. weaken.

1st ionisation energy

The outermost electrons are held more weakly because they are successively further from the nucleus in additional
shells.
In addition, the outer shell electrons become more shielded from the attraction of the nucleus by the repulsive
force of inner shell electrons

Group 2 reactions Reactivity of group 1 and 2 metals increases down the group

The reactivity increases down the group as the atomic radii increase there is more shielding. The nuclear
attraction decreases and it is easier to remove (outer) electrons and so cations form more easily
Reactions with oxygen.
Mg will also react slowly with oxygen without a flame.
Group 1 and 2 metals will burn in oxygen. Mg ribbon will often have a thin layer of magnesium oxide on it
4Na + O2  2Na2O formed by reaction with oxygen.
Mg burns with a bright white flame. 2Mg + O2  2MgO
2Mg + O2  2MgO This needs to be cleaned off by emery paper before doing reactions
with Mg ribbon.
The oxides of group 1 and 2 are usually If testing for reaction rates with Mg and acid, an un-cleaned Mg
white solids with high melting points due ribbon would give a false result because both the Mg and MgO
to their ionic bonding. would react but at different rates.
Mg + 2HCl  MgCl2 + H2
MgO + 2HCl  MgCl2 + H2O
Reactions with chlorine
The group 1 and 2 metals will react with chlorine
2 Na + Cl2  2 NaCl Mg + Cl2  MgCl2

Reactions with water.

Magnesium burns in steam to produce Mg will also react with warm water, giving a different
magnesium oxide and hydrogen. The Mg would magnesium hydroxide product.
burn with a bright white flame.
Mg + 2 H2O  Mg(OH)2 + H2
Mg (s) + H2O (g)  MgO (s) + H2 (g)
This is a much slower reaction than the reaction with steam
and there is no flame.

The other group 2 metals will react with cold water with The hydroxides produced make the water alkaline
increasing vigour down the group to form hydroxides.
One would observe:
Ca + 2 H2O (l) Ca(OH)2 (aq) + H2 (g)
fizzing, (more vigorous down group)
Sr + 2 H2O (l) Sr(OH)2 (aq) + H2 (g)
the metal dissolving, (faster down group)
Ba + 2 H2O (l) Ba(OH)2 (aq) + H2 (g)
the solution heating up (more down group)
Group 1 metals also react with cold water with increasing and with calcium a white precipitate appearing
vigour down the group to form hydroxides. (less precipitate forms down group)
2 Li + 2 H2O (l) 2LiOH (aq) + H2 (g)
2 Na + 2 H2O (l) 2NaOH (aq) + H2 (g)

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Reactions of the Oxides of Group 1 & 2 elements with water
Group 1 and 2 ionic oxides react with water to form hydroxides
The ionic oxides are basic as the oxide ions accept protons to become hydroxide ions in this reaction
(acting as a bronsted lowry base)
Na2O + H2O (l)  2NaOH (aw) pH 14 ( all group 1 oxides form similar highly alkaline solutions)

MgO (s) + H2O (l)  Mg(OH)2 (s) pH 9

Mg(OH)2 is only slightly soluble in water so fewer free OH- ions are produced and so lower pH
CaO (s) + H2O (l)  Ca(OH)2 (aq) pH 12

Reactions of the Oxides of Group 1& 2 with Acids

K2O (s) + 2 HNO3 (aq)  2 KNO3 (aq) + H2O (l)

MgO (s) + 2 HCl (aq)  MgCl2 (aq) + H2O (l)

SrO (s) + 2 HCl (aq)  SrCl2 (aq) + H2O (l)
CaO (s) + H2SO4 (aq)  CaSO4 (aq) + H2O (l)
Reactions of the hydroxides of Group 1& 2 with Acids
HCl (aq) + NaOH (aq)  NaCl (aq) + H2O (l)
2HNO3 (aq) + Mg(OH)2 (aq)  Mg(NO3)2 (aq) + 2H2O (l)
2HCl (aq) + Mg(OH)2 (aq)  MgCl2 (aq) + 2H2O (l)

Solubility of Group 2 hydroxides

Group II hydroxides become more soluble down the group.
All Group II hydroxides when not soluble appear as white precipitates.

Magnesium hydroxide is classed as insoluble in water. Calcium hydroxide is reasonably soluble in

water. It is used in agriculture to neutralise
Simplest Ionic Equation for formation of Mg(OH)2 (s)
acidic soils.
Mg2+ (aq) + 2OH-(aq)  Mg(OH)2 (s).
An aqueous solution of calcium hydroxide is
A suspension of magnesium hydroxide in water will appear slightly called lime water and can be used a test for
alkaline (pH 9) so some hydroxide ions must therefore have been carbon dioxide. The limewater turns cloudy as
produced by a very slight dissolving. white calcium carbonate is produced.
Magnesium hydroxide is used in medicine (in suspension as milk of Ca(OH)2 (aq) + CO2 (g)  CaCO3 (s) + H2O(l)
magnesia) to neutralise excess acid in the stomach and to treat
constipation.
Mg(OH)2 + 2HCl  MgCl2 + 2H2O Barium hydroxide would easily dissolve in
water. The hydroxide ions present would
It is safe to use because it so weakly alkaline. It is preferable to using make the solution strongly alkaline.
calcium carbonate because it will not produce carbon dioxide gas.
Ba(OH)2 (S) + aq  Ba2+ (aq) + 2OH-(aq)
Solubility of Group 2 Sulfates
Group II sulfates become less soluble down the group.
BaSO4 is the least soluble.

If barium metal is reacted with sulfuric acid it will only react slowly as the insoluble barium sulfate produced will
cover the surface of the metal and act as a barrier to further attack.
Ba + H2SO4  BaSO4 + H2
The same effect will happen to a lesser extent with metals going up the group as the solubility increases.
The same effect does not happen with other acids like hydrochloric or nitric as they form soluble group 2 salts.

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Thermal decomposition of Group 1& 2 carbonates

Group 2 carbonates decompose on heating to produce Thermal decomposition is defined as the use
group 2 oxides and carbon dioxide gas. of heat to break down a reactant into more than
one product
MgCO3(s)  MgO(s) + CO2(g)
CaCO3(s)  CaO(s) + CO2(g) The ease of thermal decomposition
decreases down the group
Group 2 carbonates are more thermally stable as you go down
the group. As the cations get bigger they have less of a
polarising effect and distort the carbonate ion less. The C-O
bond is weakened less so it less easily breaks down

Group 1 carbonates do not decompose with the exception of Lithium.

As they only have +1 charges they don’t have a big enough charge
density to polarise the carbonate ion. Lithium is the exception
because its ion is small enough to have a polarising effect

Li2CO3(s)  Li2O(s) + CO2(g)

There are a number of experiments that can be done to investigate the

ease of decomposition.
One is to heat a known mass of carbonate in a side arm boiling tube lime water
and pass the gas produced through lime water. Time for the first
permanent cloudiness to appear in the limewater. Repeat for different
carbonates using the same moles of carbonate/same volume of
limewater/same Bunsen flame and height of tube above flame.

Heat

Thermal decomposition of Group 1 & 2 Nitrates

Group 2 nitrates decompose on heating to produce group
2 oxides, oxygen and nitrogen dioxide gas.
2Mg(NO3)2 → 2MgO + 4NO2 + O2
You would observe brown gas evolving (NO2) and the
The ease of thermal decomposition
White nitrate solid is seen to melt to a colourless solution
decreases down the group
and then re-solidify

The explanation for change in thermal stability is the same as for carbonates
Magnesium nitrate decomposes the easiest because the Mg2+ ion is smallest and has the greater charge
density. It causes more polarisation of the nitrate anion and weakens the N―O bond

Group 1 nitrate do not decompose in the same way as group 2 with

the exception of Lithium nitrate. They decompose to give a Nitrate
(III) salt and oxygen.

2NaNO3 → 2NaNO2 + O2
Lithium nitrate decomposes in the
Sodium Sodium same way as group 2 nitrates
Nitrate(V) Nitrate(III)
4 LiNO3 → 2Li2O + 4NO2 + O2

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Flame tests
Method Lithium : Scarlet red
Use a nichrome wire ( nichrome is an unreactive metal Sodium : Yellow
and will not give out any flame colour) Potassium : lilac
Clean the wire by dipping in concentrated hydrochloric Rubidium : red
Caesium: blue
acid and then heating in Bunsen flame Magnesium: no flame colour (energy emitted
If the sample is not powdered then grind it up. of a wavelength outside visible spectrum)
Dip wire in solid and put in Bunsen flame and observe Calcium: brick red
flame Strontium: red
Barium: apple green
Explanation for occurrence of flame
In a flame test the heat causes the electron to move to a
higher energy level.
The electron is unstable at the higher energy level and so
drops back down. As it drops back down from the
higher to a lower energy level, energy is emitted in the
form of visible light energy with the wavelength of the
observed light

Testing for Negative ions (anions)

Testing for Presence of a carbonate CO32- and hydrogencarbonates HCO3-
Add any dilute acid and observe effervescence.
Bubble gas through limewater to test for CO2 – will turn limewater cloudy Fizzing due to CO2 would be
observed if a carbonate or a
2HCl + Na2CO3  2NaCl + H2O + CO2 2H+ + CO32-  H2O + CO2 hydrogencarbonate was present

HCl + NaHCO3  NaCl + H2O + CO2 H+ + HCO3-  H2O + CO2

Testing for Presence of a sulfate Ba2+ (aq) + SO42-(aq)  BaSO4 (s).

Acidified BaCl2 solution is used as a reagent to test for sulfate ions
Other anions should give a negative
If Barium Chloride is added to a solution that contains sulfate ions a
result which is no precipitate forming
white precipitate forms

The acid is needed to react with carbonate impurities that Sulfuric acid cannot be used to acidify the
are often found in salts which would form a white Barium mixture because it contains sulfate ions
carbonate precipitate and so give a false result which would form a precipitate

Testing for positive ions (cations)

Ammonia gas can be identified by
Test for ammonium ion NH4+, by reaction with warm its pungent smell or by turning red
NaOH(aq) forming NH3 litmus paper blue
NH4+ +OH-  NH3 + H2O

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Titrations

The method for carrying out the titration Safety precautions

•rinse equipment (burette with acid, pipette with alkali, conical Acids and alkalis are corrosive
flask with distilled water) (at low concentrations acids are
•pipette 25 cm3 of alkali into conical flask irritants)
•touch surface of alkali with pipette ( to ensure correct amount Wear eye protection and gloves
is added) If spilled immediately wash affected
•adds acid solution from burette parts after spillage
•make sure the jet space in the burette is filled with acid
•add a few drops of indicator and refer to colour change at end If substance is unknown treat it as
point potentially toxic and wear gloves.
•phenolphthalein [pink (alkali) to colourless (acid): end point pink
colour just disappears] [use if NaOH is used]
•methyl orange [yellow (alkali) to red (acid): end point orange] A conical flask is used in preference
[use if HCl is used] to a beaker because it is easier to
•use a white tile underneath the flask to help observe the colour swirl the mixture in a conical flask
change without spilling the contents.
•add acid to alkali whilst swirling the mixture and add acid
dropwise at end point Distilled water can be added to the
•note burette reading before and after addition of acid conical flask during a titration to wash
•repeats titration until at least 2 concordant results are the sides of the flask so that all the
obtained- two readings within 0.1 of each other acid on the side is washed into the
reaction mixture to react with the alkali.
There will be a small amount of the liquid left in the pipette when It does not affect the titration reading
it has been emptied. Do not force this out. The pipette is as water does not react with the
calibrated to allow for it. reagents or change the number of
moles of acid added.
If the jet space in the burette is not filled properly prior to
commencing the titration it will lead to errors if it then fills Only distilled water should be used to
during the titration, leading to a larger than expected titre wash out conical flasks between
reading. titrations because it does not add and
extra moles of reagents
Working out average titre results
Only make an average of the concordant titre results

lf 2 or 3 values are within 0.10cm3

Recording results
and therefore concordant or close
•Results should be clearly recorded in a table
then we can say results are accurate
•Result should be recorded in full (i.e. both initial and final
and reproducible and the titration
readings)
technique is good/ consistent
•Record titre volumes to 2dp (0.05 cm3)

Titrating mixtures
Testing batches If titrating a mixture to work out the concentration
In quality control it will be necessary to do of an active ingredient it is necessary to consider
titrations/testing on several samples as the if the mixture contains other substances that
amount/concentration of the chemical being tested may have acid base properties.
vary between samples. If they don’t have acid base properties we can
titrate with confidence.

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9
 More complicated titration calculations- taking samples

Example 26: A 25.0cm3 sample of vinegar was diluted in a Common Titration Equations
250cm3 volumetric flask. This was then put in a burette and
23.10cm3 of the diluted vinegar neutralised 25.0 cm3 of 0.100 CH3CO2H + NaOH  CH3CO2-Na+ + H2O
M NaOH. What is the concentration of the vinegar in gdm-3 ?
H2SO4 + 2NaOH  Na2SO4 +2H2O
CH3CO2H + NaOH  CH3CO2-Na+ + H2O
HCl + NaOH  NaCl +H2O
Step 1: work out amount, in mol, of sodium hydroxide
amount = conc x vol
NaHCO3 + HCl  NaCl + CO2 + H2O
= 0.10 x 0.025 Na2CO3 + 2HCl 2NaCl + CO2 + H2O
= 0. 00250 mol
Step 2: use balanced equation to give moles of CH3CO2H Example 28
1 moles NaOH : 1 moles CH3CO2H 950 mg of impure calcium carbonate tablet was crushed. 50.0
So 0.00250 NaOH : 0.00250 moles CH3CO2H cm3 of 1.00 mol dm–3 hydrochloric acid, an excess, was then
added. After the tablet had reacted, the mixture was
Step 3 work out concentration of diluted CH3CO2H in 23.1 transferred to a volumetric flask. The volume was made up to
(and 250 cm3)in moldm-3 exactly 100 cm3 with distilled water. 10.0 cm3 of this solution
conc= amount/Volume was titrated with 11.1cm3 of 0.300 mol dm–3 sodium
hydroxide solution.
= 0.00250 / 0.0231 What is the percentage of CaCO3 by mass in the tablet?
= 0.108 mol dm-3 1. Calculate the number of moles of sodium hydroxide used
Step 4 work out concentration of original concentrated amount = conc x vol
CH3CO2H in 25cm3 in moldm-3 = 0.30 x 0.0111
conc = 0.108 x 10 = 1.08 mol dm-3 = 0. 00333 mol

Step 5 work out concentration of CH3CO2H in original 2. Work out number of moles of hydrochloric acid left in 10.0 cm3
concentrated 25 cm3 in gdm-3 use balanced equation to give moles of HCl
conc in gdm-3 = conc in mol dm-3 x Mr 1 mol NaOH : 1 mol HCl
So 0.00333 NaOH : 0.00333 moles HCl
= 1.08 x 60 = 64.8 g dm-3
3. Calculate the number of moles of hydrochloric acid left in
100 cm3 of solution
Example 27. An unknown metal carbonate reacts with
hydrochloric acid according to the following equation. Moles in 100cm3 = 0.00333 x10
M2CO3(aq) + 2HCl(aq)  2MCl(aq) + CO2(g) + H2O(l) =0.0333
A 3.96 g sample of M2CO3 was dissolved in distilled water to
make 250 cm3 of solution. A 25.0 cm3 portion of this solution 4. Calculate the number of moles of HCl that reacted with
required 32.8 cm3 of 0.175 mol dm–3 hydrochloric acid for the indigestion tablet.
complete reaction. Calculate the Mr of M2CO3 and identify the
In original HCl 50.0 cm3 of 1.00 mol dm–3 there is 0.05moles
metal M
1. Calculate the number of moles of HCl used moles of HCl that =0.05 -0.0333
amount = conc x vol reacted with the =0.0167
= 0.175 x 0.0328 indigestion tablet.
= 0. 00574 mol
2. Work out number of moles of M2CO3 in 25.0 cm3 put in conical 5 Use balanced equation to give moles of CaCO3
flask CaCO3(s) + 2HCl(aq)  CaCl2(aq) + CO2(g) + H2O(l)
use balanced equation to give moles of M2CO3 2 mol HCl : 1 mol CaCO3
2 mol HCl : 1 mol M2CO3 So 0.0167 HCl : 0.00835 moles CaCO3
So 0. 00574 NaOH : 0.00287 moles M2CO3
6. work out the mass of CaCO3 in original tablet
3. Calculate the number of moles M2CO3 acid in original 250 cm3
of solution mass= amount x Mr
Moles in 250cm3 = 0.00287 x10 = 0.00835 x 100 = 0.835 g
=0.0287
percentage of
4. work out the Mr of M2CO3 = 0.835/0.950 x100
CaCO3 by mass in
Mr= mass / amount the tablet
= 87.9 %
= 3.96/ 0.0287= 138.0
5. Work out Ar of M = (138-12- 16x3)
2
Ar of M = 39 M= potassium

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Uncertainty
Readings and Measurements

Readings Measurements The uncertainty of a reading (one judgement) is at

the values found from a the values taken as the least ±0.5 of the smallest scale reading.
single judgement when difference between the The uncertainty of a measurement (two
using a piece of equipment judgements of two judgements) is at least ±1 of the smallest scale
values (e.g. using a reading.
burette in a titration)

Calculating Apparatus Uncertainties

Each type of apparatus has a sensitivity uncertainty To decrease the apparatus uncertainties
you can either decrease the sensitivity
•balance  0.001 g uncertainty by using apparatus with a
•volumetric flask  0.1 cm3 greater resolution (finer scale divisions )
•25 cm3 pipette  0.1 cm3 or you can increase the size of the
•burette  0.05 cm3 measurement made.

Calculate the percentage error for each piece of equipment used by Uncertainty of a measurement using
a burette. If the burette used in the
% uncertainty =  uncertainty x 100 titration had an uncertainty for each
Measurement made on apparatus reading of +/– 0.05 cm3 then during a
titration two readings would be taken
e.g. for pipette so the uncertainty on the titre volume
% uncertainty = 0.05/ 25 x100 would be +/– 0.10 cm3 .

To calculate the maximum percentage apparatus uncertainty in the

final result add all the individual equipment uncertainties together.

Reducing uncertainties in a titration If looking at a series of measurements

in an investigation the experiments
Replacing measuring cylinders with pipettes or burettes which have with the smallest readings will have
lower apparatus uncertainty will lower the error the highest experimental uncertainties.

To reduce the uncertainty in a burette reading it is necessary to

make the titre a larger volume. This could be done by: increasing
the volume and concentration of the substance in the conical flask
or by decreasing the concentration of the substance in the burette.

Reducing uncertainties in measuring mass

Using a more accurate balance or a larger mass will
reduce the uncertainty in weighing a solid
Weighing sample before and after addition and then
calculating difference will ensure a more accurate
measurement of the mass added.

If the %uncertainty due to the apparatus <

percentage difference between the actual value
Calculating the percentage difference between the
and the calculated value then there is a
actual value and the calculated value
discrepancy in the result due to other errors.
If we calculated an Mr of 203 and the real value is 214,
then the calculation is as follows: If the %uncertainty due to the apparatus >
Calculate difference 214-203 = 11 percentage difference between the actual value
% = 11/214 x100 and the calculated value then there is no
=5.41% discrepancy and all errors in the results can be
explained by the sensitivity of the equipment.

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 8C Halogens Fluorine (F2): very pale yellow gas. It is highly reactive
Chlorine : (Cl2) greenish, reactive gas, poisonous in high concentrations
Bromine (Br2) : red liquid, that gives off dense brown/orange poisonous fumes
Iodine (I2) : shiny grey solid sublimes to purple gas.

Trend in melting point and boiling point Trend in electronegativity

Increase down the group Electronegativity is the relative tendency of an atom in a
molecule to attract electrons in a covalent bond to itself.
As the molecules become larger they have
more electrons and so have larger London As one goes down the group the electronegativity of the
forces between the molecules. As the elements decreases.
intermolecular forces get larger more energy
As one goes down the group the atomic radii increases due
has to be put into break the forces. This
to the increasing number of shells. The nucleus is therefore
increases the melting and boiling points
less able to attract the bonding pair of electrons

The reactivity of the halogens decreases down the group as the atoms get bigger with more shielding so
they less easily attract and accept electrons. They therefore form -1 ions less easily down the group

1. The oxidation reactions of halide ions by halogens.

A halogen that is a strong oxidising agent will The oxidising strength decreases down the group.
displace a halogen that has a lower oxidising Oxidising agents are electron acceptors.
power from one of its compounds

know these
Chlorine will displace both bromide and iodide ions; bromine will displace iodide ions
observations !
Chlorine (aq) Bromine (aq) Iodine (aq) The colour of the solution in
the test tube shows which free
potassium Very pale green Yellow solution, no Brown solution, halogen is present in solution.
chloride (aq) solution, no reaction no reaction Chlorine =very pale green
reaction solution (often colourless),
potassium Yellow solution, Cl Yellow solution, no Brown solution, Bromine = yellow solution
bromide (aq) has displaced Br reaction no reaction Iodine = brown solution
(sometimes black solid
potassium Brown solution, Cl Brown Solution, Br Brown Solution,
present)
iodide (aq) has displaced I has displaced I no reaction

Observations if an organic solvent is added

Chlorine (aq) Bromine (aq) Iodine (aq)
The colour of the organic
potassium colourless, no yellow, no purple, no solvent layer in the test tube
chloride (aq) reaction reaction reaction shows which free halogen is
present in solution.
potassium yellow, Cl has yellow, no purple, no Chlorine = colourless
bromide (aq) displaced Br reaction reaction Bromine = yellow
Iodine = purple
potassium purple, Cl has purple, Br has purple, no
iodide (aq) displaced I displaced I reaction

Cl2(aq) + 2Br – (aq)  2Cl – (aq) + Br2(aq)

Cl2(aq) + 2I – (aq)  2Cl – (aq) + I2(aq)
Br2(aq) + 2I – (aq)  2Br – (aq) + I2(aq)

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 The oxidation reactions of metals and metal ion by halogens.
In all reactions where halogens
2Na  2Na+ + 2e- are reacting with metals, the
Br2(l) + 2Na (s)  2NaBr (s) Br2 + 2e-  2Br - metals are being oxidised

3Cl2(g) + 2 Fe (s)  2 FeCl3 (s) Br2(l) + Mg (s)  MgBr2 (s)

Cl2(g) + 2Fe2+ (aq)  2 Cl- (aq) + 2Fe3+ (aq) Chlorine and Bromine can oxidise Fe2+ to Fe3+. Iodine
is not strong enough oxidising agent to do this reaction.
2I- (aq) + 2Fe3+ (aq)  I2 (aq) + 2Fe2+ (aq) The reaction is reversed for Iodine

The disproportionation reactions of chlorine and chlorate(I).

Disproportionation is the name for a reaction where Chlorine is both simultaneously reducing and
an element simultaneously oxidises and reduces. oxidising changing its oxidation number from 0 to
-1 and 0 to +1
Chlorine with water:
Cl2(g) + H2O(l)  HClO(aq) + HCl (aq)

If some universal indicator is added to the solution it will

The pale greenish colour of these solutions
first turn red due to the acidity of both reaction products. It
is due to the Cl2
will then turn colourless as the HClO bleaches the colour.

Chlorine is used in water treatment to kill bacteria. It has been used to treat drinking water and the water in
swimming pools. The benefits to health of water treatment by chlorine outweigh its toxic effects.

Reaction of halogens with cold dilute NaOH solution:

Cl2, Br2, and I2 in aqueous solutions will react with cold sodium hydroxide. The colour of the halogen solution
will fade to colourless

Cl2(aq) + 2NaOH(aq)  NaCl (aq) + NaClO (aq) + H2O(l)

The mixture of NaCl and NaClO is used as Bleach and to disinfect/ kill bacteria

Reaction of halogens with hot dilute NaOH solution:

With hot alkali disproportionation also occurs but the halogen that is oxidised goes to a higher
oxidation state.

3Cl2 (aq) + 6 NaOH(aq)  5 NaCl (aq) + NaClO3 (aq) + 3H2O (l)

3I2 (aq) + 6NaOH (aq)  5 NaI (aq) + NaIO3 (aq) + 3H2O (l)

3I2 (aq) + 6OH- (aq)  5 I- (aq) + IO3- (aq) + 3H2O (l)

In IUPAC convention the various forms of sulfur and chlorine compounds where oxygen is
combined are all called sulfates and chlorates with relevant oxidation number given in roman
numerals. If asked to name these compounds remember to add the oxidation number.

NaClO: sodium chlorate(I)

NaClO3: sodium chlorate(V)
K2SO4 potassium sulfate(VI)
K2SO3 potassium sulfate(IV)

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The reaction of halide salts with concentrated sulfuric acid.

The Halides show increasing power as

Explanation of differing reducing power of halides
reducing agents as one goes down the
A reducing agent donates electrons.
group. This can be clearly demonstrated in
The reducing power of the halides increases down group 7
the various reactions of the solid halides with
They have a greater tendency to donate electrons.
concentrated sulfuric acid.
This is because as the ions get bigger it is easier for the
Know the equations and observations of outer electrons to be given away as the pull from the nucleus
these reactions very well. on them becomes smaller.

Fluoride and Chloride

The H2SO4 is not strong enough an oxidising reagent to oxidise the chloride and
fluoride ions. No redox reactions occur. Only acid-base reactions occur.

NaF(s) + H2SO4(l) NaHSO4(s) + HF(g)

These are acid –base reactions and
Observations: White steamy fumes of HF are evolved.
not redox reactions. H2SO4 plays the
NaCl(s) + H2SO4(l)  NaHSO4(s) + HCl(g) role of an acid (proton donor).
Observations: White steamy fumes of HCl are evolved.

Bromide
Br- ions are stronger reducing agents than Cl- and F- and after the initial acid-
base reaction reduce the Sulfur in H2SO4 from +6 to + 4 in SO2
Observations: White steamy
Acid- base step: NaBr(s) + H SO (l)  NaHSO (s) + HBr(g) fumes of HBr are evolved.
2 4 4

Redox step: 2HBr + H2SO4  Br2(g) + SO2(g) + 2H2O(l) Red fumes of Bromine are also
evolved and a colourless, acidic gas
SO2
Ox ½ equation 2Br -  Br2 + 2e-
Re ½ equation H2SO4 + 2 H+ + 2 e-  SO2 + 2 H2O Reduction product = sulfur dioxide

Note the H2SO4 plays the role of acid in the first step producing HBr
and then acts as an oxidising agent in the second redox step.

Iodide
I- ions are the strongest halide reducing agents. They can reduce the Sulfur from
+6 in H2SO4 to + 4 in SO2, to 0 in S and -2 in H2S.

NaI(s) + H2SO4(l)  NaHSO4(s) + HI(g) Observations:

2HI + H2SO4  I2(s) + SO2(g) + 2H2O(l) White steamy fumes of HI are evolved.
6HI + H2SO4  3 I2 + S (s) + 4 H2O (l) Black solid and purple fumes of Iodine are
8HI + H2SO4 4I2(s) + H2S(g) + 4H2O(l) also evolved
A colourless, acidic gas SO2
A yellow solid of Sulfur
Ox ½ equation 2I -  I2 + 2e- H2S (Hydrogen Sulfide), a gas with a bad egg
Re ½ equation H2SO4 + 2 H+ + 2 e-  SO2 + 2 H2O smell,

Re ½ equation H2SO4 + 6 H+ + 6 e-  S + 4 H2O

Reduction products = sulfur dioxide, sulfur
Re ½ equation H2SO4 + 8 H+ + 8 e-  H2S + 4 H2O and hydrogen sulfide

Note the H2SO4 plays the role of acid in the first step producing HI and
then acts as an oxidising agent in the three redox steps

Often in exam questions these redox reactions are

worked out after first making the half-equations

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The reactions of halide ions with silver nitrate. The role of nitric acid is to react with any carbonates
present to prevent formation of the precipitate
This reaction is used as a test to identify which halide ion Ag2CO3. This would mask the desired observations
is present. The test solution is made acidic with nitric
2 HNO3 + Na2CO3  2 NaNO3 + H2O + CO2
acid, and then Silver nitrate solution is added dropwise.

Fluorides produce no precipitate

Chlorides produce a white precipitate Effect Of Light on Silver Halides
Ag+(aq) + Cl- (aq)  AgCl(s)
The precipitates ( except AgI) darken in sunlight forming
Bromides produce a cream precipitate
silver. This reaction is used in photography to form the
Ag+(aq) + Br- (aq)  AgBr(s)
dark bits on photographic film
Iodides produce a pale yellow precipitate
Ag+(aq) + I- (aq)  AgI(s)
Silver chloride dissolves in dilute ammonia to form a
Effect Of ammonia on Silver Halides complex ion
AgCl(s) + 2NH3(aq) [Ag(NH3)2]+ (aq) + Cl- (aq)
Colourless solution
The silver halide precipitates can be
Silver bromide dissolves in concentrated ammonia to form a
treated with ammonia solution to help
complex ion
differentiate between them if the
AgBr(s) + 2NH3(aq) [Ag(NH3)2]+ (aq) + Br - (aq)
colours look similar:
Colourless solution
Silver iodide does not react with ammonia – it is too insoluble.

Producing hydrogen halides

Hydrogen halides are made by the reaction of solid

sodium halide salts with phosphoric acid
This is the apparatus
used to make the
NaCl(s) + H3PO4(l)  NaH2PO4(s) + HCl(g)
hydrogen halide using
phosphoric acid.
Observations: White steamy fumes of the Hydrogen
Notice the downward
Halides are evolved.
delivery which is used
The Steamy fumes of HCl are produced when the HCl because the hydrogen
meets the air because it dissolves in the moisture in the halides are more dense
air than air

Phosphoric acid is not an oxidising agent and so does not oxidise HBr and HI. Phosphoric acid is more
suitable for producing hydrogen halides than the ones with concentrated sulfuric acid to make HCl, HBr, and
HI because there are no extra redox reactions taking place and no other products.

Solubility in water : Hydrogen Halide All the hydrogen halides react readily with
The hydrogen halides ammonia to give the white smoke of the
are all soluble in ammonium halide
The water quickly
water. They dissolve rises up the tube
to form acidic HCl(g) + NH3 (g)  NH4Cl (s)
solutions. HBr(g) + NH3 (g)  NH4Br (s)
HCl (g)+ H2O(l)  H3O+(aq)+ Cl-(aq) HI(g) + NH3 (g)  NH4I (s)

This can be used as a test for the

presence of hydrogen halides

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