Periodic Table

 Periodic law
 The modern periodic table
 Electronic configuration
 Periodic classification of elements
 Periodic properties of elements
 Transition elements
 d block elements
 Variation of properties within periods and
groups
 Properties and nobles gases
 Usefulness of periodic table
 Limitation of periodic table
 Position of Hydrogen
 Mathematical problems and solution
What is the PERIODIC TABLE?

oShows all known

elements in the
universe.
oOrganizes the elements
by chemical properties.
During the nineteenth century,
chemists began to categorize the
elements according to similarities in
their physical and chemical
properties. The end result of these
studies was our modern periodic
table.

Lavoisier (1789) classified elements

into metals, non-metals, gases and
earths.
DOBEREINER’S TRIADS [ JOHN DOBEREINER
(1817)]

In 1829, he classified some elements into groups of

three, which he called triads.
The elements in a triad had similar chemical
properties and orderly physical properties.

Arithmetic mean of
S.N Atomic masses ofatomic masses of
Triad
o elements of triad first and third
element
1 Cl,Br,I 35.5, 80, 127 35.5 + 127 =
2 81.25
2 Li,Na,K 7, 23, 39 7 + 39
2 = 23

3 Ca,Sr,Ba 40,87.5,137 40+137

=
2 88.5
Model of triads
NEWLAND’S LAW OF OCTAVES [JOHN NEWLAND (1866)]

In 1866, he suggested that elements be

arranged in “octaves” because he noticed
(after arranging the elements in order of
increasing atomic mass) that certain
properties repeated every 8th element.
NEWLAND’S LAW OF OCTAVES [JOHN NEWLAND (1863)]

I II III IV V VI VII
Element Li Be B C N O F
Atomic mass 7 9 11 12 14 16 19

Element Na Mg Al Si p S Cl
Atomic mass 23 24 27 28 31 32 35.5

K Ca
Element 39 40
Atomic mass

Newland was first to publish the list of elements

in
increasing order of atomic masses.
LOTHER-MEYER’S ATOMIC VOLUME CURVE
[LOTHER MEYER (1869)]
DMITRI MENDELEEV 1834 - 1907

In 1869 he published a table of the

elements organized by increasing
atomic mass.
MENDELEEV’S
PERIODIC LAW

The physical and chemical

properties of elements are
periodic function of their
atomic masses.
Origin of the Periodic Table

Mendeleev proposed the first arrangement

of the periodic table.

Arranged by atomic mass

Found that as he arranged the elements,

similar properties repeated themselves.
Origin of the Periodic Table

There were “gaps” in his table, which led

other scientists to discover new elements.

Moseley devised the current periodic table

which is based on ATOMIC NUMBER
The periodic table organizes the elements in a
particular way. A great deal of information
about an element can be gathered from its
position in the period table.
For example, you can predict with reasonably
good accuracy the physical and chemical
properties of the element. You can also predict
what other elements a particular element will
react with chemically.
Understanding the organization and plan of
the periodic table will help you obtain basic
information about each of the 118 known
elements.
The Periodic Table

Dmitri Mendeleev (1834 - 1907)

 Periodic Law
• States that the repeating chemical and
physical properties of elements change
periodically with the atomic numbers of the
elements.
 Periods
• Periods: horizontal rows of elements (7)

• Just as the number of protons changes as

you move from left to right across the
periodic table, so does the number of
electrons.

• Remember that sentences are written in rows

and end with a period.
 Groups
• Groups: Vertical column of elements on
the periodic table (18)

• Remember that group is spelled group and

groups go up and down.

• Elements in the same group have the

same number of valence electrons.
 Groups
• Remember, valence electrons determine
an element’s properties so all elements in
the same group have similar properties.

• What makes them different then???

MENDELEEV’S PERIODIC
TABLE
Only 63 elements were known.
Groups
• 8 vertical rows.
• 7 groups were subdivided in A and B.
• 8th group has 9 elements in the group
of
3 each.
Periods
• 7 horizontal rows.
MERITS OF MENDELEEV’S PERIODIC TABLE

Prediction of new
2 elements 3
(Ge, Ga, Sc)

Correction of
Systematic study atomic mass
of elements (Be, Au, Pt)
Mendeleev
• stated that if the atomic weight of an
element caused it to be placed in the
wrong group, then the weight must be
wrong.
(He corrected the atomic masses of Be,
In, and U)
• was so confident in his table that he
used it to predict the physical
properties of three elements that were
After the discovery of these unknown
yet unknown.
elements between 1874 and 1885, and
the fact that Mendeleev’s predictions for
Sc, Ga, and Ge were amazingly close to
the actual values, his table was
generally accepted.
DEFECTS OF MENDELEEV’S PERIODIC
TABLE

Position of
hydrogen.

Anomalous pairs. Position of

(Ar and K, Co and isotopes
Ni, Te and I) e.g. 1H1, 1H2, 1H3
DEFECTS OF MENDELEEV’S PERIODIC
TABLE

Chemically
dissimilar
elements are
grouped together.
(Cu-IA and Na-IB)
Chemically similar
elements are
placed in different
groups.
[Cu (I) and Hg (II)].
DO YOU KNOW?
Mendeleev’s periodic table was published in
1905 when no one had an idea of the
structure of an atom.
Mendeleev’s name has been immortalized by naming
the element with atomic number 101, as Mendelevium.
This name was proposed by American scientist Glenn
T. Seaborg, the discoverer of this element, “in
recognition of the pioneering role of the great Russian
Chemist who was the first to use the periodic system
of elements to predict the chemical properties of
undiscovered elements, a principle which has been the
key to the discovery of nearly all the transuranium
elements
 MODERN PERIODIC LAW AND THE MODERN
PERIODIC TABLE

English physicist, Henry Moseley observed

regularities in the characteristic X-ray spectra.
A plot of f against atomic number (Z ) of the
elements gave a straight line and not the plot
of f vs atomic mass

He thereby showed that the atomic number is

a more fundamental property of an element
than its atomic mass.
Mendeleev’s Periodic Law was,
therefore, accordingly modified.
This is known as the Modern
Periodic Law and can be stated
as :

The physical and chemical

properties of the elements are
periodic functions of their atomic
numbers.
HENRY
MOSELEY
In 1913, through his work with X-rays, he determined the
actual nuclear charge (atomic number) of the elements*.
He rearranged the elements in order of increasing
atomic number.
*“There is in the atom a
fundamental quantity which
increases by regular steps as we
pass from each element to the
next. This quantity can only be
the charge on the central positive
nucleus.”

His research was halted when the British government sent

him to serve as a foot soldier in WWI. He was killed in the
fighting in Gallipoli by a sniper’s bullet, at the age of 28.
Because of this loss, the British government later
restricted its scientists to noncombatant duties during
WWII.
FEATURES OF LONG FORM OF
PERIODIC TABLE

• Contains elements arranged in

increasing order of atomic
numbers.
• Explains the position of an
element in relation to other
elements.
• Consists of groups and periods.
 Features of long form of periodic table

Groups Vertical column

Total 18. Numbered 1-18 or

IA to VII A, IB to VII B, VIII and zero.

Elements in a group have similar but not

identical electronic configuration and properties

Periods Horizontal column

Total 7 numbered from 1 to 7.

Contains 2,8,8,18,18,32 and 28 elements
respectively.
 ELECTRONIC CONFIGURATIONS AND TYPE
s-,p-,d-,f- Block Elements

On the basis of the nature of sub-shell

in which last electron of atom enters,
elements are divided into 4 blocks
 s-Block Element
p-Block Element
d-Block Element
f- Block Element
 s-Block Elements

In these elements last electron enters the s-

orbital
• Electronic configuration:

ns1 or ns2

• Groups: IA (alkali metals )and

IIA(alkaline earth metals
• All are metal, low ionization energy and low
melting and boiling points, electropositive
elements.

• compounds are mostly ionic & colourless.

 p-Block Elements

In these elements last electron enters the p-

orbital
• Electronic configuration:
ns2,np1 -6
• Groups:

III A to VII A and zero group (group 13-

18).
• Non-metals, electronegative.
• Form covalent compounds.
 d-Block Elements

In these elements last electron enters the d-

orbital,
Also known asconfiguration:
• Electronic transition metals.

(n-1)d1-10 ns1or2
• Groups:

I B to VII B and VIII groups (Gr- 3-12).

• Variable valency high melting and boiling point.

• Coloured compounds and catalytic property.

 f-Block Elements
In these elements last electron enters the f-
orbital,
Also known as
• Electronic Inner-Transition Elements
configuration:

(n-2)f1-14(n-1)d0-1ns2
• Present below the
periodic
table in two rows
• Lanthanides-elements
after
lanthanum(Gr.-3, Pd.-6)
• Actinides-elements after
actinium. (Gr.-3, Pd.-7)
• Have high melting and boiling point.
 FEATURES OF LONG FORM OF PERIODIC
TABLE

Representative elements
s and p block elements .
Transition elements
d-block elements. Valence shell and penultimate
Shell both are incomplete.
Inner Transition elements

f-block elements. Valence shell, penultimate shell

antipenultimate shell are incomplete.
MERITS OF LONG FORM OF PERIODIC TABLE

• Based on a more fundamental basis

- the atomic number

• Position of an element is related to the electronic

configuration of its atom.
• Due to separation of elements into groups, dissimilar
elements (e.g. alkali metals I A and coinage metals I B)
do not fall together.
Defects of long form of
periodic table

It is unable to include lanthanides and

actinides in its main body.

The problem of the position of hydrogen in

the table has not been solved completely

Configuration of Helium(1s2 ) is different

from inert gases (ns2,np6) but are placed in
the same group.
 NOMENCLATURE OF THE ELEMENTS
WITH ATOMIC NUMBER >100
Digit Name Abbrevia
tion
Name
=digits name + ium
0 nil n
1 un u e.g. atomic number
2 bi b 115
3 tri t Will be named as
4 quad q un+un+pent+ium
5 pent p
=ununpentium
and symbol is Uup
6 hex h
7 sept s
8 oct o
9 enn e
Elements are organized on
the table according to their
atomic number, usually
found near the top of the
square.
The atomic number
refers to how many
protons an atom of that
element has.
For instance, hydrogen
has 1 proton, so it’s
atomic number is 1.
The atomic number is
unique to that element.
No two elements have
the same atomic number.
 What’s in a square?
• Different periodic
tables can include
various bits of
information, but
usually:
– atomic number
– symbol
– atomic mass
– number of valence
electrons
– state of matter at room
temperature.
 Atomic Number

• This refers to how

many protons an
atom of that
element has.
• No two elements,
have the same
number of protons.

Bohr Model of Hydrogen Atom

Wave Model
 Atomic Mass
• Atomic Mass
refers to the
“weight” of the
atom.
• It is derived at by
adding the number
of protons with the This is a helium atom. Its
Hatomic mass is 4 (protons
number of plus neutrons).
neutrons.
What is its atomic number?
Atomic Mass and Isotopes
• While most atoms have
the same number of
protons and neutrons,
some don’t.
• Some atoms have
more or less neutrons
than protons. These
are called isotopes.
• An atomic mass
number with a decimal
is the total of the
number of protons plus
the average number of
neutrons.
Atomic Mass Unit (AMU)

• The unit of
measurement for an
atom is an AMU. It
stands for atomic
mass unit.
• One AMU is equal
to the mass of one
proton.
 Atomic Mass Unit (AMU)
• There are
6 X 1023 or
600,000,000,000,000,0
00,000,000 amus in
one gram.
• (Remember that
electrons are 2000
times smaller than one
amu).
 Symbols

• All elements have

C Carbon
their own unique
symbol.
• It can consist of a
single capital letter,

Cu
or a capital letter
and one or two
lower case letters.
Copper
Common Elements and
Symbols
 Valence Electrons
• The number of valence
electrons an atom has
may also appear in a
square.
• Valence electrons are the
electrons in the outer
energy level of an atom.
• These are the electrons
that are transferred or
shared when atoms bond
together.
 Elements are arranged:

Vertically into Groups

Horizontally Into Periods

Why?
 If you looked at one
atom of every element
in a group you would
see…
Each atom has the same number of
electrons in its outermost shell.

• An example…
The group 2 atoms all have 2 electrons
in their outer shells

Be (Beryllium)
Atom

Mg (Magnesium) Atom
• The number of outer or “valence” electrons
in an atom affects the way an atom bonds.

• The way an atom bonds determines many

properties of the element.

• This is why elements within a group

usually have similar properties.
If you looked at an atom from each
element in a period

you would see…

Each atom has the same number of
electron shells.

An example…
The period 4 atoms each have 4 electron
containing shells

4th Shell

K (Potassium) Kr (Krypton)
Atom
Atom
Fe (Iron) Atom
 Each group has distinct properties
• The periodic Table is divided into several
groups based on the properties of different
atoms.
Alkali Metals

Soft, silvery coloured

metals
Very reactive!!!
Group 1A: Alkali Metals

Reaction of
potassium + H2O

Cutting sodium metal

Alkali Metals reacting with water:

• Li (Lithium) – least reactive

• Na (Sodium)
• K (Potassium)
• Rb (Rubidium)
• Cs (Cesium) – more reactive
What would you expect
from Francium?!?!
Group 2A: Alkaline Earth Metals

Magnesium

Magnesium
oxide
 Alkaline Earth Metals

Silvery-White Metals
Fairly reactive
Many are found in rocks in
the earth’s crust
Transition Metals

Most are good Malleable (easily

conductors of bent/hammered into
electricity wires or sheets)
How many things can you think
of that have Transition Metals in
them?
 Metalloids lie on
either side of the
“staircase”

They share properties with

both metals and non-metals
Si (Silicon) and Ge
(Germanium) are very
important “semi-conductors”
What are semiconductors used in?
 Nonmetals

Brittle
Do not conduct
electricity
 Halogens

Most are
poisonous
Fairly reactive –
react with alkali
metals (eg) Na+
and Cl-
Chlorine Gas was used as a
chemical weapon during World
War I.

It was used by the Germans in

World War II.
 Chlorine Gas
• The Germans were the first to use Chlorine gas
at Ypres in 1915
• Chlorine gas is a lung irritant
• The symptoms of gas poisoning are bright red
lips, and a blue face
• People affected die a slow death by suffocation
• Decades later men who thought they had
survived the war died from lung diseases such
as Emphysema
CHLORINE
 Noble Gases

Unreactive
Gases at room
temperature
Jellyfish lamps made with noble
gases
 Colors Noble Gases
produce in lamp tubes:
• Ne (Neon): orange-red
• Hg (Mercury): light blue

• Ar (Argon): pale lavender

• He (Helium): pale peach

• Kr (Krypton): pale silver

• Xe (Xenon): pale, deep blue
Lanthanide Series
Actinide Series
• (A) Periods of the periodic table, and (B) groups
of the periodic table.
• Chemical “Groups”
– IA are called alkali metals because they react with
water to form an alkaline solution (basic)
• They are very reactive
– Group IIA are called the alkaline earth metals
because they are reactive, but not as reactive as
Group IA.
• They are also soft metals
– Group VIIA are the halogens
• These need only one electron to fill their outer shell
• They are very reactive
– Group VIIIA are the noble gases as they have
completely filled outer shells
• They are almost non-reactive.
• Four chemical families of the
periodic table: the alkali
metals (IA), the alkaline earth
metals (IIA), halogens (VII),
and the noble gases (VIIIA).
Metal: Elements that are usually solids at room
temperature.
Most elements are metals.

Non-Metal: Elements in the upper right corner of the

periodic Table. Their chemical and physical properties
are different from metals.

Metalloid: Elements that lie on a diagonal line between

the metals and non-metals. Their chemical and
physical properties are intermediate between the two.
Properties of Non-Metals

• Non-metals are poor

conductors of heat and
electricity.
• Non-metals are not
ductile or malleable.
• Solid non-metals are
brittle and break easily.
• They are dull.
• Many non-metals are
gases.

Sulfur
Properties of Metalloids

• Metalloids (metal-like)
have properties of both
metals and non-metals.
• They are solids that can be
shiny or dull.
• They conduct heat and
electricity better than non-
metals but not as well as
metals.
• They are ductile and
malleable.

Silicon
 The
Atom
An atom consists of a
• nucleus
– (of protons and neutrons)
• electrons in space about the nucleus.

Electron cloud

Nucleus
ATOM
COMPOSITION
The atom is mostly
empty space
• protons and neutrons in
the nucleus.
• the number of electrons is equal to the number
of protons.
• electrons in space around the nucleus.
• extremely small. One teaspoon of water has 3
times as many atoms as the Atlantic Ocean
has teaspoons of water.
 Compounds
– composed of 2 or
more elements in a
fixed ratio
– properties differ
from those of
individual elements
– EX: table salt (NaCl)
A MOLECULE is 2 more atoms
bonded together – they may be the same
element (ie diatomic molecule) or they may
be different elements (ie caffeine)
Composition of molecules is given
by a MOLECULAR FORMULA
H2O C8H10N4O2 - caffeine
ELEMENTS THAT EXIST AS Remember:
DIATOMIC MOLECULES The “GENS”
These elements
exist as PAIRS
when ALONE.
Hydrogen (H2)
Nitrogen (N2)
Oxygen (O2)
Halogens
(F2, Cl2, Br2, I2)
(P4 and S8)
 Isotopes
• Atoms of the same element (same Z)
but different mass number (A).
• Boron-10 (10B) has 5 p and 5 n
• Boron-11 (11B) has 5 p and 6 n

11
B

B
10
Isotopes &
Their Uses
Bone scans with
radioactive
technetium-99.
CARBON-14 – RADIOACTIVE
ISOTOPE
• Occurs in trace
amounts in the
atmosphere
• Absorbed into living
organisms
• The half-life of
carbon-14 is approx
5700 years (when half
the C-14 is converted
to N-14)
 Atomic Symbols
Show the name of the element, a hyphen, and
the mass number in hyphen notation

sodium-23
Show the mass number and atomic number in
nuclear symbol form
mass number
23
Na
atomic number 11
 Isotopes?
Which of the following represent
isotopes of the same element?
Which element is it?

234 234 235 238

X X X X
92 93 92 92

1 2 3 4
 IONS
• IONS are atoms or groups of atoms with
a positive or negative charge.
• Donating an electron from an atom gives
a CATION with a positive charge
• Accepting an electron to an atom gives an
ANION with a negative charge
• To tell the difference between an atom
and an ion, look to see if there is a charge
in the superscript! Examples: Na+ Ca+2
I- O-2 Na Ca I O
 Forming Cations & Anions
A CATION forms An ANION forms
when an atom when an atom
loses one or more gains one or more
electrons. electrons

Mg --> Mg + 2 e-
2+ F + e- --> F-
 PREDICTING ION CHARGES

In general
• metals (Mg) lose electrons ---> cations (Mg2+)
• nonmetals (F) gain electrons ---> anions (F-)
– When an atom or molecule gain or loses an
electron it becomes an ion.

• A cation has lost an electron and therefore has a

positive charge
• An anion has gained an electron and therefore
has a negative charge.
Charges on Common
Ions
-3 -2 -1
+1
+2

By losing or gaining e-, atom has same

number of e-’s as nearest Group 8A atom.
 Learning Check – Counting

State the number of protons, neutrons, and electrons

in each of these ions.
39
K+ O -2
16
Ca +2
41
19 8 20

#p+ ______ ______ _______

#no ______ ______ _______
#e- ______ ______ _______
– Elements with 1, 2, or 3 electrons in their outer shell
tend to lose electrons to fill their outer shell and
become cations.
• These are the metals which always tend to lose
electrons.
– Elements with 5 to 7 electrons in their outer shell
tend to gain electrons to fill their outer shell and
become anions.
• These are the nonmetals which always tend to gain
electrons.
– Semiconductors (metalloids) occur at the dividing
line between metals and nonmetals.
 EXAMPLE
What would the charge be on a sodium ion?

Since sodium in in Group IA it is a metal and so would

LOSE an electron
ou can tell how many would be lost by the group number
Group 1A elements lose 1 electron

So the charge would be +1

Remember an electron is negatively charged.
When you lose them atom becomes positively
charged…
when you gain them it becomes negatively charged
 Periodic Properties
Periodic Trends in Physical Properties
Shielding effect & Effective Nuclear
Charge
Atomic Radius
Ionic Radius
Ionization Enthalpy
Electron Gain Enthalpy
Electronegativity
 Periodic Properties
Periodic Trends in Chemical Properties
 Periodicity of Valence or Oxidation
States
 Anomalous Properties of Second
Period Elements
 Chemical Reactivity
 Shielding effect & Effective Nuclear
Charge

The decrease in nuclear charge

( nuclear force of attraction) on
outermost shell electrons due to
repulsion caused by inner shell
electron is known as shielding effect of
inner shell or intervening electrons on
outer shell electron.
 Shielding effect & Effective Nuclear
Charge
Due to shielding effect the nuclear charge is
lowered on outermost shell electrons, the net
nuclear charge acting on outermost shell
electrons is known as Effective Nuclear
Charge. It is denoted by Z* or Zeff.

 Z* or Zeff. = Z - σ

 where Z = nuclear charge( = atomic No.) &

 σ = shielding constant or screening constant
, it is a measure of shielding effect
 Shielding effect & Effective Nuclear
Charge

Determination of ENC (Z*)

If the electron resides in s or p orbital
1. Electrons in principal shell higher than the e-
in question contribute 0 to σ .
2. Each electron in the same principal shell
contribute 0.35 to σ (0.30 if it is 1S shell).
3. Electrons in (n-1) shell each contribute 0.85
to σ .
4. Eelectrons in deeper shell each contribute
1.00 to σ
 Shielding effect & Effective Nuclear
Charge

Determination of ENC (Z*)

If the electron resides in d or f orbital
1. All e-s in higher principal shell contribute 0
to σ
2. Each e- in same shell contribute 0.35 to σ
3. All inner shells in (n-1) and lower contribute
1.00 to σ
 Shielding effect & Effective Nuclear
Charge
Determination of ENC (Z*)
e.g. Calculate the Z* for the 2p electron Fluorine
(Z = 9) 1s2, 2s 2p5.
Soln. Screening constant for one of the outer electron
 6 (six) (two 2s e- and four 2p e-) = 6 X 0.35 = 2.10
 2 (two)1s e- = 2 X 0.85 = 1.70
 σ = 1.70+2.10 = 3.80
 Z* = 9 - 3.80 = 5.20
 Shielding effect & Effective Nuclear
Charge

Trend of ENC in Periodic Table

 In a Period - Effective nuclear charge Z*
increases increases rapidly along a
period(0.65 per next group)
e.g.
Li Be B C N O F Ne

1.3 1.95 2.6 3.3 3.9 4.6 5.2 5.9

 Shielding effect & Effective Nuclear
Charge

Trend of ENC in Periodic Table

 In a Group - Effective nuclear charge Z*
increases slowly along a group.
e.g. Gr-1 H Li Na K Rb Cs

Z* 1.0 1.3 2.2 2.2 2.2 2.2

 PERIODIC TREND OF ATOMIC RADIUS
In A Period-
 atomic radius decreases with increase in atomic
number (in a period left to right)
BECAUSE in a period left to right-
 1. n (number of shells) remain constant.
 2. Z increases (by one unit)
 3. Z* increases (by 0.65 unit)
 4. Electrons are pulled close to the nucleus by the
increased Z*
 In a group-
Atomic radius increases moving down the
group
 Because, along a group top to bottom
1. n increases
2. Z increases
3. No dramatic increase in Z* - almost
remains constant
 IONIC RADII
 All anions are larger than their parent
atoms.
because the addition of one or more electrons
would result in increased repulsion among the
electrons and a decrease in ENC.
 The cations are smaller than their parent
atoms
because it has fewer electrons while its nuclear
charge remains the same & hence ENC is greater in
cation than its parent atom
Cationic Radii
Anionic Radii
 ISOELECTRONIC SPECIES
 Atoms and ions which contain the same number of
electrons, are called as isoelectronic species.
For example, F–, Na+ and Mg2+ have the same
number of electrons(=10).

 The size of isoelectronic species decreases with

increase in nuclear charge. e.g.-
o2->F- >Ne>Na+>Mg2+>Al3+
---------SIZE DECREASING------
Atomic and Ionic Radii
Atomic Radius
 NOTE:
Metallic radii in the third row d-block are
similar to the second row d-block, but not
larger as one would expect given their larger
number of electrons.
This is due to Lanthanide Contraction as f-
orbitals have poor shielding properties.
 Ionization Energy (IE) or
Ionization Enthalpy (ΔiH )
 Ionization: removing an electron from an atom or ion
 Ionization energy: energy required to remove an
electron from an isolated, gaseous atom or ion is
called as Ionization energy or ionisation enthalpy.
 If the atom is neutral the above defined ionisation
energy is called as first ionisation enthalpy.
 Energy required to remove an electron from an
isolated, monovalent cation is called as second
Ionization energy.
 The ionization enthalpy is expressed in units of
kJ /mol
Ionization Energy (IE) or
Ionization Enthalpy (ΔiH )

X(g) + energy → X+(g) + e–.

1st ionization enthalpy

X+(g) + energy → X++(g) + e–.

2nd ionization enthalpy

 Ionization Energy (IE) or
Ionization Enthalpy (ΔiH )

The second ionization enthalpy will be

higher than the first ionization enthalpy
because it is more difficult to remove an
electron from a positively charged ion than
from a neutral atom because a cation has
greater ENC than a neutral atom.
In the same way the third ionization enthalpy
will be higher than the second and so on.
 Factors affecting Ionisation Enthalpy
(ΔiH )
(a) Size of the atom - IE decreases as the size
of the atom increases
(b) Nuclear Charge - IE increases with increase
in nuclear charge
(c) The type of electron - Shielding effect,
Penetration effect
(e)Electronic configuration: e.g. noble gases
passes very high value of IE due to stable
octet configuration
 Periodic Trend of Ionization Enthalpy
(ΔiH )
On moving down a group
1. nuclear charge increases
2. Z* due to screening is almost constant
3. number of shells increases, hence atomic size
increases.
4. there is a increase in the number of inner
electrons which shield the valence electrons
from the nucleus
Thus IE decreases down the group
 Periodic Trend of Ionization Enthalpy

On moving across a period(L--->R)

1. the atomic size decreases
2. Effective nuclear charge increases
Thus IE increases along a period
However there are some exceptions also e.g.
 IE of Be is higher than that of B.
 IE of N is higher than that of O.
 Periodic Trend of Ionization Enthalpy
(ΔiH )
Explain why- (a). IE of Be is higher than that of B.
Ans. - In beryllium(1s2,2s2 ), the electron removed
during the ionization is an s-electron whereas the
electron removed during ionization of
boron(1s2,2s2,2p1) is a p-electron. The penetration
of a 2s-electron to the nucleus is more than that of a
2p-electron; hence the 2p electron of boron is more
shielded from the nucleus by the inner core of
electrons than the 2s electrons of beryllium.
Therefore, it is easier to remove the 2p-electron
from boron compared to the removal of a 2s-
electron from beryllium. Thus, boron has a smaller
first ionization.
 Periodic Trend of Ionization Enthalpy
(ΔiH )
(b) Why IE of N is higher than that of O.
Ans. The first ionization enthalpy of oxygen compared
to nitrogen is smaller. This arises because in the
nitrogen atom(1s2,2s2,2p3) three 2p-electrons reside
in different atomic orbitals (Hund’s rule) whereas in
the oxygen atom (1s2,2s2,2p4), two of the four 2p-
electrons must occupy the same 2p-orbital resulting
in an increased electron-electron repulsion.
Consequently, it is easier to remove the fourth 2p-
electron from oxygen than it is, to remove one of the
three 2p-electrons from nitrogen.
 Electron Gain Enthalpy (ΔegH)
 When an electron is added to a neutral gaseous atom
(X) to convert it into a negative ion, the enthalpy
change accompanying the process is defined as the
Electron GainEnthalpy (ΔegH) or Electron Affinity.
 Electron gain enthalpy provides a measure of the
ease with which an atom adds an electron to form
anion as represented by equation –

 X(g) + e --- X- (g)+energy

(electrongainenthalpy)
 Electron Gain Enthalpy (ΔegH)
 Depending on the element, the process of
adding an electron to the atom can be
either endothermic or exothermic.

 For many elements energy is released when

an electron is added to the atom and the
electron gain enthalpy is negative.
 Factors Affecting E G E (ΔegH)
 ENC- With increase in ENC, the force of attraction
exerted by the nucleus on the electrons increases.
Consequently, the atom has a greater tendency to
attract additional electron i.e., its EGE increases i.e.
become more negative.
 ATOMIC SIZE-
With decrease in size ENC increases & hence
EGE increases.
 ELECTRONIC CONFIGURATION-
The value of EGE depends effectively upon
electronic configuration of elements, elements
with stable electronic configuration posses lower
(less -ve) value of EGE, e.g.-
 Factors Affecting E G E (ΔegH)

A. Noble gases have practically zero or +ve

EGEs. This is because they have no
tendency to gain an additional electron as
they already have the stable ns2np6
configuration
B. Halogens have high electron affinities. This
is due to their strong tendency to gain an
additional electron to change into the stable
ns2np6 configuration.
 PERIODIC TREND OF EGE (ΔegH)
IN A PERIOD-
The EGE increases i.e. become more negative as we
move across a period because the atomic size
decreases and hence the force of attraction exerted by
the nucleus on the electrons increases. Consequently,
the atom has a greater tendency to attract additional
electron i.e., its electron affinity increases
IN A GROUP-
The EGE decreases (-)vely because the atomic size
increases and therefore, the effective nuclear attraction
decreases and thus electron affinity decreases
First Electron Affinities
 Electron Gain Enthalpy (ΔegH)
 Explain why –
(a). electron gain enthalpy of O is less than that of the
S.
(b). electron gain enthalpy of F is less than that of the
Cl.
 Ans:- The electron gain enthalpy of O or F is less
than that of the succeeding element. This is because
when an electron is added to O or F, the added
electron goes to the smaller n = 2 quantum level and
suffers significant repulsion from the other electrons
present in this level. For the n = 3 quantum level (S
or Cl ), the added electron occupies a larger region
of space and the electron-electron repulsion is much
less.
 Electronegativity

 The tendency of an element in a

molecule to attract the shared pair of
electrons towards itself is known as
electronegativity.
It is measured on Pauling scale in
which F (most EN element)is attributed
to a value of 4 .
 Periodic trend of EN
In a Group- on moving down the group,
 Z increases but Z* almost remains constant
 number of shells (n) increases
 atomic radius increases
 force of attraction between added electron
and nucleus decreases
 Therefore EN decreases moving down the
group
 Periodic trend of EN
In a Period- On moving across a period left to
right
 Z and Z* increases
 number of shells remains constant
 atomic radius decreases
 force of attraction between shared electron
and nucleus increases
Hence EN increases along a period
Periodic Trends in Chemical
Properties

 Periodicity of Valence or Oxidation

States
 Anomalous Properties of Second
Period Elements
 Chemical Reactivity
 Periodicity of Valence or Oxidation
States
The valence of representative elements is usually
(though not necessarily) equal to the number of
electrons in the outer most orbitals and / or equal to
eight minus the number of outermost Electrons(w.r.t.
H)
Some periodic trends observed in the valence of
elements (hydrides and oxides) are shown in Table
Group 1 2 13 14 15 16 17
Number of
valence 1 2 3 3 5 6 7
electron

Valence 1 2 3 4 3,5 2,6 1,7

 Periodicity of Valence or Oxidation
States
The oxidation state of an element in a particular
compound can be defined as the charge
acquired by its atom on the basis of
electronegative consideration from other atoms
in the molecule.
Each group has a common (+)ve or (-)ve oxidation
state
And it show gradual change in oxidation state in a
period
 The d block:
• The d block consists of three horizontal
series in periods 4, 5 & 6
– 10 elements in each series
– Chemistry is “different” from other elements
– Special electronic configurations important
• Differences within a group in the d block are less
sharp than in s & p block
• Similarities across a period are greater
 Electronic Configuration
• Across the 1st row of the d block (Sc to Zn)
each element
– has 1 more electron and 1 more proton
– Each “additional” electron enters the 3d sub-
shell
– The core configuration for all the period 4
transition elements is that of Ar
• 1s22s22p63s23p6
Energy
4p

3d
4s

3p

3s

2p

2s
Ar
1s 1s2 2s2 2p6 3s2 3p6
Energy
4p

3d
4s

3p

3s

2p

2s
Sc
1s
1s2 2s2 2p6 3s2 3p6 3d1 4s2
 Electronic Arrangement
Eleme Z 3d 4s
nt
Sc 21 [Ar]  
Ti 22 [Ar]   
V 23 [Ar]    
Cr 24 [Ar]      
Mn 25 [Ar]      
Fe 26 [Ar]      
Co 27 [Ar]      
Ni 28 [Ar]      
Cu 29 [Ar]      
Zn 30 [Ar]      
 Chromium and Copper
• Cr and Cu don’t fit the pattern of building up
the 3d sub-shell, why?
– In the ground state electrons are always arranged
to give lowest total energy
– Electrons are negatively charged and repel each
other
– Lower total energy is obtained with e- singly in
orbitals rather than if they are paired in an orbital
– Energies of 3d and 4s orbitals very close together
in Period 4
 Chromium and Copper
• At Cr
– Orbital energies such that putting one e - into
each 3d and 4s orbital gives lower energy
than having 2 e- in the 4s orbital
• At Cu
– Putting 2 e- into the 4s orbital would give a
higher energy than filling the 3d orbitals
Energy
4p

3d
4s

3p

3s

2p

2s
Cr
1s 1s2 2s2 2p6 3s2 3p6 3d5
4s1
Energy
4p

3d
4s

3p

3s

2p

2s
Cu
1s 1s2 2s2 2p6 3s2 3p6 3d10
4s1
 What is a transition metal?
• Transition metals [TM’s] have characteristic
properties
– e.g. coloured compounds, variable oxidation states
• These are due to presence of an inner
incomplete d sub-shell
• Electrons from both inner d sub-shell and outer s
sub-shell can be involved in compound
formation
 What is a transition metal?
• Not all d block elements have incomplete
d sub-shells
– e.g. Zn has e.c. of [Ar]3d104s2, the Zn2+ ion
([Ar] 3d10) is not a typical TM ion
– Similarly Sc forms Sc3+ which has the stable
e.c of Ar. Sc3+ has no 3d electrons
 What is a transition metal?
• For this reason, a transition metal is
defined as being an element which forms
at least one ion with a partially filled sub-
shell of d electrons.
– In period 4 only Ti-Cu are TM’s!
– Note that when d block elements form ions
the s electrons are lost first

SS CI 11.5 The d block 163

The transition elements (d block) and inner
transition elements (f block) in the periodic table.
 What are TM’s like?
• TM’s are metals
• They are similar to each other but different from
s block metals eg Na and Mg
• Properties of TM’s
– Dense metals
– Have high Tm and Tb
– Tend to be hard and durable
– Have high tensile strength
– Have good mechanical properties

SS CI 11.5 The d block 165

 What are TM’s like?
• Properties derive from strong metallic bonding
• TM’s can release e- into the pool of mobile
electrons from both outer and inner shells
– Strong metallic bonds formed between the mobile
pool and the +ve metal ions
– Enables widespread use of TMs!
– Alloys very important: inhibits slip in crystal lattice
usually results in increased hardness and reduced
malleability

SS CI 11.5 The d block 166

Effect of Alloying on TM’s

SS CI 11.5 The d block 167

 TM Chemical Properties
• Typical chemical properties of the TM’s
are
– Formation of compounds in a variety of
oxidation states
– Catalytic activity of the elements and their
compounds
– Strong tendency to form complexes
– Formation of coloured compounds

SS CI 11.5 The d block 168

 Variable Oxidation States
• TM’s show a great variety of oxidation
states cf s block metals
• If compare successive ionisation
enthalpies (Hi) for Ca and V as follows
M(g)  M+(g) + e- Hi(1)
M+(g)  M2+(g) + e- Hi(2)
M2+(g)  M3+(g) + e- Hi(3)
M3+(g)  M4+(g) + e- Hi(4)

SS CI 11.5 The d block 169

 Hi for Ca and V
Ionisation Enthalpies
[kJ mol-1]
Element
Hi(1 Hi(2 Hi(3
Hi(4)
) ) )
+115 +491 +648
Ca [Ar]4s 2
+596
2 8 0
V +142 +283 +451
+656
[Ar]3d34s2 0 4 3
SS CI 11.5 The d block170
 Hi for Ca and V
• Both Ca & V always lose the 4s electrons
• For Ca
– Hi(1) & Hi(2) relatively low as corresponds to
removing outer 4s e-
– Sharp increase in Hi(3) & Hi(4) cf Hi(2) due to
difficulty in removing 3p e-
• For Sc
– Gradual increase from Hi(1) to Hi(4) as removing
4s then 3d e-

171
 Oxidation States of TM’s
• In the following table
– Most important OS’s in boxes
– OS = +1 only important for Cu
– In all others sum of Hi(1) + Hi(2) low
enough for 2e- to be removed
– OS = +2, where 4s e- lost shown by all except
for Sc and Ti
– OS = +3, shown by all except Zn

172
 Oxidation States of TM’s
S Ti V C M F C N C Z
c r n e o i u n
+1

+2 +2 +2 +2 +2 +2 +2 +2

+3 +3 +3 +3 +3 +3 +3 +3 +3

+4 +4 +4

+5

+6 +6 +6

+7
 Oxidation States of TM’s
• No of OS’s shown by an element increases from
Sc to Mn
– In each of these elements highest OS is equal to no.
of 3d and 4s e-
• After Mn decrease in no. of OS’s shown by an
element
– Highest OS shown becomes lower and less stable
– Seems increasing nuclear charge binds 3d e- more
strongly, hence harder to remove

174
 Oxidation States of TM’s
• In general
– Lower OS’s found in simple ionic
compounds
• E.g. compounds containing Cr3+, Mn2+, Fe3+,
Cu2+ ions
– TM’s in higher OS’s usually covalently
bound to electronegative element such as
O or F
• E.g VO3-, vanadate(V) ion; MnO4-,
manganate(VII) ion
• Simple ions with high OS’s such as V5+ & Mn7+
are not formed
175
 Stability of OS’s
• Change from one OS to another is a redox
reaction
• Relative stability of different OS’s can be
predicted by looking at Standard Electrode
Potentials
– E values

176
 Stability of OS’s
• General trends
– Higher OS’s become less stable relative to
lower ones on moving from left to right
across the series
– Compounds containing TM’s in high OS’s
tend to be oxidising agents e.g MnO4-
– Compounds with TM’s in low OS’s are
often reducing agents e.g V2+ & Fe2+

177
 Stability of OS’s
• General trends (continued)
– Relative stability of +2 state with respect to +3
state increases across the series
– For compounds early in the series, +2 state highly
reducing
• E.g. V2+(aq) & Cr2+(aq) strong reducing agents
– Later in series +2 stable, +3 state highly oxidising
• E.g. Co3+ is a strong oxidising agent, Ni3+ & Cu3+ do not
exist in aqueous solution.

178
 Catalytic Activity
• TM’s and their compounds effective and
important catalysts
– Industrially and biologically!!
• The “people in the know” believe
– catalysts provide reaction pathway with lower EA
than uncatalysed reaction (see CI 10.5)
• Once again,
– availability of 3d and 4s e-
– ability to change OS
– among factors which make TM’s such good
catalysts

179