MODULE I CONTENTS

COORDINATION CHEMISTRY – INTRODUCTION

CRYSTAL FIELD THEORY

COLOUR AND MAGNETIC PROPERTIES OF COMPLEXES

ISOMERISM IN COORDINATION COMPLEXES

SLATER’S RULE – CALCULATION OF EFFECTIVE NUCLEAR CHARGE

PERIODIC PROPERTIES

HSAB PRINCIPLE
Coordination number and geometries
The number of atoms or ions immediately surrounding a central atom in a
complex is called coordination number.
 Crystal Field Theory (CFT)

CFT is largely replaced VB Theory for interpreting the chemistry of coordination

compounds.

It was proposed by the physicist Hans Bethe in 1929. Subsequent modifications were
proposed by J. H. Van Vleckin 1935 to allow for some covalency in the interactions.
These modifications are often referred to as Ligand Field Theory

Salient Features of CFT

 Crystal Field Splitting of Octahedral Complexes

The octahedral arrangement of six ligands surrounding the central metal ion is as
shown in the figure.

In an octahedral complex, the metal ion is at the centre and the ligands are at the six
corners of octahedron. In the figure, the directions x, y and z point to the three
adjacent corners of the octahedran. The lobes of the eg orbitals (dx2-y2 and dz2) point
along the x, y and z axis while the lobes of the t2g orbitals (dxy, dzx and dyz)point in
between the axes. As a result, the approach of six ligands along the x, y z, -x,-y and –z
directions will increase the energy of dx2-y2 and dz2 orbitals (which point towards the
ligands) much more than that it increases the energy of dxy, dzx and dyz orbitals (
which point in between the metal-legand bond axis).

Thus, under the influence of an octahedral field, the d orbitals split into triply
degenerate orbitals with less energy and another as doubly degenerate orbitals with
higher energy. The main energy level between these two sets of orbitals is taken as
zero, which is called bari centre. The splitting between these two orbitals is called
crystal field splitting. The magnitude of stabilization will be 0.4 Δo and the magnitude
of destabilization will be 0.6 Δo.
Depending upon the nature of ligands, either transition metal complex is high- or low-spin in
nature.

The d orbital energy splitting is influenced by how strongly the ligand interacts with the
metal.

Ligands that cause a transition metal to have a small crystal field splitting, which leads to
high spin, are called weak-field ligands. Ligands that produce a large crystal field splitting,
which leads to low spin, are called strong field ligands.

For ex, let us take d4-octahedral system

Low Spin, Strong Field (∆o˃P) High Spin, Weak Field (∆ o˂P)

Splitting for a d4 complex under a strong field (left) and a weak field (right). The strong field
is a low spin complex, while the weak field is a high spin complex.

According to the Aufbau principle, electrons are filled from lower to higher energy orbitals.
Following Hund's rule, first 3 electrons are filled in order: dxy, dxz, and dyz orbitals. If one
were to add an 4th electron, however, it has the ability to fill a higher energy orbital ( dz² or dx²-
y²) or pair with an electron residing in the dxy, dxz, or dyz orbitals, this pairing of the electrons
requires energy (spin pairing energy). If the pairing energy is less than the crystal field
splitting energy, ∆₀, then the next electron will go into the dxy, dxz, or dyz orbitals due to
stability. This situation allows for the least amount of unpaired electrons, and is known
as low spin. If the pairing energy is greater than ∆₀, then the next electron will go into
the dz² or dx²-y² orbitals as an unpaired electron. This situation allows for the most number of
unpaired electrons, and is known as high spin.

Octahedral Crystal Field Splitting of d1-d10 configuration

Spectrochemical series

CFT is based primarily on symmetry of ligands around a central metal/ion and how this
anisotropic (properties depending on direction) ligand field affects the metal's atomic orbitals;
the energies of which may increase, decrease or not be affected at all. Once the ligands'
electrons interact with the electrons of the d-orbitals, the electrostatic interactions cause the
energy levels of the d-orbital to fluctuate depending on the orientation and the nature of the
ligands. A series of ligands arranged in the order in which they cause splitting of the energy
levels of d-orbitals in metal complexes is called as spectrochemical series.

I− < Br− < Cl− − < F− < OH− < C2O42− < H2O < NCS− < py < NH3 < en < bipy < phen
< NO2− < PPh3 < CN− < CO
 Crystal Field Splitting of Tetrahedral Complexes

The tetrahedral arrangement of four ligands surrounding the metal ions is as shown in
the figure.

A regular tetrahedron is a cube. One atom is at the centre of the cube and four of the
eight corners of the cube are occupied by ligands. The directions x, y and z point to
the face centres. The dx2-y2 and dz2 orbitals point along the x, y and z directions and
dxy, dzx and dyz orbitals point in between x, y and z directions. The direction of
approach of ligands does not coincide exactly with either the e or t2 orbitals. The t2
orbitals are pointing close to the direction in which the e orbitals are lying in between
the ligands. As a result, the energy of t2 orbitals increases compared to the energy of e
orbitals. Thus, d orbitals again split into two sets- triply degenerate t2 of higher energy
and doubly degenerate e orbitals of lower energy. That is, t2 orbitals are raised by 0.4
Δt in energy and the e orbitals are stabilized by 0.6 Δt in energy. The energy difference
between the two sets of orbitals (Δt) will be about half the magnitude of that in an
octahedral complex (Δo). The d-orbitals will thus split as shown below:
Effect of Crystal Field Splitting
Calculation of CFSE
CFSE for octahedral complexes = [-0.4 t2g e- + 0.6 eg e-]∆o + mP
∆o = 10 Dq
m- No. of paired electron; P- Pairing energy

CFSE for tetrahedral complexes = [-0.6 e (e-) + 0.4 t2 e-]∆t

∆t = 0.45 ∆o

Spin value S= n/2

n- no. of unpaired electron
Weak field vs strong field complexes

d4,d5,d6,d7,d8 octahedral complexes only have different CFSE values depending on

weak field ligand or strong field ligands
No difference in CFSE value for tetrahedral complexes based on weak field or strong
field ligands.
CFSE calculation for weak field octahedral complexes:

CFSE calculation for strong field octahedral complexes:

Problem 2:
The electronic spectrum of [Ti(H2O)6]3+ shows a single broad peak with a maximum at 20,300
cm-1. The crystal field stabilisation energy (CFSE) of the complex ion, in kJ mol-1, is (1 kJ mol-1 =
83.7 cm-1)
Spin-only magnetic moment calculation of octahedral complexes
CFSE and Spin-only magnetic moment calculation of tetrahedral
complexes
Color of Transition Metal Complexes
The variety of color among transition metal complexes has long fascinated the chemists.
For example, aqueous solutions of [Fe(H2O)6]3+ are red, [Co(H2O)6]2+ are pink,
[Ni(H2O)6]2+ are green, [Cu(H2O)6]2+ are blue and [Zn(H2O)6]2+ are colorless. Although
the octahedral [Co(H2O)6]2+ are pink, those of tetrahedral [CoCl4]2- are blue. The green
color of [Ni(H2O)6]2+ turns blue when ammonia is added to give [Ni(NH3)6]2+. Many of
these facts can be rationalized from CFT.

Why we see Color?

When a sample absorbs light, what we see is the sum of the remaining colors that strikes
our eyes. If a sample absorbs all wavelength of visible light, none reaches our eyes from
that sample, and then the sample appears black. If the sample absorbs no visible light, it
is white or colorless. When the sample absorbs a photon of visible light, it is its
complementary color we actually see. For example, if the sample absorbed orange color,
it would appear blue; blue and orange are said to be complementary colors.

The Color Wheel

The visible part of the electromagnetic spectrum contains light of wavelength 380-750
nm. The color wheel below gives information on the wavelength of different color and
also the complementary
color. For example: If red

light is absorbed, the

complex appears green; If
purple light is absorbed, the complex appears yellow.
Color of Coordination Complexes
The color of coordination complexes arises from electronic transitions between levels
whose spacing corresponds to the wavelengths available in the visible light. In
complexes, these transitions are frequently referred to as d-d transitions because they
involve the orbitals that are mainly d in character (for examples: t2g and eg for the
octahedral complexes and e and t2 for the tetrahedral complexes). Obviously, the colors
exhibited are intimately related to the magnitude of the spacing between these levels.
Since this spacing depends on factors such as the geometry of the complex, the nature of
the ligands, and the oxidation state of the central metal atom, variation on colors can
often be explained by looking carefully at the complexes concerned. Below are a few
examples to illustrate this point.


[V(H2O)6]3+ [V(H2O)6]2+
V(III) = d2 ion V(II) = d3 ion

violet light absorbed yellow light absorbed

complex appears yellow complex appears violet

eg
eg
∆oct ∆oct
t2g

t2g
∆ small
∆ large


The variation in the color of the Cr(III) complexes can be explained following
similar argument

We observe the appearance of a shoulder in the case of [Ti(H2O)6]3+. Perfectly

octahedral [Ti(H2O)6]3+ should give only one d-d Transition. However, distortion
occurs to eliminate the degeneracy of the system. If a complex distorts from
regular octahedral geometry, the t2g and eg levels are split, the consequence of
which is the appearance of a shoulder as shown in the figure right.
dz 2

dx2-y2

dxz dyz
dxy

Complexes that contain metal ions of d10 electron configuration are usually
colorless. Examples are [Cu(PPh3)4]+ and [Zn(H2O)6]2+. One would expect a
metal complex with no d-eletron to be colorless as well. However, a few of such
complexes are strongly colored, for example, MnO4- or [Cr2O7]2-. The origin of
the color in these complexes is not the d-d transitions, rather due to ‘charge
transfer’ that we will briefly discuss later.

Multi-electron systems exhibit multiple transitions and the assignment of
absorption bands is not straightforward. The complexity arises due to inter-
electron repulsions that we will not discuss in this course but will take a simpler
approach to understand the color of coordination complexes.
Problems related to colour of coordination complexes:

Strong field ligands like NH3, CN- cause large splitting so those complexes
absorb high energy/low wavelength and appeared as Orange or red.
Weak field ligands like F- and H2O cause small splitting so those complexes
absorb low energy/high wavelength and appeared as Green or Blue.
Problems:

Problem 2:

Problem 3:

Solution
The ligands for each complex ions are: (a) CN− (b) NH3, (c) F− and (d) H2O, which
are ranked in increasing Δo magnitude:

F− < H2O < NH3 < CN−

From the complementary color wheel, we get the following relationships (arranged
from highest energy absorbed to lowest):

• 400-nm Violet light absorbed → Green-yellow observed

• 430-nm Blue light absorbed → Orange observed
• 450-nm Blue light absorbed → Yellow observed
• 490-nm Blue-green light absorbed → Red observed
• 570-nm Yellow-green light absorbed → Violet observed
• 580-nm Yellow light absorbed → Dark blue observed
• 600-nm Orange light absorbed → Blue observed
• 650-nm Red light absorbed → Green observed
The smaller λλ of absorbed light corresponds to the higher energy photons, so we
would correlate the four wavelengths of absorbing photons in terms of increasing
energy to observed color
 Isomerism in Coordination Compound
Compounds that have the same chemical formula but different structural arrangements are called isomers.
Due to their complicated formulae of many coordination compounds, the variety of bond types and the number
of shapes possible, many different types of isomerism occur.
Ionization Isomerism:
 This type of isomerism is due to the exchange of groups between the complex ion and the ions outside it. (i.e.
exchange of ligated anion with a counterion) .
 e.g. [Co(NH3)5Br]SO4 and [Co(NH3)5(SO4)]Br
 [Co(NH3)5Br]SO4 is red-violet. An aqueous solution gives a white precipitate of BaSO4 with
BaCl2 solution, thus confirming the presence of free SO42- ions.
 In contrast [Co(NH3)5(SO4)]Br is red. A solution of this complex does not give a positive sulphate test
with BaCl2. It does give a cream-coloured precipitate of AgBr with AgNO3, the confirming the presence of free
Br– ions.
No. ppt. ← Ag+ + [Co(NH3)5Br]SO4 (Red-Violet) + Ba2+ → BaSO4 ↓

AgBr↓ ← Ag+ + [Co(NH3)5(SO4)]Br (Red) + Ba2+ → No ppt.

 other examples are [Pt(NH3)4Cl2]Br2 and [Pt(NH3)4Br2]Cl2

[Co(en)[Link]]NO2 and [Co(en)2Cl.NO2] SCN and [Co(en)[Link]]Cl
 Hydrate isomerism

 There is a replacement of co-ordinated group by water of hydration.

 They differ in chemical and physical properties
 Coordination number remains same.
 Differ in coordinated water molecules
 e.g. Three isomers of CrCl3.6H2O are known. From conductivity measurements and quantitative
precipitation of the ionized chlorine, they have been given the following formuale:

 [Cr(H2O)6]Cl3 : violet (three ionic chlorines)

 [Cr(H2O)5Cl]Cl2.H2O : green (two ionic chlorines)

 [Cr(H2O)4Cl2].Cl.2H2O : dark green (one ionic chlorine)
Linkage Isomerism:
 Certain ligands contain more than one atom which could donate an
electron pair. In the NO2- ion, either N or O atoms could act as the
electron pair donor.
 Thus there is the possibility of isomerism.
 Two different complexes [Co(NH3)5NO2]Cl2 have been prepared, each
containing the NO2- group in the complex ion.
Coordination isomerism
 When both the positive and negative ions are complex ions, isomerism may be
caused by the interchange of ligands between the complex anion and the
complex cation.
 Ligands are distributed differently between two metal centres.

 e.g. [Co(NH3)6][Cr(CN)6] and [Cr(NH3)6][Co(CN)6] octahedral

[Cu(NH3)4][PtCl4] and [Pt(NH3)4][CuCl4] square planar

[Pt(NH3)4][PtCl4] and [PtCl(NH3)3][PtCl3(NH3)]

Geometric isomerism:
 In disubstituted complexes, the substituted groups may be adjacent or opposite to each other. This gives
rise to geometric isomerism. Thus square planar complexes such as [Pt(NH3)4Cl2] can be prepared in two
forms, cis and trans. When the chlorine atoms are adjacent to each other it is called cis form. While when two
chlorine atoms are opposite it is called transform.
 This type of isomerism takes place mainly in heteroleptic complexes because of the different possible
geometric arrangements of ligands around the central metal atom.
 This type of isomerism is mainly found in coordination compounds with coordination numbers 4 and 6.
 In a square planar complex (i.e. coordination compounds with coordination number 4 which have [MX2L2]
type formula (X and L are unidentate ligands), the two ligands X may be present adjacent to each other in a
cis isomer, or opposite to each other to form a trans isomer.
 Square planar complex with MABXL type formula (where A, B, X, L are unidentate ligands) show three
isomers-two cis and one trans.
 Cis trans isomerism is not possible for a tetrahedral geometry.

MABXL

[MX2L2] [MX2L2]
 But octahedral complexes do show cis trans isomerism. In complexes with formula [MX2L4] type, two
ligands X may be oriented cis or trans to each other.
 This type of isomerism is also observed when bidentate ligands L–L [e.g.,NH2 CH2 CH2 NH2 (en)] are
present in complexes with [MX2(L–L)2] type formula
 There is another type of geometrical isomerism which occurs in octahedral coordination entities with
[Ma3b3] type formula. Examples is [Co(NH3)3(NO2)3].
 If three donor atoms of the same ligands occupy adjacent positions at the corners of an octahedral face,
we have the facial (fac) isomer.
 When the positions are around the meridian of the octahedron, we get the meridional (mer) isomer
 Facial Isomers: A set of three ligands (similar) arranged on an octahedron in all cis – fashion.
 Meridional Isomers: A set of three similar ligands arranged on an octahedron with one pair trans

[MX2L4]
[MX2(L–L)2] [Ma3b3]
Optical Isomerism
 ¨The complexes which are non-superimposable on their mirror images are optically active.
 Optically active complexes are asymmetric in nature i.e. not divisible into two identical halves.
o Levorotatory (l) – the compound which rotates plane polarised light to left hand side.
o Dextrorotatory (d) – the compound which rotates plane polarised light to right hand side
o d and l isomers of a compound are called enantiomers
 Octahedral complexes with coordination number 6 involving 2 or 3 bidentate ligands show optical
isomerism.
TUTORIAL
TUTORIAL
TUTORIAL
 Aufbau Principle (Building-Up) TUTORIAL

“Electrons are filled into atomic orbitals in the

increasing order of orbital energy level.”

Lowest energy levels are occupied before those with

higher energy levels.”

- dictates the manner in which electrons are filled in

the atomic orbitals of an atom
 Aufbau Principle TUTORIAL

Energy of orbital = (n+l) value

where the n = Principal and l = azimuthal
quantum numbers

Lower (n+l) values correspond to lower

orbital energies.

If two orbitals share equal (n+l) values, the

orbital with the lower n value is said to have
lower energy associated with it.
 Apply Aufbau Principle TUTORIAL

n+l
1s 1+0 = 1
2s 2+0 = 2
3s 3+0 = 3
3p 3+1=4
3d 3+2 = 5
4s 4+0=4
4p 4+1 = 5
4d 4+ 2 = 6
4f 4+3=7
5s 5+0 = 5
Expected Order
1s < 2s < 2p <3s < 3p < 3d < 4s < 4p < 4d < 5s
< 5p < 5d < 5f…

Actual Order
1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d
< 5p < 6s…
Electron build-up using Aufbau Principle
 Pauli Exclusion Principle
In a single atom no two electrons will have an
identical set or the same quantum numbers (n,
l, ml, and ms).

Every electron should have or be in its own

unique state.

Salient features of the Pauli Exclusion Principle:

Only two electrons can occupy the same orbital.

The two electrons that are present in the same orbital

must have opposite spins or it should be antiparallel.
Pauli Exclusion Principle
 Pauli Exclusion Principle TUTORIAL

1s 2s
n=1 n=2
l=0 l=0
ml=0 ml=0
ms=-1/2 ms=-1/2
 Hunds Rule of Maximum Multiplicity TUTORIAL

This rule deals with the filling of electrons into the

orbitals belonging to the same subshell

It states that pairing of electrons in the orbital’s

belonging to same sub – shell [ p, d, f], does not take
place until each orbital gets singly occupied.

All the orbitals which are singly occupied have parallel

spins which can be either clockwise or anticlockwise.

Electrons are negatively charged and, as a result, they

repel each other. Electrons tend to minimize repulsion by
occupying their own orbitals, rather than sharing an
orbital with another electron.
TUTORIAL
Electronic Structure of Elements – Method 1
Electronic Structure of Elements – Method 2
 Arrangement of Elements in Groups and Periods in
the Periodic Table
The Vertical columns in the periodic table are called as
Groups .

The horizontal rows in the periodic table are called as

Periods.

There are 7 periods in the periodic table .

Numbered from 1 to 7.
The groups are numbered from 1 to 18.

In a Group, Elements having same number of valence

electrons in their outermost orbit

In a period, Elements having same number of shells

Arrangement of Elements in Groups and Periods in the Periodic Table
Arrangement of Elements in Groups and Periods in the Periodic Table
Slater’s Rule
 Slater’s Rule
Slaters rule helps to calculate the shielding constant and effective
nuclear charge

Slater's Rules is classified into two cases A and B:

Rule for case A:
To calculate the screening constant of e- residing in ns- or
np orbital

Remaining electrons within nth shell contributes S= 0.35,

except the 1s which shield 0.30
electrons within the n-1 shell contributes S = 0.85
electrons within inner shell contributes S = 1.00
Rule for case B:
To calculate the screening constant of e- residing in nd or
nf orbital
Remaining electrons in nd orbital contributes S = 0.35
Remaining electrons contributes S = 1.00
No contribution of shielding from higher shell electrons
Periodic Trends:

Atomic Radii
Ionic Radii
Ionization Energy
Electron affinity
Electronegativity
 Atomic Radius
Technically atomic radius is calculated as half of the distance
between the nuclei of identical atoms that are bonded together.

The units for atomic radii are picometers, equal to 10−12 meters.
As an example, the internuclear distance between the two hydrogen
atoms in an H2 molecule is measured to be 74 pm. Therefore, the
atomic radius of a hydrogen atom is 74/2=37 pm.
Trend of Atomic radii in periodic table
 The trend of atomic radius across Period
The atomic radius of atoms generally decreases from left to right across a
period.
Within a period, protons are added to the nucleus as electrons are being
added to the same principal energy level.
These electrons are gradually pulled closer to the nucleus because of its
increased positive charge.
Since the force of attraction between nuclei and electrons increases, the size
of the atoms decreases. The effect lessens as one moves further to the right
in a period because of electron-electron repulsions that would otherwise
cause the atom’s size to increase.
Trend of atomic radius along the Group
The atomic radius of atoms generally increases from top to bottom within a
group.
As the atomic number increases down a group, there is again an increase in
the positive nuclear charge. However, there is also an increase in the
number of occupied principle energy levels. Higher principal energy levels
consist of orbitals which are larger in size than the orbitals from lower
energy levels. The effect of the greater number of principal energy levels
outweighs the increase in nuclear charge and so atomic radius increases
down a group.
 Factors affecting Atomic Radius

Number of Shells:
Atomic size increases with the increase in the number of electronic shells. Thus atomic
radius is directly proportional to the number of electronic shells.
Nuclear Charge:
As the nuclear charge increases the atomic radius decreases due to an increase in
the attractive force on the outermost electrons. Thus atomic radius is inversely proportional
to the nuclear charge.

Screening Effect:
In an atom having more electrons and particularly more electron shells, it is observed that
the inner orbits decrease the attraction between the electrons in the outer orbit and
nucleus. Thus they act as a screen or shield between the nucleus and electrons of outer
orbit. This effect is known as the screening effect. As the screening effect increases, the
atomic radius increases. Thus atomic radius is directly proportional to the screening effect.
For a given quantum shell, the shielding ability of inner electrons decreases in the order of
s > p > d > f.
Effective nuclear charge: The effective nuclear charge is the difference between the actual
nuclear charge and the screening effect [Link]. Zeff = Z – σ. The atomic radius is
inversely proportional to the effective nuclear charge.
 Exceptions in the trend of atomic radii in periodic table

atomic radius of noble gases is greeter than the adjacent halogen

atom.

This is because noble gas atoms are held together by van der waal
forces (which are weaker and hence the atoms are apart from each
other) while the halogen atoms are bound together by covalent bonds
which are much stronger than the van der waal forces and hence held
the atoms closer.

Thus we can modify the trend as “ The atomic radius of the atoms
decrease on going from left to right upto group 17, then it increases in
group 18.”
Why the atomic radii of Al and Ga are same?
 Ionic radius

Ionic radius is the distance from the nucleus of an ion

up to which it has an influence on its electron cloud.
 Determination of Ionic radius

Internuclear distance (d) = rcation + ranion

To calculate ion radii, Lande used

ionic compound under solid state
(ex: NaCl).

This will minize the distribution of

electrons.
Find the radii of anion (r-) atom.

Find internuclear distance (d)

between anion and cation.

Use Internuclear distance formula to

find the r+.
Size: Anion > neutral atom > cation
Trend of Ionic Radius in Periodic Table

The Ionic radius generally decreases from left to

right across a period.
The Ionic radius generally increases from top to
bottom within a group.
Atomic and ionic radius follow the same trend
 TUTORIAL

Arrange the order of ionic radii

Na+ , Mg2+ , Al3+ , Si4+
11 12 13 14

1) N3- 2) O2- 3) F- 4) Na+

 TUTORIAL
Arrange the order of ionic radii 11Na+ 12Mg2+ 13Al3+ 14Si 4+

Atom Na Mg Al Si
Atomic
number, Z 11 12 13 14
(or) # protons
# electrons 11 12 13 14
Ion Na+ Mg2+ Al3+ Si4+
# electrons 10 10 10 10
Z /e 11/10 = 1.1 12/10 = 1.2 13/10 = 1.3 14/10 = 1.4

Less Z/e value = Less attraction between p and e- = Large Size

The correct order of ionic radii is

Na+ > Mg2+ > Al3+ > Si4+ or Si4+ < Al3+ < Mg2+ < Na+
 Which of the following is the smallest in size?
1) N3- 2) O2- 3) F- 4) Na+ TUTORIAL
Atom N O F Na
Atomic
number, Z
7 8 9 11
(or) #
protons
# electrons 7 8 9 11
Ion N3- O2- F- Na+
# electrons 10 10 10 10
Z /e 7/10 = 0.7 8/10 = 0.8 9/10 = 0.8 11/10 = 1.1

The ratio between no. of protons (Z) to number of electrons correlates

effective nuclear attraction. Greater this value, greater is the attraction
and smaller is the size.
For example, in Na+ ion, there is 1.1 proton for each electron. Hence
the attraction is maximum and the ion is smallest among the given
species.
However, in N3- ion, there is only 0.7 proton for each electron. Hence
the attraction is minimum and the ion is largest.
 Ionization energy/Ionization Potential
The amount of energy required to remove the
most loosely bound electron in an isolated
gaseous atom in the ground electronic state

H(g) → H+(g)+e−

This energy is endothermic and usually expressed in

kJ/mol
 Successive Ionization energy
When considering an initially neutral atom, expelling the
first electron will require less energy than expelling the
second, the second will require less energy than the third,
and so on.

Each successive electron requires more energy to be

released. This is because after the first electron is lost,
the overall charge of the atom becomes positive, and the
negative forces of the electron will be attracted to the
positive charge of the newly formed ion.

The more electrons that are lost, the more positive this
ion will be, the harder it is to separate the electrons from
the atom.
 1st, 2nd, and 3rd Ionization Energies

The symbol I1 stands for the first ionization energy (energy required to take
away an electron from a neutral atom)

Symbol I2 stands for the second ionization energy (energy required to take
away an electron from an atom with a +1 charge.

Each succeeding ionization energy is larger than the preceding energy.

I1<I2<I3<...<In

Mg(g)→Mg+(g)+e−I I1 = 738kJ/mol

Mg+(g)→Mg2+(g)+e− I2=1451kJ/mol
Trend Variation of Ionization energy in group and period

•Across a period from left to right, the ionisation energy increases.

This is due to the increase in nuclear charge having a greater pull on
the electrons and therefore more energy is required to remove
electrons.
•Going down a group, the ionisation energy decreases. Electrons
are further from the nucleus and in this way simpler to remove the
electron
FACTORS AFFECTING IONIZATION ENERGY
FACTORS AFFECTING IONIZATION ENERGY
FACTORS AFFECTING IONIZATION ENERGY
 Exceptions in the trend of Ionization energy

Nitrogen is larger in size than oxygen. However, the I.E of N

is higher than oxygen . Why?
Ga has higher I.E than Al. Why?
 TUTORIAL

Arrange the following atoms in the order of

Increasing first ionization energy.

F, Li, N, Rb
 TUTORIAL

Arrange the following atoms in the order of

Increasing first ionization energy.

F, Li, N, Rb

Soln: Increasing I.E (Less to High value of I.E)

Less to High value of I.E = large to small in size

Rb < Li < N < F

 TUTORIAL
Based on the periodic trends for ionization energy,
which element has the highest ionization energy?

Fluorine (F)
Nitrogen (N)
Neon (Ne)
 Electron affinity

Electron affinity is defined as the change in energy (in

kJ/mole) of a neutral atom (in the gaseous phase) when an
electron is added to the atom to form a negative ion.

In other words, the neutral atom's likelihood of gaining an

electron.

• First Electron Affinity (negative energy because energy

released):
X(g)+e−→X−(g) (1)

• Second Electron Affinity (positive energy because energy

needed is more than gained):

− 2−
 Electron affinity

Metals: Metals like to lose valence electrons to form

cations to have a fully stable octet. They absorb energy
(endothermic) to lose electrons. The electron affinity of
metals is lower than that of nonmetals.

Nonmetals: Nonmetals like to gain electrons to form

anions to have a fully stable octet. They release energy
(exothermic) to gain electrons to form an anion; thus,
electron affinity of nonmetals is higher than that of
metals.
 Periodic Trend - Electron Affinity

Electron affinity increases from left to right across periods

of a periodic table because the electrons added to energy
levels become closer to the nucleus, thus a stronger
attraction between the nucleus and its electrons.

Electron affinity decreases down the on the periodic table

because the electrons are placed in a higher energy level far
from the nucleus, thus a decrease from its pull.

The stronger the attraction, the more energy is released.

Completely –Filled and Half-Filled configuration has less

electron affinity
Periodic Trend - Electron Affinity
Why electron affinity of fluorine is less than
chlorine?

It is generally true that the electron affinity

becomes less down a group, because of the
increase in atomic radius.

There is a well-known exception that the electron

affinity of Cl is more electron affinity than that of F,
because fluorine has a high electron density;
adding electrons would be unfavorable because of
the electron-electron repulsions.

electron affinity of fluorine is less than chlorine; However fluorine is more reactive
than chlorine because of its higher electronegativity
 Electronegativity

Electronegativity is a measure of the tendency

of an atom in a molecule to attract a bonding
pair of electrons towards itself.
 Electronegativity
The Pauling scale is the most commonly used.
Electronegativity vs Electron Affinity
 Factors Affecting Electronegativity

1. Size of an Atom:
A greater atomic size will result in less value of
electronegativity, this happens because electrons being
far away from the nucleus will experience a lesser force of
attraction.

2. Nuclear Charge:
A greater value of nuclear charge will result in a greater
value of electronegativity. This happens because an
increase in nuclear charge causes electron attraction with
greater force.
 Factors Affecting Electronegativity

3. Charge on the ion (i.e., Oxidation state).

Electro-negativity varies with the change in the oxidation
state of the element.

The element in higher oxidation state has more value of

electronegativity than in the lower oxidation state. Thus
the value of electronegativity of Fe3+ is higher than that of
Fe2+

A cation has high electronegativity while an anion has

less electronegativity than its parent atom.

A cation with a higher positive charge is more

electronegative.
 Factors Affecting Electronegativity
4. Effect of Substituent/ Nature of atoms to which the atom is
bonded (Group electronegativity):

The electronegativity of an atom depends upon the nature of the

substituent attached to that atom.

For example,
- electro-negativity value of P atom in PCl3 molecule is different
from that in PF5 molecule

5. Ionization energy and Electron affinity.

The atoms of the elements that have higher values of ionization
power and electron
affinity also have higher electronegative values.
 Factors Affecting Electronegativity
6. Type of hybridization.

The magnitude of electronegativity of an atom also depends

on the type of hybridization which the atom undergoes in the
formation of different bonds in the molecule. The magnitude
of electronegativity inereases as the s_character in hybrid
orbitals increases.

This is because the 's' orbitals being more near to the

nucleus have greater tendency to attract the shared pair of
electron.

.
Three types of hybridisation − sp, sp2 and sp3, are seen in
carbon atoms depending upon how many atoms are
linked to the carbon.

An sp hybrid orbital has 50% s-character and 50% p-

character;

An sp2 hybrid orbital has 33.33% s-character and 66.66%

p-character;

An sp3 hybrid orbital has 25% s-character and 75% p-

character.

The greater the s-character of the hybrid orbitals, the

greater is the electronegativity because an s orbital holds
electrons more tightly to the nucleus.
In terms of Electronegativity: sp > sp2 > sp3.
 HSAB Principle

According to HSAB concept, hard acids prefer binding to the hard bases to
give ionic complexes, whereas the soft acids prefer binding to soft bases to
give covalent complexes.

 The large electronegativity differences between hard acids and hard bases
give rise to strong ionic interactions.

 The electronegativities of soft acids and soft bases are almost same and
hence have less ionic interactions. i.e. the interactions between them are more
covalent.

 The interactions between hard acid - soft base or soft acid - hard base are
mostly polar covalent and tend to be more reactive or less stable. The polar
covalent compounds readily form either more ionic or more covalent compounds
if they are allowed to react.
 Drawback of HSAB principle

1) The Pearson's HSAB theory is in direct contradiction with Fajan's rules.

For example, the later predict the nature of Beryllium salts to be more
covalent. But according to HSAB principle, the Be2+ ion is hard acid and is
expected to show charge controlled bonding that results in more ionic nature
for beryllium compounds. But this is not true.

2) Since hydrogen ion, H+ is a hard acid and hydride ion, H- is a soft base,
according to HSAB principle the interactions between them must be polar
covalent and H2 must be unstable. Indeed H2 is a stable molecule with
pure covalent nature.
Hard-soft trends for acids
Acids
Hard-soft trends for bases
Bases
Suggest which of the following Answer a:
ions is harder. Zn(II), because it is smaller and less
polarizable.
a) zinc(II) or mercury(II)
Answer b:
b) potassium(I) or copper(I) K+, because it is less electronegative.

c) iron(II) or iron(III) Answer c:

Fe(III), because of the higher charge.

Answer a:

Me3P, because phosphorus is larger and

Suggest which of the following
more polarizable than nitrogen.
bases is softer.
Answer b:
a) Me3P or Me3N Iodide, which is larger and more
b) chloride or iodide polarizable than chloride.

Answer c:
c) amide (NH2-) or azide (N3-)
Azide, which has a more polarizable,
delocalized pi bonding system.