1.

Size: Trends in the atomic/ionic radii,

2. Ionization energy (IE): Definition, factors affecting IEs; trends in IEs; variation in the
1st IEs of the elements.

3. Electron affinity(EA): Definition, some values; determination of EA (Born-Haber

cycle)

4. Electronegativity: Definition, Pauling’s scale, graphical representation of % ionic

character vs. E.N. differences; Mulliken’s scale; relation between Pauling’s and
Mulliken’s values; Allred Rochows method, Fajan’s rules.

5. Solubility of ionic solids - lattice and solvation energies.

6. Use of reduction potentials. Reduction potential (Latimer) diagram, Specific

illustrative examples.
1. Alkali Metal Family: Solutions of alkali metals in liquid ammonia. Chemistry of oxides:
complexation tendency (complexes, crowns and cryptands).

2. Alkaline earth metal family: Chemistry of hydrides; structure of BeH2; complexation

tendency of Be & Mg [examples of [Be4O(Ac)6], [Be4O(NO3)6] and chlorophyll]. Stability
of oxo-salts

3. Boron Family: Hydrides: Structures of Li[AlH4], Na[BH4], Al(BH4)3, Be(BH4)2, B2H6;

Halides: Structures of BF3, BCl3 and AlCl3(dimer); Oxides / oxyacids: Structures of
H3BO3 (with and without H-bonding), metaborate (chain, ring forms), Borax and
peroxoborate ion.

4. Carbon Family: Principles of silicate structures; structures of: orthosilicate, pyrosilicate,

cyclic silicates (Si3O96-, Si6O1812-);
5. Nitrogen Family: Hydrides: Electronic structures (VB Theory) of the tri-hydrides;
structure of hydrazine, NH2OH and HN3. Halides: Structure of: PCl5 (gas and solid). Oxides
and oxo-acids: Structures of oxides of N (+I to +V states); P4O6, P4O10, Oxo-acids of P.

6. Oxygen Family: Oxides and oxo-acids: structures of (i) oxides (SO2, SeO2, SO3), (ii)
oxoacids of sulphur or their anions; (iii) H2O2(gas-phase), and (iv) halides (MX6, MX4, and
MX2 series) .

7. Halogen Family: Structures of (i) oxygen fluorides (OF2, O2F2, O4F2), (ii) halogen oxides
(Cl2O, Br2O, ClO2, BrO2, I2O5, Cl2O6, ClO3, Cl2O7), (iii) oxo-acids (HOX, HXO2, HXO3,
HXO4), (iv) Inter halogens [ClF3, BrF3, (ICl3)2, ClF5, BrF5, IF5, IF7] and (v) polyhalides (I3,
ICl2, ICl4)

8. Noble gases: Structures of Xe compounds: XeF2, XeF4, XeF6, XeO3, XeO2F2, XeOF4,
XeO4, XeO3F2 and [XeO6]4.
Suggested Readings:
1.Basic Inorganic Chemistry, F. A Cotton, G. Wilkinson, and Paul L. Gaus, 3rd
Edition (1995), John Wiley & Sons, New York.
2.Concise Inorganic Chemistry, J. D. Lee, 5th Edition (1996), Chapman & Hall, London.
• In general the size of atom or ion means distance from the nucleus to the outermost shell of
electrons.

• We can also define size of an atom as the volume occupied by total electron density in
quantum mechanical orbital.

Limitations to this Approach:

• Exact position of electron can not be defined as atoms do not have sharp boundaries.

• The electron density is defined by probability of finding the electron in space which does not
stop at a distance from the nucleus.
• It is really difficult to isolate single atom for size determination.

• The probability of finding the electron around nucleus is always affected by presence of
another atom in the environment.

The atomic radius is defined as half of the distance between nuclei of neighboring atoms.
• It is half of the distance between the nuclei of two covalently bonded atoms of same element
in a molecule.

Cl2, d= 198 pm ,then r = 198/2 = 99pm

Diamond C-C distance d= 154 pm ,then r = 77pm

Factors affecting covalent radius of heterodiatomic molecules:

• Electronegativity difference between atom A and B.

• Multiplicity of bond between A and B.
• Steric Hindrance.
Half of the internuclear distance between two adjacent identical atoms belonging to two
neighboring molecules is called Van der waals’ radius. Van der Waal radius is always greater
than covalent radius.

The distance between two adjacent chlorine atoms of different Cl2 molecules is 360pm, Van
der Waals’ radius of Cl is 180pm.
Periodic Trend in Size of atoms:

The size of atoms decreases from left to right across a period in the periodic table. For
example if we move from Li to Be, one extra positive charge is added to the nucleus, and an
extra orbital electron is also added. Increasing the nuclear charge results in all of the orbital
electrons being pulled closer to the nucleus.

In a given period, the alkali metal is the largest atom and the halogen the smallest. When a
horizontal period contains ten transition elements the contraction in size is larger, and when in
addition there are 14 inner transition elements in a horizontal period, the contraction in size is
even more marked.

On descending a group in the periodic table such as that containing Li, Na, K, Rb and Cs, the
sizes of the atoms increase due to the effect of extra shells of electrons being added, this
outweighs the effect of increased nuclear charge.
 Distance from the nucleus upto which it has influence on its electron cloud.

Size of ions

Metals usually form positive ions. These are formed by removing one or more electrons from
the metal atom. Metal ions are smaller than the atoms from which they were formed for two.
reasons:

1. The whole of the outer shell of electrons is usually ionized, i.e. removed. This is one
reason why cations are much smaller than the original metal atom.

2. A second factor is the effective nuclear charge. In an atom, the number of positive charges
on the nucleus is exactly the same as the number of orbital electrons. When a positive ion is
formed; the number of positive charges on the nucleus exceeds the number of orbital
electrons, and the effective nuclear charge (which is the ratio of the number of charges on
the nucleus to the number of electrons) is increased. This results in the remaining electrons
being more strongly attracted by the nucleus. Thus the electrons are pulled in - further
reducing the size.
 A positive ion is always smaller than the corresponding atom, and the more electrons which
are removed (that is, the greater the charge on the ion), the smaller the ion becomes.

Metallic radius Na 1.86Å Ionic radius Na+ 1.02Å

Atomic radius Fe 1.17 Å,

Ionic radius Fe2+ 0.780Å (high spin), Ionic radius Fe3+ 0.645 Å (high spin)

When a negative ion is formed, one or more electrons are added to an atom, the effective
nuclear charge is reduced and hence the electron cloud expands. Negative ions are bigger than
the corresponding atom.

Covalent radius Cl 0. 99 Å
Ionic radius Cl 1.84Å
Difficulties in measurement of Ionic Radii

There are several problems in obtaining an accurate set of ionic radii.

1. Though it is possible to measure the internuclear distances in a crystal very accurately by

X-ray diffraction, for example the distance between Na+ and F- in NaF, there is no universally
accepted formula for apportioning this to the two ions. Historically several different sets of
ionic radii have been estimated. The main ones are by Goldschmidt. Pauling and Ahrens.
These are all calculated from observed internuclear distances, but differ in the method used to
split the distance between the ions. The most recent values, which are probably the most
accurate, are by Shannon (1976) .
2. Corrections to these radii are necessary if the charge on the ion is changed.

3. Corrections must also be made for the coordination number, and the geometry.

4. The assumption that ions are spherical is probably true for ions from the s- and p-blocks
with a noble gas configuration, but is probably untrue for transition metal ions with an
incomplete d shell.
5. In some cases there is extensive delocalization of d electrons, for example in TiO where
they give rise to metallic conduction, or in cluster compounds. This also changes the radii.

Thus ionic radii are not absolute constants, and· are best seen as a working approximation.
Periodic Trend in Ionic Radii:

1 . In the main groups, radii increase on descending the group, e.g. Li+ = 0.76 Å, Na+ = 1.02 Å,
K+ = 1.38 Å, because extra shells of electrons are added.

2. The ionic radii decrease moving from left to right across any period in the periodic table,
e.g. Na+ = 1.02 Å, Mg2+ = 0.720 Å and Al3+ = 0.535 Å.

This is partly due to the increased number of charges on the nucleus, and also to the increasing
charge on the ions.
3. The ionic radius decreases as more electrons are ionized off, that is as the valency increases,
e.g. Cr2+ = 0.80 Å(high spin), Cr3+ = 0.615 Å, Cr4+ = 0.55 Å, Cr5+ = 0.49 Å and Cr6+ = 0.44 Å.

4. The d and f orbitals do not shield the nuclear charge very effectively. Thus there is a
significant reduction in the size of ions just after 10d or 14f electrons have been filled in. The
latter is called the lanthanide contraction, and results in the sizes of the second and third row
transition elements being almost the same.
Pauling Method:

Pauling assumed that the radius of the ion having noble gas configuration (Na+ and F-
having 1s2 , 2s2 , 2p6 configuration) is inversely proportional to the effective nuclear charge
felt at the periphery of the ion.

Where Zeff is the effective nuclear charge

Zeff = Z – σ
σ = Screening constant
• The minimum amount of energy required to remove the most loosly bound
electron(i.e outer- most shell e-)from an isolated neutral gaseous atom is known
as Ionization energy/Ionization potential/Ionization enthalpy(IE/ iH) (Isolated -
> without any bonding with other atom)

M(g) + IE1→ M+ (g) + 1e-

• It is an endothermic process.

• It is measured in eV/atom or KJ/mol or Kcal/mol

1eV/atom = 23.06 K.cal/mol = 96.45KJ/mol = 1.6.02x10-19J/atom

• II Ionization Enthalpy is the energy required to remove an electron from

unipositive ion to convert it into dipositive ion (IE2)

M+(g) + IE2 → M++ (g) + 1e-

Here IE2 greater than IE1

The factors that influence the ionization energy:

1. The size of the atom.

2. The charge on the nucleus.

3. How effectively the inner electron shells screen the nuclear charge.

4. The type of electron involved (s. p, d or/).

• In a small atom the electrons are tightly held. whilst in a larger atom the electrons are less
strongly held. Thus the ionization energy decreases as the size of the atoms increases.

Comparison of the first and second ionization energies for the Group I elements shows that
removal of a second electron involves a great deal more energy, between 7 and 14 times
more than the first ionization energy. Because the second ionization energy is so high, a
second electron is not removed. The large difference between. the first and second ionization
energies is related to the structure of the Group I atoms. These atoms have
just one electron in their outer shell. Whilst it is relatively easy to remove the single outer
electron, it requires much more energy to remove a second electron, since this involves
breaking into a filled shell of electrons.
The ionization energy also depends on the type of electron which is removed. s. p, d and f
electrons have orbitals with different shapes. s electron penetrates nearer to the nucleus, and is
therefore more tightly held than a p electron. For similar reasons a p electron is more tightly
held than a d electron, and a d electron is more tightly held than an f electron. Other factors
being equal, the ionization energies are in the order
s > p > d > f.

The first ionization energy for a Group III element (where a p electron is being removed) is
actually less than that for the adjacent Group U element (where an s electron is being
removed).

In general, the ionization energy decreases on descending a group and increases

on crossing a period.
1. The noble gases He, Ne, Ar, Kr, Xe and Rn have the highest ionization energies in their
respective periods.
2. The Group I metals Li, Na, K and Rb have the lowest ionization energies in their respective·
periods.
3. There is a general upward trend in ionization energy within a horizontal period, for example
from Li to Ne or from Na to Ar.
The graph does not increase smoothly. The values for Be and Mg are high, and this is
attributed to the stability of a filled s level. The values for N and P are also high, and this
indicates that a half filled p level is also particularly stable. The values for B arid Al are lower
because removal of one electron leaves a stable filled s shell, and similarly with O and S, a
stable half filled p shell is left.
In general the first ionization energy decreases in a regular way on descending the main
groups. A departure from this trend occurs in Group III, where the expected decrease occurs
between B and Al, but the values for the remaining elements Ga, In and Tl do not continue the
trend, and are irregular. The reason for the change at Ga is that it is preceded by ten elements
of the first transition series (where the 3d shell is being filled). This makes Ga smaller than it
would otherwise be
The energy released when an electron is added to a neutral gaseous atom which is in
its ground state to form a gaseous negative ion is defined as the first electron affinity.
The symbol is EA, and the unit is kJ/mol.
Usually only one electron is added, forming a uninegative ion. This repels further electrons
and energy is needed to add on a second electron: hence the negative affinity of O2-

The first electron affinities of elements are negative in general and second electron
affinities of all elements are positive.

Electron affinities depend on the size and effective nuclear charge. They can not be
determined directly but obtained from ‘Born-Haber Cycle’.
Where does the energy come from for formation of O2- and S2-?
Energy is evolved when one electron is added to an O or S atom, forming the species
O- and S-, but a substantial amount of energy is absorbed when two electrons are
added to form O2- and S2- ions. Even though it requires energy to form these divalent
ions, compounds containing these ions are known. It follows that the energy required
to form the ions must come from some other process, such as the lattice energy when
the ions are packed together in a regular way to form a crystalline solid. or from ·
solvation energy in solution.

EA generally decreases from the left to the right across the periodic table. According
to the elements of one main group, EA generally increases from the top to the bottom
of the periodic table.

Electronegativity is a measure of the attraction of an atom for bonding electrons in

molecules compared to that of other atoms. Or
Electronegativity is the tendency of an atom to attract electrons in a molecule.
Pauling pointed out that since reactions of the type:

are almost always exothermic, the bond formed between the two atoms A and B must be
stronger than the average of the single bond energies of A-A and B-B molecules. For
example:

The bonding molecular orbital for AB (fAB) is made up from contributions from the
wave functions for the appropriate atomic orbitals (ψA and ψB).

ϕ𝐴𝐵 = ψ𝐴 + constant (ψ𝐵 )

If the constant is greater than 1 the molecular orbital is concentrated on the B atom,
which therefore acquires a partial negative charge, and the bond is partly polar.

Conversely. if the constant is less than 1, atom A gains a partial negative charge.
Because of this partial ionic character, the A-B bond is stronger than would be
expected for a pure covalent bond. The extra bond energy is called delta Δ.

The bond energy can be measured, but the energy of a 100% covalent bond must be
calculated. Pauling suggested the 100% covalent bond energy be calculated as the
geometric mean of the covalent energies of A-A and B-B molecules.

𝐸100% 𝑐𝑜𝑣𝑎𝑙𝑒𝑛𝑡 𝐴−𝐵 = √(𝐸𝐴−𝐴 · 𝐸𝐵−𝐵 )

The bond energy in A-A and B-B molecules can be measured and so:
• Pauling states that the electronegativity difference between two atoms is equal to
0.208√Δ, where Δ is the extra bond· energy in kcal mo1-1.

• If we convert the equation to SI units gives 0.1017√Δ, where Δ is measured in

kJmo1-1.

If χH = 0 then the electronegativity values for C, Cl and N would be 0.50, 1.02 and
1.04 respectively. Pauling changed the origin of the scale from χH = 0 to χH = 2.05 to
avoid having any negative values in the table of values, and this made the value for C
become 2.5 and the value for F become 4.0. At the same time the values for a number
of other elements approximated to whole numbers: Li = 1.0, B = 2.0, N ·= 3.0. Thus
by adding 2.05 to the values calculated in this way we can obtain the usually accepted
electronegativity values
Fifty per cent ionic character occurs when the electronegativity difference between
the atoms is about 1.7, so for a larger difference than this a bond is more ionic than
covalent. Similarly, if the electronegativity difference is less than 1.7, the bond is
more covalent than ionic.
• In 1934, Mulliken suggested an alternative approach to electronegativity based
on the ionization energy and electron affinity of an atom.
• Consider two atoms A and B. If an electron is transferred from A to B, forming
ions A+ and B-, then the energy change is the ionization energy of atom A (IA)
minus the electron affinity of atom B (EB), that is IA - EB .
• Alternatively, if the electron was transferred the other way to give B+ and A-
ions, then the energy change would be IB - EA.

• If A+ and B- are actually formed, then this process requires less energy, and
(𝐼𝐴 − 𝐸𝐵 ) < (𝐼𝐵 − 𝐸𝐴 )

It can be rearranged to

(𝐼𝐴 + 𝐸𝐴 ) < (𝐼𝐵 + 𝐸𝐵 )

Thus Mulliken suggested that electronegativity could be regarded as the average of
the ionization energy and the electron affinity of an atom.

𝐼+𝐸
𝐸𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑒𝑔𝑎𝑡𝑖𝑣𝑖𝑡𝑦 =
2
Here I and E are measured in eV (electron volts) and the electronegativity values are
2.8 times larger than Pauling values.

If we measure I and E in kJmol-1 then the equation will be:

1eV/molecule = 96.48 kJmol-1

so the commonly accepted Pauling values are more nearly obtained by performing this
calculation

𝐼+𝐸 𝐼+𝐸
𝐸𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑒𝑔𝑎𝑡𝑖𝑣𝑖𝑡𝑦 = =
2 × 2.8 × 96.48 540

This method has a simple theoretical basis, and also has the advantage that different values
can be obtained for different oxidation states of the same element. It suffers from the
imitation that only a few electron affinities are known .
In 1958 Allred and Rochow considered electronegativity in a different way and
worked out values for 69 elements. They defined electronegativity as the attractive
force between a nucleus and an electron at a distance equal to the covalent radius.
This force F is electrostatic, and is given by:

𝑒 2 · 𝑍𝑒𝑓𝑓𝑒𝑐𝑡𝑖𝑣𝑒
𝐹=
𝑟2
where e is the charge on an electron, r is the covalent radius, and Zeffective is the
effective nuclear charge.

These F values may be converted to electronegativity values on the Pauling scale of

values using an empirical relationship:

0.359 𝑍𝑒𝑓𝑓𝑒𝑐𝑡𝑖𝑣𝑒
χ = 0.744 +
𝑟2

The electronegativity values. so obtained agree quite closely with those obtained by Pauling
and Mulliken.