T.Y.B.Sc.

Chemistry Paper-II Ionic Solids

T.Y.B.Sc. Chemistry

Paper –II Inorganic Chemistry

Sem- IV

Chapter -3. Ionic Solids

Nita Dilip Dongare

Assistant Professor,
Department of Chemistry,
Hutatma Rajguru Mahavidyalaya,
Rajgurunagar

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 T.Y.B.Sc. Chemistry Paper-II Ionic Solids

3. IONIC SOLID
Introduction : Crystaline and Amorphous Solids
In crystalline solid, there is regular arrangement of atom, ions or
molecules & these particles are held together by strong force. Due to this solids
are rigid, having definite shape. The solids can be crystalline or amorphous.
These regular arrangements of solid are responsible for their characteristic
properties.
Characteristic properties of solid state:
a. Solids have definite mass, volume and shape
b. Solids are incompressible and rigid
c. In solids, intermolecular distances are very short
d. In solids, intermolecular forces are very strong
e. The constituent particles of solids have fixed positions.
f. The constituent particles of solids can only oscillate about their mean
positions.
Classification of solid:
They are classified into crystalline & amorphous solids.
1. Crystalline solid:
These solids have regular arrangement & particle in crystal. They have
typical geometrical forms. A crystalline substance has sharp Melting Point. The
constituent particles of crystalline solid are arranged in regular pattern which is
repeated periodically over the entire crystal. Such type of arrangement is called
long range order. Crystalline solids are anisotropic in nature, i.e. many physical
properties, such as electrical resistance, refractive index, etc. are different along
different axes. Crystal of NaCl, Quartz, Ice, HCl, Iron, etc. are some examples of
crystalline solid.
Characteristics of crystalline solid –
 Crystalline solids have definite characteristic geometrical shape.
 Crystalline solids have sharp characteristic melting point.
 Crystalline solids have definite and characteristic heat of fusion.
 Crystalline solids produce pieces with plain and smooth surface when
cut with a tool of sharp edge.
 Crystalline solids are anisotropic in nature.
 Crystalline solids are true solid.
 Constituent particles of crystalline solids are arranged in long range order.

2. Amorphous solid:
These solids possess random arrangement of Constituent units. Amorphous
solids do not have definite meeting point. Solids having irregular shapes of
particles are known as Amorphous Solids. The word ‘Amorphous’ came from
Greek ‘Amorphos’ which means no shape. The constituent particles of
amorphous solids have only short range order of arrangement, i.e. regular and
periodical arrangement of particles is seen to a short distance only. The structures
of amorphous solids are similar to that of liquids. Glass, rubber, plastics, etc.
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are some of the examples of amorphous solids. Amorphous solids are isotropic
in nature, i.e. physical properties of amorphous solids are same in all
directions.
Characteristic of amorphous solid –
 Particles of amorphous solids are irregular in shape.
 Amorphous solids soften gradually over a range of temperature.
 Amorphous solids produce pieces of irregular shapes when they are cut
into two pieces.
 Amorphous solids do not have definite heat of fusion.
 Amorphous solids are isotropic in nature, i.e. they have same physical
properties in all directions.
 Amorphous solids are not true solids and hence these are also known
as Pseudo Solid or Super Cooled Liquid.
 The arrangement of constituent particles is in short range order.
Difference between crystalline & amorphous solid:

Crystalline solid Amorphous solid

1) It is homogeneous solid. 1) It may not homogeneous.

2) They have definite geometry. 2) They do not have definite geometry.

3) They have definite & orderly 3) They have completely random
arrangement of particles. particle arrangement.
4) It has sharp M.P. i.e. it changes 4) It does not have sharp M.P. It
sharply into liquid state. softens
on heating & starts flowing.
5) The crystal has plane faces. 5) It does not have plane faces.

6) It is Anisotripic- its physical

6) It is isotropic – its physical properties
properties are different in
are same in all directions.
different direction.
7) e.g. NaCl, sugar, sulphur etc. 7) e.g. Rubber, Glass, plastic etc.

Crystalline solids are divided into four types –

1) Molecular solid, 2) Metallic solid, 3) Covalent solid, 4) Ionic solid
Molecular Solids: - Solids are having molecules as their constituent particles
are called Molecular solids. Example: Hydrogen (H2), Chlorine(Cl2),
Water(H2O), HCl, solid carbon dioxide(CO2), sucrose(C12H22O11), etc.
Metallic Solids: – All metals are referred as Metallic solids. Their constituent
particles are positive ions. These positive ions are surrounded by free moving
electrons. Eg. – Iron (Fe), Aluminium (Al), etc.
Covalent Solids: – Crystalline solids are formed by non-metals because of
formation of covalent bonds between the adjacent molecules throughout the

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crystal. These are also known as Network Solids. These are also called giant
molecules. Eg. – Diamond, Graphite, Silicon carbide, etc.
Ionic solids: - Solids, in which ions are the constituent particles, are called
ionic solids. These solids are formed because of three dimensional
arrangements of cations and anions bound together with strong electrostatic
forces. Ionic solid made up of positive & negative ions. These ions are held
together by electrostatic interaction of oppositely charged ions. This electrostatic
force of attraction between cation of anion is called Ionic bond. Eg. NaCl, the
Na+Cl– ion are held by electrostatic force & compound is ionic. The formation
of bond takes place by complete transfer of one or more electrons from the
valence shell of one atom to valence shell of another atom. Generally element
achieve octate configuration either by losing or gaining electron.
Characteristic Properties of Ionic compounds: -
1) Ionic bond: - The cation & anion held together by electrostatic force of
attraction.
2) Hardness: - Ionic compounds are very hard. Hardness depends on ionic
charge & interionic distance. As interionic distance decrease, & ionic
charge increases, hardness of crystal is increases.
3) Melting point and Boiling point: - Ionic compounds have high M. P.
& B. P.
4) Electrical conductivity: - Ionic compound in solid state do not
conduct electricity. Because ions are fixed & tight. But in molten state or
in solution ions are free. These free ions can move & hence conduct
electric current.
5) Solubility: - The ionic compounds are polar and are soluble in polar
solvents with high dielectric constant. The polar solvent such as water
dissolves ionic compounds. The solubility is mainly due to the lowering of
inter-ionic electrostatic attraction and ion-solvent interaction. Ionic
compounds are insoluble in nonpolar solvent such as CCl4, C6H6, etc.
6) Ionic compounds are ionisable in fused state or in solution. The solutions
of these compounds are good conductors of electricity.
Crystallography: -
It is a special branch of science, which deals with properties of crystals
such as geometry, structure, is called as Crystallography.
 Unit cell: - It is smallest building unit of crystal. The crystal consists of
infinite number of unit cell. In unit cell atoms, ions or molecules are
symmetrically arranged.
 Lattice:- It is define as an infinite set of points repeated regularly through
space. The lattices are one-dimensional (1-D), two-dimensional (2-D) &
three- dimensional (3-D).
 Crystal Lattice: - The definite and ordered arrangement of the
constituent atoms, ions or molecules extends over large distance in crystal is
called crystal lattice.
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 Space lattice: - The positions of atom, ion or molecule in crystal, relative to

one another in space. Such representation is called space lattice.
Types of Unit cell: -
The unit cell is the smallest portion as well as complete representation of
crystal. The crystal is made up of infinite number of unit cells. There are main
three types such as simple cubic, body centered cubic and face centered cubic…

1) Simple cubic unit cell: - The atoms are placed one at each corner of cube.
2) Body centered cubic unit cell: - There is an atom at each corner and
one at the center of the cube.
3) Face centered cubic unit cell: - There is an atom at each corner and
one in the each face of cube.
The unit cell in 3-D lattice is characterized by the length a, b, c and angle  


Bravais Lattices
There are only 14 possible crystal lattices, which are called Bravais Lattices.
Cubic Lattice – There are three types of lattice possible for cubic lattice.
Primitive or Simple, Body centred, Face centred lattices. In these types of
lattices all sides are of equal length. The angles between their faces are 900
in a cubic lattice.
Length: a=b=c and Angle °

Tetragonal Lattice – There are two possible types of tetragonal lattices.

Primitive and Body centred unit cells. In these lattices one side is different in
length and angles between faces are equal to 900.
Length: a=bc and angle °

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Orthorhombic Lattice – Four types of orthorhombic lattice are possible. They

are four types Primitive, End-centred, Body centred and Face centred. They have
unequal sides. The Angles between their faces are equal to 900.
Length: abc and angle°

Monoclinic Lattice – There are two possible types of monoclinic lattice.

They are Primitive and End centred. They have unequal sides and two faces
have angles other than 900.
Length: abc and angle ° and °

Hexagonal lattice – Hexagonal lattice is of one type only. It has one side
is different in length to the other two and the angles on two faces are 600.
Length: abc and angle ° and °

Rhombohedral Lattice – Only one type of lattice is possible for

Rhombohedral lattice. It has two types such as all sides equal and angles
on two faces are less than 900.

Length: a=bc and angle °

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Triclinic Lattice – Triclinic lattice has only one type of lattice. It has
unequal sides and none of the angles between faces are equal to 900.
Length: abc and angle °

Close packing: -
The arrangement of maximum number of ions or atoms into smallest
possible space is called close packing. In crystal atoms, ions or molecules are
arranged in regular way in three-dimensional space.

Each constituent atom or ions.in crystal is packed as closely as possible. This

arrangement has minimum energy and possesses maximum stability.
There are mainly two types Hexagonal close packed and Cubic close packed.

1) Hexagonal Close Packed structure (H.C.P.): -

In close packed structure ions are packed together in the tightest way. The
structure consists of number of layers one over other. Each atom is surrounded by
six nearest neighbors lying in plane. The symmetry is hexagonal. The close
packed layers of ions are arranged in an alternation sequence usually A B A B A
B ……. In this case each third layer will be directly above the first layer. This
ABAB… pattern of layers gives lattice with hexagonal unit cell. Thus it is called
hexagonal close packed (HCP) structure.
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2) Cubic Close Packed (C.C.P.) or Face Centered Cubic (F.C.C): -

In the CCP arrangement sphere of the third layer are placed exactly above the
gap of first layer. In ccp structure, the sequence of close packed layers of ions
repeats every fourth layer of ions is exactly same & lies directly above first layer.
The sequence is ABC ABC ABC ……… This arrangement of lattice is
corresponds with Face Centered Cubic (FCC) unit cell. Hence the crystal
structure obtained is CCP or FCC.
The voids OR Holes: -
The unoccupied volume between layers of close packed arrangement of
sphere is called as voids or holes. There are two types of holes in crystal lattice.
1) Tetrahedral Holes: -
These holes are bounded by four spheres. The four-sphere lie at the regular
tetrahedron & space between them is called as tetrahedral holes. The co-
ordination number of tetrahedral hole is four.
2) Octahedral holes: -
There are holes bounded by six spheres. The octahedral hole is formed
between CCP or HCP structure. In the HCP, there are two tetrahedral & one
octahedral hole is present. The co-ordination number of octahedral hole is six.

The octahedral holes are larger than tetrahedral holes. The size of
each hole is depends on size of the sphere, i.e. larger size of the sphere; it is
greater size of hole made by them.
Polarization of Ions & Fajan’s Rules: -
In ionic compounds when cation & anion are close to each other, the net
positive charge on cation attracts electron cloud of anion towards itself due to
electrostatic force of attraction. Size of anion is larger than cation. Due to this force
electron cloud of anion are elongated towards cation. The distortion of the electron
cloud of one ion by the electron cloud of the other ion is called as polarization of
anion by the cation or distortion or deformation. As distortion is increased, the
bond between anion and cation takes more covalent characters.
When ion is easily polarizable, the valence electrons will be shared between
the ions and therefore ionic character of bond will change into covalent bond
characters. The net result of the ion polarization is the degree of the electron
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sharing or increase in the degree of covalent characters.

The polarization of ionic bond depends upon capacity of cation to cause

polarization & capacity of anion to get polarized. With polarization, ionic compound
convert into covalent character.
he polarization of ion depends upon –
1. Size of cation or anion.
2. Charge on cation or anion
3. Electronic configuration & cation.

Fajan’s Rules: -
The polarization of ion is increased with increase in degree of covalent
character. The covalent characters are favored by- a) Small size of cation b) Large
size of anion, c) High charge on cation or anion or both
1. Covalent bonding character increases with decreasing cation size or
increasing cation charge. The high charge density of small and/or highly
charged cations is able to exert a powerful polarizing effect which distorts
the electron cloud around the anion. Compare NaCl (mp 800°C) with
CaCl2 (mp 772°C; charge effect) and KI (mp 686°C) with LiI (mp 449°C;
size effect).
2. Covalent character increases with an increase in anion charge or anion
size. The electrons of larger, more negatively charged anions are more
loosely held because they are more shielded from the nuclear charge. Thus,
these anions are more easily polarized by cations. Compare LiBr with Li3P
(charge effect), and LiF (mp 845°C) with LiI (mp 449°C; size effect).
3. Covalent character is greater for cations with a non-noble gas electron
configuration (i.e., 18-electron, pseudo-noble-gas cations) than for cations
with a true noble-gas configuration (8-electron cations).

Favorable conditions for

Ionic character Covalent character
1) Low positive charge. 1) High positive charge.
2) Large cation. 2) Small cation.

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3) Small anion. 3) Large anion.

Structures of Ionic compounds: -

The large no. of simple ionic substance crystallizes in one of the following six
common structure:-
1) Face Centered Cubic (FCC): - NaCl structure
2) Body Centered Cubic (BCC): - CsCl structure
3) Cubic Close Packing (CCP): - Zinc blende (ZnS) structure
4) Hexagonal Close Packing (HCP): - Wurtzite (ZnS) structure
5) Fluorite: - CaF2 structure
6) Rutile: - TiO2 structure

Lattice Co. Radius Ratio

No.
FCC-NaCl 6:6 0.42 –0.73
BCC- CsCl 6:6 > 0.73
CCP- Zinc blende 4:4 0.21 to 0.42
HCP- Wurtzite 4:4 0.21 to 0.42

Fluorite-CaF2 8:4 >0.73

Rutile – TiO2 6:3 0.42 to 0.73

1)Sodium Chloride Structure:

NaCl (FCC): -
The radius ratio for Na+ and
Cl– ion is 0.95/1.81 = 0.525. For the
octahedral structure with coordination
number 6, radius ratio between 0.41
to
0.73. Hence for NaCl crystal has FCC
type structure. Central Na+ ion is
surrounded by six Cl- ions
octahedrally.
The sodium chloride structure is known as “Rock salt structure “. The Na+ ions
are found at 8 corner of cube & also at center of each face the arrangements of
ion in crystal lattice is called as face centered cubic (FCC). Another examples: -

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CaCO3, CaC2, etc.

2) Caesium Chloride Structure: CsCl (BCC): -

The radius ratio for Cs+ and Cl– ion is 1.69 /1.81 =
0.93. This value is close to one, the Coordination Number
should be eight & cubic structure. The Cs+ & Cl– ions
have same size. These ions have simple cubic structure.
Each Cs+ ion has 8 Cl– ions as nearest neighbors. The Co.
No. of both these ions is 8. Each Cs+ ion occupies center
of cube and Cl– ion occupies 8 corners of cube. The
structure is neither close packed nor BCC.
In BCC center of corner
atoms are same, but in CsCl structure center and corner atoms are different. But
it is nearest to Body centered cubic structure.
Another examples: - CsBr, CsI, NH4Cl But CsF is a NaCl type structure.
Effect of temp: - CsCl converted into NaCl structure -At 4900c. NH4Cl having
CsCl structure is converted into NaCl structure - at 1840c.

3) Zinc Blende Structure: ZnS

(CCP):
The radius ratio of Zn2+ & S2- is
0.4. This value suggests that Co.
No. is 4. Each Zn2+ ions is in contact
with only four S2- ions. The s2- ions
are in cubic close packed
arrangement in zinc blendes
structure.

4) Wurtzite structure: ZnS (HCP): -

In this structure sulphide ion are

present in hexagonal Closed Packed
(HCP). In two close packed layers of
sphere (A B A B…sequence) tetrahedral
& octahedral holes are formed. The Co.
No. of Zn2 + & S2– ions are 4.
Another examples: - CuX, CuO, CuS, etc.

5) Fluorite structure (CaF2): -

In fluorite structure of
CaF2, each Ca2 + ion is
surrounded by eight F– ion
at corners of cube, i.e. Face
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Centered Cubic & each F-

ion is surrounded by four
Ca2+ ion arranged
octahedrally. The Co. No.

of Ca2+ are 8 & F- is 4.

Examples: - Difluorides of Ca, Ba, Cd, Hg, etc.
6) Rutile Structure (TiO2): -
The radius ratio of TiO2 is in between
0.41 to 0.73 each Ti4+ ion is surrounded by six
O2– ions octahedrally & each O2- ion
surrounded by three Ti4+ ions triangularly. The
Co. No. of O2- ion is 6 while Ti4+ ion is 3.
Another Examples: - MgF2, FeF2, CoF2, SnO2, etc.

Ionic Radii: -
Definition:-
a) The space occupied by an ion in any direction in lattice is called as an
ionic radii.
b) The distance bet nucleus of an ion & its electron cloud.
The x – ray analysis used to measure internuclear distance between two ions
in ionic compound & expressed in (n.m.). The internuclear distance between two
ions will be equal to the sum of the ionic radii of two ions as they touching one
another.

Figure shows the radius of atom A, in homo-nuclear diatomic molecule and

internuclear distance of molecule AB, in hetero-nuclear diatomic molecule.
Where, rA = radius of cation, and rB = radius of anion.

Palings univalent radii: -

Paling determined the ionic radii of univalent ion such as the ions of alkali
metals & halogens. He studies four ionic compounds – NaF, KCl, RbBr, CsI.
He selects these four compounds because,
1) They have same radius ratio (0.75)
2) The bond is ionic character.
3) The cation & anion are is electronic.
4) All have NaCl type structure.

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Assumptions: -
1) The measured internuclear distance, d = rc +ra.
2) The ratio rc /ra should be inversely proportional to the ratio of effective
nuclear charge.
rc /ra = Zeff ra /Zeff rc
While, Effective nuclear charge (Zeff) = Actual nuclear charge – Screening constant.
The screening constant for Neon configuration is 4.15.

Example:- NaF,
For Na+ having actual nuclear charge of 11 & F- having actual nuclear charge
of 9 Zeff for Na+ = 11- 4.15 = 6.85
Zeff for F- = 9 –4.15 =4.85
According to Assumption No.- 2
rNa+ /rF- = 4.85 / 6.85 = 0.71 -----------------------------1.
The measured interionic distance in NaF is 2.31 Ǻ.
rNa+ + rF- = 2.31-------------------------------------------- 2.
On solving equation (1)
rNa+ = 0.71 x rF-
By substituting value of rNa+ in eq. (2), we get
(0.71 x rF-) + rF- =
2.31, rF- x (0.71 +1)
= 2.31
1.71 rF- = 2.31
rF- = 2.31 /1.71 = 1.35 Ǻ
Hence, rNa+= 2.31 – 1.35 = 0.96 Ǻ
rNa+ = 0.96
Ǻ & rF- =
1.35 Ǻ
Pauling univalent Radii are given below in Ǻ
For cations: - Na+ = 0.96, K+ = 1.33, Rb+ = 1.48, Cs+ =
1.69 For anions: - F- = 1.36, Cl- = 1.81, Br- = 1.95, I- =
2.16
The ionic radius of cation is always smaller than parent atom. Where as ionic
radius of anion is always greater than parent atom.

Pauling crystal Radii: -

Pauling ionic radii for univalent ions quite match with observed inter ionic
distance. But in polyvalent ion it is fails.
Eq. 1) Calculated univalent radii of Mg2+ - 0.82 & 02-- 1.76 Ǻ.
Hence rMg2+ + rO2- = 0.82 +1.76 =2.58 Ǻ. But observed Mg –0 distance is
2.05 Ǻ. The calculated values do not agree with the observed value because the
ions (Mg2+) are not univalent. It is divalent.
Eq. 2) Univalent radii of Ca2+ = 1.18 Ǻ, O2- = 1.76 Ǻ,
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Inter ionic distance (d) = 2.94 Ǻ, observed distance = 2.39 Ǻ.
Conversion of univalent radii to crystal radii: -
rcry = run x Z –2/(n-1)
Where rcry = crystal radius, run = univalent radius, Z= charge on ion, n = Born
exponent constant, Born exponents for: - He (Li+, Be2+) n = 5, Ne (Na+, Mg2+, O2-,
F-) n
= 7, Ar (K+, Ca2+, Cl-) n = 9, Kr (Rb+, Br-) n = 10, Xe (Cs+,I –) n = 12

For Mg2+ ion, run of Mg2+ = 0.82, Z = 2, n = 7

Crystal radius rcry = 0.82 x 2 –2 / (7-1) = 0.65 Ǻ For O2- ion
run of O2- = 1.76, Z = 2, n = 7
Crystal radians rcry = 1.76 x 2-2 /(7-1) = 1.40 Ǻ Observed inter
ionic distance,
d = rc + rA = 0.65 + 1.40 = 2.05 Ǻ.
Trends in the value of ionic radii: -
1) There is decrease in ionic radii values with increase in atomic number of
elements.
2) This decrease is observed for …
a. d-block elements
b. lanthanide elements and
c. actinide elements
3) for a series of isoelectronic ions O2-, F-, Mg2+, Al3+ the ionic radii
decreases with increase in atomic number.
4) The cation with low charge is larger in size than the ion with higher
charge for same elements. eg. Fe2+ has larger radii than Fe3+ ion.
5) In a group, the ionic radii is increases in atomic number.
Radius Ratio Effect:-
Radius Ratio =Radius of Cation / Radius of Anion, i.e. rC / rA < 1.
The effect of radius ratio in determining the Coordination number and shapes of
ionic solids is known as Radius Ratio Effect.

Co. rC / rA Shape of
No. crystal
2 0 to 0.155 Linear
3 0.155 to 0.255 Triangular
4 0.255 to 0.414 Tetrahedral
4 0.414 to 0.732 Square planar
6 0.414 to 0.732 Octahedral
8 0.732 to 1.000 Cubic or BCC

Lattice Energy / crystal Energy: -

Definition:-
1) It is amount of energy released when the number of gaseous cation & anion
are condensed into crystal to form one mole of compound.
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Na+(g) + Cl–(g) NaCl(s), U = ΔH = - 411KJ/mol

Where ΔH=Heat of formation & U=Lattice energy. Negative sign means
release of energy,
2) The energy required separates a mole of solid substance into gaseous
ions. NaCl(s) Na+(g) + Cl –(g) , ΔH = + 411 KJ/mol
The stability of ionic solid depends upon value of its lattice energy. Greater the
lattice energy, more energy to separates ions & hence grater the stability.
Calculation of lattice Energy: -
1) Theoretical method: - using Born – Lande equation & Madelung constant.
2) Experimental method: - using Born – Haber cycle.

Theoretical method: - Born – Lande equation

Lattice energy (U) can be calculated for ionic solid by using the equation.
NA2(Z+)(Z-) 1
U=- r X (1 - n )

Where, N = Avogadro’s No. 6.023 x 1023 mol –1, A = Madelung const, Z+

& Z-
= charge on cation & anion, e = charge on electron, r = distance between cation &
anion, n = Born exponent constant.
The Madelung constant (Ǻ): - NaCl – 1.7475, CsCl – 1.7627, Zinc blende –
1.6381, Wurtzite – 1.6410, Fluorite – 5.0388, Rutile – 4.816
Conclusion from Born – Lande Equation: -
1. The lattice energy is varies directly as product of charge on ions.
2. The lattice energy (U) varies inversely as internuclear distance.
3. The lattice energy (U) is depends upon type of crystal structure.
Experimental method: Born – Haber cycle
The formation of solid NaCl may takes place by combination of solid
sodium & gaseous chlorine by two methods:-
Method (1) : - Direct combination
Combination of solid sodium metals & gaseous chlorine to form solid
NaCl
Na(s) + ½ Cl2(g) NaCl(s) , ΔHf = -411 kJmol-1
Method (2): - Stepwise
combination Step –1:
Sublimation of sodium
Na(s) Na(g), SNa = + 108.7 KJmol-1
Energy is absorbed, called Heat of sublimation.
Step – 2: Dissociation of chlorine molecule
½ Cl2(g) Cl(g), ½ DCl2 = + 121.4
KJmol-1 Energy is absorbed, called Heat of
Dissociation.
Step –3 : Formation of sodium ion

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Na(g) Na+(g) + e- , INa = +502.0 KJ mol-1

Energy is absorbed, called Ionization err ray.
Step – 4 : Formation of chloride ion
Cl(g) + e- Cl–(g) , ECl = - 354 KJ mol-1 Energy is
released, called Electron affinity.
Step – 5 : Formation of solid ionic Na + Cl- Na+(g)
+ Cl–(g) Na+ Cl-(s) , UNaCl =

According to Hess Law:-

It states that the enthalpy of reaction is the same whether the reaction
takes place in one or several stapes.
Heat of formation: ΔHf = SNa + ½ DCl2 + INa + ECl + UNaCl
- 411 = + 108.7 + 121.4 +502.0 - 354 + U
Nacl
UNacl = -411 – 108.7 – 121.4 – 502.0 + 354
= - 788.96 KJ mol –1
Problem: 2. Calculate lattice energy of NaF from following
data.
i) Heat of formation Hf = -569 KJ mol –1
ii) Heat or Sublimation SNa = +100.4 KJ mol –1
iii) Heat of Ionization INa = + 493.7 KJ mol –1
iv) Heat of Dissociation ½ DF2 = + 153.0 KJ mol –1
v) Heat of Ionization E. A.F = - 332.6 KJ mol (UNaF= -991.9
kJmol-1)
Problem: 3. Calculate lattices energy of NaI from Following
Hf = - 287.6 KJ mol-1, SNa = +108.7 KJ mol-1, INa = 493.8 KJ mol-
1, ½DI2 = + 106 KJ mol-1, E.A. I2 = - 305.9 KJ mol-1 (UNaI= -
690.8 kJmol-1)
Applications of Born Huber cycle: -
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 T.Y.B.Sc. Chemistry Paper-II Ionic Solids
1) The Born Huber cycle is used to calculate any one of quantities in
following equation when all of other are known,
Hf = S + I + ½ D + E + U
2) The cycle can be used to find electron affinities of element for which direct
experimental method is not available.
3) The cycle is useful as variation in stability of various ionic compounds.
4) It is also useful in knowing the nature of bonding i.e. Ionic or covalent bond
in compound.
5) It can be used to explain why does metals fails to form stable ionic
compounds in low oxidation state example:- CaCl, MnCl, AlO, etc.

Defect structure:
The crystal may have some imperfections & such structure is called as
defect structure. The defect structure is due to, (1) Ion vacancies in lattice, (2)
Dislocation of ions - Interstitial position, (3) foreign ions or impurities in lattice, (4)
non stoichiometric proportion of the ions.
A) Stoichiometric defect:
In perfect crystal definite arrangement of ions are at absolute zero
temperature. But as temperature increases, same vacancies are created. There are
two types of defect. In both defects, vacant sites are created which increases with
increase in temperature.
1) Schottky defect:
It is due to vacancies in lattice, there is equal number of missing positive &
negative ions in crystal lattice. Crystal remains neutral. It occurs when there is
small difference in size of cation & anion. i.e. rc/ra = 1. example:- NaCl, KCl,
NiO etc. It is found in strongly ionic compound with Coordination number
6.
2) Frankel defect:
It is due to dislocation of ion in lattice. Usually positive ions (cation)
occupy interstitials position rather than negative ion (anion) due to smaller size of
cation. This defect occurs when there is large deference in size between cation
& anions.
i.e. rc/ra < 1. It is found in covalent compounds with low Coordination number
Example:- AgBr, AgI, ZnS, etc.

Difference between Schottky Defect and Frenkel Defect

Sr. Schottky Defect Frenkel Defect
No.
1 Equal number of cations and A cation leaves the normal
anions are missing from the lattice site and occupies an
lattice interstitial
sites. site.

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 T.Y.B.Sc. Chemistry Paper-II Ionic Solids
2 Found in highly ionic compounds Found in ionic compounds with
with high coordination numbers low coordination numbers and
and where the cations and where the anions are much larger
anions in size than cations.
are of similar size.
3 Density of the solid decreases Density of the solid remains the
same.

Effect of Scottky & Frenkel Defect:

1) Density: - Lowers in density in Schottky, while no change in density in
Frenkel defect.
2) Electrical conductivity: -Ionic crystal is weak conductor, but when
defects in crystal electrical conductivity increases due to movement of ion
from its lattice site to hole & new hole is created. Another ion close to this
new hole move into it. In this way holes migration takes place & conductivity
in creases.
3) As number of holes increases in crystal lattice energy is less & hence stability
of crystal is less.

B) Non – Stoichiometric Defect. :

In these compounds the ratio of action & anion differs from that indicated by
ideal chemical formula. The crystal is electrically neutral. The crystal structure
becomes irregular & this creates the defect eq. Scottky defect – NiO. (2)
Frenkel defect - ZnO.
Solubility of Ionic solids:
Ionic substances are soluble in polar solvent like water. The energy, which
must be provide for separation & ion from crystal. This energy gain from solvent,
when water is solvent, energy is termed as hydration energy.
Anion, cation & salts are get hydrated in water. Metal ion interacts
strongly with water molecule called primary hydration sphere. Negative
oxygen end of H2O is towards cation (positive end). The Coordination number
for Li+, Na+, K+, is four
(IV) i. e. four H2O molecules are in primary hydration sphere; while for Rb+ &
Cs+ the Coordination number is six (VI). The water molecule in first sphere form
H–bond to other water molecule through hydrogen gives secondary sphere.
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 T.Y.B.Sc. Chemistry Paper-II Ionic Solids

Anions also can be hydrogen bonded to water with positive end of H2O i.e. H+
ions.
If hydration energy is greater than lattice energy (Exothermic) the salt is
soluble. While lattice energy is greater than hydration energy (Endothermic) it
remains insoluble in water.
Interaction of cation & Anion with water molecule separate hydration of
cation (Na+) & Anion (Cl-) gives NaCl dissolve in water.

Effect of Hydration Energy (Salvation energy):

1) Hydration energy & solubility increases with increase in value of dielectric
constant.
2) With increase in size of cation & anion, solubility increases.
3) Lattice energy & hydration energy opposite to each other.
4) The solubility of ionic solid is low if the cation is strongly polarizing and
the anion is easily polarizable.

Reference :

1. http://studymaterial.unipune.ac.in:8080/jspui/bitstream/123456789/6524/1/I
onic%20Solids%20%20TYBSC%20Navgire%20M.pdf

2. Text book of Manali Publication

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 T.Y.B.Sc. Chemistry Paper-II Ionic Solids

HRM Chemistry Notes