SOLID STATE CHEMISTRY

SOLID STATE
1. Introduction :
Matter can exists in three physical states namely ; solid, liquid and gas. Matter consists of tiny particals
(atoms, ions or molecules). If the particles are very far off from one another, they behave like gases ;
nearer, they behave like liquids, and nearest, like solids.
The fundamental difference between the three states of aggregation lies essentially in the difference of
the relative amounts of energy possessed by the particles in the three states. The relative energies in the
different states of matter are governed by two universal opposing tendencies associated with the particles:
(i) They have tendency of mutual attraction.
(ii) They have tendency of escape from one another which is known as escaping tendency.
Whether a given system would exist as a solid, liquid or gas depends upon the relative strength of these
opposing tendencies. If the escaping tendency is greater than the attraction between them, the molecules
will be carried far from each other to distances which are large as compared with their diameters, the
system will exists in gaseous state. But in the liquid state the molecular attraction exceeds the escaping
tendency and in the solid state the forces of attraction are so much greater than those of escaping
tendency that each particles is bound into a definite place in a rigid position by the mutual attraction of
molecules.

2. Solids :
Solids are characterised by the state of matter in which particles are closely packed and held together
by strong inter molecular attractive force.

Properties of Solids :

(a) In solid state the particles are not able to move randomly.

(b) They have definite shape and volume.

(c) Solids have high density.

(d) Solids have high and sharp melting point which is depend on the strength or value of binding energy.

(e) They are very low compressible.

(f) They show very slow diffusion.

Types of Solids :

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SOLID STATE CHEMISTRY
Crystalline solids :
(a) In this type of solids the atoms or molecule are arranged in a regular pattern in the three dimensional
network.
(b) They have well defined geometrical pattern, sharp melting point, definite heat of fusion and anisotropic
nature.
(c) Anisotropic means they exhibit different physical properties in all directions.
e.g. The electrical and thermal conductivities are different directions.
(d) They are generally incompressible.
(e) The general examples of crystalline solids are as Quartz, diamond etc.
Amorphous Solids :
(a) In this type of solids, the arrangement of building constituents is not regular.
(b) They are regarded as super cooled liquids with high viscosity in which the force of attraction holding the
molecules together are so great, that the material becomes rigid but there is no regularity in structure.
(c) They do not have sharp melting points.
(d) They are isotropic as they exhibit same physical properties in all the directions.
(e) The general examples of this solids are as glass, Rubber, plastics etc.

Defference between crystalline and amorphous solids :

Property Crystalline solids Amorphous solids
1. Shape They have definite and regular They do not have definite and
geometrical form. regular geometrical form.
2. Melting point They have definite melting point They do not have definite
melting point
3. Heat of fusion They have a definite heat of fusion They do not have definite
heat of fusion
4. Compressibility They are rigid and incompressible. These may be compressed to
any appreciable extent.
5. Cutting with a They are given cleavage i.e. they They are given irregular
Sharp edged tool break into two pieces with plane cleavage i.e. they break
into two pieces with
surfaces. irregular surface.

6. Isotropy and They are anisotropic. They are isotropic.

Anisotropy

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Questions based on types of solids :

Q.1 A solid X melts slightly above 273K and is a poor conductor of heat and electricity. To which of the
following categories does it belong -

(1) Ionic solid (2) Covalent solid (3) Metallic (4) Molecular

Q.2 In a crystal, the atoms are located at the position of -

(1) Zero P.E. (2) Infinite P.E. (3) Minimum P.E. (4) Maximum P.E.

Q.3 Graphite is an example of -

(1) Ionic solid (2) Covalent solid (3) Vander waals crystal (4) Metallic crys-
tal

Q.4 Amorphous solids -

(1) Possess sharp melting points

(2) Undergo clean cleavage when cut with knife

(3) Do not undergo clean cleavage when cut with knife

(4) Possess orderly arrangement over long distances

Answers : (1) 4 (2) 3 (3) 2 (4) 3

3. study of crystals :
Crystal :

A crystal is a homogeneous portion of a solid substance made by regular pattern of structural units
bonded by plane surface making definite angles with each other.

Space lattice :
The arrangement of constituents like atom, ions and molecules in different sites in three dimensional
space is called space lattice.

Unit cell :
The smallest repeating unit in space lattice which when repeats over and over again, results in a crystal
of the given substance called unit cell.

Face :

The plane surface of the crystal are called faces.

Edge :

An edge is formed by the intersection of two adjacent faces.

Interfacial angles :
The angle between the perpendiculars two intersecting faces called interfacial angles.

4. Law of constancy of symmetry :

(a) According to this law, all crystals of a substance have the same elements of symmetry.

(b) A crystal possess following three types of symmetry.

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Plane of symmetry :

It is an imaginary plane which passes through the centre of a crystal can divide it into two equal portions
which are exactly the mirror images to each other.

l efer h d k r y

Axis of symmetry :
(a) It is an imaginary line about which the crystal may be rotated so that it presents the same appearance
more than once in a complete rotation through 360.
(b) The axes of symmetry are called diad, triad, tetrad and hexad respectively. It is the original appearance
and is repeated twice (180), thrice (120), four times (90) and six times (60) in one rotation.
(c) These axes of symmetry are also called as two fold, four and six fold respectively.
(d) Five fold symmetry is not found in crystals.

(e)

(i) Axis of two fold symmetry. (ii) Axis of three fold symmetry.

(iii) Axis of four fold symmetry. (iv) Axis of six fold symmetry.

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Centre of symmetry :
(a) It is a point in the crystal that any line drawn through it intersects the surface of the crystal at equal
distance on either side.

Centre of
symmetry

X
Z

Note : Only simple cubic system have one centre of symmetry. Other system do not have centre of
symmetry.

5. Elements of symmetry :
(a) The total number of planes, axes and centre of symmetries possessed by a crystal is termed as elements
of symmetry.

(b) A cubic crystal possesses total 23 elements of symmetry.

(i) Plane of symmetry (3 + 6) = 9

(ii) Axes of symmetry (3 + 4 + 6) = 13

(iii) Centre of symmetry (1) = 1

Total symmetry = 23

6. crystal system :
(a) On the basis of geometrical consideration theoritically there can be 32 different combinations of ele-
ments of symmetry of crystal.

(b) But on the other hand Bravais showed that there are only seven types of crystal system.

These are :

(i) Cubic (ii) Tetragonal

(iii) Orthorhombic (iv) Trigonal or Rhombohedral

(v) Hexagonal (vi) Monoclinic

(vii) Triclinic
(c) There are 14 Bravais lattices under seven crystal systems as follows :

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The Bravais Lattices
Crystal Axial Axial Space Unit cell
system distance angles lattice

1. Cubic a=b=c = = = 90 a. Simple :

Lattice points at the

eight corners of the unit
cells.

b. Body centered :

Points at the eight

corners and at the body
centered

c. Face centered :

Points at the eight

corners and at the six
face centeres

2. Tetragonal a=bc = = = 90 d. Simple :

Points at the eight

corners of the unit cell

e. Body centered :

Po int s at the eight

corners and at the body
centre.

3. Orthorhombic a b c = = = 90 f. Simple :

Points at the eight

corners of the unit cell

g. End centered :

Also called side centered

or base centered points
at the eight corners and
at two face centres
opposite to each other

h. Body centered :

Points at the eight

corners and at the body
centre
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h. Body centered :

Points at the eight

corners and at the body
centre

i. Face centered :

Points at the eight

corners and at the six
face centres

4. Rhombohedral a=b=c = = 90 j. Simple :

or Points at the eight
Trigonal corners of the unit cell.

5. Hexagonal a=bc = = 90 k. Simple :

= 120

i. Po int s at the twelve

corners of the unit cell
out lined by thick line.

or

ii. Po int s at the twelve

corners of the
hexagonal prism and
at the centres of the
two hexagonal faces.

6. Monoclinic abc = = 90 I. Simple :

Po int s at the eight

corners of the unit cell.

m. End centered :
Po int s at the eight
corners and at two face
centres opposite to the
each other.

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7. Triclinic abc 90 n. Simple :
y
Po int s at the eight
c
corners of the unit cell.

b a
z
x

S.No. Crystal system Space lattice Examples

1. Cubic Simple Pb, Hg, Ag, Au, Cu, Diamond, NaCl,
KCl, ZnS, Cu2O, CaF2 and Alums.
2. Tetragonal Simple SnO2, ZnO2, TiO2, NiSO4, ZrSiO4,
PbWO4, White Sn.
3. Orthorhombic Simple KNO3, K2SO4, PbCO3, BaSO4,
Rhombic sulphur, MgSO4, 7H2O.
4. Trigonal or Rhombohedral Simple NaNO3, CaSO4, Calcite, ICl, Quartz,
As, Sb, Bi.
5. Hexagonal Simple ZnO, Pbl2, CdS, HgS, Graphite, Ice,
Beryl, Mg, Zn, Cd.
6. Monoclinic Simple Na2SO4. 10H2O, Na2B4O7. 10 H2O,
CaSO4. 2H2O, Monoclinic sulphur
7. Triclinic Simple CaSO4 . 5H2O, K2Cr2O7, H3BO3.

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7. mathematical analysis of cubic system (types and analysis) :
Simplest crystal is to be studied in cubic system. Three types of cubic systems are following.
(a) Simple Cubic (SC) : Atoms are arranged at the corners of the cube.
(b) Body Centered Cubic (BCC) : Atoms are arranged at the corners and at the centre of the cube.
(c) Face Centered Cubic (FCC) : Atoms are arranged at the corners and at centered of the each faces.

Atomic radius :
It is defined as the half of the distance between nearest neighbouring atoms in a crystal. It is expressed
in terms of length of the edge (a) of the unit cell of the crystal.
(a) Simple cubic structure [S.C.]

a
Radius of atom r =
2

a
(b) Face centered cubic structure (FCC) r =
2 2

3a
(c) Body centered cubic structure (BCC) r =
4

a=b=c
= = = 90
Number of atoms per unit cell / unit cell contents :
The total number of atoms contained with in the unit cell for a simple cubic called the unit cell content.
(a) Simple cubic structure (sc) :

1
Q Each corner atom is shared by eight surrounding cubes. Therefore, it contributes for of an atom.
8

1
z=8
8

(b) Face centered cubic structure (fcc) :

1
(i) The eight corners atoms contribute for of an atom and thus one atom per unit cell.
8

(ii) Each of six face centered atoms is shared by two adjacent unit cells and therefore one face centred
atom contribute half of its share. Means

1
6 = 3 atom per unit cell.
2

(iii) So, total Z = 3 + 1 = 4 atoms per unit cell.

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(c) Body centered cubic structure (bcc) :
(i) Eight Corner atoms contribute one atom per unit cell.
(ii) Centre atom contribute one atom per unit cell.
(iii) So, total 1 + 1 = 2 atoms per unit cell.

1
Z = 8 + 1=2
8

Number of Atoms in Unit Cell

nc nf ni
It can be determined by the simplest relation = + +
8 2 1
where nc = number of atoms at the corners of the cube = 8
nf = number of atoms at six faces of the cube = 6
ni = number of atoms inside the cube = 1
Cubic unit cell nc nf ni Total atom in
per unit cell
1. Simple cubic 8 0 0 1
2. Body centered cubic 8 0 1 2
3. Face centered cubic 8 6 0 4

Co-ordination number (C.N.) :

(a) It is defined as the number of nearest neighbours or touching particles with other particle present in a
crystal is called its co-ordination number.
(b) It depends upon structure of the crystal.
(c) For simple cubic system CN = 6.
(d) For bcc CN = 8.
(e) For fcc CN = 12.
Density of lattice matter :
(a) It is defined as the ratio of mass per unit cell to the total volume of unit cell.

mass per unit cell Z At. wt.

(b) Density of lattice matter = volume of unit cell = N volume of unit cell

Where Z is the number of atoms per unit cell and N is the Avogadro number.
Packing fraction (P.F.) :
It is defined as ratio of the volume of the unit cell that is occupied by spheres of the unit cell to the total
volume of the unit cell.

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SOLID STATE CHEMISTRY
(a) Simple cubic unit cell :
Let the radius of atom in packing = r
Atoms are present at the corner of the cube, each of the eight atom present at the eight corners shared
amongst eight unit cells.

1
Hence number of atoms per unit cell = 8 =1
8

a
again r=
2
4 3
r
therefore, P.F. = 3 = 0.52 % P.F. = 52%
( 2r )3
% of void = 100 52 = 48%
(b) Body centered cubic unit cell :
1
Number of atoms per unit cell = 8 +1=2
8

3a
r=
4
4 3
2 r
3
3
P.F. = 4r = 0.68

3
% P.F. = 68%
% of void = 100 68 = 32%
(c) Face centered cubic unit cell :
Number of atoms per unit cell = 4

2a
r=
4

4 3
4 r
3
3
P.F. = 4r = 0.74 % P.F. = 74% % of void = 100 74 = 26%

2

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Crystal Structure of Some Cubic lonic Solids

Crystal Structure Brief description Co-ordination No. of formula

Units and Examples Number per Unit cell
+ +
1. Rock Salt Cl ions in C.C.P, Na ions occupy Na 6 4

(NaCl-type) all the octahedral voids. Cl 6

Example : Halides of Li, Na, K

and Rb, AgCl, AgBr, NH4Cl etc.
+
2. CsCl - type Cl ions at the corner of cube and Cs 8 1
(B.C.C.) structure
+
Cs ions in the cubic void Cl 8
Example : CsCl, CsBr, CsI etc.
2 +2 +2
3. Zinc. Blende S ions in C.C.P., Zn ions occupy Zn 4 4
2
(ZnS) alter tetrahedral voids i.e. only half S 4
of the total number of tetrahedral
voids are occupied
Examples : ZnS, CuCl, CuBr, CuI,
AgI etc.
+2 +2
4. Fluorite Structure Ca ions (+ve ions) in C.C.P. and F Ca 8 4

(CaF2 type) ions(-ve ions) in all the tetrahedral F 4
voids.
Example : CaF2, SrF2, BaF2, BaCl2
etc.
2 +
5. Antifluorite Negative ions means O in CCP Na 4 4
+ 2
Structure and Positive Li ions in all the O 8
(Li2O type) tetrahedral voids.
Example : Na2O

8. ionic radii :
X-ray diffraction or electron diffraction techniques provides the necessary information regarding unit
cell. From the dimensions of the unit cell, it is possible to calculate ionic radii.
Let, cube of edge length a having cations and anions say NaCl structure.
Then : rc + ra = a/2

Where rc and ra are radius of cation and anion.

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( a / 2)2 + ( a / 2)2 a
Radius of Cl = =
2 4
Cl

For body centered lattice say CsCl. a/2

90
Na+ Cl
3a a/2
rc + ra =
2
Limiting Radius Ratio and Structure
Limiting radius ratio C.N. Shape
(r+) / (r)
< 0.155 2 Linear
0.155 0.225 3 Planar triangle
0.225 0.414 4 Tetrahedral
0.414 0.732 4 Square planar
0.414 0.732 6 Octahedral
0.732 0.999 8 Body-centred cubic
Examples based on characteristics of cubic system :
Ex.1 A metallic element exists as cubic lattice. Each edge of the unit cell is 2.88 . The density of the metal
3 2
is 7.20 g cm . How many unit cell will be present in 100 g of the metal - (1) 6.85 10 (2) 5.82
23 5 6
10 (3) 4.37 10 (4) 2.12 10 Ans (2)
3
Sol. The volume of the unit cell = (2.88 )
24 3
= 23.9 10 cm

m 100
The volume of 100 g of the metal= =
7.20
3
= 13.9 cm .

13.9 cm3 23
Number of unit cells in this volume = = 5.82 10
23.9 10 24 cm3

Ex.2 Fraction of total volume occupied by atoms in a simple cube is -

3 2
(1) (2) (3) (4)
2 8 6 6
Ans (4)
Sol. In a simple cubic system, number of atoms
a = 2r

Volume occupied by one atom

Packing fraction = Volume of unit cell

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SOLID STATE CHEMISTRY
4 3 4 3
r r
= 3 = 3 3 =
a3 ( 2r ) 6

Questions based on characteristics of cubic system :

Q.1 A crystal may have one or more planes and one or more axes of symmetry but it possesses-
(1) Two centres of symmetry (2) One centre of symmetry
(3) No centre of symmetry (4) None
Q.2 TiO2 is well known example of -
(1) Triclinic system (2) Tetragonal system
(3) Monoclinic system (4) None
Q.3 The arrangement ABC ABC ........ is referred to as -
(1) Octahedral close packing (2) Hexagonal close packing
(3) Tetrahedral close packing (4) Cubic close packing
+
Q.4 A binary solid (A B ) has a rock salt structure. If the edge length is 400 pm and radius of cation is 75
pm the radius of anion is -
(1) 100 pm (2) 125 pm (3) 250 pm (4) 325 pm
Q.5 If a is the length of unit cell, then which one is correct relationship -

a
(1) For simple cubic lattice, Radius of metal atom =
2

3a
(2) For bcc lattice, Radius of metal atom =
4

a
(3) For fcc lattice, Radius of metal atom =
2 2

(4) All
Q.6 The number of atoms present in a simple cubic unit cell are -
(1) 4 (2) 3 (3) 2 (4) 1
Q.7 The number of atoms/molecules contained in one face centred cubic unit cell of a monoatomic sub-
stance is -
(1) 4 (2) 6 (3) 8 (4) 12
Answer : (1) 2 (2) 2 (3) 4 (4) 2 (5) 4 (6) 4 (7) 1

9. classification of crystals :
According to attractive force which hold crystal together are generally of five types and thus crystal
can be classified into five types.

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SOLID STATE CHEMISTRY
Ionic Crystals :
(a) The lattices in ionic crystal consists of alternative positive and negative ions in equivalent amount ar-
ranged in an order so that the potential energy of the ions in the lattice is minimum.
(b) Such crystal are normally found in ionic compound.
+
e.g. NaCl Na + Cl
Covalent Crystals :
(a) In covalent crystals, atoms at their lattice point are held together by shared pairs of electrons between
them.
(b) The covalent bonding extends through out the crystals in spatial direction and has no small molecules in
the conventional sense.
e.g. Diamond, Graphite.
Molecular Crystals :
(a) In molecular crystals, the repeating unit is chemically identifiable atoms or molecules which do not carry
a net charge.
(b) Molecular bonds are formed for those elements or compounds whose electronic configuration is such
that there is little transfer of electrons between their atoms.
e.g. Noble gases.
(c) The molecules having H-atom attached on N, O or F give hydrogen bonding crystals. The existence of
H-bonding in the crystal lattice is beyond doubt.
e.g. Ice Crystal etc.
Mettallic Crystals :
In metallic crystals, the lattice consists of assemblage of positive ions immersed in a sea of mobile
electrons. The binding force is due to -
(a) Attraction between positive ions or ion cores of the metal and electron cloud.
(b) The mutual repulsion of free electrons.
(c) The mutual repulsion of ion cores.
Example based on types of crystals :
Ex.1 Iodine crystal are -
Ans (3)
(1) Metallic Solid (2) Ionic solid (3) Molecular solid (4) Covalent solid
Sol. Molecular solids are the substances having molecules as constituent units having interparticle forces
such as Vander Waals forces or hydrogen bonds.
Ex.2 Which of the following is molecular crystal -
(1) Noble gas (2) Ice (3) 1 and 2 both (4) None Ans (3)

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Questions based on types of crystals :
23
Q.1 An element occurring in the BCC structure has 12.08 10 unit cells. The total number of atoms of
the element in these cell will be -
23 23 23 23
(1) 24.16 10 (2) 36.18 10 (3) 6.04 10 (4) 12.08 10

Q.2 Which is covalent solid -

(1) Fe2O3 (2) Diamond (3) Graphite (4) All

Q.3 A certain metal fluoride crystallises in such a way that F atoms occupy simple cubic lattice sites, while
metal atoms occupy the body centres of half the cubes. The formula of metal fluoride is -

(1) M2F (2) MF (3) MF2 (4) MF8

Q.4 Certain crystals produce electric signals on application of pressure. This phenomenon is called-

(1) Pyro electricity (2) Ferroelectricity (3) Piezoelectricity (4) Ferrielectricity

Answer : (1) 1 (2) 4 (3) 3 (4) 3

10. packing of constituents in crystals :

In order to understand the packing of the constituent particles in a crystal, it is assumed that these
particles are hard spheres of identical size. The packing of these spheres takes place in such a way that
they occupy the maximum available space and hence the crystal has maximum density. This type of
packing is called close packing.

It is of two types :

Close packing in two dimensions :

The two possible arrangements of close packing in two dimensions.

Square close packing :

In which the spheres in the adjacent row lie just one over the other and show a horizontal as well as
vertical alignment and form square. Each sphere in this arrangement is in contact with four other
spheres.

X X X X

X X X X

Fig. One and two surfaces of square lattice.

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Hexagonal close packing :

In which the spheres in every second row are seated in the depression between the spheres of first row.
The spheres in the third row are vertically aligned with sphere in first row. The similar pattern is noticed
throughout the crystal structure.

Fig. One and two surfaces of hexagonal lattice.

Comparison between Hexagonal Close Packing and Square Close Packing :

1. Hexagonal close packing is more dense than square close packing.

2. In hexagonal close packing about 60.4% of available space is occupied by spheres. Whereas, square
close packing occupies only 52.4% of the space by spheres.

3. In square close packing the vacent spaces (voids) are between four touching spheres, whose centres lie
at the corners of a square are called square voids. While in hexagonal close packing the vacent spaces
(voids) are between three touching spheres, whose centres lie at the corners of an equiliateral triangle
are called triangular voids.

Close packing in three dimensions :

There are also two different ways to arrange spheres in three dimensional close packing.

Hexagonal close packing :

To arrange the spheres vertically above those in the first layer so that each sphere of the third layer lies
strictly above a sphere of the first layer. This arrangement if continued indefinitely in the same se-
quence is represented as AB AB AB .................

A
A

B
B

A
A

Fig. Hexagonal close packing (HCP) structure.

The arrangement is found to represent hexagonal close packing (hcp) symmetry which means that
whole structure possesses one six fold of symmetry.

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SOLID STATE CHEMISTRY
Cubic close packing :
To arrange the spheres on the other set of hollow marked B. In this way the spheres in fourth layer will
correspond with those in the first layer. This arrangement, If continued indefinitely in the same se-
quence, is represented as ABC ABC ABC ............ This arrangement possesses cubic close packing
(CCP).

A
A

B
B

C
C

Fig. Cubic close packing (CCP) structure

Body centred cubic arrangement :
This structure will be obtained if the spheres in first layer (marked A) of cubic closed pakcing are
slightly opened up and thus none of these is in contact with each other.
One can put the second layer of the spheres (marked B) on the top of the first layer in such a way that each
sphere of the second layer is in contact with four spheres of the layer below it.

11. IMPERFECTIONS IN SOLID :

Any deviation from the perfectly ordered arrangement constitutes a defect or imperfection. These
defects sometimes called thermodynamic defects because the number of these defects depends on the
temperature. Crystals may also possess additional defect due to the presence of impurities. Imperfec-
tion not only modify the properties of solids but also give rise to new properties.
Electronic imperfection :
Generally, electrons are present in fully occupied lowest energy state. But at high temperatures, some
of the electrons may occupy higher energy state depending upon the temperature.
For example, in the crystals of pure Si or Ge some electrons are released thermally from the covalent
bonds at temperature above 0 K. These electrons are free to move in the crystal and are responsible
for electrical conductivity. This type of conduction is known as intrinsic conduction.
The electron deficient bond formed by the release of an electron is called a hole. In the presence of
electric field the positive holes move in a direction opposite to that of the electrons and conduct electric-
ity.
Atomic imperfection :
The defect which arise due to irregularity in the arrangement of atoms or ions are called atomic imper-
fection. Point defect is caused by missing as misplaced atoms or ions.
1. Stoichiometric defect :
The compounds in which the number of positive and negative ions are exactly in the ratio indicated by
their chemical formula are called stoichiometric compound. e.g. NaCl (1 : 1)

These solids show following types of defects :

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(a) Schottky defect :

This type of defect is created when same number of positive ion and negative ion are missing from their
respective positions leaving behind a pair of holes. Schottky defect is more common in ionic compounds
which high co-ordination number and where the size of positive and negative ions are almost equal.

The presence of large number of schottky defects in crystal results in significant decrease in its density.

Eg. NaCl, KCl, CsCl, KBr etc.

(b) Interstitial Defect :

This type of defect is caused due to the presence of ions in the normally vacant interstitial sites in the
crystal.

(c) Frenkel Defect :

This type of defect is created when an ion leaves its correct lattice site and occupies an interstitial site.
Frenkel defects are common in ionic compounds which have low co-ordination number and in which
there is large difference in size between positive and negative ions.

+ +
M X M X

+ +
X M X M

+
X M X
+
M
+ +
X M X M
Frenkel Defect

Eg. ZnS, AgCl, AgBr, AgI etc.

2. Non Stoichiometric Defect :

There are many compound in which the ratio of positive and negative ions present in the compound
differs from that required by ideal formula of the compound. Such compounds are called Non-stoichio-
metric compounds.

e.g. VOx (Where x can very between 0.6 to 1.3)

In these compounds balance of positive and negative charges is maintained by having extra electrons or
extra positive charge.

So, these defects are of following types :

(a) Metal excess defects due to anion vacancies :
A compound may have excess metal ion if a negative ion is absent from its lattice site, leaving a hole
which is occupied by electron to maintain electrical neutrality. The holes occupied by electrons are
called F-centres and are responsible for the colour of the compound.

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M+ X M+ X

X M+ e M+
F - Center

M+ X M+ X

X M+ X M+
Metal excess defects
due to anion vacancies
Eg. :
* The excess sodium in NaCl makes the crystal appears yellow.
* Excess potassium in KCl makes it violet.
* Excess lithium in LiCl makes it pink.
Greater the number of F-centres greater is the intensity of colour. This type of defects are found in
crystal which are likely to possess schottky Defects.
(b) Metal excess defects due to interstitial cations :
It may occur if an extra positive ion is present in an interstitial site. Electrically neutrality is maintained
by the presence of an electron in the interstitial site.

+ +
M X M X

X M
+
X M+
+
M
+ +
M X M X

e
+
X M X M
+

Metal excess defects

due to interstitial cation

This type of defects are exhibited by the crystals which are likely to exbit Frenkel defects.
(c) Metal deficiency due to cation vacancies :

M+ X M+ X M+

X X M+ X

M+ X X M+
M+
+ +
X M X M X

Metal deficiency
due to cation vacancies

The non-stoichiometric compound may have metal deficiency due to the absence of metal ion from its
lattice site. The charge is balanced by an adjacent ion having higher positive charge.

This type of defects are generally shown by compounds of transition metals.

# [77]
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SOLID STATE CHEMISTRY
Examples based on imperfections in solid :

Ex.1 In a crystal both ions are missing from normal sites in equal number. This is an example of -
(1) F - centres (2) Interstitial defect

(3) Frenkel defect (4) Schotty defect

Ans(4)

Sol. Schottky defects are arised when one positive ion and one negative ion are missing from their respec-
tive positions leaving behind a pair of holes. These are more common in ionic compounds with high
coordination number and having almost similar size of cations and anions.

Ex.2 Frenkel defect is noticed in -

(1) AgBr (2) ZnS (3) AgI (4) All Ans (4)

Sol. Frenkel defect is arised when the cations are missing from their lattice sites and occupy interstitial sites.
As a result of Frenkel defect, density remains unchanged but dielectric constant increases.

Questions based on imperfections in solid :

Q.1 Transition metals, when they form interstitial compounds, the non-metals (H, B, C, N) are accomodated
in -

(1) Voids or holes in cubic - packed structure

(2) Tetrahedral voids

(3) Octahedral voids

(4) All of these

Q.2 In a close pack array of N spheres, the number of tetrahedral holes are -

(1) 4N (2) N/2 (3) 2N (4) N

Q.3 In antiflourite structure, the negative ions -

(1) Occupy tetrahedral voids (2) Occupy octahedral voids

(3) Are arranged in ccp (4) Are arrange in hcp

Answer : (1) 4 (2) 3 (3) 3

12. Experimental Method of Determining Crystal Structure :

Crystal structure has been obtained by studying on the diffraction of X-rays by solids.
A crystal, having constituents particles arranged in planes at very small distances in three dimension
array, acts as diffraction grating for X - rays which have wavelenghts of the same order as the spacing
in crystal.
Thus X - ray diffraction results from the scattering of X - rays by a regular arrangement of atoms or
ions.

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SOLID STATE CHEMISTRY

Diffraction pattern

Crystal
Lead-box
with slit Photographic plate

+
10,000 40,000
Volts Spots form diffraction
X-rays

Spots form incident beam

Photographic plate
(Front view)

When a beam of X - rays passes through a crystalline solid, each atom in the beam scatters some of the
radiations. If waves are on same phase means if their peak are through coincides they add together to
give wave of greater amplitude. This enhancement of intensity is called constructive interference.

If waves are out of phase, they cancel. This cancellation is called destructive interference.

(Addition)

(a) Constructive interference of waves

(Cancellati on)

(b) Destructive interference of waves

Braggs Law :

X-rays are electromagnetic waves of short wavelength and may be diffracted by suitable diffracting
centres.

In solid crystals,atoms are arranged in fairly regular pattern with interatomic gaps of the order of 0.1
nm. Common salt is an example of a crystalline solid. Almost all the metals at ordinary temperature are
crystalline. These metals may act as a natural three-dimensional gratings for the diffraction of X - rays.

# [79]
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SOLID STATE CHEMISTRY

A D
B E
C F

O
L M

X-ray reflection from crystals

This method is based upon the principle that a crystal may be considered to be made up of a number of
parallel equidistant atomic planes, as represented by the lines XX, YY, ZZ etc.

Suppose a beam of Xrays is incident on the crystal at angle . A part of the beam e.g., the ray AB is
reflected at the point B along the path BC. On the other hand, some rays like DE, GH etc. penetrate into
the crystal and are reflected by the atoms present in the atomic planes YY, ZZ, etc.

Evidently, as compared to the ray AB, a ray like DE has to travel a longer distance, which is equal to
JEK where BJ and BK are perpendiculars drawn on the lines DE and EF respectively. The reflected
beams like BC, EF, etc. then undergo interference with each other. If these reflected rays are in phase,
they reinforce into each other and the intensity of the reflected rays is maximum. On the other hand, if
the reflected rays are out of phase, the intensity of the reflected beam is very low.

It is obvious that in order that the reflected rays, BC and EF may be in phase, the extra distance JEK
traversed by the ray DEF should be an integral multiple of the wavelength of the Xrays, i.e.,

Distance JEK = n ............ (i)

where n is an integer, i.e., 1, 2, 3, 4, etc. If d is the distance between the successive atomic planes, it is
obvious from fig that

JE EK = d sin

so that JEK = 2d sin .............(ii)

Putting this value in equation (i), we get

2d sin = n .............(iii)

This equation is called Braggs equation.

For monochromatic X - rays, is constant and there are some specific angles 1, 2, 3......etc, corre-
sponding to n = 1, 2 , 3,........ etc, in the above equation. Thus, if the X - rays are incident at one of these,

# [80]
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SOLID STATE CHEMISTRY
they are reflected ; otherwise they are absorbed. When they are reflected, the laws of reflection are
obeyed i.e. (a) the angle of incidence is equal to the angle of reflection and (b) the incident ray, the
reflected ray and the normal to the reflecting plane are coplanar.

The interplaner spacing d and several informations about the structure of the solid canbe obtained with
the help of monochromatic X-ray beam.

13. Properties of solids :

Electric Properties :

On the basis of electrical conductivity the solids can be broadly classified into the three types:

(a) Metals (conductors)

(b) Insulators

(c) Semi-conductors.

Electrical conductivity of solids may arise through the motion of electrons and positive holes (electronic
conductivity) or through the motion of ions (ionic conductivity). The conduction through electrons is
called n-type conduction and through positive holes is called p-type conduction. Pure ionic solids
where conduction can take place only through motion of ions are insulators. However, the presence of
defects in the crystal structure increases their conductivity.

Unlike metals, the conductivity of semi-conductors and insulators is mainly due to the presence of
interstitial electrons and positive holes in the solids due to imperfections. The conductivity of semicon-
ductors and insulators increases with increase in temperature while that of metals decreases.

The electrical behaviour of some oxides of transition metals (belonging to fourth period) is given in
table. It may be noted that these oxides show wide variation in their electrical behaviour.

Electrical Properties of Some Trasition Oxides

TiO(M) VO(M) MnO(I) FeO(I) CoO(I) NiO(I) CuO(I)

Ti2O3(M-I) V2O3M(I) Cr2O3(I) Mn2O3(I) Fe2O3(I)

TiO2(I) VO2(M-I) CrO2(M) MnO2(I)

V2O5(I)

M = Metal ; I = Insulator ; M-I = shows a transition from metal to insulator behaviour at a certain
temperature.

MAGNETIC PROPERTIES :

On the basis of magnetic properties, substances are classified into the following two types.

(i) Paramagnetic substances

(ii) Diamagnetic substances

(iii) Ferromagnetic substances

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SOLID STATE CHEMISTRY
(i) Paramagnetic substances : Substances which are weakly attracted into the magnetic field are called
paramagnetic. These substances lose their magnetism on removing the magnetic field. Paramagnetism
is caused by the presence of unpaired electrons and since most of the transition metal atoms have
unpaired d-electrons, they are paramagnetic in behaviour.

(ii) Diamagnetic substances : Substances which are repelled by magnetic field are called diamagnetic.
It is the property of the completely filled electronic subshells.

Since most of the transition metal ions have unpaired d-electrons, they show paramagnetic behaviour.
3+ 4+ 2+ +
The exceptions are Sc , Ti , Zn , Cu , etc. which do not contain any unpaired d-electrons and hence
these are diamagnetic. The presence of an unpaired electron in an element causes it to behave like a
permanent magnet. As a result of permanent magnet, a paramagnetic substances when placed in an
applied magnetic field, takes up a parallel position to the field.

It is important to note that diamagnetic substances show a decrease in weight while paramagnetic
substances show an increase in weight in presence of a magnetic field.

(iii) Ferromagnetic substances : The substances possessing unpaired electrons are further classified in
three different groups based on the alignment of magnetic moments of unpaired electrons.

(a) Ferromagnetic substances

(b) Antiferromagnetic substances

(c) Ferrimagnetic substances

(a) Ferromagnetic substances : The substances which are strongly attracted by magnetic field are
termed as ferromagnetic substances. This type of substance have alignment of all the unpaired electrons
in the same direction (orientation) These substances are permanently magnetised i.e. these substances
show magnetism even in the absence of magnetic field. Examples are Ni, Fe, Co and CrO2.

(b) Antiferromagnetic substances : When equal number of unpaired electrons are aligned in opposite
directions, their magnetic moment (electron spin) will compensate each other magnetic moment. Such
substances are termed as antiferromagnetic substances. For example, MnO, Mn2O3 and MnO2.

(c) Ferrimagnetic substances : When unequal number of unpaired electrons are aligned in opposite
directions, the net magnetic moment is not zero. Such substances are termed as ferrimagnetic substances
e.g. ferrite Fe2O3.

It has been observed that the ferro-magnetic, ferrimagnetic and antiferromagnetic substances show
paramagnetic nature at higher temperatures. This arises due to randumisation of spins at higher
temperature e.g. Fe3O4 is ferrimagnetic at room temperature but becomes paramagnetic at 850 K.

Magnetic Properties of Some Transition Metal Oxides

TiO(p) VO(p) MnO(af) FeO(af) CoO(af)NiO(af) CuO(p)

Ti2O3(p)V2O3 (af) Cr2O3(af) Mn2O3(af) Fe2O3(af)

Ti2O2(p)VO2(p) CrO2(f) MnO2(af) Fe3O4(fe)

V2O5(d)

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SOLID STATE CHEMISTRY
p = paramagnetic ; af = anti-ferromagnetic ; fe = ferrimagnetic ; f = ferromagnetic ; d = diamagnetic.

DIELECTRIC PROPERTIES :

A dielectric is a substance in which an electric field gives rise to no net flow of electric charge. This
is due to the reason that electrons in a dielectric are tightly held by individual atoms. However, under
the effect of applied field displacement of charges takes place, resulting in the creation of dipoles.

(i) Piezoelectricity : A dielectic crystal which has a resultant dipole moment can produce electricity or
show electrical property when external pressure is applied. Such a crystal is known as piezoelectric
crystal and this property is called piezoelectricity.

The mechanical stress caused by the applied pressure results in electric current because of the dis-
placement of the ions in the crystals.

Such piezoelectric crystals find applications as pick-ups in record players since electric signals are
produced on applying pressure.

(ii) Pyroelectricity : Some polar crystals upon heating produce small electric current. This phenomenon is
known as pyroelectricity. Actually certain atoms or ions get displaced upon heating.

(iii) Ferroelectricity : In certain piezoelectric crystals, the dipoles are permanently polarised even in the
absence of applied electric field. However, the direction of polarisation may change on applying cur-
rent. This phenomenon is known as ferroelectricity and the effect involved is called ferroelectric
effect. The examples of some ferroelectric solids are.

Pota ssium dihydrogen phosphate (KH 2 PO 4 ) Potassium tartarate or Rochelles salt

(KOOCCH(OH)CH(OH)COOK) and barium titanate (BaTiO2).

(iv) Anti-ferroelectricity : When the dipoles in alternate lattices point up and down, the two dipoles cancel
on another so that there is no resultant dipole moment. Such crystals are known as antiferroelectric
crystals and the phenomenon is called antiferroelectricity.

For example, lead zirconate (PbZrO3) is an antiferroelectric solid.

14. SPECIAL POINTS :

1. The space occupied by hard spheres in fcc and hcp is 74%, in bcc it is 68%, in simple cubic it is 52% and
in diamond it is 34%. Thus only fcc and hcp are close packed structures.

2. Out of the seven crystal system triclinic is the most unsymmetrical system (a b c, 90).
+ +
3. In NaCl crystal, if there are 14 Na ions, then there are 13 Cl ions. Out of 14 Na ions, 8 are on the

corners and 6 are on the face-centres. Then 12 Cl ions are on the edge centres and 1 Cl at the body-
centre. It can be vice-versa also.
+
4. Halides of all alkali metals (except those of Cs) and those of NH4 , oxides and sulphides of alkaline
earths (except BeS) and halides of siver (except AgI) have rock-salt (NaCl) type structure.

5. CsBr, CsI, CsCN, TlCl, TIBr, TlI and TlCN have CsCl structure.

6. CuCl, CuBr, CuI, AgI, BeS have zinc blende (ZnS) structure.

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SOLID STATE CHEMISTRY
7. SrCl2, SrF2, BaCl2, BaF2, CdF2, HgF2 have fluorite (CaF2) structure.

8. Na2O, K2O, Na2S, K2S have antifluorite (Li2O type) structure.

9. HCP is present in Be, Mg, Ca, Cr, Mo, V, Zn.

10. CCP is present in Fe, Cu, Ag, Au, Pt, Al and Ni.

11. BCC is present in all alkali metals.

12. All noble gases have ccp structure except. He which has hcp structure.
22 1 1
13. The conductivity of insulators is of the order of 10 ohm cm whereas conductivity of semiconduc-
9 2 1 1
tors lies in the range 10 to 10 ohm cm .

14. Beryl (Be3Al2Si6O18) is a cyclic/ring silicate, pyroxenes and asbestos are chain silicates, clay is a sheet
silicate and quartz is a three dimensional silicate.

15. TiO2, NaCl and benzene are diamagnetic, Fe, Ni, Co, CrO2 are ferromagnetic, MnO is anti ferromag-
netic, ferrites are ferrimagnetic,

16. Barrium titanate (BaTiO3), sodium potassium tartarate (Rochelle salt) and potassium dihydrogen phos-
phate (KH2PO4) are ferroelectric solids.

17. Lead zirconate (PbZrO3) is an example of anti-ferroelectric crystal.

18. Some super conductors and temperatures of their superconductivity.

Substance Temp. Substance (oxides) Temp.

Hg 4K Y Ba2 Cu3 O7 90 K

Most metals 2K 5K Bi2 Ca2 Sr2 Cu3 O10 105 K

Some organic compounds <5K Tl2 Ca2 Ba2 Cu3 O10 125 K

19. Piezoelectric crystals are used as pick ups in record players.

20. Amorphous silica is used for making photovoltaic cell (used for converting sunlight into electricity).

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