1 | SOLID STATE CHEMISTRY

Introduction
Solids have a definite shape and rigidity. This is due to the fact that constituent particles cannot posses enough
energy to move about to kept up different positions.
Solids are characterized by their definite volume which does not depend on the size and shape of the container. This
is due to the close packing of molecules and strong short range intermolecular forces between them.

Amorphous and Crystalline Solids

Solids are divided into two classes on the basis of haphazard and regular arrangement of the building constituents.
(i) Amorphous solids:
(ii) Crystalline solids:
Difference between crystalline and amorphous solids
S.N. Crystalline Solids Amorphous solids
1 The have a definite and regular geometry due to They do not have any pattern of arrangement of
definite and orderly arrangement of atoms, ions or atoms, ions or molecules and thus, do not have
molecules in three–dimensional space. any definite geometrical shape.
2. They have sharp melting points and change abruptly Amorphous solids do not have sharp melting
into liquids. points and do not change abruptly into liquids.
They melt over a range of temperature.
3. Crystalline solids are anisotropic. Some of their Amorphous solids are isotropic. Their physical
physical properties like refractive index, electrical properties like refractive index, electrical
conductivities etc. are different in different directions. conductivities etc. are same in all directions.
4. These are considered as true solids. These are considered pseudo–solids or
supercooled liquids of high viscosity. Window
glass panes of old buildings are thicker at the
bottom because glass has the property to flow.
5. They undergo clean cleavage. They undergo rough or irregular cut.
CHEMISTRY SOLID STATE | 2
Classification of Crystalline Solids
Crystalline solids can be further categorized as ionic, covalent, molecular or metallic depending upon the nature of
bonding.
S. Characteris Ionic solid Covalent or Molecular solid Metallic solid
No. tics network solid
1. Constituent Positive and negative ions Neutral atoms Molecules (polar or Positive ions and
particles non–polar) electrons
(delocalised)

2. Bonding/ Electrostatic or coulombic Shared pairs of Weak polar forces electrostatic attraction
Attractive electrons or between positive ions
forces (covalent) Vander Waal's and electrons
forces or hydrogen
bonding

3. Hardness Hard and brittle Very hard Very soft Hard or soft
4. Melting High – 1500 Very high  Low High or low
point (k) 4000
5. Electrical Bad conductors (insulators) due to Bad conductors Bad conductors Good conductors
conductivity absence of free ions. Good (insulators) with (insulators)
conductors in fused state or in few exceptions
aqueous solution due to presence of like graphite
free ions.
6. Examples NaCl, MgO, KCl, CsCl,ZnS, Diamond (C), Ice,Solid CO2, s–block and d–block
Na2SO4, KNO3,CuSO4.5H2O Graphite (C), Sulphur (S8), metals and some p–
Carborundum Glucose, block elements. Na,
(SiC), Quartz Naphthalene, etc. Cu, Ag, Au, Ni, Pt.
(SiO2), Boron– Cr. etc.
nitride (BN)
The sites which are occupied by constituent units (atoms, molecules and ions) are called lattice sites or lattice points.
When lattice points are joined together then they form crystal lattice.

Unit Cells :It can be defined as the smallest repeating unit in space lattice which, when repeated over and over again
results in a crystal of the given substance.
Each unit cell is characterized by two parameters shown in fig. 1.1 The lengths of the edges of the unit cell (a, b and
c) and (ii) The angles between three imaginary axes OX, OY and OZ, respectively( and .

Fig. 1.1
CHEMISTRY SOLID STATE | 3
Crystal System
There are seven types of basic or primitive unit cells that have been recognized between crystals. These are cubic,
orthorhombic, tetragonal, monoclinic, triclinic, hexagonal and rhombohedral.
S. System Edges Angles Examples
No.
1. Cubic, a = b = c,  =  All the three All right angles NaCl, KCl, ZnS, diamond, alums, Cu
=  = 90º are equal
2. Orthorhombic all unequal All right angles KNO3, BaSO4, K2SO4, rhombic sulphur
a  b  c,  =
90º
3. Tetragonal Two equal All right angles TiO2, SnO2, NH4Br, CaSO4, white tin
a = b c,  =  =  = 90º
4. Monoclinic all unequal Two right Monoclinic sulphur
a  b  c, 90º ,  angles KClO3, CaSO4.2H2O, Na2B4O7.10H2O,
= 90º CuSO4.5H2O,H3BO3,K2Cr2O7
5. Triclinic all unequal None of right CuSO4. 5H2O, H3BO3,K2Cr2O7
    c,   angles
90
6. Hexagonal Two equal Angle between ZnO, CdS, HgS, SiC, AgI
a  b  c, 90º ,  equal edges =
= 120º 120º
7. Rhombohedral All these equal All equal but NaNO3, ICl, quartz, (CaCO3) calcite
a = b = c, none 90º CaCO3.HgS (cinnabar)
90º
Unit cells are divided into two main types :
(a) Primitive or simple unit cells: In this type of unit cell, constituent particles are present only at the corners.
(b) Non–Primitive unit cells: In these unit cells, constituent units are located not only at corners but also at some
other positions like face centres, body centres etc.
There are three type of non–primitive unit cells:
(i) Body–centred unit cells : There are lattice points at the corners as well as in the body centre of unit
cell.
(ii) Face–centred unit cells : There are lattice points at the corners as well as at the centre of each face of
the unit cell.
(iii) End centred unit cell : In this type of unit cells, the constituent particles are situated at each corner and
at the centres of any two opposite faces.

Simple Cubic bcc fcc

Coordination number:
In case of ionic solids the coordination number of a particular ion is the number of oppositely charged ion
surrounding that particular ion.
CHEMISTRY SOLID STATE | 4
CALCULATION OF NUMBER OF PARTICLES IN A UNIT CELL
Types of lattice points Contribution to one unit cell
Corner 1/8 particle / atom / ion
Edge ¼ particle / atom / ion
Face–centred ½ particle / atom / ion
Body–centred 1 particle / atom / ion
(a) Simple or Primitive cubic unit cell: In this unit cell, only corners are occupied hence number of particles per
unit cell may be calculated as
1
Z  8  1
8
(b) Body centred cubic unit cell (bcc)
1
Z  8 1 2
8
(c) Face–centred cubic unit cell (fcc) :
1 1
Z  8  6   4
8 2

Example 1.1
In a face–centred cubic arrangement of 'A' and 'B' atoms, 'A' atoms occupy the corners and 'B' atoms
occupy the face centres of the unit cell. One of the corners in each unit cell remains vacant. What is the
simplest formula of the compound?
Ans. Seven of the corners of the unit cell are occupied by 'A' atoms. Thus,
1 7
Its contribution of the unit cell = 7  
8 8
1
Contribution of 'B' atoms to the unit cell = 6   3
2
7 7 24
A:B  :3  :  7:24
8 8 8
 Simplest formula of the compound is A7 B24.

Example 1.2
A unit cell consists of a cube in which there are anions 'Y' at each corner and cations 'X' at the centre of
alternate faces of a unit cell. What is the simplest formula of the compound?
1
Ans : Contribution of the anions to the unit cell  8   1
8
1
Contribution of the cations to the unit cell  2  1
2
X : Y = 1 : 1 The simplest formula of the compound is XY.

Relationship between nearest neighbour distance (D) and radius of atom (R) and edge of the unit cell (a) in
the cubic systems
1. Simple cubic unit cell: In a simple cubic unit cell, atoms at the corners touch each other along the edge.
 d  a  2r 
(Where r = radius of the atom)
a
or Atomic radius , r   0.5a
2
CHEMISTRY SOLID STATE | 5
2. Body–centred cubic unit cell:
3
d  2r  a
2
3
atomic radius, r  a
4
3. Face centred cubic unit cell:
1
d  2r  a
2
a
or Atomic radius, r 
2 2

Example 1.3
Xenon crystallizes in the face–centred cubic lattice and the edge of the unit cell is 620 pm. What is the
nearest neighbour distance and what is the radius of the xenon atom?
Ans. In the face–centred cubic lattice, the nearest neighbour distance 'd' can be calculated as
a
d (a  edgelength  620pm)
2
620

1.414
= 438.47 pm
Relation between radius of constituent unit and edge length may be given as
a 2  4r ( For face–centred cubic lattice)
a 2 620 1.414
r   219.17 pm
4 4

Example 1.4
Chromium metal crystallizes with a body centred cubic lattice. The length of unit cell is found to be 287 pm.
Calculate the atomic radius, the number of atoms per unit cell?
Ans. Number of chromium atoms in unit cell (body centred cubic)
1
 8 1 2
8
In body–centred cubic unit cell.
a 3  4r ……(i)
Where a = 287 pm (edge length of unit cell)
 From eq. (i) 287  3  4r
287 1.732
r  124.27 pm
4
6 | SOLID STATE CHEMISTRY

Practice Problems:
1. Classify each of the following solids as an ionic, network, molecular or metallic solids :
Sn, S8, Se, SiO2, Na2SO4, naphthalene (C10H8) Glucose (C6H12O6), white phosphorus (P4) silicon (Si), Silicon
carbide (SiC), Silver (Ag)
2. Compare what happens when crystalline and amorphous solids are broken into pieces.
3. Answer the following questions :
(i) Write two examples of amorphous solids
(ii) Name the type of solids which have long range orders
(iii) Write down the difference between isotropy and anisotropy
4. Which of the following do you expect to be molecular solids?
(a) Sodium hydroxide, (NaOH) (b) Solid ethane, (C2H6)
(c) Nickel, (Ni) (d) Solid Silane (SiH4) (e) Dry ice (Solid CO2)
5. Which network solid is an exceptionally good conductor of electricity?
6. A compound is formed by two elements ‘P’ and ‘Q’. The compound crystallizes in cubic arrangement in which
‘P’ atoms occupy the corners of a cube and ‘Q’ atoms are present at face-centres. What is the formula of the
compound?
7. In a face-centred cubic arrangement of ‘A’ and B atoms ‘A’ atoms occupy the corners and ‘B’ atoms occupy
the face-centeres of the unit cell. One of the corners in each unit cell remains vacant. What is the simplest
formula of the compound?
8. A unit cell consists of a cube in which there are anions ‘Y’ at each corner and cations ‘X’ at the centre of
alternative faces of a unit cell. What is the simplest formula of the compound?
9. A compound made up of elements A and B crystallizes in a cubic structure. Atoms A are present on the
corners as well as face-centres, whereas atoms B are present on the edge-centres as well as body-centre. What
is the formula of the compound? Draw the structure of the unit cell.
10. A cubic solid is made of two elements X and Y. Atoms Y are at the corners of the cube and X at the body
centre. What is the formula of the compound?
11. A unit cell consists of a cube in which the atoms of A are occupying the corners while the atoms of B are
occupying the centre of each face. If the atoms of A are missing from two corners. What is the simplest
formula of the compound?
12. If three elements P,Q and R crystallise in a cubic type lattice with P atoms at the corners, Q atoms at the cube
centre and R atoms at the edges, then write down the formula of the compound.
13. A compound alloy of gold and copper crystallizes in a cubic lattice in which gold atoms occupy corners of
cubic unit cell and copper atoms occupy the centre of face of cube. What is the formula of alloy compound?
14. Metallic gold crystallizes in face centred cubic lattice. What is the approximate number of unit cells in 2 g of
gold? (Atomic mass of gold is 197)
15. What are the unit cell parameters for the following types of unit cells?
(i) hexagonal & (ii) monoclinic
16. Name the crystal class for which all four types of unit cells are possible
17. Calculate the number of atoms in a cubic based unit cell having one atoms on each corner and two atoms on
each body diagonal.
18. Potassium crystallizes in a body centred cubic lattice. What is the approximate number of unit cells in 4 g of
potassium? (Atomic mass of potassium is 39 amu.)
19. What is the simplest formula of a solid whose cubic unit cell has the Atom A at each corner, the atom B at
each face centre and a ‘C’ atom at the body centre?
20. A compound is formed by elements X and Y crystallizes in the cubic structure where Y atoms are at the
corners of the cube and X atoms are at the centre of one set of opposite face. What is the formula of the
compound?
21. What is the total number of atoms per unit cell in a face-centred cubic (fcc) crystal structure?
CHEMISTRY SOLID STATE | 7
Calculation of percentage of occupied space or packing efficiency in the cubic systems:
1. In a simple cubic unit cell:
suppose Length of the unit cell = A and Radius of sphere (atom) = r
Volume of the unit cell = a3 = (2r)3 = 8r3
1
No. of atoms per unit cell = 8 × 1
8
4 3
Volume of the atom = r (This is the occupied volume)
3
Occupied volume
 Packing fraction =
Total volume
 4 / 3  r 3
=  0.5233
8r 3
Thus, the percentage of occupied volume or packing efficiency = 0.5233 × 100 = 52.33%
2 In a body–centred cubic unit cell:
suppose Length of the unit of cell = a and Radius of the sphere (atom) = r
4
In this unit cell. a r
3
   3 64 3
Total volume of the unit of cell = a 3   r  r
 3 3 3
No. of atoms per unit cell = 2
4
Volume of the two atoms = 2  r 3 (This is the occupied volume)
3
Occupied volume
 Packing fraction =
Total volume
4
2  r 3
 3  0.68
64 3
r
3 3
Thus, the percentage of occupied volume or packing efficiency = 68%
3. In face–centred cubic unit cell :
Suppose Length of the unit cell = a and Radius of the sphere (atom) = r
In this unit cell, a 2 2 r

 
3
Total volume of the unit cell = a 3  2 2 r 3 16 2r 3
No. of atoms per unit cell = 4
4
Volume of four atoms  4  r 3 (This is the occupied volume)
3
ocupied volume
 Packing fraction =
Total volume
4
4  r 3
 3  0.7401
16 2r 3
Thus, the percentage of occupied volume of packing efficiency = 74.01%
CHEMISTRY SOLID STATE | 8
Cubic unit cell Distance between Radius of the No. of particles Percentage of occupied
nearest neighbours (d) particle (atom) (atoms) per unit cell volume or packing efficiency
Simple a a/2 1 52.33%
Body – centred  
3 /2 a  
3 /4 a 2 68.00%

0.866 a = 0.433 a
Face–centred a/ 2 
a/ 2 2  4 74.01%
= 0.707 a = 0.3535 a

Close Packing in Solids

Packing in one dimension:

In one dimension, spheres are placed linearly in a horizontal row, touching each other as shown in fig. 1.3

Fig. 1.3

Packing in two dimensions:

(a) Square close packing: In this arrangement, the rows have horizontal and vertical alignment, Fig. 1.4
In this packing the coordination number is found to be 4 as each central sphere is in contact with four other
spheres.
(b) Hexagonal close packing: In this arrangement, the rows are so arranged that sphere in every second row
occupy the depressions between the spheres of first row (fig.1.5). The spheres in the third row are vertically
aligned with the spheres in the first row and those in the fourth row are vertically aligned with the spheres in
the second row. The similar pattern is followed throughout. Each sphere is surrounded hexagonally by six
other spheres. In this packing, the coordination number is 6.

Fig. 1.4 Fig. 1.5

Packing in three dimensions:

In order to develop three dimensional close packing, let us retain the
hexagonal close packing in the first layer. For close packing, each spheres in
the second layer rests in the hollow at the centre of three touching spheres in
the layer as shown in figure 1.6.
The spheres in the first layer are shown by solid lines while those in second
layer are shown by broken lines. It may be noted that only half of the
triangular voids in the first layer are occupied by spheres in the second layer
(i.e., either b or c). The unoccupied hollows or voids in the first layer are indicated by (c) in figure
There are two alternative ways in which species in third layer can be arranged over the second layer,
CHEMISTRY SOLID STATE | 9
(i) Hexagonal close packing: The third layer lies vertically above the first and the spheres in third layer rest in
one set of hollows on the top of the second layer. This arrangement is called ABAB type and 74% of the
available space is occupied by spheres.
(ii) Cubic close packing : The third layer is different from the first and the spheres in the third layer lie on the
other set of hollows marked ‘C’ in the first layer. This arrangement is called ABCABC. type and in this also
74% of the available space is occupied by spheres. The cubic close packing has face centred cubic (fcc) unit
cell. The coordination no. in both type of packing is l2.

Voids or Interstitial Voids or Interstitial Sites

In a close packing of spheres, there is always some empty space left. The empty space is called hole or void or
interstitial site. Common interstitial sites in closely packing spheres are tetrahedral and octahedral.
Number of octahedral voids = Number of constituent units at packing sites.
Number of tetrahedral voids = 2  Number of constituent units present at packing sites.

Example 1.5
Magnetite, magnetic oxide of iron used on recording tapes, crystallize with iron atoms occupying 1/8 of the
tetrahedral holes and ½ of the octahedral holes in a closed packed array of oxide ions. What is the formula
of the magnetite?
Sol. Let number of oxide ions in packing = n
 Number of tetrahedral voids = 2n
and Number of octahedral voids = n
1
Number of iron atoms =  number of octahedral voids
8
1 1
  2n   n
8 2
n n 3n
  
4 2 4
3n
Ratio of iron and oxygen atoms (Fe : O) =  :n 3 :4
4
 Molecular formula of magnetic = Fe3O4
CHEMISTRY SOLID STATE | 10
Example 1.6
In a cubic lattice, the closed packed structure of mixed oxides of the lattice is made up of oxide ions; one
eight of the tetrahedral voids are occupied by divalent ions (A2+) while one–half of the octahedral voids are
occupied by trivalent ions (B3+). What is the formula of the oxide?
Ans. Let there be 80 O2– ions in the crystal
Octahedral voids = 80
Tetrahedral voids = 160
1
A2+ ions = 160  20
8
1
B3+ ions =  80  40
2
A : B :O 2  20:40:80 1:2:4
2 3

 Molecular formula of oxide will be AB2O4

Example 1.7
In corundum, oxide ions are arranged in hcp array and the aluminium ions occupy two–third of octahedral
voids. What is the formula of corundum?
Ans. Number of O2– ions present in packing = n
 Number of octahedral voids = n
2
Number of Al3+ ion   n
3
2
Al3+ : O2–  n :n  2:3
3
 Simplest formula of corundum is Al2O3.

Derivation of the relationship between radius (r) of the octahedral void and the radius
(R) of the atoms in close packing:
An octahedral void is shown in fig.. The shaded sphere represents an octahedral void. Let the radius of the
void be r. Cross–section of octahedron is represented by square ABCD. Let the radii of the spheres used in packing
be R.
Length AB = Length BC = 2R
Length AC = 2R + 2 r
In  ABC, AC2 = AB2 + BC2
(2R + 2r)2 = (2R)2 + (2R)2
= 8 R2
or 2R + 2r = 8R
or 2r  8R  2 R
r
or  2 1 1.414 1  0.414
R
r
Thus, for an octahedral void, void  0.414
R sphere
CHEMISTRY SOLID STATE | 11
Practice Problems:
1. Magnetite, a magnetic oxide of iron used on recording tapes, crystallizes with iron atoms occupying 1/8 of the
tetrahedral holes and ½ of the octahedral holes in a closed packed array of oxide ions. What is the formula of
the magnetitle?
2. In cubic lattice, the closed packed structure of mixed oxides of the lattice is made up of oxide ions; one-eighth
of the tetrahedral voids are occupied by divalent ions (A2+) while one-half of the octahedral voids are occupied
by triavalent ions (B3+). What is the formula of the oxide?
3. In a crystalline solid anions ‘C’ are arranged in cubic close packing. cations ‘A’ occupy 50% of tetrahedral
voids and cations ‘B’ occupy 50% of octahedral voids. What is the formula of the solid?
4. In corundum, oxide ions are arranged in hcp array and the aluminium ions occupy two third of octahedral
voids. What is the formula of corundum?
5. In a solid oxide ions (O2-) are arranged in ccp. Cations (A3+) occupy one-sixth of the tetrahedral void and
cations (B3+) occupy one-third of the octahedral voids. What is the formula of the compound.
6. In chromium (III) chloride CrCl3, the chloride ions have a ccp arrangement. Cr3+ ions are present in the
octahedral voids. What fraction of octahedral voids and what fraction of total voids are occupied?
2
7. In a cpound atoms of element Y from ccp lattice and those of element X occupy rd of tetrahedral voids.
3
What will be the simplest formula of the compound?
8. Ferric oxide crystallizes in hexagonal closed packed array of oxide ions with two out of every three octahedral
holes occupied by ferric ions. Derive the formula of ferric oxide
9. A solid is made of two elements P and Q. Atoms ‘Q’ are present in ccp arrangement while atoms P occupy all
the tetrahedral voids. What is the formula of the compound?
10. A solid between A and B has the following arrangement of atoms:
(i) Atoms A are arranged in ccp array
(ii) Atoms B occupy all the octahedral voids and half the tetrahedral voids.
What is the formula of the compound ?
11. In an ionic compound the anions B form a close packed lattice and the cations A occupy one half of the
tetrahedral voids. What is the formula of the compound?
2
12. Atoms of element B from hcp lattice and those of the element A occupy of tetrahedral voids. What is the
3
formula of the compound formed by the elements A and B?

Calculation of Density of Cubic Crystal from its structure:

By knowing the edge of a cubic crystal from X–ray studies and the type of crystal whether it is simple cubic or
body–centred cubic or face–centred cubic, i.e., if number of particles present in a unit cell are known, the
density of the crystal can be calculated.
Let the edge length of the cubic unit cell be = a cm
 Volume of the cubic unit cell = a3 cm3
Mass of unit cell
Density of the unit cell =
Volume of thecell
Mass of the unit cell = Number of atoms in unit cell × Mass of each atom
= Z × Mass of each atom
Let the atomic mass of an element be = M
Atomic mass M
 Mass of one atom = 
Avogadro 's number N A
Z M / NA Z M
Density of unit cell,    3 g cm 3
a3 a  NA
CHEMISTRY SOLID STATE | 12
Example 1.8
An element crystallizes in a structure having a fcc unit cell of an edge 200 pm. Calculate its density of 200 g
of this element contains 24 × 1023 atoms.
Mass of unit cell
Sol. Density of a unit cell =
Volume of unit cell
200
Mass of one atom = g
24 1023
Z for fcc unit cell = 4
4  200
 Mass of unit cell =  33.31023 g
24 10 23

Volume of unit cell = a3 = (200 × 10–10)3 cm3 = 8 × 10–24 cm3

33.310 23
 Density of unit cell =  41g cm 3
8 1024
Example 1.9
Calculate the value of Avogadro's number from the following data:
Density of NaCl = 2.165 g cm–3,Distance between Na+ and Cl– ions in NaCl crystal = 281 pm
Ans. NaCl has fcc structure. Therefore, number of formula units or molecules per unit cell. Z = 4
Formula mass, M = 23 + 35.5 = 58.5
Edge length of the unit cell

= 2 rNa   rCl 
= 2 × distance between Na+ and Cl– ions
= 2 × 281 = 562 pm = 562 × 10–10 cm
Applying the formula
Z M 4  58.5
NA  3 
 
a  562 1010 3  2.165

= 6.09 × 1023
Example 1.10
The density of a face centred cubic element is 6.25 g cm–3. Calculate the length of the edge of the unit cell.
(At. mass of the element = 60.2 amu)
Ans. Applying the formula
Z  M  Zfor fcc  4;M  60.2amu ;   6.25g cm 
3
3
a =  
 N A  N A  6.02 1023 ;a  length of theedge  ? 
1/3
 4  60.2 
a  23 
 0.25  6.02 10 
= 400 × 10–10 cm = 400 pm
CHEMISTRY SOLID STATE | 13

Practice Problems:
1. Edge length of unit cell of NaCl crystal lattice is 5.6 Å. The density is 2.2 g cm-3. Find the number of formula
units of NaCl per unit cell.
2. Lead (II) sulphide crystal has NaCl structure. What is its density? The edge length of the unit cell of PbS
crystal is 500 pm. (NA = 0.23 × 1023, atomic mass : Pb = 207.2, S = 32)
3. An element crystallizes in a structure having a fcc unit cell of an edge 200 pm. Calculate its density if 200 g of
this element contains 24 × 1023 atoms
4. Calculate the value of Avogadro’s number from the following data :
Density of NaCl = 2.165 g cm-3
Distance between Na+ and Cl- ions in NaCl crystal = 281 pm
5. A metal crystallizes as face-centred cubic lattice with edge length of 450 pm. Molar mass of metal is
50 g mol-1. Find the density of metal.
6. The nearest neighbor silver atoms in silver crystal are 2.87 × 10-10 m apart. What is the density of silver? Silver
crystallizes in fcc form (atomic mass of Ag = 108)
7. The edge of length of the unit cell is 408 pm. Its density is 10.6 g cm-3 Predict whether the metal ‘X’ is
body –centred or face-centred or simple cubic, molar mass of metal X = 107.9 g mol-1 and NA = 6.023 × 1023
8. Chromium forms cubic crystals whose unit cell has an edge length of 289 pm. Density of chromium is
7.20 g cm-3. Calculate the number of atoms per unit cell of chromium assuming that all atoms are at the lattice
points. Also predict the type of crystal structure of chromium (At mass of Cr = 52)
9. A metallic element exists as body-centred cubic lattice. Each edge of the unit cell is 288 pm. The density of the
metal is 7.2 g cm-3. How many atoms and unit cells are there in 100 g of the metal?
10. The density of a face centred cubic element is 6.25 g cm-2. Calculate the length of the edge of the unit cell
(At. mass of the element = 60.2 amu)
11. KF crystallizes as NaCl structure. Compute the edge length of the unit cell if the density is 2.48 g cm-3. What is
the distance between K+ and F– ions in KF? Molar mass of KF is 58 g mol-1
12. An element has a body-centred cubic (bcc) structure with cell edge of 288 pm. The density of the element is
7.2 g cm-3 How many atoms are present in 208 g of the element?
13. KBr has NaCl type structure. What is the distance between K+ and Br- in KBr, if the density is 2.75 g cm-3?
14. Thallium chloride TICI crystallizes in either a simple cubic lattice or a face centred cubic lattice of Cl– ions
with TI+ ions in the holes. If the density of the solid is 9 g cm-3 and edge of the unit cell is 3.85 × 10-8 cm, what
is the unit cell geometry?
15. A metallic element has cubic lattice, edge length of lattice cell is 2 Å. The density of metal is 2.4 g cm-3 . How
many unit cells are present in 200 g metal?
16. KF has NaCl structure. Its density is 2.48 g cm-3. Find distance between K+ and F– ions in KF
17. Find the type of lattice for the cube having edge length of 400 pm atomic mass of element 60 amu and density
6.25 g/cc.
18. MgO has NaCl structure and its unit cell edge length is 421 pm. What is its density?
19. Sodium crystallizes in the cubic lattice and the edge length of the unit cell is 430 pm. Calculate the number of
atoms in a unit cell.
(atomic mass of sodium = 23 amu, density of sodium = 0.9623 g cm-3 and NA = 6.023 × 1023)
20. Calculate the distance between Na+ and Cl- ions in NaCl crystal if the density is 2.165 g cm-3
Molar mass of NaCl = 58.5 g mol-1 NA = 6.023 × 1023
21. Compound AB2 has CaF2 type structure. Write the coordination number of A2+ and B- ion
22. Tungsten has a density of 19.35 g cm-3 and the length of the side of the unit cel is 316 pm. The unit cell is a
body centred unit cell. How many atoms does 50 gm of element contain?
23. A compound CuCl has face-centred cubic structure. Its density is 3.4 g cm-3. What is the length of unit cell?
24. An element of atomic mass 40 occurs in focc structure with a cell edge of 540 pm. Calculate the avogadro’s
number if density is 1.7 g/cm3
25. A face centred cubic element (atomic mass 60) has a cell edge of 400 pm. What is the density of unit Cell?
CHEMISTRY SOLID STATE | 14

Imperfection in Solids:
An ideal crystal is one which has the same unit cell containing the same lattice points across the whole crystal.
Any departure from perfectly ordered arrangement of constituent particles in the crystals is called imperfection or
defect.
When the deviations exists in the regular or periodic arrangement of the constitutent particles (atoms or ions)
in the crystal, these defects are termed as atomic imperfections or point defects.

Types of points defects:

Point defects are classified into the following three types :
(A) Stoichiometric defects,
(B) Non stoichiometric defects,
(C) Impurity defects.

(A) Stoichiometric defects:

The crystals in which cations and anions are exactly in the same ratio as indicated by their molecular formulate
are termed as stoichiometric crystals. Point defects do not alter the stoichiometry of the solid. Two types of point
defects are observed in these crystals:
(i) Schottky defect
(ii) Frenkel defect.

(i) Schottky defect :

In this defect equal number of cations and anions are missing from their normal lattice sites. Due to
Schottky defect, the density of crystalline solid decreases.
This defect is usually observed in strongly ionic compounds which have high coordination number and
the size of two ions (cations and anions) is almost same.
(ii) Frenkel defect :
This defect is caused if some of the ions (usually the cations) of the lattice occupy iterstitial sites leaving
a corresponding number of normal lattice sites vacant.
This defect is usually observed in compounds which have low coordination number and the size of anion
should be bigger than cation.
Examples : This defect is not found in alkali metal halides because cations and anions have almost
equal sizes and cations cannot be accommodated in interstitial sites. This defect is mainly found in
transition metal halides like AgCl, AgBr, AgI, ZnS, etc. Silver ion (Ag+) being smaller in size can be
accommodated in interstitial site. There is no change in the density of the solid.
AgBr shows both Frenkel and Schottky defect.
CHEMISTRY SOLID STATE | 15
(B) Non stoichiometric defects:
The compounds in which the number of positive and negative ions are not exactly in the ratio as indicated by
their chemical formulae are called non–stiochiometric compounds
Non–stoichiometric defects are of two types:
1. Metal excess defect : In this defect, metal ions or cations are in excess. This defect may develop on
account of the following two ways:
(a) Anion vacancies : A negative ion may be missing from its lattice site leaving behind a vacancy or
hole. This vacancy or hole is occupied by an extra electron to maintain electrical neutrality. This
defect is somewhat similar to Schottky defect but differs in having only one hole and not a pair as
in the latter case.
Anion vacancies in alkali metal halides are produced by heating the metal halides in the
atmospheres of alkali metal vapours. Meal atoms get absorbed on the surface of the metal halides.
Halide ions move towards the surface and combine with metal ions formed by the adsorbed atoms
on account of their ionization. The electrons released in the process diffuse into the crystal and
occupy anion vacancies. The electrons trapped in anion vacancies are referred to as F–centres. 'F'
stands for Farbe, a German word, meaning colour, For example, non–stoichiometric sodium
chloride with excess sodium is yellow, non–stoichiometric potassium chloride with excess of
potassium is violet and non–stoichiometric lithium chloride with excess of lithium is pink.
(b) Excess cations occupying interstitial positions : Metal excess defect may also be developed by
the presence of extra cation in the interstitial site.
For example, when ZnO is heated, it loses oxygen and turns yellow.
ZnO  Zn2+ + (1/2)O2 + 2e-
The Zn2+ ions thus formed occupy interstitial sites and the electrons occupy the neighbouring
interstitial sites.
2. Non–metal excess or metal deficiency defect : These defect contains lesser number of positive
particles than negative particles. These defects arise due to cation vacancies or anions occupying
interstitial sites.

(C) Impurity defects in ionic crystalline solids:

A defect in an ionic solid can be introduced by adding foreign ions. If the impurity ions have a different
oxidation state than that of the host ions, vacancies are created. For example, if molten NaCl containing a little
SrCl2 or CaCl2 as impurity is allowed to cool, some lattice sites will be occupied either by Ca2+ ions or Sr2+
ions are removed in the crystal lattice in order to maintain electrical neutrality. Thus, one of these lattice sites
in occupied by Ca2+ or Sr2+ ions and the other site remains vacant.

Cationic vacancies developed due to introduction of impurity cause higher electrical conductivity of ionic
solids. Addition of about 0.1% SrCl2 to NaCl increases the electrical conductivity by 10000 times. Solid
solution of CdCl2 and AgCl is another example of this type of impurity defect.
CHEMISTRY SOLID STATE | 16
Example 1.11
Analysis shows that a metal oxide has the empirical formula of M0.96O1.00. Calculate the percentage of
M2+ and M3+ ions in this crystal.
Ans. Let the number of M2+ and M3+ ions are x and (0.96 – x). Total charge of the oxide will be zero.
 x × (+2) + (0.96 – x) (+3) + 1(–2) = 0
2x + 2.88 – 3x – 2 = 0
x = 0.88
Number of M2+ ions = 0.88
Number of M3+ ions = 0.96 – 0.88 = 0.08
0.88
Percentage of M2+ ions = 100  91.66 %
0.96
Percentage of M3+ ions = 100 – 91.66 = 8.34%

Example 1.12
The composition of a sample of Wustite is Fe0.93O1.00. What percentage of iron is present in the forms of
Fe(III)?
Ans. In wustite both Fe2+ and Fe3+ ions are present.
Let x atoms of Fe3+ ions be present
 Number of Fe2+ ions = (0.93–x)
Number of O2– ions = 1
For electrical neutrality of the compound,
Total positive charge contributed by Fe2+ and Fe3+ ions
= Total negative charge contributed by O2– ions
i.e., 3x + (0.93 – x) × 2 = 2
or x + 1.86 = 2
or x = (2 – 1.86) = 0.14
0.14
% of Fe3+ ions = 100 15.05
0.93

Properties of Solids

1. Electrical properties of solids (Conductions in solids):

The capacity of a substance to allow the flow of current is measured in terms of its conductivity. On the basis
of the ability of current conduction, solids are classified as conductors, semiconductors and insulators. The
conductivity of the solids varies from 108 ohm–1 cm–1 for metals to 10–12 ohm–1 cm–1 for insulators.
(a) Concutors: Substances which allow the passage of electric current to a large extent through them are
called conductors. The conductors are of two types:
(i) Metallic or electronic conductors : Conductors which transfer electric current by transfer of
electrons, without transfer of any matter, are known as metallic or electronic conductors. Metals
such as copper, silver, aluminium etc., non–metals like graphite and various alloys belong to this
class. These materials contain free electrons which are responsible for conduction of electricity.
Conductivity of metals is nearly independent of the presence of impurity and lattice defects. It has
been observed that the conductivity of the metals decreases with increase of temperature. Metals
have fixed kernels at the lattice sites.
M   M n   ne 
Kernel Free electrons

At high temperatures, the kernels start vibrating and create obstruction in the flow of electrons
and thus, resistance increases.
CHEMISTRY SOLID STATE | 17
(ii) Electrolytic conductors: Ionic solids like NaCl, KCl, etc. are bad conductors in pure state but
when defects are present in crystals, they conduct electric current to a small extent. However,
when ionic solids are present in aqueous solutions or in a molten state, ions become free to move
and conduct electric current, i.e. ions are current carriers. The ionic solids are thus called
electrolytic conductors. In electrolytic conductors, chemical decomposition occurs as the ions are
discharged at the respective electrodes. Cations undergo reduction at cathode while anions
undergo oxidation at anode.
(b) Insulators : The solids which almost do not allow the electric current to flow through them, i.e. their
conductivity is negligible or very small ( ̴ 10–12 ohm–1 cm–1) are termed insulators. Examples are: rubber,
wood, sulphur, phosphorus, plastics etc.
(c) Semiconductors: The solid materials whose electrical conductivity lies between those of the typical
metallic conductors and insulators are termed semiconductors. The semiconductors possess conductivity
in the range of 102 to 10–9 ohm–1 cm–1.
Semiconductors are of two types :
(i) Intrinsic semiconductors: These are insulators at room temperature and become semiconductors
when temperature is raised. For example, silicon and germanium are insulators under normal
conditions as they contain covalent bonds only and no free electrons are present (fig.1.12)
However, when heated, some covalent bonds are broken to give free electrons. These free
electrons make them as semiconductors.

(ii) Extrinsic semiconductors or impurity of lower or higher group element: These are formed by
adding impurity of either lower group element or higher group element.
(a) n–type semiconductors: Doping of higher group element impurity forms the n–type
semiconductor, e.g., when 'As' is doped in 'Ge' an extra electron of arsenic makes the
mixture of n–type semiconductor. Current carriers are negatively charged, hence called
n–type.
(b) p–type semiconductors: Impurity of lower group forms electron deficient bond in the
structure. Electron deficiency develops p–hole (positively charged hole). On application of
potential difference, these p–holes conduct electric current.
Explanation of conduction behavior on the basis of band model:
The atomic orbitals of solids combine to form molecular orbitals which are so close in energy to each other as
to form a band. The lowest lying empty band is called conduction band and the outermost filled band is called
valence band.
(i) In metals, the conduction band is very close in energy to the valence band. In other words, there is no energy
gap (forbidden zone has zero width) between valence band and the conduction band.
(ii) In case of insulators, the energy gap between valence band and conduction band is very large (wide forbidden
zone). Thus, electrons do not pass from valence band to the conduction band when a potential difference is
applied.
(iii) In semiconductors, the energy gap between valence band and conduction band is very small. At room
temperature, these are not good conductors of electricity. When temperature is raised a number of electrons of
valence band get sufficient energy to pass into conduction band and the substance behaves as a semiconductor.
Pure substances like silicon and germanium, which have such behavior, are called intrinsic semiconductors.
CHEMISTRY SOLID STATE | 18

Magnetic Properties of solids:

(i) Diamagnetic solids: The solids, which are weakly repelled by external magnetic field, are called
diamagnetic solids and the property thus exhibited is called diamagnetism.
In diamagnetic solids, all electrons have paired spins, i.e., only fully filled orbitals are present. Examples are :
NaCl, TiO2,ZrO2, KCl, etc.
(ii) Paramagnetic solids: The solids, which are weakly attracted by external magnetic field, are called
paramagnetic solids and the property thus exhibited is called paramagnetism.
In paramagnetic solids, there are permanent magnetic dipoles due to the presence of one or more unpaired
electrons in atoms, ions or molecules. Examples are: O2 NO, CuO, TiO, Ti2O3, VO2, Cu2+, Fe3+ , Cr3+, etc.
Paramagnetic solids lose their magnetism in absence of external magnetic field. Thus, these solids cannot be
permanently magnetized.
(iii) Ferromagnetic solids: The solids, which are strongly attracted be external magnetic field and do not lose
their magnetism when the external field is removed, are called ferromagnetic solids. The property thus,
exhibited is termed ferromagnetism.
Ferromagnetism arises due to spontaneous alignment of magnetic moments due to unpaired electrons in the
same direction as shown below Fig. 1.13

(iv) Antiferromagnetic solids: The solids which are expected to show paramgnetism or ferromagnetism on the
basis of unpaired electrons but actually have zero net magnetic moment are called antiferromagentic solids.
Magnetic moments are aligned in a compensatory way so as to give zero net magnetic moment.
Antiferromagnetism is due to the presence of equal number of magnetic moments in opposite directions as
shown below (fig.1.14). The important examples are : MnO MnO2, Mn2O3, NiO, CoO, etc.

(v) Ferrimagnetic solids: The solids which are expected to show large magnetism due to the presence of
unpaired electrons but in fact have small net magnetic moment are called ferrimagnetic solids. Ferrimagnetism
arises due to alignment of magnetic moments in parallel and antiparallel directions in unequal numbers
resulting in some net magnetic moment. This alignment has been shown below (fig. 1.15) Example are
Fe3O4 and ferrites of the formula M2+ ,Fe2O4 where M = Zn, Cu, Mg, etc.
Each ferromagnetic solid has a characteristic temperature above which it becomes paramagnetic. The
characteristic temperature is called Curie point or Curie temperature.
CHEMISTRY SOLID STATE | 19

Additional Questions
1.1 A compound is formed by two elements X and Y. Atoms of the element Y (as anions) make ccp and those of
the elements X (as cations) occupy all the octahedral voids. What is the formula of the compound?
Ans. Let n atoms of Y are present in ccp arrangement then number of octahedral voids will also be equal to n
 Number of atoms of X = n
X:Y=n:n
=1:1
 Simplest formula of the compound will be XY.

1.2 Atoms of element B form hcp lattice and those of the element 'A' occupy 2/3rd tetrahedral voids. What is
the formula of the compound formed by the elements A and B?
Ans. Number of atoms of B = n
Number of tetrahedral voids = 2n
2 4n
Number of atoms of A   2n 
3 3
4
A:B  :1
3
= 4:3
 Formula of the compound = A4B3

1.3 An element crystallizes in bcc structure. The edge length of its unit cell is 288 pm. If the density of the
crystals is 7.2 g cm–3, what is the atomic mass of the element?
Ans. Given: Z for bcc = 2 ; a = 288 pm = 288 × 10–10 cm
–3 23
 = 7.2 g cm , NA = 6.023 × 10
Applying the formula,
 a 3  N A
Atomic mass, M 
Z
 
3
7.2  2881010  6.0231023
=
2
= 51.79 g mol–1

1.4 Why is glass considered a supercooled liquid?

Ans. Like liquids, amorphous solids have a tendency to flow but very slowly. Glass being an amorphous solid is
sometimes called pseudo solid or supercooled liquid.

1.5 Refractive index of a solid is observed to have same value along all directions. Comment on the nature of
this solid. Would it show the cleavage property?
Ans. Amorphous solids are isotropic hence they have same value of refractive index in all directions. These solids
do not show the cleavage property. When cut with sharp knife or blade, they cut into two pieces with irregular
surfaces.

1.6 Solid A is very hard, electrical insulator in solid as well as in molten state and melts at extremely high
temperature. What type of solid is it?
Ans. Covalent or network solids like quartz (SiO2), diamond (Cn), aluminium nitride (AlN) are hard and have very
high melting points. These solids are insulators in solid as well as in molten state.
CHEMISTRY SOLID STATE | 20
1.7 Ionic solids conduct electricity in molten state but not in solid state. Explain
Ans. Ionic solids are bad conductors in solid state because ions are not free in solid state. However, in molten state,
the ions become free to conduct electric current.

1.8 Give the significance of "lattice point"

Ans. A regular three dimensional arrangement of points in space is called crystal lattice. Each point in lattice is
called lattice point or lattice site. Each lattice point represents one constituent unit (atom molecule or ion)

1.9 Distinguish between:

(i) Hexagonal and monoclinic unit cells
(ii) Face–centred and end–centred unit cell.
Ans. (i) Hexagonal unit cell:
a=bc
 = 90º  = 120º
Monoclinic unit cell :
c,  =  = 90º,   90º
(ii) In a face–centred unit cell, all the corners and centre of all the six faces are occupied by the constituent
units. However, in an end–centred unit cell, corners and centre of any two opposite faces are occupied.

1.10 Explain how much portion of an atom located at corners of a cubic unit cells is part of its neighbouring unit
cell.
Ans. Constituent unit at corners are common among 8 unit cells hence contribute 7/8 portion to the neighbouring
unit cell.

1.11 A compound forms a hexagonal closed–packed structure. What is the total number of voids in 0.5 mol of it?
How many of these are tetrahedral voids?
Ans. Number of constituent units in packing = 0.5 × 6.022 × 1023
Number of octahedral voids = 0.5 × 6.022 × 1023
Number of tetrahedral voids = 2 × 0.5 × 6.022 × 1023
Total number of voids = 9.033 × 1023

1.12 A compound is formed by two elements M and N. The element N forms ccp and atoms of M occupy 1/3rd of
tetrahedral voids. What is the formula of the compound?
Ans. Let number of atoms of N, present in packing is equal to x'.
Number of tetrahedral voids = 2x
1 2
Number of atoms of M   2x  x
3 3
2
M:N  x:x
3
= 2:3
 formula of compound = M2N3

1.13 What type of stoichiometric defect is shown by

(i) ZnS
(i) AgBr
Ans. (i) ZnS shows Frenkel defect.
(ii) AgBr shows both Schottky and Frenkel defect.
CHEMISTRY SOLID STATE | 21
1.14 Explain how vacancies are introduced in an ionic solid when a cation of higher valence is added as an
impurity in it.
Ans. When a cation of higher valency is added then two or more cations of lower valency are replaced to maintain
electrical neutrality, thus some cationic vacancies are produced, e.g. when CdCl2 is added to AgCl, cationic
vacancies are created because two Ag+ ions are replaced by a Cd2+ ion.

1.15 Ionic solids which have anionic vacancy due to metal excess defect, develop colour. Explain with the help of
a suitable example.
Ans. When NaCl is heated in the atmosphere of sodium vapour, sodium atoms are deposited on the surface of solid.
The Cl– ions diffuse to the surface of solid and combine with sodium atoms to form NaCl.
Na  Na+ + e–
Na+ + Cl–  NaCl
The electrons released, diffuse into the solid and occupy the anionic vacancy. The anionic vacancies occupied
by electrons are called F–centres. F–center is responsible for colour. NaCl with metal excess defect show light
yellow colour.

1.16 What type of substances would make better permanent magnets, ferromagnetic or ferrimagnetic. Justify
your answer.
Ans. Ans. Ferromagnetic materials would make better permanent magnets than ferrimagnetic materials because in
ferromagnetic solids, the magnetic moments of unpaired electrons spontaneously align themselves in same
direction. However in ferrimagnetic solids the magnetic moments of the domains are aligned in parallel and
antiparallel direction in unequal numbers.

1.17 What makes glass different from a solid such as quartz? Under what conditions could quartz be converted
into glass?
Ans. Glass is an amorphous solid while quartz is a crystalline solid. Quartz can be converted into glass by melting
and rapid cooling.

1.18 (i) What is meant by the term coordination number?

(ii) What is the coordination number of atoms:
(a) in a cubic close packed structure
(b) in a body centred cubic structure?
Ans. (i) The number of nearest neighbours of a particle in its close packing is called its coordination number.
In case of ionic solids, the number of oppositely charged ions surrounding each ion is termed its
coordination number
(ii) (a) 6 (b) 8

1.19 A cubic solid is made up of two elements P and Q. Atoms Q are present at the corners of the cube and
atoms P at the body–centre. What is the formula of the compound? What are the coordination numbers of
P and Q?
1
Sol. Contribution of Q atoms to the unit cell = 8  1
8
Contribution of P atoms to the unit cell = 1
Hence, the formula of the compound is PQ.
Coordination umber of both P and Q atoms in body–centred cubic unit cell (bcc) will be 8.
CHEMISTRY SOLID STATE | 22
1.20 Ferric oxide crystallizes in hexagonal close packed array of oxide ions with two out of every three
octahedral holes are occupied by ferric ions. What is the formula of ferric oxide?
Ans. Number of oxide (O2–) ions = n
Number of octahedral voids = n
2
Number of Fe3 ions  n
3
2
Fe3+ : O2– = n:n
3
=2:3
Formula = Fe2O3

1.21 Aluminium crystallizes in a cubic close–packed structure. Its metallic radius is 125 pm.
(a) What is the length of a side of the unit cell?
(b) How many unit cells are there in 1 cm3 of aluminium?
Ans. (a) In case of a cubic close packed structure, there will be a face– centred unit cell.
 a 2  4r
a 2 2 r
= 2 × 1.414 × 125 = 353.3 pm
(b) Volume of one unit cell = a3
= (353.3 × 10–10) cm3
= 4.416 × 10–23 cm3
Number of unit cells in 1 cm3 of aluminium
1
= 23
 2.2637 1022
4.417 10

1.22 If NaCl is doped with 10–3 mol per cent SrCl2, what is the concentration of cation vacancies?
Ans. 100 moles of NaCl are doped with 10–3 moles of SrCl2,
103
 1 mole of NaCl is doped with SrCl2 = 105 mol
100
As one ion in Sr2+ introduces one cation vacancy, therefore, concentration of cationic vacancy
= 10–5 × 6.022 × 1023
= 6.022 × 1018

1.23. How do the structures of quartz and quartz glass does not same?
Ans. Quartz is a crystalline solid in which constituent particles (SiO4 tetrahedra) are arranged in a regular manner
whereas glass is an amorphous solid in which the SiO4 tetrahedra do not have a long range order.

1.24. CaCl2 will introduce Schottky defect if added to AgCl crystal Explain
Ans. Two Ag+ ions will be replaced by one Ca2+ ions to maintain electrical neutrality. Thus a hole is created at the
lattice site for every Ca2+ ion introduced .

1.25. Give reason : (a) why is Frenkel defect found in AgCl?

(b) What is the difference between Phosphorus doped and Gallium doped semiconductors?
Ans. (a) Due to small size of silver cations (Ag+) .
(b) Silicon doped with phosphorus gives n-type whereas silicon doped with gallium forms p-type
semiconductors.
CHEMISTRY SOLID STATE | 23
1.26. Crystalline solids are anisotropic in nature. What does this statement mean?
Ans. An isotropic nature of crystalline solids means that properties like electrical conductivity, refractive index etc.
have difference values in different directions.

1.27. In a crystal, Frenked defect is not shown by akali metal halides but silver halides show. Why?
Ans. Frenkel defect is found in silver halides due to small size of Ag+ ion. It is not found in alkali metal halides, as
the alkali metal ions are too big to fit into the interstitial sites.

1.28. At what temperature range most of the metals becomes superconductors?

Ans. 2K – 5K

1.29. Examine the illustration of a portion of the defective crystal given in the fig.
and answer the following questions:
(i) What are these types of vacancy defect called?
(ii) How is the density of a crystal affected by these defects?
(iii) Name one ionic compound which can show this type of defect in the
crystalline state.
(iv) How is the stoichiometry of the compound affected?
Ans. (i) Schottky defect .
(ii) Density of the crystal decreases .
(iii) NaCl crystal .
(iv) Stoichiometry is not affected .

1.30. Calcium metal crystallizes in a face-centred cubic lattice with edge length of 0.556 nm. Calculate the density
of the metal if it contains (i) 0.5% Frenkel defects (ii) 0.2% Schottky defects.
Ans. (i) Frenkel defects have no effect on the density because number of atoms per unit cell remains the same
For FCC, Z = 4 For Ca, M = 40 g mol-1
Also, a = 0.556 nm = 0.556 × 10-7 cm
Z M 4 40 g mol 1
 Density, 𝜌  3   1.5458g cm 3

a  N A (0.55610 7 cm)3  6.02210 23 mol1 
(ii) If there were no defects (or there were only Frenkel defects ), number of atoms per unit = 4 (being FCC)
Due to 0.2% Schottky defect, number of atoms per unit cell decreases. Thus now number of atoms per unit cell
0.2
=  4  4  3.992
100
Z M (3.992) (40 g mol 1 )
 Density, 𝜌 =   1.5427 g cm 3
a 3  N 0 (0.55610 7 cm)3  6.0221023 mol1
 
CHEMISTRY SOLID STATE | 24

Answer Key

Introduction & Types of Unit cell

1. Sn, Ag 4. Solid ethane, (C2H6) Solid Silane (SiH4), Dry ice (Solid CO2)
5. Graphite 6. PQ3 7. A7B24
8. XY 9. AB 10. XY
11. AB4 12. AQR3 13. AuCu3
21
14. 1.5 × 10
15. Tetragonal – a = b  c,  =  =  = 90º Triclinic a  b  c,       90º
16. Orthorhombic 17. 9 18. 309 × 1022
19. AB3C 20. XY 21. 4

Octahedral & Tetrahedral Voids & Impurity Defect

1. Fe3O4 2. AB2O4 3. A2BC2
4. Al2O3 5. ABO3
1
6. fraction of total number of voids occupied = 7. X4Y3
3
8. Fe2O3 9. P2Q
10. AB2 11. AB 12. A4B3

Density of unit cell

1.  4 2. 12.7 g cm-3 3. 41.6 g cm-3
4. 6.09 × 1023 5. 3.64 g cm-3 6. 10.72 g cm-3
7. fcc 8. bcc 9. 5.81 × 1023
10. cm = 400 pm 11. cm = 268.7 pm 12. 2.418 × 1024
13. 3.3 × 10-8 cm 14. 1 15. 1.04 × 1025
16. 2.68 × 10-8 17. z = 4 4, fcc unit cell 18. 3.56 g cm-3
19. 2 20. 282 pm 21. A2+ (8), B-(4)
22. 1.64 × 1023 atoms 23. 5.783 Å 24. 6 × 1023
25. 6.23 g/cc