Chapter 5

The Solid State

Classification of Solids
Crystalline solid Amorphous solid
These have definite regular geometry
These do not have definite order
which extends throughout the crystals i.e.,
arrangement.
these solids have long range order.
They have sharp melting point They melt over a range of temperature.
These are aniso tropes i.e., their physical They are isotropic i.e., their physical
properties such as refractive index, properties such as refractive index
conductivity etc. have different values in conductivity etc. have same value in all the
different directions. directions.

Seven crystal systems: The seven crystal systems are given below.

Crystal System Bravais Lattices Parameters of Unit Cell

Intercepts Crystal angle
1. Cubic Primitive, Face Centered, Body Centered = 3 a = b = c  =  =  = 90o
Primitive, Face Centered, Body Centered,
2. Orthorhombic abc  =  =  = 90o
End Centered = 4
3. Tetragonal Primitive, Body Centered =2 a=bc  =  =  = 90o
 =  = 90o,
4. Monoclinic Primitive, End Centered = 2 abc
  90o
5. Triclinic Primitive = 1 abc       900
6. Hexagonal Primitive = 1 a=bc  =  = 900,  = 120o
7. Rhombohedral Primitive = 1 a=b=c  =  = 90o,   90o
Total = 14

Unit Cell

. Unit cells arranged together

The smallest amount of the solid whose properties resemble the properties of the entire solid irrespective
of the amount taken is called a unit cell. It is the smallest repeating unit of the solid.
Types of Cubic Unit Cell

Simple cubic or primitive unit cell

In primitive unit cell one atom is present at each corner of the unit
cell. Atom present at corner in primitive contributes 1/8 th of its total
volume to the unit cell, hence effective atom(s) in unit call is/are
1
given by  8   1
8
volumeof atom
Packing fraction  a
volume of unit cell
4 3
r
3 3
a
where ‘r’ is the radius of atom and ‘a’ is edge length of the unit cell, because in primitive unit cell a = 2r,
4 3
r
packing fraction  3
 2r 3


6
= 0.52 or 52%
This indicates that the void fraction in primitive unit cell is 48% and rest is occupied by atoms.

The co-ordination number in simple cubic (Primitive) unit cell is 6

Body centered cubic unit cell (BCC)

In BCC one atom is present at each corner and contributes 1/8 th of

its volume to the unit cell and one is present at centre and
contributed 100% to the unit cell, total atoms can be calculated as
1
 8 1 2 a3 a
8
volumeof atoms a2 a
Packing fraction  ,
volume of unit cell a
In given unit cell body diagonal is given by = a3
or a3 = 4r
4r
or a
3
4
2  r 3
Packing fraction  3
3 =0.68
 4r 
 
 3
If means in above unit cell 68% volume is occupied by atoms and rest 38% is void.
The co-ordination number is 8, atom present at body centre touches all the
corner atoms.

Face centred cubic unit cell or cubic close packing (fcc or ccp).

In this type of unit cell atoms are present at all corners and faces, corner atom contributes 1/8 th and
face centred atom contributes ½ of its total volume to unit cell, effective atoms can be calculated as.
1 1
 8  6  4
8 2
4
4  r 3
Packing fraction  3
a3 a
The face diagonal is given by =a2
a
or a2 = 4r
4r
or a 2 2r
2
4
4  r 3
Packing fraction  3
 
3
2 2r
= 0.74 or 74%
Hence 26% volume of unit cell is unoccupied.

Co-ordination number of any atom in fcc or ccp unit cell is 12

Hexagonal close packing unit cell

In hcp atoms are present at corners, top and bottom faces and inside the unit cell,
corner and face atoms contribute 1/6 and ½ of its total volume respectively and three
atoms situated inside the unit cell effectively contribute 100%, atoms can be calculated
as
1 1
 12   2   3  6
6 2
volume of atoms
Packing friction 
volume of unit cell
4
6  r 3
 3
area of base  height

Volume of unit cell

Area of base is formed by six equilateral triangles and each equilateral triangle has side length ‘a’
3 2
(a = 2r). The area of one triangle is a , hence area of the base is
4
 3 2
 6 a
4
3
 6  2r 2
4
Height of the unit cell is distance between centres of top and bottom face atoms
4 2
h
3

volume of unit cell = Area of base x height  24 2 r 3

4
6  r 3
Packing fraction  3  0.74
24 2r 3
Hence in hcp and fcc. (or ccp) percent occupancy (74%) and void fraction present are same.

Co-ordination number of any atom in hcp is also 12

Octahedral and Tetrahedral Voids

Tetrahedral and octahedral voids in FCC/CCP

In FCC total number of tetrahedral voids = 8

In FCC total number of octahedral voids = 4

Tetrahedral and octahedral voids in hcp

In hcp total number of tetrahedral voids = 12
In hcp total number of octahedral voids = 6

It is obvious that the number of tetrahedral voids in fcc and hcp will be twice the no of octahedral voids
and octahedral voids will be equal to effective number of atoms in fcc or hcp.

Radius Ratio Rules

Trigonal void (CN = 3)

r+ + r –

30
r–

r
 0.155
r
r
hence for trigonal void 0.155  < 0.225
r
Tetrahedral void (CN = 4)

A
(r+ + r)
5444’
B C
r– O

r
=0.2247 0.225
r
Hence for tetrahedral void
r
0.225    0.414
r

Square planer (CN = 4)/Octahedral void (CN = 6)

(r+ + r)
45°

r

r
 0.414
r
r
Hence for square planer and octahedral voids 0.414   0.732
r
Cubical void (CN = 8)
Anion

Cation

r
 0.732
r
r
Hence for cubical void 0.732  1
r
Calculation of Density of a System Crystal
Cubic Crystal
Let number of atoms per unit lattice = n
Mass of unit cell = number of atoms per unit cell (n) × Mass of one atom
Atomic Mass of Atom
Mass of each atom =
Avogadro's number NA
nM
Mass of unit cell =
NA
Mass of unit cell
Density of unit cell =
Volume of unit cell
Length of edge = a cm
Volume of cube = a3 cm3

nM
Density = gm/cc
NA  a 3

Classification of Ionic Structures

Rock Salt Structure
Cl- is forming a fcc unit cell in which Na+ is in the octahedral voids. The coordination number of Na+ is 6
and therefore that of Cl- would also be 6.

Zinc Blende Structure

Sulphide ions are face centered and Zinc is present in alternate tetrahedral voids. Formula is Zn 4S4, i.e,
ZnS. Coordination number of Zn is 4 and that of sulphide is also 4.

Fluorite Structures
Calcium ions are face centered and fluoride ions are present in all the tetrahedral voids. There are four
calcium ions and eight fluoride ions per unit cell. Therefore the formula is Ca 4F8, (i.e, CaF2).

Anti-Fluorite Structure
Oxide ions are face centered and lithium ions are present in all the tetrahedral voids. There are four oxide
ions and eight lithium ions per unit cell.

Cesium Halide Structure

Chloride ions are primitive cubic while the cesium ion occupies the center of the unit cell. There is one
chloride ion and one cesium ion per unit cell. Therefore the formula is CsCl. The coordination number of
cesium is eight and that of chloride ions is also eight.

Effect of Temperature and Pressure on Crystal Structure

1. As temperature increases the molecular forces are the ionic forces are lowered and there by the
coordination number decreases.
2. On increasing the temperature the particles are brought together and the coordination number
increases.
Imperfections in Solids
Defects in Stoichiometric Solids Stoichiometric solids are those in which the number of positive
and negative ions are exactly in the ratio indicated by their chemical formulae.
The causes give rise to two types of defects as:

Schottky defect
Frenkel defect
Schottky defect: A pair of ‘holes’ or vacancies exists in the crystal A
+
B
–
A
+
B
–
A
+

lattice due to one cation and one anion missing from the normal
lattice sites. The crystal as a whole remains neutral because the
– – + –
number of missing cations and anions remains the same. B B A B

This sort of defect occurs in highly ionic compounds with a high

coordination number and where the ions (both cations and anions) + – +
A B A
+
A
are of similar size.
Example: NaCl, KCl, KBr, and CsCl show this defect.
–
B
–
A+ B A
+
B
–

Frenkel defect: When a ‘hole’ or ‘vacancy’ exists in the crystal lattice because an ion occupies an
interstitial lattice site, it gives rise to Frenkel defect.
A+ B– A+ B– A+

A+
– – + –
B B A B

–
A+ B
–
A+ B A
+

B– A
+
B– A+ B–
.
The defect occurs more frequently in solids which have low coordination number and possess ions
(cations and anions) of different sizes. Since cations are generally smaller than anions, it is more
common to find the cations occupying the interstitial sites. For example, in AgBr and ZnS crystals,
Ag+ ions and Zn2+ ions are missing from their normal lattice sites and are present in the interstitial
positions.
AgBr, AgCl and AgI contains Schottky defects also.
Since the presence of Frenkel defects does not change the
number of ions in the lattice, the density of the solid
remains the same.
Metal Excess Defects

Metal excess due to anionic vacancies. A negative ion may be A

+
B– A
+
B
–

missing from its lattice site, leaving a hole which is occupied by an

A+
electron which was associated with the negative ion and remains –
B–
+
B A A+
trapped in the vacancy thereby maintaining the electrical neutrality.
–
When NaCl is treated with sodium vapours, a yellow coloured e
non-stoichiometric form of NaCl is obtained in which there is an A
+
B– A
+
B
–

excess of sodium ions.

– + – +
B A B A

Sodium atom removes chlorine atom from the anionic lattice site leaving its electron trapped in the
vacancy and makes the lattice excess of solid ions. Similarly excess of potassium in KCl makes the
crystal to appear violet and excess lithium in LiCl makes it pink. The electrons trapped in anion
vacancies are referred to as ‘F’ centres (F = Farben in German means colour).
These electrons absorb energy of the white light, giving yellow colour to NaCl, pink colour to LiCl
and violet colour to KCl.
 TEST YOUR KNOWLEDGE
UNIT CELL AND PROPERTIES

1. How many unit cells are present in 39 gm potassium that crystallizes in bcc structure?
NA
(A) NA (B)
4
NA 3N A
(C) (D)
2 4

2. The minimum distance of two face centre atoms in fcc lattice is ( a is the edge length of one unit
cell)
a
(A) a (B)
2
a a
(C) (D)
2 3

3. This figure is designed by placing four spherical

marbles of radius r. Then AC distance is ( a is A
the edge length of one unit cell)
(A) 3 r B D
(B) 2r
C
(C) 2 2r
(D) 2 3 r

4. The distance between edge centre and body centre octahedral void is
(A) a (B) 2a
a
(C) 2a (D)
2

5. The distance between two opposite tetrahedral voids is

3a
(A) 3a (B)
4
3a 2a
(C) (D)
2 4

6. What is the third possible nearest distance in fcc lattice of Fe? a  side length of cube
3 3
(A) a (B) a
2 2
a
(C) (D) none of these
2

7. In the closest packing of atoms A (radius: ra), the radius of atom B that can be fitted into
tetrahedral void is
 (A) 0.155 ra (B) 0.225 ra
(C) 0.414 ra (D) 0.732 ra

8. A crystal is made of particles x, y and z. x forms fcc packing. y occupies all the octahedral voids
and z occupied al tetrahedral voids. If all the particles along one body diagonal are removed, the
formula of crystal would be
(A) xyz2 (B) x2yz2
(C) x8y4z5 (D) x5y4z8

9. Coordination number of the atom in FCC is

(A) 12 (B) 6
(C) 8 (D) none of these

9. Fraction of total volume occupied by atoms in a simple cube is

 3
(A) (B)
2 8
2 
(C) (D)
6 6

10. In a given compound AB2, A++ ions are present at corners and faces in fcc unit cell, while B¯ is
present in tetrahedral voids, then co-ordination number of A and B are respectively
(A) 4, 6 (B) 8, 4
(C) 4, 8 (D) 6, 12

11. In a fcc arrangement of A & B atoms, where A atoms are at the Corners of the unit cell, B
atoms at the face centers, two atoms are missing from two corners in each unit cell, then the
simplest formula of the compound is
(A) A7B6 (B) A6B7
(C) A7B24 (D) AB4

12. In closest packing of A type of atoms (radius, r A), the radius of atom B that can be fitted into
Octahedral void is
(A) 0.155 rA (B) 0.125 rA
(C) 0.414 rA (D) 0.732 rA

13. An ionic compound AB has ZnS type of structure, if the radius A + is 22.5pm, then the
ideal radius of B- is
(A) 54.35pm (B) 100pm
(C) 145.16pm (D) None of these

DENSITY

14. The density of nickel (face centered cubic cell) is 8.94 g / cm 3. What is the radius of the atom?
(Atomic weight: Ni = 59)
(A) 0.124 nm (B) 0.136 nm
(C) 0.149 nm (D) 0.110 pm

15. The density of CaF2(fluorite structure) is 3.18 g / cm3. The length of the side of the unit cell is:
(A) 253 pm (B) 344 pm
(C) 546 pm (D) 273 pm
CRYSTAL LATTICE

16. Which of the following expressions is correct for an NaCl unit cell with lattice parameter ‘a’?
a
(A) rNa   rCl   (B) rNa   rCl   4a
2
a 3
(C) r r  (D) r r  a
Na  Cl  Na  Cl 
4 4

17. The CsCl type structure is exhibited by alkali halides only when the radius of the cation is large
enough to keep touching its eight nearest neighbour anions. The minimum ratio of cation to
anion radii (r+/r) is
(A) 0.225 (B) 0.414
(C) 0.632 (D) 0.732

18. An alloy of copper, silver and gold is found to have copper constituting the ccp lattice. If silver
atoms occupy the edge centres and gold is present at body centre, the alloy will have the
formula:
(A) Cu4Ag2Au (B) Cu4Ag4Au
(C) Cu4Ag3Au (D) CuAgAu

19. In sodium chloride unit cell, the incorrect statement is

(A) fcc unit cell is made by Cl¯
(B) sodium ions are present at octahedral voids
(C) the unit cell formula is Na4Cl4
(D) The edge length of unit cell is equal to (rNa  rCl )


20. Which of the following expression is correct in case of a CsCI unit cell (edge length, a)?
(A) rc + ra = a (B) rc + ra = a/2
3a
(C) rc + ra = (D) rc + ra = a/2
2

21. If a is the edge length of unit cell of sodium chloride, the distance between two nearest Na + and
CI ion is
(A) a (B) 2 a
(C) a/2 (D) 3 a

22. If a is the edge length of unit cell of sodium chloride, the distance between two nearest Na + ions
is
(A) a (B) 2 a
(C) 3 a (D) a/2

DEFECTS

23. Select the incorrect statement

(A) The C.N. of cation occupying a tetrahedral hole is 4
(B) The C.N. of cation occupying a octahedral hole is 6
(C) In Schotky defects, density of the lattice decreases.
(D) In Frenkel defects, density of the lattice increases.

24. In a solid, stoichiometic crystal lattice, a cation leaves its original site and moves to an interstitial
position. The lattice defect is called
(A) Frenkel defect (B) Schottky defect
 (C) Metal excess defect (D) Metal deficiency defect

25. Mark the false statement:

(A) CsCl crystal shows Schottky defect
(B) Crystal having F-centres are coloured and paramagnetic
(C) Photosensitivity of AgBr is due to the presence of Frenkel defect in this crystal
(D) None of these

26. Which of the following statements for crystals having Frenkel defect is not correct?
(A) Frenkel defects are observed where the difference in size of cations and anions is large
(B) The density of crystals having Fenkel defect is lesser than that of a pure perfect crystal
(C) In an ionic crystal having Frenkel defect may also contain Schottky defect
(D) Usually alkali halides do not have Frenkel defect

Assertion and Reason

In the following question, a statement of Assertion (A) is given which is followed by a
corresponding statement of reason (R). Mark the correct answer out of the following
options/codes.
(A) If both A and R are correct and R is correct explanation of A
(B) If both A and R are correct but R is not correct explanation of A
(C) If A is correct R is wrong
(D) If A is wrong R is correct

27. A: Fe3O4 is ferrimagnetic at room temperature but becomes paramagnetic at 850 K.

R: The magnetic moment in Fe3O4 are aligned equally in parallel and antiparallel directions
which on heating randomize

28. A: BaTiO3 is an example of pervoskite structure.

R: In BaTiO3, fcc is made by T14+.

29. A: Schottky type defect is shown by crystals with high co-ordination number
R: In schottky defect equal number of cations and anions are missing from their lattice sites

30. A: Metals are generally good conductors of electricity

R: Electrical conductivity of metals is due to Schottky type defects

QUIZ
1. Which of the following expressions is correct for an NaCl unit cell with lattice parameter ‘a’?
(A) (B)
(C) (D)

2. The number of tetrahedral voids in HCP crystal

(A) 6 (B) 8
(C) 10 (D) 12

3. If ‘a’ is the length of the unit cell and r is the radius of the metal atom, then which one is the
correct relationship?
(A) For SC lattice, r = a/2 (B) For BCC lattice, r = 3a/4
(C) For FCC lattice, r = a/22 (D) All of these
4. The unit cell cube length for LiCl (just like NaCl) is 5.14 A Assuming anion – anion contact, the
ionic radius for chloride ion is
(A) 1.815 A (B) 2.57 A
(C) 3.8 A (D) 4.815 A

5. In a compound oxide ions have cubic close packing arrangement. Cations A are present in half
of the tetrahedral holds and cation B occupy the octahedral holes. The simplest formula of the
compound
(A) AB2O4 (B) A2BO4
(C) ABO2 (D) ABO

6. TlCl exist in a cesium chloride lattice. The number of Cl - ions present per unit cell equal is
(A) 1 (B) 2
(C) 4 (D) 6

7. CsBr has bcc structure with edge length 4.3 unit. The shortest inter ionic distance in between
Cs+ and Br– is
(A) 3.72 (B) 1.86
(C) 7.44 (D) 4.3

8. Packing fraction of BCC lattice is

(A) 0.51 (B) 0.62
(C) 0.68 (D) 0.74

1. The density of nickel (face centered cubic cell) is 8.94 g / cm3. What is the radius of the atom?
(Atomic weight: Ni = 59)
(A) 0.124 nm (B) 0.136 nm
(C) 0.149 nm (D) 0.110 pm

2. If the ratio of coordination number of A to that of B is x:y, then the ratio of number of atoms of A
to that number of atoms of B in unit cell is
(A) x:y (B) y:x
(C) x2:y (D) y :x2

3. In the closest packing of atoms A (radius: ra), the radius of atom B that can be fitted into
tetrahedral void is
(A) 0.155 ra (B) 0.225 ra
(C) 0.414 ra (D) 0.732 ra

4. The CsCl type structure is exhibited by alkali halides only when the radius of the cation is large
enough to keep touching its eight nearest neighbour anions. The minimum ratio of cation to
anion radii (r+/r) is
(A) 0.225 (B) 0.414
(C) 0.632 (D) 0.732

5. An alloy of copper, silver and gold is found to have copper constituting the ccp lattice. If silver
atoms occupy the edge centres and gold is present at body centre, the alloy will have the
formula:
(A) Cu4Ag2Au (B) Cu4Ag4Au
(C) Cu4Ag3Au (D) CuAgAu

6. Which of the following statements is correct in the zinc blende type structure of an ionic
compound?
 (A) Co-ordination number of each cation and anion is two
(B) Co-ordination number of each cation and anion is four
(C) Co-ordination number of each cation and anion is six
(D) Co-ordination number of each cation and anion is eight

7. A certain sample of cuprous sulphide is found to have composition Cu1.8S, because of

incorporation of Cu2+ ions in the lattice. What is the mole % of Cu 2+ in total copper content in this
crystal?
(A) 99.8% (B) 11.11%
(C) 88.88% (D) none of these

8. When heated above 916C, iron changes its bcc crystalline form to fcc without the change in the
radius of atom. The ratio of density of the crystal before heating and after heating is:
(A) 1.069 (B) 0.918
(C) 0.725 (D) 1.231

9. The density of a pure substance ‘A’ whose atoms pack in cubic close pack arrangement is 1
g/cc. If B atoms can occupy tetrahedral void and if all the tetrahedral voids are occupied by ‘B’
atom. What is the density of resulting solid in g/cc. [atomic mass (A) = 30 g / mol and atomic
mass (B) = 50 g/mol]
(A) 3.33 (B) 4.33
(C) 2.33 (D) 5.33

10. The density of CaF2(fluorite structure) is 3.18 g / cm3. The length of the side of the unit cell is:
(A) 253 pm (B) 344 pm
(C) 546 pm (D) 273 pm

11. A crystal of lead (II) sulphide has NaCl structure. In this crystal the shortest distance between a
Pb2+ ion and S2- ion is 297 pm. What is the volume of unit cell in lead sulphide?
(A) 209.6 10-24 cm3 (B) 207.810 - 23 cm3
(C) 22.310 - 23 cm3 (D) 209.810 - 23 cm3

12. Potassium metal crystallizes in the form of a body-centered cubic structure. The number of
nearest neighbour atoms for each potassium atom in the solid is
(A) Four (B) Six
(C) Twelve (D) Eight
 TEST YOUR KNOWLEDGE
1. C
2. C
3. C
4. D
5. B
6. A
7. B
8. D
9. A
9. D
Sol.: In simple cubic arrangement, no. of atoms = 1
a = 2r
4 3 4 3
r r
Volume occupied by one atom 
Packing fraction = = 3 3  3 3 
Volume of unit cell a (2r ) 6
10. C
Sol.: Because B is present in tetrahedral void., so its coordination number is 4.
1
co-ordination number ratio =
Atoms ratio
1
=
½
2
=
1
co-ordination number of A x 2
 
co-ordination number of B 4 1
or x = 8
11. D
Sol.: Since there are six atoms (A) in the corner of the unit cell. So, contribution of atoms in 1 unit
6
cell is .
8
Since 3 face-centered atoms (B) contributes to one unit cell
So, formula is A6/8 B3
or A6 B24, or AB4
12. C
Sol.: For octahedral void
rB
 0.414
rA
or, rB = 0.414 rA
13. B
Sol.: Since ionic compound AB has ZnS type of structure, therefore it has it has tetrahedral holes,
for which,
radius of cation
= 0.225
radius of anion
r
= 0.225
r
22.5
= 0.225
r
Hence, r– = 100 pm
14. A
15. C
16. A
17. D
18. C
19. D
Sol.: The edge length of unit cell is equal to 2rNa 2rCl
 

20. C
Sol.: CsCI crystallizes in body-centred cubic unit cell. Hence 2rc + 2ra = 3 a, i.e. rc + ra  3a .
2
21. C
Sol.: For sodium chloride, r+ + r = a/2.
22. D
Sol.: The distance between two nearest Na + in sodium chloride unit cell is half of the face diagonal of
the cube, i.e. 2 a / 2  a / 2 .
23. D
Sol.: Since tetrahedral holes are surrounded by 4 nearest neighbours. So, the C.N. of cation
occupying tetrahedral hole is 4. Since octahedral hole is surrounded by six nearest
neighbours, so, C.N. of cation occupying octahedral is 6.
In schottky a pair of anion and cation leaves the lattice, so density of lattice decreases.
24. A
25. D
26. B
27. A
28. C
29. B
30. C

QUIZ
1. A
2. B
3. B
4. D
1. A
2. B
3. B
4. D
5. C
6. B
7. B
8. B
9. B
10. C
11. A
12. D