6.

SOLID STATE
 What are crystalline and amorphous solids?
 Crystalline solids:
Solids in which its constituents have an orderly arrangement over a long range are
called crystals.
 Amorphous solids:
Solids in which its constituents are randomly arranged are called amorphous solids.
 What is Isotropy and anisotropy?
 In solid state, Isotropy means identical values of physical properties in all directions.
 Anisotropy is the property which depends on the direction of measurement.
 Crystalline solids are anisotropic and they show different values of physical properties
when measured along different directions.
 Amorphous solids are isotropic and they show similar properties irrespective of the
direction of measurement.

 Differentiate crystalline solids and amorphous solids.

S.no Crystalline solids Amorphous solids
1 Orderly arrangement of Random arrangement of constituents.
constituents over a long range.
2 They have definite shape. They have Irregular shape.
3 Anisotropic in nature. Isotropic in nature.

4 True solids. Pseudo solids (or) super cooled liquids

5 They have definite heat of fusion They do not have definite heat of fusion
6 They have sharp melting points. Gradually soften over a range of temperature
and so can be molded.
7 Examples: NaCl , diamond etc., Examples: Rubber , plastics, glass etc

Unit -6 –solid state The Turning Point [1]

 Write a note on ionic solids.
❖ The structural units of an ionic crystal are cations and anions.
❖ They are bound together by strong electrostatic attractive forces.
❖ Ionic crystals possess definite crystal structure; many solids are cubic close packed.
Example: NaCl crystal.
 Give the characteristics of ionic crystals.
❖ Ionic solids have high melting points.
❖ They do not conduct electricity in solid state, because the ions are not free to move.
❖ They do conduct electricity in molten state or in solution because, the ions are free to
move.
❖ They are hard as only strong external force can change the relative positions of ions.
 Write a note on covalent solids.
➢ In covalent solids, the constituent atoms are connected by covalent bonds forming a
three-dimensional network.
➢ They are very hard, and have high melting point.
➢ They are usually poor thermal and electrical conductors: Diamond, SiC etc.
 Write a note on molecular solids.
 The constituents of molecular solids are neutral molecules.
 They are held together by weak van der Waals forces.
 They are soft and they do not conduct electricity.
 Explain the types of molecular solids.
a) Non-polar molecular solids:
❖ Molecules are held together by weak dispersion forces or London forces.
❖ They have low melting points, and are liquids or gases at room temperature.
❖ Examples: naphthalene, Anthracene etc.,
b) Polar molecular solids
 Molecules with polar covalent bonds are held together by relatively strong dipole-
dipole interactions.
 They have higher melting points than the non-polar molecular solids.
 Examples: solid CO2, solid NH3 etc. (Ref mcq # 4)
c) Hydrogen bonded molecular solids
 Molecules are held together by hydrogen bonds.
 They are generally soft solids under room temperature.
 Examples: solid ice (H2O), glucose, urea etc.,
 Give the characteristics of metallic solids?
❖ In metallic solids, the lattice points are occupied by positive metal ions and a cloud of
electrons spread around the metal ions.
❖ They are hard, and have high melting point.
❖ They are excellent electrical and thermal conductors.
❖ They possess bright lustre. Examples: Metals and metal alloys.

Unit -6 –solid state The Turning Point [2]

 Define unit cell.
The fundamental repeating structural unit of a crystalline solid is called a unit cell. A unit
cell is characterized by the three edge lengths (a, b & c) and the angle between the edges
α,β and  ( interfacial angles)

 Why ionic crystals are hard and brittle?

 The ionic crystals are hard, because the ions are held together by the strong
electrostatic forces of attraction between the cations and the anions as well as the
repulsion between the ions of like charges.
 If we apply a pressure on the ionic compounds the layers shift slightly. The similar
charged ions in the lattice comes closer. A repulsive force arises between them. This
repulsion will shatter the crystal lattice of the ionic compound.
 What are Primitive and non-primitive unit cell?
 A unit cell in which only the corner positions are occupied by constituents is called a
primitive unit cell.
 A unit cell in which constituent particles present either at body Centre or at face
centers in addition to those at corners is called non-primitive unit cell.

 Write the Bragg’s equation? Explain the terms in it.

The fundamental equation that relates inter planar distance (d) in a crystal, the wave
length of X rays and the angle of diffraction is called a Bragg’s equation.
n = 2d sin 
Where
 the wavelength of X-ray ; θ -The angle of diffraction and d- inter planar distance

Unit -6 –solid state The Turning Point [3]

 Calculate the number of atoms in a simple cubic (SC) unit cell.

 In SC unit cell, each corner is occupied by identical constitutes.

 They touch along the edges of the cube and do not touch diagonally.
 The coordination number of each atom is 6.
1
 Each corner atom is shared by 8 neighboring unit cells, and makes ( ) contribution to
8

the unit cell.

 Nc 
 no of atoms in a SC unit cell = 
 8 
8
=   =1
8
 Calculate the number of atoms in a body centred cubic (BCC) unit cell.

 In a bcc unit cell, all the corners and a body center are occupied by constitutes. Those
atoms in the corners do not touch each other, however they all touch the one that
occupies the body Centre.
 Hence, each atom is surrounded by eight nearest neighbours and coordination number
is 8. An atom present at the body centre belongs to only to a particular unit cell.
 Nc   N b 
 Number of atoms in a bcc unitcell =  + 
 8   1 
 8  1
=  + 
 8  1
=2
Unit -6 –solid state The Turning Point [4]
 Calculate the number of atoms in a face centred cubic (FCC) unit cell.

 In a fcc unit cell, all the corners and all the face centers are occupied by identical
constitutes. Those atoms in the corners touch those in the faces but not each other.
 Each face centered atom is shared by two-unit cells and its share to the particular unit
1
cell is   .
 2 
 Each atom is surrounded by 12 nearest neighbours (coordination number is 12).

 Nc   Nf 
 Number of atoms in a fcc unitcell =   +  
 8   2 

8  6
= + 
8  2
=4
 How is the density of a unit cell calculated?
Using the edge length (a), the density ( ρ ) of the unit cell can be calculated.

ρ=
( Mass of the unit cell)
( Volume of the unit cell)
 Total No. of atoms   mass of 
  
ρ=
per unit cell   one atom 
( volume of the unit cell )
 Total No. of atoms   Molar Mass (gmol−1) 
  −

 per unit cell 
  Avagadro Number (mol ) 
1
ρ=
( volume of the unit cell )
 M
(n) 
ρ=  NA 
( a3 )
 nM 
ρ= 
 a3 N 
 A 

Unit -6 –solid state The Turning Point [5]

 Calculate the packing fraction in simple cubic crystal.
In SC unit cell, each corner is occupied by identical constitutes. They touch along the edges
of the cube and do not touch diagonally.

If the edge length of the unit cell is a.

𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 = 𝑎3
If the radius of the sphere is r then
𝑎
a = 2r ⇒ r = ( )
2
4
 Volume of the sphere with radius ‘r’ is V=   π r3
3

3
4
V =   π  
a
3  2
π
V =   a3
6
In a simple cubic arrangement, number of spheres belongs to a unit cell is 1
π
 Total volume occupied by the spheres in SC unit cell = 1    a3
6
 Total volume occupied by 
 
spheres in a unit cell
Packing fraction =    100
 Volume of the unit cell 
 
 
  a3 
 
 6 
Packing fraction =    100
a3 ( )
100 
=
6
= 52.33%
In simple cubic packing, the packing fraction is only 52.33%.

Unit -6 –solid state The Turning Point [6]

 Calculate the percentage efficiency of packing in case of body centred cubic crystal.
In bcc arrangement, the spheres are touching along
the leading diagonal of the cube.
Volume of the unit cell = a3
Length of the cube diagonal DF = 3 a
If the radius of the sphere is r then
4r = 3 a
3
r= a
4
 Volume of the sphere with radius ‘r’ is

4
V=   π r 3
3
3
4  3 
V= π  a 
3  4 
3
V= π a3
16
In a bcc arrangement, number of spheres belongs to a unit cell is 2
 3 π a3 
Total volume occupied by the spheres in unit cell =2   
 16 
 
3 π a3
=
8
 Total volume occupied by 

 spheres in a unit cell 
Packing fraction = 100
 Volume of the unit cell 
 
 
 3 π a3 
 
8
Packing fraction =   100
a 3
( )
3 1.732  3.14 × 100
= 100 =
8 8
= 68 %
In body centered cubic packing, the packing fraction is 68%. The available space is used more
efficiently than in simple cubic packing.

Unit -6 –solid state The Turning Point [7]

 IMPERFECTION IN SOLIDS
 What are point defects?
Irregularity (or) deviation from ideal arrangement around a point (or) an atom in a
crystalline substance is called as Point defect. Examples: Schottky defect, Frenkel defect,
metal excess defect, metal deficiency defect etc.
 Explain Schottky defect.

 Schottky defect arises due to the missing of equal number of cations and anions from
the crystal lattice.
 This defect is shown by the crystals in which the cation and anion are of almost of
similar size. Example: NaCl.
 This defect does not affect the stoichiometry of the crystal.
 Schottky defect lowers the density of a crystal.
 Write a note on Frenkel defect.

 Frenkel defect arises due to the dislocation of ions from their lattice points to
interstitial position.
 This defect is shown by the crystals in which cation and anion differ in their sizes.
Example AgBr.
 In AgBr, small Ag+ ion leaves its normal site and occupies an interstitial position.
 This defect does not affect the density of the crystal.

Unit -6 –solid state The Turning Point [8]

 Explain metal deficiency defect with an example.

 This defect arises due to the presence of lesser number of cations than the anions.
 This defect is observed in a crystal in which, the cations have variable oxidation states.
Example : FeO and FeS.
 In FeO crystal, some of the Fe2+ ions are missing from the crystal lattice. To maintain
the electrical neutrality, twice the number of other Fe2+ ions in the crystal is oxidized to
Fe3+ ions.
 In such cases, overall number of Fe2+ and Fe3+ ions is less than the O2- ions.
 Explain metal excess defect with an example.
 It arises due to the presence of excess of metal ions as compared to anions.
 The electrical neutrality of the crystal can be maintained by the presence of anionic
vacancies equal to the excess metal ions (or) by the presence of extra cation and
electron present in interstitial position. Examples: NaCl, KCl

✓ When NaCl crystals are heated in the presence of sodium vapour, ( Na )

+
ions are
formed and are deposited on the surface of the crystal.
✓ Chloride ions Cl ( ) diffuse to the surface from the lattice point and combines with
−

( Na ) ion.
+

Unit -6 –solid state The Turning Point [9]

 ✓ The electron lost by the sodium atoms diffuse into the crystal lattice and occupies the
( )
−
vacancy created by the Cl ions.
✓ Such anionic vacancies occupied by unpaired electrons are called F centers. They
impart yellow colour to NaCl crystal.
✓ Hence, the formula of NaCl can be written as Na Cl .
1+ x
 What are F centers? (or) What happens when sodium chloride crystal is heated in the
presence of sodium vapour?
( you can find answer from the above question)
 ZnO crystal is yellow when hot and white when cold. Account
• ZnO is colorless at room temperature. When it is heated, it becomes yellow in colour.
• On heating, it loses oxygen and thereby forming free Zn2+ ions.
• The excess Zn2+ ions move to interstitial sites and the electrons also occupy the
interstitial positions.
 Write a short note on Impurity defect.
 A general method of introducing defects in ionic solids is by adding impurity ions.
 If the impurity ions are in different valance state from that of host, vacancies are
created in the crystal lattice of the host.
 For example, addition of CdCl2 to silver chloride yields solid solutions where the
divalent cation Cd2+ occupies the position of Ag+. This will disturb the electrical
neutrality of the crystal. In order to maintain the same, proportional number of Ag +
ions leave the lattice.
 This produces a cation vacancy in the lattice, such crystal defects are called impurity
defects.
 What is coordination number? What is the coordination number of atoms in a bcc
structure?
The number of nearest neighbours that surrounding a particle in a crystal is called the
coordination number of that particle. In bcc structure each atom is surrounded by 8
neighboring atoms. Hence its coordination number is 8.

EVALUATION
Choose the best answer:
1. Graphite and diamond are
a) Covalent and molecular crystals b) ionic and covalent crystals
c) both covalent crystals d) both molecular crystals
2. An ionic compound A x B y crystallizes in FCC type crystal structure with B ions at the centre
of each face and A ion occupying entre of the cube. the correct formula of A x B y is
a) AB b) AB3
c) A3B d) A8B6

Unit -6 –solid state The Turning Point [10]

3. Solid CO2 is an example of
a) Covalent solid b) metallic solid
c) Molecular solid d) ionic solid
4. Assertion : monoclinic sulphur is an example of monoclinic crystal system
Reason: for a monoclinic system, a  b  c and  =  = 900 ,   900
a) Both assertion and reason are true and reason is the correct explanation.
b) Both assertion and reason are true but reason is not the correct explanation.
c) Assertion is true but reason is false.
d) Both assertion and reason are false.
5. In calcium fluoride, having the fluorite structure the coordination number of Ca2+ ion and F-
Ion are (NEET)
a) 4 and 2 b) 6 and 6
c) 8 and 4 d) 4 and 8
6. The number of unit cells in 8 gm of an element X ( atomic mass 40) which crystallizes in
bcc pattern is (NA is the Avogadro number)
a) 6.023 X 1023 b) 6.023 X 1022
 6.023 1023 
c) 60.23 X 1023 d)  
 8  40 
7. The number of carbon atoms per unit cell of diamond is
a) 8 b) 6 c) 1 d) 4

8. The composition of a sample of wurtzite is Fe0.93O1.00 what % of Iron present in the form of
Fe3+?
a) 16.05% b) 15.05% c) 18.05% d) 17.05%
9. The ionic radii of A + and B − are 0.98  10−10 m and 1.81  10−10 m . the coordination number
of each ion in AB is
a) 8 b) 2
c) 6 d) 4
10. CsCl has bcc arrangement, its unit cell edge length is 400pm, its inter atomic distance is
a) 400pm b) 800pm
 3
c) 3 100pm d)    400pm
 2 
11. The vacant space in bcc lattice unit cell is
a) 48% b) 23%
c) 32% d) 26%
12. The radius of an atom is 300pm, if it crystallizes in a face centred cubic lattice, the length
of the edge is
a) 488.5pm b) 848.5pm
c) 884.5pm d) 484.5pm

Unit -6 –solid state The Turning Point [11]

13. The fraction of total volume occupied by the atoms in a simple cubic is
   
a)   b)  
4 2 6
   
c)   d)  
 4  3 2 

14. The yellow colour in NaCl crystal is due to

a) Excitation of electrons in F centers b) Reflection of light from surface Cl- ions
c) Refraction of light from Na+ ion d) all of the above
15. if ‘a’ stands for the edge length of the cubic system ; sc , bcc, and fcc. Then the ratio of
radii of spheres in these systems will be respectively.
1
a)  a :
2 2
3
a:
2 
a
2 
b) ( 1a : 3a : 2a )
1 3 1  1 1 

c)  a : a : a  d)  a : 3a : a
 2 4 2 2  2 2 
16. if ‘a’ is the length of the side of the cube, the distance between the body centred atom and
one corner atom in the cube will be
 2   4   3  3
a)  a b)  a c)   a d)   a
 3  3  4   2 
17. Potassium has a bcc structure with nearest neighbour distance 4.52 A0.Its atomic weight is
39. its density will be
a) 915 kg m-3 b) 2142 kg m-3 c) 452 kg m-3 d) 390 kg m-3
18. Schottky defect in a crystal is observed when
a) Unequal number of anions and anions are missing from the lattice
b) Equal number of anions and anions are missing from the lattice
c) An ion leaves its normal site and occupies an interstitial site
d) No ion is missing from its lattice.
19. The cation leaves its normal position in the crystal and moves to some interstitial position,
the defect in the crystal is known as
a) Schottky defect b) F center
c) Frenkel defect d) non-stoichiometric defect
20. Assertion: due to Frenkel defect, density of the crystalline solid decreases.
Reason: in Frenkel defect cation and anion leaves the crystal.
a) Both assertion and reason are true and reason is the correct explanation.
b) Both assertion and reason are true but reason is not the correct explanation.
c) Assertion is true but reason is false.
d) Both assertion and reason are false
21. The crystal with a metal deficiency defect is
a) NaCl b) FeO c) ZnO d) KCl

Unit -6 –solid state The Turning Point [12]