Unit-I

THE SOLID STATE

POINTS TO BE REMEMBERED:-

IMPORTANT FORMULAE

Density of unit cell = Mass of unit cell = z×M

Volume of unit cell N a × a3

z- Number of atoms per unit cell M – Atomic mass or formula mass for ionic solids
Na – Avogadro number a – Edge length

Radius ratio = r+ = Radius of the cation

r- Radius of the anion


If R is the radius of spheres in the close packed arrangement then
I. Radius of octahedral void = r = 0.414 R
II. Radius of tetrahedral void = r = 0.225 R

Packing fraction = Volume occupied by atoms in unit cell
Total volume of the unit cell
 Different types of solids (table)

Unit cell Distance Radius Coordination Packing Number of
between constituent no. fraction constituent
nearest Atom Atoms
neighbour
(d)
Simple a a/2 6 0.52 1/8×8 = 1
cubic
Face 12 0.74 (1/8×8) +
a/ a/2
centred (1/2×6) = 4
cubic (FCC)
Body 8 0.68 (1/8×8) + 1
/2a /4a
centred =2
cubic (BCC)

Where , a = edge length of unit cell

Radius ratio Possible Structural Structural Coordination

r+ /r- condition no. arrangement type no.
0.225-0.414 4 Tetrahedral ZnS Zn2+= 4S2-

=4
0.414-0.732 6 Octahedral NaCl Na+ = 6Cl-

=6
0.732-1.0 8 cubic CsCl Cs+ = 8 Cl- = 8
 

*Types of point defects (flow chart)

*Classification of solids on basis of electrical properties (flow chart)
*Classification based on magnetic properties (flow chart)

Different Type Of Solids

Type of Constituent Bonding/ Examples Physical Electrical Melting
Solids Particles Attractive Nature Conductivity Point
Forces
1. Molecular
Solids
(i)Non -polar Molecules Dispersion or Ar, CCl4 , Soft Insulator Very
London H2 , I2 , Co2 low
forces
Soft Insulator
(ii)Polar Dipole-dipole HCl , SO2 Low
Interactions
Hard Insulator
(iii)Hydrogen Hydrogen H2O(ice) Low
bonded bonding

2. Ionic solids Ions Coulombic or NaCl, MgO Hard but Insulators in High
electrostatic Zns, CaF2 brittle solid state but
conductors in
molten state
and in aqueous
solutions
3. Metallic Positive ions Metallic Fe, Cu, Ag, Hard but Conductors in Fairly
solids In a sea of bonding Mg malleable solid state as high
delocalised and well as in
electrons ductile molten state

4. Covalent or Atoms Covalent SiO2(quartz), Hard Insulators Very

Network bonding SiC , high
solids C(diamond),
AIN,
C(graphite) Soft Conductor
 (exception)

Classification of solids on basis of electrical properties

Conductors Semi-conductors Insulators

Inductivity of conductivity Intermediate conductivity ranging very low conductivity ranging

the order of 10 7(ohm.m)-1 from 10 -6 to 104(ohm.m)-1 between 10 -20 to 10-10(ohm.m)-1

conduction conduction Empty conduction

band band band band

small energy gap forbidden zone

Partially Overlapping (large energy gap)

filled band bands filled band filled band

Intrinsic semi-conductors
Cause of conductors ( electrical conducting of semi-conductors
number of valence increases with rise in temperature since
electron more electrons can jump to the conduction
 band) e.g. Si and Ge
conductivity can be increased by doping i.e., adding

impurity in appropriate amount to intrinsic semi-conductors

n – type p – type
adding electron rich impurities adding electron-deficit impurities
e.g. adding Group 15 members to e.g. adding Group 13 members to
Group 14 members Group 14 members

Positive hole
Mobile electron
(no electron)
As
B

Classification based on magnetic properties

Paramagnetic Diamagnetic Ferromagnetic Ferrimagnetism

- weakly attracted by a - weakly repelled by a - attracted strongly by - magnetic moments of

magnetic field magnetic field magnetic field all domains align in

- lose magnetism in - all electrons are - can be permanently parallel and anti-parallel

absence of magnetic paired therefore lose magnetised direction in equal numbers

field their magnetic character - metal ions are grouped - weakly attracted by

- due to presence of - e.g. H 2O , NaCl , C6H6 etc. in small groups i.e., domains magnetic field

one or more unpaired - e.g., Fe3O4(magnetic

electrons attracted by ferrites like MgFe2O4 ,

magnetic field ZnFe2O44

e.g., O2 , Cu2+ , Fe3+ , Cr3+ etc.

VERY SHORT ANSWER TYPE QUESTION

(1 marks)
1. What is the total number of atoms per unit cell in a face centred cubic ( fcc ) crystal
structure?
Ans : 4
2. What is the co-ordination number of each ion in a rock-salt type structure ?
Ans : 6 : 6 or 6
3. Which point defect of its crystal decreases the density of a solid ?
Ans : Schottky defect
4. How do metallic and ionic substances differ in conducting electricity ?
Ans : Metallic solid conducts electricity in solid state but ionic solids do so only in
molten or solution
OR
 Metals conduct through electrons and ionic substance through ions
5. Name the non-stoichiometric point defect responsible for colour in alkali halides .
Ans: F-centres
6. A compound AB2 possesses the CaF2 type crystal structure. Write the co-

ordination number of A2+ and B- ions in its crystals.

Ans : Co-ordination number of A = 8 & B = 4
7. Name the type of point defect that occurs in a crystal of zinc sulphide.
Ans :Frenkel defect
8. On heating crystals of KCl in potassium vapours, the crystal starts exhibiting a violet
colour, why ?
Ans : As there are excess of K+ which attract Cl- and electrons are trapped at site of
anion and electrons are trapped at site of anion
forming F-centre.
9.Name a salt that can be added to AgCl so as to produce cation vacancies.
Ans: CdCl2 or any other appropriate salt
10. What happens when a ferromagnetic substance is heated to high temperature?
Ans: Ferromagnetic substance changes to paramagnetic substance due to
randomisation of domains ( spins ) on heating.

SHORT ANSWER TYPE QUESTION

(2marks)
1. Account for the following :
(i) Silicon is an insulator but silicon doped with phosphorus acts as a semi-
conductor.
(ii) Some of the glass objects recovered from ancient monuments look milky
instead of being transparent.
Ans (i) Phosphorus atom (dopant) uses four of it’s  electrons for covalent bonding but
the fifth electron becomes delocalised and free to 
Conduct electricity. This produces n-type semi-conductor.
(ii) because crystallisation has occurred in them due to annealing i.e. heated and
cooled slowly.
2. The electrical conductivity of a metal decreases with rise in temperature while
that of a semi-conductor increases. Explain.
Ans :In metals, with increase of temperature, the kernels begin to vibrate and thus
offer resistance to the flow of electrons decreasing
conductivity. In semi-conductors with increase of temperature, more electrons can
move from valence band to conduction band
thus increasing conductivity.
3.A compound is formed by two elements X and Y. Atoms of the element Y (anions)
make ccp and those of the element X (cations)
occupy all the octahedral voids. What is the formula of the compound ?
Ans :Suppose no. of atoms Y in ccp = N

:. No. of octahedral voids = N

:. No. of atoms X = N
Ratio of X : Y = N : N =1: 1
 Formula of compound is XY

4. In corundum, oxide ions are arranged in hexagonal close packing and aluminium
ions occupy two-third of the octahedral voids.
What is the formula of corundum?
Ans :Let oxide ions be N, octahedral voids = N
:. Al3+ ions = 2 N
3
:. Ratio Al3+ : O2- = 2 N : N = 2: 3
3
i.e. formula is Al2O3

5. A solid is made up of two elements P and Q. Atoms Q are in ccp arrangement

while atoms P occupy all the tetrahedral sites.
What is the formula of the compound?
Ans :Suppose number of atoms Q = N
So number of tetrahedral sites = 2N
:. Number of atoms P = 2N
Ratio P : Q = 2N : N = 2 : 1
Formula is P2Q
6. How many atoms can be assigned to it’s unit cell if an element forms:
(i) a body centred cubic cell 
(ii) face centred cubic cell?
Ans : (i) 2 (ii) 4
7. What type of stoichiometric defect is shown by :
(i) AgCl (ii) AgBr
Ans (i) AgCl : Frenkel defect
(ii) AgBr : Frenkel as well as Schottky
8. Classify each of the following as being either a p-type or a n-type
semiconductor.
9. (i) Ge doped with In
(ii) Si doped with P
Ans (i) Ge belongs to group 14 and In to group 13. An electron deficient hole is
created and it is a p-type semiconductor.
(ii) Si belongs to group 14 and P to group 15. There will be a free electron and it
is a n-type semiconductor.
9. Explain the following terms with suitable examples :
(i) Schottky defect (ii) F-centres
Ans (I) Stoichiometric defect when equal number of cations and anions are missing
from the lattice. Cations and anions are of almost
same size. It lowers the density of solid e.g. NaCl , KCl etc.
(ii)The electrons trapped at the anion vacancies are referred to as F-centres
from German word Farbenzenter meaning colour centre e.g. yellow colour imparted
to NaCl when heated in an atmosphere of sodium vapour.
10. Gold (atomic radius = 0.144 nm) crystallises in a face centred unit cell. What is the
length of a side of the cell?
Ans :For fcc structure , the edge length of the unit cell (a) and radius (r) of the atom
are related by
a = 2√2 r = 2√2 × 0.144 nm = 0.407 nm
11. Analysis shows that a metal oxide has the empirical formula M0.96O1.00 

Calculate the percentage of M2+ and M3+ ions in this

crystal?
Ans : Let , the number of M2+ ion = x
then, the number of M3+ ion will be = (0.96-x)
2x + 3(0.96-x) = 2 i.e. x = 0.88
% of M2+ ion = 0.88 × 100 = 91.67%
0.96
% of M3+ ion = 0.08 × 100 = 8.33%
0.96

SHORT ANSWER TYPE QUESTION

(3 marks)
1. An element X with an atomic mass of 60 g/mol has density of 6.23 g cm -3 If the
edge length of it’s cubic unit cell is 400 pm, identify the type of cubic unit cell.
Calculate the radius of an atom of this element.
Ans : d = z x M
a3 x NA
6.23 = z x M ; z = 4
(400 x 10-10)3 x 6.023 x 1023
The unit cell is face centred cubic
Radius r = a= 400 = 141.4pm
2√2 2√2
2. Silver crystallises with face centred cubic unit cells. Each side of the unit cell has a
length of 409 pm. What is the radius of an atom of silver? (Assume that each face
atom is touching the four corner atoms)
Ans : For fcc unit cell
r = d =a
2 2√2
 Given a = 409 pm
:. r = 409 = 144.62pm
2√2
3. Iron has a body-centred cubic unit cell with a cell edge of 286.65 pm. The density
of iron is 7.87 g cm-3 Use this information to calculate Avogadro’s number. (At. Mass
of iron = 56 g mol-1)
Ans : d= zxM
a3 x N A
For bcc lattice , z = 2
7.87 g cm-3 = 2 x 56 g mol-1
(286.65 x 10-10 cm)3 x NA

NA = 6.04 x 1023 mol-1

4. What is a semi-conductor? Name the two main types of semi-conductors and
explain their conduction mechanism.
Ans: The solids with intermediate conductivities between insulators and conductors
are termed semi-conductors.
(i) n-type semi-conductors : obtained by doping silicon with a group 15
element like P. In 5 valence electrons, only 4 are involved in bond
formation and fifth electron can be easily provided to the conduction
band. Conduction is due to movement of electron.
(ii) p-type semiconductor :  obtained by doping silicon with a group 13
element like Gallium which contains only 3 valence  electrons. Due to
missing of 4th valence electron, electron hole or electron vacancy is
created. Movement of these positively charged hole is responsible for the
conduction.
5. Calculate the distance between Na+ and Cl- ions in NaCl crystal if it’s density is
2.165 g cm-3
( Molar mass of NaCl =58.5 g mol-1 ; NA = 6.02 x 1023 mol-1)
Ans : d = z x M
 a3 x NA
For NaCl it is fcc, :. Z = 4
2.165 g cm-3 = 4 x 58.5 g mol-1
a3 x 6.02 x 1023 mol-1
a3 = 1.795 x 10-22 cm3
a = 5.64 x 10-8 cm = 564 pm
Distance between Na+ and Cl- = a = 564 pm = 282 pm
2 2

6. (a) What is Curie-Temperature?

(b) Iron (II) oxide unit cell has a cubic structure and each of the unit cell side is 5Å. If
the density of this oxide is 4.0 g cm-3,calculate the number of Fe2+ and O2- ions
present in each unit cell. (At. Mass Fe = 56, O = 16)
Ans : (a) The temperature at which a ferromagnetic substance loses it’s
ferromagnetism and attains paramagnetism.
(b) d =z x M M of FeO = 56 + 16 =72
a3 x NA
4.0 = z x 72
(5 x 10-8) x 6.023 x 1023
z=4

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