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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 Na × 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 Coordinati Packing Number


between constitue on no. fraction of
nearest nt Atom constitue
neighbou nt
r (d) Atoms
Simple a a/2 6 0.52 1/8×8 =
cubic 1
Face a/ a/2 12 0.74 (1/8×8)
centred +
cubic (1/2×6)
(FCC) =4
Body /2a /4a 8 0.68 (1/8×8)
centred +1=2
cubic
(BCC)

Where , a = edge length of unit cell

Radius Possible Structural Structural Coordinatio


ratio r+ /r- condition arrangeme type n no.
no. nt
0.225- 4 Tetrahedra ZnS Zn2+= 4S2-
0.414 l
=4
0.414- 6 Octahedral NaCl Na+ = 6Cl-
0.732
=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 Constitue Bonding/ Examples Physica Electrical Meltin
Solids nt Attractiv l Conductivit g
Particles e Nature y Point
Forces
1. Molecular
Solids
(i)Non Molecules Dispersion Ar, CCl4 , Soft Insulator Very
-polar or H2 , I2 , Co2 low
London
forces Soft Insulator
HCl , SO2 Low
(ii)Polar Dipole-
dipole Hard Insulator
Interaction H2O(ice) Low
(iii)Hydrog s
en
bonded Hydrogen
bonding
2. Ionic Ions Coulombic NaCl, Hard Insulators in High
solids or MgO but solid state
electrostat Zns, CaF2 brittle but
ic conductors
in
molten
state
and in
aqueous
solutions

3. Metallic Positive Metallic Fe, Cu, Hard Conductors Fairly


solids ions bonding Ag, Mg but in high
In a sea mallea solid state
of ble as well as in
delocalise and molten
d ductile state
electrons

4. Covalent Atoms Covalent SiO2(quar Hard Insulators Very


or bonding tz), high
Network SiC ,
solids C(diamon
d), Soft Conductor
AIN, (exception)
C(graphit
e)

Classification of solids on basis of electrical


properties

Conductors Semi-conductors
Insulators
Inductivity of conductivity Intermediate conductivity ranging very lo
conductivity ranging

the order of 107(ohm.m)-1 from 10-6 to 104(ohm.m)-1 between 10


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. H2O , NaCl , C6H6 etc. in small groups i.e., domains
magnetic field

one or more unpaired


- e.g., Fe3O4(magnetic

electrons attracted by ferrites like MgFe2O


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 NA
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
a 3 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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