PHYSICAL CHEMISTRY

TARGET IIT-JEE 2013

XIII (ALL)

SOLID STATES
CONTENTS
" A SPECIALLY DESIGNED KIT FOR LEARNING."
THE KEY  Basic principles of subjects. An outline of the topics to be
discussed in class lectures.
THE ATLAS  Basic layout of subject. A route map correlating different subtopics
in coherent manner.
EXERCISE I  Introductory problems to get first hand experience of problem
solving.
PROFICIENCY TEST  To check you newly acquired concepts.
EXERCISE II  A collection of good problems.
EXERCISE III  Test your skills as per New JEE pattern.
EXERCISE IV  A collection of JEE problems.

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Solid State
Special Highlights
BRAIN TEASERS: GENERAL MISTAKE:

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 TEACHER’S ADVICE:
 THE KEY
AMORPHOUS SOLIDS:
Amorphous solids are those whose constitutent particles are randomly arrange and have no ordered
long range structure. example: Rubber, Glass etc.

CRYSTALLINE SOLIDS:
Crystalline solids are those whose atom, molecules or ions have an ordered arrangement extending over
a Long Range. example-NaCl,diamond, graphite etc.
TYPES OF CRYSTALLINE SOLIDS:
Type of Solid Intermolecular forces Properties Examples

Brittle, hard, high Melting point

Ionic Ion-Ion forces Insulator in solid but conductance NaCl, KCl, MgCl2
fused and aqueous solution

Dispersion
Molecular forces/Dipole-Dipole Soft, low melting point, Insulators H2 O, Br2 , CO 2 , CH4
/H-bond
Covalent
Covalent bonds Hard, Very high melting point C-Diamond SiO 2
network
Variable hardness and melting
Metallic Metallic bonds point, malleable and ductile, Na, Zn, Cu, Fe
conducting
1. UNIT CELL:
Collection of lattice points, whose repetition produce whole lattice is
called a unit cell. The whole lattice can be considered to be made by
repetion of unit cell.

TYPES OF UNIT CELL:

Unit Cell Parameters

Crystal Systems Bravais Lattice Example
Intercepts Crystal Angles
Primitive, Face Centered,
1 Cubic a=b=c  NaCl, Zinc blend, Cu
Body Centered
Primitive, Face Centered, Rhombic sulphur, KNO 3 ,
2 Orthorhombic abc 
Body Centered, End Centered BaSO4
White tin, SnO2 , TiO 2 ,
3 Tetragonal Primitive, Body Centered a=bc 
CaSO4
Monoclinic sulphur,
4 Monoclinic Primitive, End Centered abc 
Na2 SO 4 .10H2 O
Caccite (CaCO3 ), HgS
5 Rhombohedral or Trigonal Primitive a=b=c 
(Cinnabar)
K 2 Cr2 O 7 , CuSO4 .5H2 O,
6 Triclinic Primitive abc 
H3 BO3
7 Hexagonal Primitive a=bc  Graphite, ZnO, CdS

Solid State [3]

SEVEN CRYSTAL SYSTEM

Rhombohedral
abc
   90°

BRAVAIS LATTICE

Although there are only 7 crystal systems or shapes, there are 14 different crystal lattices, called Bravais
Lattices. (3 different cubic types, 2 different tetragonal types, 4 different orthorhombic types, 2 different
monoclinic types, 1 rhombohedral, 1 hexagonal, 1 triclinic).

Solid State [4]

1.1 Primitive or simple cubic (PS/SC) unit cell: Spheres in one layer sitting directly on top of those in
previous layer, so that all layers are identical. Each sphere is touched by six other, hence coordination
number is 6. 52% of available space occupied by spheres.
Example: Polonium crystallises in simple cubic arrangement.

Z = 1 ; C.N. = 6

1.2 Body Centered cubic (BCC) unit cell: Spheres in one layer sit in the depression made by first layer in
a-b-a-b manner. Coordination number is 8, and 68% of available space is occupied by atoms.
Example: Iron, sodium and 14 other metal crystallises in this manner.

Z = 2 ; C.N. = 8

1.3 Face centered cubic (FCC) unit cell:

Examples : Al, Ni, Fe, Pd all solid noble gases etc.

Z = 4 ; C.N. = 12

Solid State [5]

1.4 Hexagonal primitive unit cell

Example : Be, Mg, Ti, Zr etc.

PACKING TYPES AMONG THE METALS

Solid State [6]

2. TYPE OF PACKING IN TWO DIMENSION :

Square close packing Hexagonal close packing

3. PACKING OF ATOMS IN THREE DIMENSIONS:

(i) Hexagonal close pack (A-B-A-B) type packing :

Each layer has hexagonal arrangement of touching sphere and 3rd layer is similar (exactly on top) of first
layer.

Solid State [7]

(ii) Cubic close pack (A-B-C-A-B-C):
AB layers are similar to HCP arrangement but third layer is offset from both A and B layers. The fourth
layer is exactly on top of first layer.

Solid State [8]

4. TYPES OF VOIDS IN CLOSEST PACKING:

4.1 Tetrahedral void in FCC

4.2 Octahedral void in FCC

Solid State [9]

 Circles labeled O represent centers of the Circles labeled T represent the centers of
octahedral interstices in the ccp the tetrahedral interstices in the ccp
arrangement of anions (fcc unit cell). The arrangement of anions. The cell "owns" 8
cell "owns" 4 octahedral sites. tetrahedral sites.

5. RADIUS RATIO:

5.1 Radius ratio for co-ordination number 3

r
(Triangular Arrangement): = 0.155
r

Solid State [10]

5.2 Radius ratio for coordination number 4
(Tetrahedral arrangement):

r
= 0.225
r

5.3 Radius ratio for coordination number 6:

r
(Octahedral Arrangement) or = 0.414
r
Radius ratio for coordination number 4
(Square plannar arrangement)

5.4 Radius ratio for coordination number 8 :

(Body centered cubic crystal)

r
= 0.732
r

Solid State [11]

6. TYPES OF IONIC STRUCTURES:
6.1 Rock salt structure:(NaCl) Larger atom formic ccp arrangement and smaller atom filling all octahedral
voids.

Cl¯
+
Na

Rock salt structure

6.2 Zinc blende (sphalerite) structure:(ZnS) Larger atom formic ccp arrangement and smaller atom
filling half of alternate tetrahedral voids

2–
S
+2
Zn

Zinc blende structure

6.3 Cesium halide str uctur e: (CsCl) Cl– at the corners

of cube and Cs+ in the center.

Solid State [12]

6.4 Fluor ite str uctur e: (CaF2) Ca2+ forming ccp arrangement and F– filling all tetrahedral voids.

6.5 Antifluorite structure :(Li2O) O2– ion forming ccp and Li+ taking all tetrahedral voids.

6.6 Corundum Structure: (Al2O3) O2– forming hcp and Al3+ filling 2/3 octahedral voids.

6.7 Rutile structure: (TiO2) O2– forming hcp while Ti4+ ions occupy half of the octahedral voids.

6.8 Pervoskite structure:(CaTiO3) Ca2+ in the corner of cube O2– at the face center and Ti4+ at the
centre of cube.

6.9 Spinel and inverse spinel structure: (MgAl2O4)O2– forming fcc, Mg2+ filling 1/8 of tetrahedral voids
and Al3+ taking half of octahedral voids.In an inverse spinel structure, O2– ion form FCC lattice, A2+ ions
occupy 1/8 of the tetrahedral voids and trivalent cation occupies 1/8 of the tetrahedral voids and 1/4 of
the octahedral voids.

Solid State [13]

7. CRYSTAL DEFECTS:

Real crystals are never perfect: they always contain a considerable density of defects and imperfections
that affect their physical, chemical, mechanical and electronic properties. The existence of defects also
plays an important role in various technological processes and phenomena such as annealing, precipitation,
diffusion,sintering, oxidation and others. It should be noted that defects do not necessarily have adverse
effects on the properties of materials. There are many situations in which a judicious control of the types
and amounts of imperfections can bring about specific characteristics desired in a system.
The electrical behavior of semiconductors, for example, is largely controlled by crystal imperfections.
The conductivity of silicon can thus be altered intype (n or p) and by over eight orders of magnitude
through the addition of minute amounts of electrically active dopant elements. In this case, each atom of
dopant,substitutionally incorporated, represents a point defect in the silicon lattice. The fact that such
small amounts of impurity atoms can significantly alter the electrical properties of semiconductors is
responsible for the development of the transistor and has opened up the entire field of solid state device
technology.

POINT DEFECTS : When some ion's are missing from ionic crystals from their theoretical lattice point, the
crystal is defected structure.
Defect due to missing of ions from theoretical lattice point is called point defect.
Point defect increases with increase in temperature. At absolute zero temperature, ionic
crystal may not have any defect.

POINT DEFECTS ARE OF TWO TYPES :

(i) Stoichiometric defect : Defects due to which overall formula of ionic compound do not change is called
stoichiometric defect.
(ii) Non- Stoichometric defects are those due to which overall formula of compound changes.
Stoichiometric defect :(i) Schottky defect (ii) Frenkel defect
Schottky :- When pair of holes exist in crystal lattice due to missing of positive and negative ions in
pair, the defect is called schottky defect.

 Schottky defect

Solid State [14]

 This defect is common in ionic compounds with high coordination number. It absolute zero temperate
crystals tends to have perfectly order arrangement. As temperature is increased, some vacancies are
always created in crystal lattice.
Ex. of crystals showing schottky defect: NaCl, KCl, NaBr etc.
Frenkel defect : In this type of defect, holes are created due to transfering of an ion from usual lattice
site to a interstitial site. This type of defect very common in compounds in which there
is large difference between size of cation and anion.

 Frenkel defect e.g.ZnS ; AgBr; etc

Consequence of defects:
- Due to schottky defect density of crystal decreases
- Crystal can conduct electricity to a small extent.
Non-stoichiometric defects :
Non stoichiometric compounds are those in which the ratio of positive and negative ions present in the
compounds differ from that indicated by their chemical formula. eg. Fe0.95O, Cu1.97S, etc.
These defects arise due to excess of metal or non-metal atoms–
(i) Metal excess defect (ii) Metal deficiency defect
Metal excess defect arise due to
(i) Missing of a negative ion from lattice site and position taken by an electron. This defect is similar to
schotty defect and also found in crystals showing schotty defect. Ex. When sodium vapours passed over
NaCl crystal a yellow non-stoichiometric form of NaCl is obtained. Vaccant lattice site occupied by
electron's is called F-centre (Farbe colour). Which is responsible for colour of crystal.

(ii) An extra metal occupy interstitial site and to maintain electrical neutrality, electrons occupy another interstitial site.
This type of defect is very close to Frenkel defect and found in ZnO.

When ZnO is heated, it turns yellow as it's loses some oxygen. The Zn2+ ion move to an interstitial site.
Note: In this defect there is no hole in the crystal.
— Crystals with metal excess defect contain free electrons and if these migrate, they conduct an
electric current.
— As amount of current carried is very small, they behave like semiconductor's. (n-type
semiconductor)

Solid State [15]

 Metal deficiency defect:–

(i) A metal ion is missing from it's normal lattice point the electrical neutrality is maintained by extra positive
charge of same of the remaining metal ions.
FeO, FeS, NiO - exhibit this type of defect.
(ii) An extra negative ion is present in the interstial position and electrical neutrality is maintained by extra–
positive charge on remaining metal ions. This type of defect is not known.
Crystal with metal deficiency defect behaves like p-type semiconductors.

A+ B A+ B
B e B A2+
A+ B A+ B

(a) Ex. FeO, NiO, FeS

Metal deficency defect

Solid State [16]

 THE ATLAS

TYPES OF SOLIDS

Crystalline Solids Amorphous Solids

Crystalline solids have long range order i.e. the
constituent particles are arranged in a regular
fashion and this symmetrical arrangement extends
throughout the crystal length.

Lattice - Unit Cells

(i) A unit cell is the smallest repeating structural unit the crystalline solid. Bravais has
predicted that there are only 14 unit cells that exists in nature.
(ii)The relation between the edge length (a) and the radius of atom (r) forming lattice
are as follows. PC :a=2r, BCC: 3a=4r;FCC:2a=4r& HP:a=2r height(c) =4r 2
3

Packing fraction and density determination

(i) The ratio of volume occupied by the effective atoms to the volume of the unit cell
is called packing fraction. Its values for various unit cells are PC = 0.52,
BCC = 0.68, FCC & HP = 0.74.
(ii)Density () of cubic crystal is calculated using the relation  = z×M 3 where
NAV×a
z=number of effective atoms, M=Atomic mass,NAV=Avogadro's number and
a= Edge length.

Type of void and radius ratio rule

(i) Tetrahedral & octahedral voids are present only inclosest packed structures. The
effective number of octahedral voids in a unit cell is equal to the effective
number of atoms in the unit cell & effective number of tetrahedral voids is equal
to double the number of effective atoms in the unit cell.
(ii)The sum of radius of the atom of host lattice (rh) and the radius of atom occupying
void(rf(t)or rf(o)) is given by
For octahedral void, rh+rf(o)= a & for tetrahedral void,rh+rf(t)= 3a
2 4
(iii)Limiting radius is defined as the minimum ratio of cation to anion radius. It is
defined when cation is in contact with anions and anions are also in contact
with each other.
(iv)Radius ratio depends on the co-ordination number. The limiting radius ratio for
the various co-ordination numbers are
C.N.3 : 0.155, C.N.4 (Tetrahedral) : 0.225, C.N.4(Square planar) : 0.414,
C.N.6 (Octahedral) : 0.414, C.N.8 (BCC) : 0.732, C.N.12 (Ideal FCC) : 1

Defects in Solids
Ionic lattice has 2 major defects. Schottky defect
occurs due to the cation-anion pair vacancy,
which decreases the density of crystal. Frenkel defect
occurs when an ion leaves its lattice site and fits
into an interstitial space. Due to Frenkel defect,
density of crystal remains unaffected.

Solid State [17]