SOLID STATE www.crackjee.
xyz
Difference between Crystalline and Amorphous Solids :
Crystalline solids Amorphous solids
They have definite and regular geometry due They do not have any pattern of arrangement
to definite and orderly arrangement of atoms, of atoms, ions or molecules and, thus do not
ions or molecules in three-dimensional space. have any definite geometrical shape.
TYPES OF CRYSTALLINE SOLIDS :
Ionic Metallic Covalent molecular
Particles Anions, Metal ions in Atoms Molecules (or
occupying cations electron cloud atoms)
lattice points
Binding force Electrostatic Metallic Covalent Van der waals
attraction bonds bonds dipole-diople
Properties Hard, Brittle, Soft to very Very hard, Soft, poor
poor thermal hard, good poor thermal thermal and
and electrical thermal and and electrical electrical
conductors electrical conductors conductors
conductors
Example NaCl, CaBr2, Li, K, Ca, Cu, C(diamond) H2O, H2,
KNO2, etc Na, etc. SiO2 (quartz), CO2, Ar etc
etc
Space lattice or crystal lattice :
It may be defined as a regular three dimensional arrangement of identical points in space.
Seven Crystal Systems :
Physical & Inorganic By A-479 Indra vihar, kota Organic Chemistry By
NV Sir Ph. - 9982433693 (NV Sir) 9462729791(VKP Sir) VKP Sir SOLID STATE # 1
B.Tech. IIT Delhi M.Sc. IT-BHU
Seven Crystal Systems and Fourteen Bravais Lattice :
CUBIC
a
a
a
Simple Face Centred Body Centred
ORTHORHOMBIC
b
a Simple End Centred Body Centred Face Centred
TETRAGONAL MONOCLINIC
c c
a b b
a a
Simple Body Centred End Centred
Simple
RHOMBOHEDRAL TRICLINIC HEXAGONAL
a
c
a c
a b g 120o a
a a b a
a
Type of Lattice point Contribution to one unit cell
Corner 1/8
Edge 1/4
Facecenter 1/2
Body Center 1
Calculation of number of particles in a unit cell
Type of unit cell Lattice points Lattice points Lattice points Z = no. of lattice
at corners at face-centered at body centered points per unit cell
1
SCC 8 0 0 8× =1
8
1
BCC 8 0 1 8× +1×1 = 2
8
1 1
FCC 8 6 0 8× +6 × =4
8 2
Physical & Inorganic By A-479 Indra vihar, kota Organic Chemistry By
NV Sir Ph. - 9982433693 (NV Sir) 9462729791(VKP Sir) VKP Sir SOLID STATE # 2
B.Tech. IIT Delhi M.Sc. IT-BHU
Relation between edge length of unit cell and radius of atoms :
Simple cubic or Primitive : edge length of unit cell a = 2 r
3a
Body centre cubic : atomic radius, r =
4
2a
Face centre cubic/cubic close packed : atomic radius r =
4
Fraction of volume occupied by atoms in a cube :
Packing Fraction = Volume of atoms in the cube/Total volume of cube)
Item Primitive BCC FCC
1. Atoms occupy : 8 corners 8 corners, 1 centre 8 corners, 6 face centres
2. Each atom contributes
(a) corner atom :
1 th × 8 1 th × 8 1 th × 8
8 8 8
(b) Face centre atom : nil nil
1 ×6
6
(c) Body centre atom : nil one × one nil
3. No. of atoms in the cube (Z): one two four
4. Radius of the atom : r r r
5. Total volume of atoms : 1 4 r3 2 4 r3 4 4 r3
3 3 3
6. Edge of the cube : a a a
4 r 4r
7. Edge of the cube in terms of r : a = 2r a= a=
3 2
3 3
4 r 4 r
8. Total volume of the cube, a3 : (2 r)3
3 2
9. Fraction of volume occupied : 4 r3 8 r3 16 r3
3 3 3
Total volume of atoms 64 3 64 3
8 r3 r r
Total volume of cube 3 3 2 2
10. (or) packing fraction :
3 2
6 8 6
11. (or) volume occupied by atoms : 0.52 0.6802 0.7405
12. % volume occupied by atoms : 52% 68.02 % 74.05%
13. Fraction of void volume : 0.48 0.3198 0.2595
14. % of void volume in cube : 48% 31.98% 25.95%
15. % of empty space in cube : 48% 31.98% 25.95%
Physical & Inorganic By A-479 Indra vihar, kota Organic Chemistry By
NV Sir Ph. - 9982433693 (NV Sir) 9462729791(VKP Sir) VKP Sir SOLID STATE # 3
B.Tech. IIT Delhi M.Sc. IT-BHU
Density of unit cell :
Z M
Density of unit cell (and hence density of a crystal) =
a N 0 10 30
2
where a is edge of unit cell in pm
N0 = Avogadro number (6.02 × 1023)
M = Atomic mass of element or formula mass of the compound
Z = No. of atoms present per unit cell or formula units. e.g.
for fcc, Z = 4, for bcc, Z = 2, for simple cubic, Z = 1
Close packing in crystals :
Close packing in three dimensions
When the third layer is placed over the second layer. This arrangement is called ABAB.,… pattern
or hexagonal (HCP) close packing.
(a) For HCP geometry Coordination number = 12
(b) For HCP geometry no. of atoms per unit cell
1 1
= 12 (corners) × + 2(face centres)× + 3 (inside the body) ×1 = 6
6 2
(c) For HCP geometry packing efficiency = 74 %
The ABC ABC ....... peaking has cubic symmetry and is known as cubic close packing (ccp). The cubic
close packing close packing has face centered cubic (fcc) unit cell.
Types of Voids
rvoid rvoid
Triangular : 0.155 Tetrahedral : 0.225 .
rsphere rsphere
rvoid rvoid
Octahedral : 0.414 cubical void : 0.732
rsphere rsphere
Common coordination numbers are 3, 4, 6 and 8.
ra
Limiting radius ratio Co-ord. No. Shape
rc
Example
< 0.155 2 Linear BeF2
0.155 – 0.225 3 Trigonal planar B2O3
0.225 – 0.414 4 Tetrahedral ZnS
0.414-0.732 4 square planar PtCl4–2
0.414-0.732 6 octahedral NaCl
0.732 - 0.999 8 B.C.C. CsCl
Structure of ionic compounds :
Structures of Type AB :
1. Rock salt (NaCl) type 2. Cesium chloride (CsCl) type
3. Zinc blende (ZnS) type
Physical & Inorganic By A-479 Indra vihar, kota Organic Chemistry By
NV Sir Ph. - 9982433693 (NV Sir) 9462729791(VKP Sir) VKP Sir SOLID STATE # 4
B.Tech. IIT Delhi M.Sc. IT-BHU
Rock salt structure (NaCl) :
(a) Cl¯ is forming a FCC unit cell in which Na+ is in the octahedral voids. The co-ordination number of Na+ is
6 and that of Cl¯ would also be 6.
rNa
(b) Ratio of ionic radii = 0.525
r –
Cl
1
(c) No. of sodium ions = 12 (At edge centre) × + 1 (At body centre) × 1 = 4
4
1 1
No. of chloride ions = 8 (At corners) × + 6 (At face centres) × = 4 (Thus formula is Na4Cl4 i.e. NaCl)
8 2
Caesium chloride structure (CsCl) :
(a) CsCl has body-centered cubic (bcc) arrangement. This structure has 8 : 8 co-ordination,
i.e., each Cs+ ion is touching eight Cl – ions and each Cl – ions in touching eight Cs+ ions. (bcc)
1
(b) No. of Cl – ions = 8 (At corners) × = 1
8
No. of Cs+ ions = 1 (At the body centre) × 1 = 1
No. of CsCl unit per unit cell = 1
Zinc blende structure or sphalarite structure (ZnS) :
(a) Sulphite ions are face centered and zinc is present in alternate tetrahedral voids.
rZn 2
(b) 0.40 No. of ZnS units per unit cell = 4
rS2–
Fluorite structure (CaF2) : The cations are arranged in cubic close packing (ccp) while the anion
occupy all the tetrahedral voids. Calcium fluoride has 8 : 4 co-ordination. (ccp)
No. of CaF2 units per unit cell = 4
Antifluorite structure : In antifluorite structure e.g., (Na 2O)
(a) The anions are arranged in cubic close packing (ccp) while the cations occupy all the tetrahedral
voids.
(b) Na 2O has 4 : 8 co-ordination
WURTZITE structure : Sulphide ions have hcp arrangement and zinc ions occupy tetrahedral
voids.
Spinal structure : General formula of compound is AB2O4 e.g., MgAl2O4, ZnFe2O4
Oxide ions are arranged in ccp arrangement. Divalent cations are in tetrahedral sites and trivalent
ions are in octahedral sites.
Imperfections or defects in solids :
Stoichiometric point defects :
(a) Schottky Defects : This type of defect is created when one positive ion and one negative ion are
missing from their respective positions leaving behind a pair of holes. Schottky defects are more common in
ionic compounds with high co-ordination number.
(b) Frenkel Defect – This type of defect is created when an ion leaves its correct lattice site and occupies an
interstitial site. Frenkel defects are common in ionic compounds which have low co-ordination number and in
which there is large difference in size between positive and negative ions.
Non Stoichiometric defects :
Metal excess Defects due to Anion Vacancies. A compound may have excess metal ion if a
negative ion is absent from its lattice site, leaving a ‘hole’, which is occupied by electron to
maintain electrical neutrality.
Metal Deficiency due to cations vacancies. The non-stoichiometric compounds may have metal
deficiency due to the absence of a metal ion from its lattice site. The charge is balanced by an
adjacent ion having higher positive charge.
Physical & Inorganic By A-479 Indra vihar, kota Organic Chemistry By
NV Sir Ph. - 9982433693 (NV Sir) 9462729791(VKP Sir) VKP Sir SOLID STATE # 5
B.Tech. IIT Delhi M.Sc. IT-BHU
