----- -------

Solid State
[POoosTORE~ M~E["°~ br! e! concept } I
=====------- - - - - - - - ,
Introduction

~ - -- -- ~ Fixed mass volume, s h ape , den sity

\ S olid Stat e I~Hard incompressible, rigid
~ Stron g intermolecula r forces of attraction.
----------------
Classification of Solids
atalllne Solids: definite shape , true solid, may or may not be isotropic.
orphous Solids: irregular shape, pseudo solid, isotropic like liquid .
Classification of Crystalline Solids
(ii Molecular solids: Molecules of same compounds
(a} Polar molecular solids : HCl, SO 2 , etc.
(b} Non polar molecular solids : CO 2 , H2 , Cl 2 , CH 4 , CO, etc.
(c} Hydrogen bonded molecular solids : H - 0, H - N, H - F
(ill Ionic Solids : Ionic salt are formed by molecules containing +vely charged smaller in size cations and
negatively charged relatively bigger anions.
(iii) Metallic Solids: They are the crystalline solids formed by atom of same metallic elements.
(iv) Covalent Solids : They are formed by chemical bond. i.e. covalent bonds between the neighbouring constituent
atoms of non-metallic solids. eg. Diamond, graphite and Fullerene.
C@ Unit Cell and Two, Three Dimensional Lattices \
* Unit cell is the smallest repeating structural unit of crystalline solids.
* Each point at the intersection of the lines in the unit cell represents constituent particles.
* Lattice point: any point at the intersection.
* Space lattice: Collection of all the points on the crystal having similar environment.
0 Type of Unit cells their Edge length, Angle, & Examples.
No. Crystal System Type Edge length Angle kamplea
a=b=c

}
(1} Cubic Simple Polonium
Body centred
Face centred
} a=b=c
a=b=c
a= 13 = y = 90° Fe,Rb,Na
Cu, Al, Ni
SnO 2
(2) Tetragonal Primitive
Body centred
} a=b.t:c } a = 13 = y .= 90°
TiO 2 , CaSO 4
(3) Orthorhombic Primitive Rhombic Sulphur
Body centred
Face centred
End centred
} a.t: b.t: c

a* b * c
} a=~=y=90'
KN0 3
BaSO 4
MgSO 4 -7H 2 O
(4) Monoclinic Primitive
End centred
} } a= 13 = 90°
y * 90°
Monoclinic Sulphur
N~SO 4 , 10H 2 O
(5) Triclinic Primitive a.t: b .t: c a* y * 13 * 90° Ki Cr2O 7 .H 3 BO 3
(6) Hexagonal Primitive a= b .t: c a = 13 = 90° ZnO, BeO, CoS
~.
y = 120°
(7) Rhombohedral Primitive a = b=c a = 13 = y * 90° Calcite

Total number of spheres in Simple cubic unit = 1

Total number of spheres in Body centred unit = 2
Total number of spheres in Face centred unit-= 4

(5)
r--
-t •

6 Uttam 's MHT- CET (Chem1 .

,1 //)'J

Pa~ki-;g_i~ _Sol! ds \
(i) Stage I : Linear p acki n g in one dire c tion
(ii) Stage 11: Pla nar p acking arnmge m e nt of s ph eres
(u) AAM type (b ) ABAB type .
(iii) Three dimensional packing:
(a) MAA type = Si mpl e cu b ic stru c ture
(b) ABAB ty p e = Hexagon a l close packing structure
Density of Unit Cells
0 Radius of atoms:
For s imp le c ubi c stru cture = %
For fee Structure = %.J2 , a = edge length
For b ee Structure = J3 ~
4
0 Density of solid:
ZxM ZM
d

where, Z = No of atom per unit cells

a = Edge length
V = Volume
N0 = Avogadro's number
M = Atomic mass .
Packing in Void of Ionic Solids
* In a closed packed array of anions with cations in all tetrahedral holes have cation to anion ratio is 2: I .
* The ratio of octahedral holes to the number of anions in either hexagonal or cubic closed packed structure is
I.I.
0 Radius Ratio Rules·
Radius Ratio CN Type of hole occupied Example
r+/r-
0. 1555 - 0.225 3 Planar triangular B203
0.225 - 0.414 4 Tetrahedral ZnS
0.414 - 0.732 6 Octahedral NaCl
0 .732 - 1.00 8 Cubic CsCl

■: Defects in Crystal Structure I

Defects
'V
Point defect Line defect
(due to fault produced in arrangement of a point) (due to irregularity in complete line)
• Vacancy defect
• Inte rstitial defect
• lm o uri tv defect
(a} Vacancy/ Schottky defect: Due to vacancies caused by abse nce of anions and cations in the crystal lattice.
e.g. NaCl , KCI.
(b) Interstitial/Frenkel defect: When cation or anion from ionic solid leaves it's regular site and move to occupy
a place between interstitial position e.g. AgCl, ZnS.
(c ) Impurity defect: It's due to when a regular cation of the crystal is re placed by some different cations. e .g.
brass, stai nless steel.

- Electrical Properties J

., Band theory: Atomic orbitals of the atoms in the crystal combine to form molecular orbitals which are spread
ove r the c om Jete c stal structure.
 Solid S1.1tc 7

Conduction
Band
Conduction
11,
Band
Conduction Overlapping or I!'
Band Small e nergy Very la rge
very
ga p energy gap

l/ Valence
Band
small en ergy
gap
"

Valence
J

'/
Band Valence
Metal
(Conductor) Semi -conductor Band
Insulator
Electrical conductivity of semi-conductors increases with rise in temperature because more electrons can jump
to the conduction band.
Sem!conductora: A substance containing completely filled band with electrons and completely empty band
behaves as semiconductor
Two types: n-type and p-type semiconductors.

■ 11@ Magnetic Properties

While electrons are revolving round the nucJeus in various orbits, they are also spinning about their own axis.
I
A spinning charge generates a magnetic field.
I• The magnetic properties of solids are related to the electronic structure and on the basis of response toward
magnetic field solids are divided as follows:
r Solids l
I
,I/ ,I/ ,I,.
r Diamagnetic l l Paramagnetic j [ Ferromagnetic j
• Weakly repelled by • Possess permanent dipole and • Strongly attracted by magnetic
magnetic field. attracted by magnetic field. field and show permanent
• They contain unpaired magnetism even when
• These materials have all magnetic field is removed.
paired electrons. electrons.
e.,. NaCl, water, benzene, etc. e.,. Cu 2 +, Fe 3 +, Cr3 +, TiO, CuO, etc. e.g. Fe, Co, Ni, Cr02

l
'1,, -_I,, '1,,
l Ferromagnetism j f Antiferromagnetism J f Ferrimagnetism j
• Magnetic moment of • Magnetic moment of domains • Magnetic moment of domains
domains in the same in a compensatory way so as are aligned in parallel and
direction. to give a net zero magnetic anti-parallel directions in
moment. . unequal number
e.1., iiii
e.,. iJ.iJ. e.,. ii.J, it J.
Determination of Mapetic Property (Guo:,'• method):
The method consists of weighing the substances in and out of magnetic field.
• If the substance is diamagnetic then it is weightless in the magnetic field .
• ff the substance is paramagnetic then it weighs more in the magnetic field because the substance is pulled
in magnetic field .
If the substance is ferromagnetic then its weight is more than that of paramagnetic in the magnetic field
because the substance is ulled more in the ma etic field.
000

- l