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Solid State Short Notes
Solid State Short Notes
Solid State Short Notes
p a
r y
st
Solid is a state of matter which has strong intermolecular forces of attraction.
. i n m i
g e
The melting point of solids will be much above the room temperature.
h e
p a / c
t r ysolids arem
i s .co
Some of the characteristic features of
1. Strong intermolecularm
e b e
forces and short intermolecular distances
2. Rigid, possess. c h
definite
u t
shape, usize and volume
3. Solidsw
w . y o
w w
are almost incompressible
4. Solids havew
w high density
5. Solids have negligible fluidity
6. The diffusion of the particles in the solid state is negligible
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Types of Solids
g e
p a
Based on the three dimensional arrangement of particles in space, the solids are classified into two types.
• Crystalline solids
r y
• Amorphous solids
i n
. em i st
g e h
p a / c
t r y m
i s .co
e m b e
. c h u t u
w w . yo
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w
NaCl, KCl, CsCl Glass, Rubber and Plastics
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Classification of Crystalline Solids
g e
p a
y
Based on the nature of inter-molecular forces and the component particles, crystalline solids are
r
classified into four types
i n
. em i st
g e h
p a / c
t r y o m
i s . c
m b
1. Molecular Solids
e e
. c h
2. Ionic Solids
u t u
w w . y
3. Metallic solido
w w
w4. Covalent solid
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p a
1. Molecular Solids
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. i n i st
g e e m
h
1. These solids have molecules as the component particles.
p a / c
y
2. In these crystals the molecules are held together by weak vander Waal’s forces of attraction.
t r
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i
3. These are subdivided into three types.
m
e tu b e
. c h u
w w . yo 1. Non polar Molecular Solids
w ww
2. Polar Molecular Solids
3. Hydrogen Bonded Molecular Solids
w
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1. Non polar Molecular Solids
p a
r y
i n
. em st
They contain either atoms (Ar and He) or the molecules formed by non polar covalent bonds
i
for example ۶ , ۱ܔ , ۱۶ and ۷ .
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g ch
p a /
t r y m
1.
i s .co
The atoms or molecules are held by weak dispersion forces or London forces
2.
e m b e
They are soft and non-conductors of electricity
3.
. c h u t u
They have low melting points and are usually in liquid or gaseous state at room temperature and pressure.
w w . yo
w ww
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2. Polar Molecular Solids
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They contain substances like HCl, ଶ , etc.
. i n sti
g e e m
p a / c h
1)
t r
They are held together by stronger y o m
dipole-dipole interactions.
i s . c
2)
m b e
These are soft and non-conductors of electricity.
e
3)
. c h
Their melting points t
are higher
u uthan those of non polar molecular solids
Solid wand solid yo are some examples of such solids.
4)
w ww w ଶ
. ଷ
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3. Hydrogen Bonded Molecular Solids
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t r y
1) They contain polar covalent bonds between H andn
. i i s
F, O or N atoms.
Strong hydrogen bonding binds moleculesg e m
of such solidselike (ice).
2)
p a / c h ଶ
3)
t r y
They are non-conductors of electricity.
m
o under room temperature and pressure.
i s or soft.csolids
4)
m
Generally they are volatile liquids
e b e
. c h u t u
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2. Ionic Solids
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r y
1) They contain ions are the constituent particles. i n st
i
g e e m
p a
2) The ions are held together by strong electrostatic
/ c h
force of attraction (Ionic bond).
t r y m
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3) These are hard and brittle in nature.
m point. e
h e
4) They possess high melting
t u b
w . c
5) These are non-conductors u in solid state but conduct in solution and molten state.
w . yo
w ww
Ex: NaCl, KCl, NaNO 3
w
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3. Metallic Solids
p a
t r
1) In these solids metal ions known as Kernels are the constituentsparticles.
y
. i n m i
g e h
2) These kernels are held together by a sea of freely moving e electrons.
p a
electricity / c
r
3) These solids are good conductors of
t y o m in solid state as well as molten state
i
due to the presence of freelysmoving.electrons.
c
e m b e
h
4) These solids are malleable
. c t u
and ductile.
w a lustrous u
5) They possess
w . y o nature due to the presence of free electrons.
wmetalsw
Ex: All w mercury
except
w
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4. Covalent Solids
p a
r y
i n
. em i st
2) These atoms are held together by strong a
e
1) These solids have non metal atoms as their constituent particles.
g bonds. h
y p covalent
/ c
s t r
3) They are also called as giant molecules.
o m
m i e . c
4) They are very hard and brittle.
h e t u b
.
5) They possess very
w c u
high melting point and may even decompose before melting.
Ex: Diamond, Graphite y
w . o
w ww
w
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p a
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t r y o m
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. c h u t u
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Crystal Lattices and Unit Cells
g e
A regular three dimensional arrangement of points in
p a
space is called a crystal lattice.
r y
i n
. em i st
e
g ch
p a /
t r y m
i s .co
e m b e
. c h u t u
The following are the characteristics of a crystal lattice
w w . yo
1) Each point in the lattice is called lattice point or lattice position (location).
w ww
2) Each point in the crystal lattice represents one constituent particle which can be an atom, molecule or ion.
w
3) The lattice point are connected by straight lines, so that the geometry of the lattice can be indicated.
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Unit Cell
p a
r y
st
It is the smallest portion of the crystal lattice which when repeated in three dimensions generates the entire
lattice.
. i n m i
g e h e
p a / c
t r y m
i s .co
m
e tu b e
. c h u
Each unit cell is characterised by 6 basic parameters.
w w . yo
w ww
(a) Unit lengths (a, b and c) along three edges of the unit cell
w
(b) Three angles (α, β and γ) between the three edges.
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p a
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. em i st
e
g ch
p a /
t r y m
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e m b e
. c h u t u
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w ww
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Types of Unit Cell
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p a
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. i n i st
Primitive (Simple)
Unit Cell
Face Centred
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Unit Cell
e m Body Centred
h
Unit Cell
p a / c
t r y m
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m
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. c h u
w w . yo
w ww
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e m b e
. c h u t u
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Packing in Crystal g e
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Close Packed Structures
i
. em st
e
g ch
p a /
t r y m
s .co (b) Close Packing (c) Close Packing
(a) Close Packing
in One Dimension
m i e
in Two Dimensions in Three Dimensions
h e t u b
w. c u
w . yo 1. Square close-packed layers
w ww
w 2. Hexagonal close packed layers
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(a) Close Packing in One Dimension
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i n
. em i st
g e h
p a / c
t r y m
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1.
m e
The number of nearest neighbours of a particle is called its coordination number.
e b
2.
. c h t u
Thus, in one dimensional close packed arrangement, the coordination number is 2.
u
w w . yo
w ww
w
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a
(b) Close Packing in Two Dimensions
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p a / c h
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e m b e
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Square close packing Hexagonal close packing
w ww
coordination number is 4 coordination number is 6.
w
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a
(c) Close Packing in Three Dimensions
r y p
1. Square close-packed layers
i n
. em i st
e
g ch
The lattice thus generated is the simple cubic lattice, and its unit cell is the primitive cubic unit cell
p a /
t r y m
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e m b e
. c h u t u
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w ww
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2. Hexagonal close packed layers
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t r y m
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e m b e
. c h u t u
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Types of Voids
g e
(Hexagonal close packed layers)
p a
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. i n i st
g e e m
p a / c h
t r y m
i s .co
m
e tu b e
. c h u
T = Tetrahedral void; O = Octahedral void
w w . yo
w ww
Let the number of close packed spheres be N
w
The number of octahedral voids generated = N
The number of tetrahedral voids generated = 2N
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(b) Placing third layer over the second layer there are two possibilities.
g e
p a
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st
(i) Covering Tetrahedral Voids:
i n
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e
g ch
p a /
t r y m
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e m b e
. c h u t u
w o
This structure is called
w . y
hexagonal close packed (hcp) structure
w ww
w
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(ii) Covering Octahedral Voids:
p a
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. i n i st
g e e m
p a / c h
t r y m
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e m b e
. c h u t u
This pattern of layers is often written as ABCABC ...........
w w . yo
This structure is called cubic close packed (ccp) or face-centred
w ww
cubic (fcc) structure.
w
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Hexagonal close packed layers
g e
there are two possibilities
p a
r y
i st
(i) Covering Tetrahedral Voids (ii) Covering Octahedral Voids
e. i n m
a g h e
y p / c
t r
s .co m
m i e
h e tu b
w. c u
w . yo
w ww
w
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Size of octahedral and tetrahedral voids
g e
p a
If the R is the radius of the sphere in the close packed structure
tr y
. i n i s
g e e m
p / c h
Radius (r) of tetrahedral voids = 0.225 R
a
t y
Radius (r) of octahedral voids = 0.414 R
r o m
i s .c
m e
In ionic solids, the bigger ions (usually anions) form the close packed structure and the smaller ions
e b
. c h u t u
(usually cations) occupy the voids.
w
If the latter ion is small enough then tetrahedral voids are occupied, if bigger, then octahedral voids.
Not all octahedral or tetrahedral voids are occupied.
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Locating Tetrahedral and Octahedral Voids
g e
p a
We know that close packed structures have both tetrahedral and octahedral voids.
r y
i n i
Let us take ccp (or fcc) structure and locate these voids in it.
. em st
e
g ch
p a /
Locating Tetrahedral Voids
t r y m
s .co
Let us consider a unit cell of ccp or fcc lattice
m i e
h e t u b 1. There is one tetrahedral void in each small cube and eight tetrahedral
w. c u
o
voids in total.
w . y 2. Each of the eight small cubes have one void in one unit cell of ccp
w ww structure.
w 3.
4.
We know that ccp structure has 4 atoms per unit cell.
Thus, the number of tetrahedral voids is twice the number of atoms.
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Locating Octahedral Voids
g e
p a
Let us consider a unit cell of ccp or fcc lattice
r y
. i n i st
g e e m
p a / c h
t r y o m
i s .c
e m b e
. c h u t u
w w . o
One octahedral void at the
y
body centre of the cube.
One octahedral void at the centre
w ww
of each of the 12 edges
w
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Radius Ratio Rule
g e
p a
y
For the stability of an ionic compound each cation should be surrounded by maximum number of anion and vice versa
r
st
The umber of opposite charge ions surrounding each ion is called its coordination numbers
i n
. em i Radius (r) of tetrahedral void = 0.225 R;
e
g ch
Radius (r) of octahedral void = 0.414 R
p a /
where R is the radius of the spheres in close packing.
t r y m
s .co
Greater the radius ratio the largest is the size of the cation and hence greater is its CN
m i e
h e t u b
w. c u
w . yo
w ww
w
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Relationship of Atomic Radii and Edge Lengths
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p a
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. i n i st
g e e m
p a / c h
t r y o m
i s .c
e m b e
. c h u t u
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Relationship of Atomic Radii and Edge Lengths
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. em i st
e
g ch
p a /
t r y m
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e m b e
. c h u t u
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w ww
w
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Packing Fraction or Packing Efficiency
g e
p a
Packing efficiency is the percentage of total space filled by the particles.
r y
. i n i st
g e e m
p a / c h
t r y m
i s .co
e m b e
. c h u t u
w w . yo
w ww
w
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p a
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. i n ist
g e e m
p a / c h
t r y o m
i s .c
e m b e
. c h u t u
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Calculations of density of Solids
g e
p a
r y
. i n i st
g e e m
p a / c h
t r y m
i s .co
e m b e
. c h Z =
u t u
number of atoms per unit cell
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Imperfections in solids
g e
The defects are basically irregularities in the arrangement of constituenty p a
s t r particles.
. i n m i
g e h e
Point defects
p a / c Line defects
t r y o m
i s or an e.c
The irregularities or deviations from The irregularities or deviations
atom in a crystallinee
m
ideal arrangement around a point
substance b
from ideal arrangement in entire
w w . yo
w ww
w
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Types of Point Defects
p a
r y
. i n st
i
g e e m
1) stoichiometric defects
p a
2) impurity defects
/ c h 3) non-stoichiometric defects
t r y m
i s .co
1. Vacancy defect
e m b e 1. Metal excess defects
w w
2. Interstitial defect
. yo
w defect
3. Schottky
w w
w
4. Frenkel defect
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g e
p a
1. Vacancy defect
r y
2. Interstitial defect
. i n i 1. st
When some constituent particles occupy an
1.
e
When some of the lattice sites are vacant
g e m
h
interstitial site
2.
a c
This results in decrease in density of the substance.
p /
y
2. This defect increases the density of the substance
3.
r m
This defect can also develop when a substance is heated.
t
s .co
m i e
h e t u b
w. c u
w . yo
w ww
w
Vacancy and interstitial defects shown by non-ionic solids.
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Frenkel and Schottky Defect
g e
p a
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i n
. em i st
e
g ch
p a /
t r y m
i s .co large difference in the size of ions
e m e
KCl, AgBr
b
AgCl, AgBr
. c h u t u
w w . yo
w ww
w
1. Vacancy defect in ionic solid
2. Electrical neutrality maintain
3. AgBr shows both, frenkel as well as schottky defects
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Impurity Defects
g e
p a
r y
1. If molten NaCl containing a little amount of ܚ܁۱ܔ is crystallised
. i n i st
2.
g e e m
Some of the sites of ܉ۼା ions are occupied by ܚ܁ା
3.
a
Each ܚ܁ା replaces two Na+ ions.
p / c h
4.
t r y m
It occupies the site of one ion and the other site remains vacant.
i s .co
e
5. The cationic vacancies thus produced are equal in number to that of ܚ܁ା ions.
m
e tu b
6.
. c h
Example ܚ܁۱ܔ , ۱܌۱ܔ and AgCl.
u
w w . yo
w ww
w
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3) Non-Stoichiometric defects 1. Metal excess defects
p a
2. Metal deficiency defect
r y
i n
. em i st
e
1. Metal excess defects
a g c h
p /
Metal excess defect due to anionic vacancies
t r y m
s .co
1. This happens by loss of electron by sodium atoms to form Na+ ions.
m i 2.
e The released electrons diffuse into the crystal and occupy anionic sites
w. c u
w . yo 4. The anionic sites occupied by unpaired electrons are called F-centres.
w ww 5.
6.
They impart yellow colour to the crystals of NaCl.
The colour results by excitation of these electrons when they absorb
w energy from the visible light falling on the crystals.
7. Similarly, excess of lithium makes LiCl crystals pink and excess of
potassium makes KCl crystals violet
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1. Metal excess defects
p a
r y
i n
. em st
Metal excess defect due to the presence of extra cations at interstitial sites
i
e
g ch
a
1. Zinc oxide is white in colour at room temperature.
r y p /
2. On heating it loses oxygen and turns yellow.
m
i t
s .co
e m b e
. c h u t u
w w . yo 1. The excess ܖ܈ା ions move to interstitial sites and the electrons to
w 2. Now there is excess of zinc in the crystal and its formula becomes
ܖ܈ା۽ ܆.
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(ii) Metal Deficiency Defect
p a
r y
1.
n i
In metal deficiency defect, a cation is missing from its lattice site.
i
. em st
2.
e
To maintain electrical neutrality, one of the nearest metal ions acquires an extra
g ch
positive charge.
p a /
3.
t r y m
This type of defect occurs in compounds where the metal can exhibit variable
i s .co
m e
valency. e.g., Transition metal compounds.
e b
4.
. c h u t u
Example: Ferrous oxide, Nickel oxide.
w w . yo
w ww
w
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. em i st
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g ch
p a /
t r y m
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e m b e
. c h u t u Gd
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. i n i s
g e e m
p a / c h
t r y o m
i s .c
e m b e
. c h u t u
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Band Theory
p a
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. em i st
g e h
p a / c
t r y m
i s .co
e m b e
. c h u t u
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Conduction of Electricity in Semiconductors
p a
r y
st
1. Their conductivity is increased by adding an appropriate amount of suitable impurity.
2. This process is called doping.
i n
. em i
e
g ch
p a /
t r y
Doping
m
i s .co
m e
By adding an appropriate amount of suitable impurity to increase the conductivity of semiconductors.
e b
. c h u t u
w w . yo
w ww
w
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n-type semiconductor p-type semiconductors
g e
p a
r y
. i n i st
g e e m
p a / c h
t r y o m
i s .c
e m b e
. c h u t u
w w . yo Applications of n-type and p-type semiconductors
w ww
w
1. They are used for making electronic components.
2. Diode is a combination of n-type and p-type semiconductors and is used as a rectifier.
3. Transistors are type of semiconductor used to detect or amplify radio or audio signals.
4. The solar cell is an efficient photo-diode
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