The Solid State
The Solid State
The Solid State
Singh Bhadouriya
Photovoltaic Material: The material which converts sun light into electricity is called photo voltaic material.
[ Amorphous silica ]
Crystalline solid
[1] In a crystalline solid the particles (atoms, molecules or ions) are arranged in a regular and repetitive
three dimensional arrangements
[2] These solids have sharp melting point.
[3] These solids are anisotropic, i.e. their physical properties such as electrical conductivity, refractive
index, thermal expansion etc. have different values in different directions.
[4] These solids can under go a clean cleavage.
[5] These solids are generally incompressible.
Examples: All the metallic elements like iron, copper and silver;
Non – metallic elements like sulphur, phosphorus and iodine and
Compounds like sodium chloride, zinc sulphide and naphthalene
Amorphous solid
[1] In amorphous solid the particles (atoms, molecules or ions) are arranged in an irregular and
non repetitive three dimensional arrangements.
[2] Rapidly solidified liquids are amorphous substances, e.g. Glass, rubber etc.
[3] These solids are generally isotropic, i.e. physical properties are same in all directions.
[4] These solids on cleavage form smaller pieces with non-planar faces.
[5] These solids do not have sharp melting point and boiling point i.e. they melt gradually over a
temperature range.
[6] These solids are compressible.
What makes a glass different from a solid such as Quartz? Under what conditions quartz could be
converted into glass?
In glass, amorphous silica ( SiO2 ) is present. SiO4 tetrahedral have an irregular arrangement.
In quartz, crystalline silica ( SiO2 ) is present. SiO4 tetrahedral have a regular arrangement.
When quartz (SiO2 ) is melted and the melt is cooled very rapidly, quartz converted into glass.
Fluid
Liquids and gases are called fluids because of their ability to flow. The fluidity is due to the fact that the
molecules are free to move about.
Why glass pans fixed to windows or doors of old building are invariably found to be slightly thicker at the
bottom than at the top?
Due to fluidity property, the glasses flows down very slowly and make the bottom portion slightly thicker.
Why some glass objects from ancient civilizations are found to become milky in appearance?
Glass becomes crystalline at some temperature. For which glass objects from ancient civilizations become
milky in appearance because of some crystallization.
Types of solid
Types of solid Constituent Attractive forces Examples Physical Electrical conductivity Melting
particles nature point
[1] Molecular solids Molecules
(a) Non-polar Dispersion or London forces Ar, CCl4 , H2 , I2 , CO2 Soft Insulator Very low
(b) Polar Dipole-dipole interactions HCl , SO2 Soft Low
Insulator
(c)Hydrogen bonded Hydrogen bonding H2O ( ice) Hard Low
Insulator
[2] Ionic solids Ions coulombic or electrostatic Na Cl, MgO,ZnS , Ca F 2 Hard but Insulator in solid state but
conductors in molten state and in High
brittle
aqueous solutions
[3] Metallic solids Positive ions Fe, Cu, Ag, Mg Hard but
in a sea of Metallic bonding malleable Conductors in solid state Fairly high
delocalised and as well as in molten state
electrons ductile
[2] Non-Primitive unit cell / centered unit cell- In this type of unit cells, particles as points are present not
only at the corners but also at some other positions.
[Particles as points are located at the corners [ Particles as points are located at the corners
and also at the centre of the cube] and also in the centre of each face ]
End-centred- Particles as points are located at the corners and laso at the centres of any two opposite faces
- Ten lattice points
Parameters of a unit cell Depending upon the symmetry of the axial distance(a,b,c)and also the axial anglebetween
the edge ( ) the various crystals can be divided into seven systems . Further the
Z seven crystal systems on the basis of unit cells present, classified into fourteen different
types of lattices , called Bravis lattices
Relationship between edge length (a) and radius of the sphere ( r ) in unit cell.
4
For FCC , a = 2 2 r For BCC , a = r For simple cubic , a=2r
.
.
3
.
.
Calculate the efficiency of packing in case of a metal crystal for Simple cubic, body centred cubic and face
centred cubic
[1] For simple cubic a=2r Rank ( Z ) = 1 3
4 r
So volume occupied by one sphere in the unit cell = π
Volume of the unit cell = ( 2 r ) 3 = 8r3 3
4 r3
3
π
Hence, packing efficiency = x 100 = 52.36 %
8r3
[2] For body centred cubic
4
ra= Rank (z) =2
.
3
.
3 .
4 r .
3
.
3
.
π
4x 4 r3 π
3
So packing efficiency = x 100 = 74 %
2 2r 3
.
.
Gold(At.radius= 0.144nm)crystallizes in aFCC unit cell. What is the length of the side oftheunitcell?
Atomic radius= 0.144 nm
So, length of side a = 2 √ 2 r = 2 √ 2 x 0.144 = 0.406 nm
Aluminum crystallizes in a cubic closed packed structure. Its metallic radius is 125 pm.
[1] What is the length of the side of the unit cell ?
[2] How many unit cells are there in one c.c of aluminium?
[1] For FCC , a = 2 √ 2 r = 2 √ 2 x 125 = 354 pm, So the edge length of the unit cell = 354 x 10 -10 cm
[2] Volume of unit cell = a3 = ( 354 x 10 -10 ) 3 cm 3
Therefore, number of unit cells in 1 cc of aluminum = 1/ ( 354 x 10 -10 ) 3 cm 3 = 2.254 x 10 22 Unit cells
Radius ratio in ionic crystal
The ratio of the radius of the smaller sphere with that of the larger is called the radius ratio.
Radius of cation ( r + )
Radius ratio in ionic crystal =
Radius of anion ( r - )
High pressure increases the cordination number and high temperature decreases the cordination number
Thus high pressure converts NaCl structure into CsCl structure and high temperature converts CsCl into
NaCl
If the radius of the octahedral void is r and radius of the atoms in close packing is R,
derive relation between r and R.
The figure shows the cross section of an octahedral void. In Triangle ABC, BC 2 = AB2 + AC2 A
r
r
.
=> 2 R2 = (r + R) 2
=> r+R = 2 R
.
=> R +1= 2
.
=> = 2 -1 =1.414 -1
. .
.
R
r =0.414 R
=>
Ferric oxide crystallizes in a hexagonal closed pack array of oxide ions with two out of every three
octahedral holes occupied by ferric ions. Deduce the formula of the ferric oxide.
No. of atoms in one unit cell of hcp structure = 6 No. of oxide ions per unit cell = 6
No. of octahedral voids = 6
Since ferric ions occupy only two out of every three octahedral voids, there fore, no. of octahedral voids
occupied by ferric ions = ( 2/3 ) x 6 = 4 Stoichiometric ratio of Fe 3+ and O 2- is 4 : 6 = 2 : 3
Hence the formula of ferric oxide is Fe2O3
Analysis shows that nickel oxide has the formula Ni 0.98 O 1.00. What fraction of nickel exist as Ni 2+
and Ni3+ ions?
Let amount of Ni3+ be x mol. Then amount of Ni2+ is (0.98 – x)
Total oxidation number of Ni in the compound is 3x + 2 (0.98 – x)
Oxidation number of oxygen is -2
Since the sum of the oxidation number of all the constituents in a compound is zero.
=> 3x + 2 (0.98 – x) – 2 = 0 => 3x + 1.96 – 2x – 2 = 0 => x = 0.04
Hence % of Ni3+ = ( 0.04 / 0.98 ) x 100 = 4.08 % % of Ni2+ = 100 – 4.08 = 95.92 %
Relationship between density (d) and the dimension of unit cells.
Let the edge length of unit cell be a There fore volume of unit cell = a 3
Let no. of atoms in unit cell = Z Gm. Atomic mass = M
There fore mass of one atom = M / NA Where NA = Avogadro’s number i.e. 6.023 x 1023
Mass of Z atoms = ZM ZM
NA Mass of unit cell NA ZM
Density of unit cell ( d ) = = d=
Volume of unit cell
a3 a3 NA
Silver crystallizes in FCC lattice. If edge length of the cell is 4.05 x 10 –8 cm and density is
10.5 gm/cm3 . Calculate atomic mass of silver.
Given data-
Edge length ( a ) = 4.07 X 10 – 8 cm Density ( d ) = 10.5 gm/ cm 3
Since silver crystallizes in fcc lattice, so rank , i.e. the no. of silver atoms per unit cell ( z ) = 4
NA = 6.023 X 10 23
So d =
ZM d a3 NA 10.5 X ( 4.07 X 10 -8 ) 3 X 6.023 X 10 23
M= M = 4
a3 NA z
= 107.1 gm / mol
So atomic mass of silver = 107.1 amu
Niobium crystallizes in body-centered cubic structure. If density is 8.55 g / cm3, calculate atomic
radius of niobium using its atomic mass 93 u .
.
.
a= ( 36.09 X 10 - 24 ) 1/3 = 3.305 X 10 -8
cm
4 a -8
r = 3 3 X 3.305 X 10
.
.
In bcc, a = r
.
r
.
-8
3 = 1.43 X 10 cm = 14.3 nm
.
4 =
4
Copper crystallises into a fcc lattice with edge length 3.61 × 10 -8 cm. Show that the calculated
density is in agreement with its measured value of 8.92 g cm -3.
For fcc , rank ( Z ) = 4 ; Edge length,( a ) = 3.61 X 10 - 8cm ; Mol.mass ( M )= 63.5 gm/mol.
ZM
d= 4 X 63.5
a3 NA d= = 8.96 gm / cm3
( 3.61 X 10 -8 ) X 6.023 X 10 23
So, the measured value is nearly equal to the calculated value
Frenkel defect
[1] When an ion leaves its position in the lattice and occupy interstitial site leaving a gap in the crystal i.e.
it creates a vacancy defect and interstitial defect.
[2] This defect will occur if size of cation is smaller than anion, with low coordination number.
[3] Frenkel defects are not found in pure alkali halide. Due to larger size of cations, ions can not
accommodate in interstitial site.
[4] Frenkel defect are found silver halide, because silver ions are smaller in size and can get into the
interstitial site.
[5] The Frenkel defect does not change the density of the solid.
[6] In silver bromide, both Schottky and Frenkel defects are found.
Metal excess defect
[a] F-Centers ( Farbe: means colour )
[1] When there is an excess of metal ions in non-stoichiometric compounds, the crystal lattice has vacant
anion site. The anion sites occupied by electrons are called F-centre.
[2] The F-centers are associated with the colour of the compounds. Excess of K in KCl makes the crystal
violet. Excess of Li in LiCl makes the crystal pink.
[3] Solid containing F-centre are paramagnetic, because the electrons occupying the F-centers are
unpaired.
[4] When the crystal having F-centers are exposed to light, they become photoconductor.
[b] Metal excess defect due to presence of extra cation at the interstitial site
Zinc oxide is white in colour at room temperature on heating, it looses oxygen and turns yellow.
Now there is excess of zinc in the crystal and its formula becomes Zn 1+ x O
The excess zinc ions move to interstitial site and the electrons to neighboring interstitial site.
Metal deficiency defect
FeO, mostly found with a composition of Fe 0.95 O i.e. range from Fe0.93O – Fe0.96O. In crystals of FeO, some
Fe2+ ions are missing and the loss of positive charge is made up by the presence of required number of
Fe3+ ions.
Electron sea model of metallic bonding
[1] A metal consists of a lattice of positive ions ( Kernel ) immersed in a sea of valence electrons ( mobile
electrons )
[2] The force of attraction between the mobile electrons and the the kernels is known as metallic bond.
[3] The electrical and thermal conductivity of metals can be explained by the presence of mobile electrons
in metal.
The Band Model Of Metallic Bonding
The band model of metal is based on molecular orbital theory.
When a large no. of orbital overlap in metal, it results a continuous energy level produced by a large
number of molecular orbital is called energy band.
[ conductor ]
1s2 1s- band
Valence band
[ Semi conductor ]
Conductivity of Insulator 10 -20 - 10-10 ohm -1
m -1
[ Insulator ]
Semiconductor 10 - 6 - 104 ohm -1
m -1
If NaCl is doped with 10-3 mol % of SrCl2. What is the concentration of cation vacancies?
The addition of SrCl2 to NaCl produces cation vacancies equal in number to that of Sr2+ ions.
No. of moles of SrCl2 added to one mol of NaCl = 10-3 / 100 = 10-5 mol.
No. of holes created in one mole of NaCl = 10-5 X 6.023 X 1023 = 6.023 x 1018
Semiconductor
These are solids whose conductivity lies in between those of conductors and insulators. The conductivity
of semiconductors increases with increase of temperature.
Intrinsic semiconductor
An insulator capable of conducting electric current at higher temperature or when irradiated with
electromagnetic radiations, are known as intrinsic semiconductor.
This happens because certain covalent bonds are broken and the released electrons are in a position to
conduct electric current. e.g. Silicon , Germanium.
Extrinsic semiconductor
These are formed when impurities of certain elements are added (doped) to insulator.
N-type semiconductors
It is obtained by doping group – 14 elements with group – 15 elements.
Suppose Si is doped with P with 5 valence electrons, out of 5 valence electrons, only 4 valence electrons
are involved in bond formation.
The fifth electron is not bound any where and can be easily promoted to the conduction band. The
conduction is thus mainly caused by the movement of electrons.
P-type semiconductors
It is obtained by doping group – 14 elements with group – 13 elements.
Suppose Si is doped with Ga which has 3 valence electrons, 3 valence electrons are involved in bond
formation with neighboring Si atom.
A vacancy is left which can be filled by the transfer of a valence electron from a neighboring Si atom.
The movement of electron into the vacancy leaves behind a hole which carries positive charge.
Another electron from a neighboring Si atom can move into the hole leaving behind another hole. It
appears as if the hole has moved through the lattice.
The movement of positively charged hole is responsible for the conduction of charge.