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whole chemistry By – Dr . C.K.Rai
Unit -1 Class – 12th (Solid state)
Solid
• Definite shape ,volume & mass .
• High density & low compressibility.
• Short Intermolecular distance.
• Strong intermolecular force .
• Definite M .P.
• Incompressible .
• Rigid.
• There Atoms / ions / molecules have fixed position.
Types of Solid
1. Amorphous solid 2. Crystalline solid

Amorphous Solid
• Shapeless solid
• Not definite geometrical shape
• Not regular arrangement of its ion / atom / molecule .
• ion / atom / molecule arrange short range only.
• Not sharp M.P
• Isotropic (Same physical property in all direction) .
• Not definite heat of fusion .
• Not very rigid .
• Irregular cut .
• Pseudo solid & super cooled liquid .
• Not any symmetry .
• Eg – glass , rubber , plastic etc

Crystalline solid
• Definite geometrical shape
• Regular arrangement of its ion / atom / molecule .
• ion / atom / molecule arrange short range as well as long range order .
• Sharp M.P
• Anisotropic (different physical property in different direction)
• Definite heat of fusion .
• Very rigid .
 • Regular cut & undergo clean cleavage.
• True solid .
• They have Plane of symmetry .
• Eg – all solid
Types of crystalline solid
1. Ionic solid
2. Molecular solid
3. Covalent solid (Network solid )
4. Metallic solid
Ionic solid
• The solid are formed by the cations and anions with strong electrostatic forces that is
known as ionic solid .
• Hard & brittle
• High M.P & B.P
• Soluble in polar solvent.
• Insoluble in non-polar solvent.
• Electric insulator in solid state .
• Good conductor in molten state .
• Eg – NaCl , MgO , ZnS
Molecular solid
The solid are formed by molecule is known as molecular solid .Eg - 𝑯𝟐 , 𝑯𝟐 O , C𝑶𝟐 etc
Types of molecular solid
1. Polar molecular solid
2. Non-polar molecular solid
3. Hydrogen bounded molecular solid .
Non - Polar molecular solid
The solid are formed by non - polar molecule is known as non - polar molecular solid .
• Soft
• Non conductor of electricity .
• Low M.P & B.P.
• Low Density and Volume .
• Weak London dispersion forces. Eg - 𝑯𝟐 , 𝑪𝒍𝟐 , 𝑰𝟐
Polar molecular solid
• The solid are formed by polar molecule is known as polar molecular solid .
• Soft
• Dipole – Dipole force of attraction .
• Non conductor of electricity .
• M.P & B.P are higher then non-polar molecular solid .
• Density & volume are higher then non-polar molecular solid .
• Eg – HCl , NaCl
Hydrogen bonded molecular solids :-
• The solid is formed by polar covalent bonds between H & F O , N - atoms or hydrogen
bond is known as hydrogen bonded molecular solid .
• Exist as volatile liquid at R T P .
• Non conductor of electricity .
• MP & BP are higher then polar & non polar molecular solid.
• Eg - 𝐇𝟐 𝐎 , N𝐇𝟑
Covalent or Network solid
• The solid is formed by non-metal atoms linked to the adjacent atoms by covalent
bonds through out the crystal is known as covalent or network solids .
• Very hard and brittle.
• Extremely high MP .
• Do not conduct electricity .
• Eg – Diamond , Silicon Carbide , graphite (exception ) .
Metallic solid
• The solid is formed by positively charged metal ions and sea of free electrons with
help of metallic bond is known as metallic solid .
• Very hard
• High electrical & thermal conductivity .
• Highly malleable and ductile .
• High M P
• High density .
• Luster
• color in some case
Space lattice or crystal lattice
• It is the arrangement of various points show how the atoms , molecule or ions of a
crystal are arranged in 2D or 3D – Space .
• Each point in a lattice is called lattice point or lattice site .
• Each point in a crystal lattice represents may be an atom , a molecule or an ion .
• Lattice points are joined by straight lines to bring out the geometry of lattice .
Types of Lattice
1. Two dimensional lattice 2. Three dimensional lattice
Types of two dimensional lattice
1. Square lattice 2. Rectangular lattice 3. Parallelogram lattice 4. Rhombic lattice
5. Hexagonal lattice
Unit cell
• The smallest 2D & 3D repeated portion of a crystal lattice is known as unit cell.
• Its dimensions along the three edges a , b , c .there edges may or may not be mutually
perpendicular .
• Angle between the edge is , 𝜷, 𝜸 .
• A crystal lattice may be consists of infinite number of unit cell .
 In cube
• Edges = 12
• Face = 6
• Corner or vertex = 8
• Body Centered = 1
• Edge Centre = 12
• Face Centre = 6
• Face diagonals = 12
• Body diagonal = 4
Types of unit cell
1. Simple unit cell (primitive unit cell ) 2. Centred unit cell
Simple unit cell (primitive unit cell ) :-
When the atoms , ions or molecule are presented only on the corner position of a unit cell
is known as primitive or sample unit cell .
Types of Simple unit cell (primitive unit cell )
1. Cubic unit cell
Edges - a = b= c Angles - 𝜶 = 𝜷 = 𝜸 = 𝟗𝟎𝒐 Eg – NaCl , KCl , ZnS
2. Orthorhombic
Edges - 𝐚 ≠ 𝒃 ≠ 𝒄 Angles - 𝜶 = 𝜷 = 𝜸 = 𝟗𝟎𝒐 Eg - KN𝑶𝟑 , BaS𝑶𝟒 , 𝑲𝟐 𝑺𝑶𝟒
3. Tetragonal
Edges - 𝐚 = 𝒃 ≠ 𝒄 Angles - 𝜶 = 𝜷 = 𝜸 = 𝟗𝟎𝒐 Eg - Ti𝑶𝟐 , PbW𝑶𝟒 , 𝑺𝒏𝑶𝟐
4. Monoclinic

Edges - 𝐚≠ 𝒃 ≠ 𝒄 Angles - 𝜶 = 𝜸 = 𝟗𝟎𝒐 , 𝜷 ≠ 𝟗𝟎𝒐 Eg - KC𝒍𝑶𝟑 , CaS𝑶𝟒 , 𝑺𝒏𝑶𝟐 2𝑯𝟐 𝑶

5.Triclinic
Edges - 𝐚≠ 𝒃 ≠ 𝒄 Angles - 𝜶 ≠ 𝜷 ≠ 𝜸 = 𝟗𝟎𝒐 Eg – ZnO , CdS

6.HexagonalEdges - 𝐚=𝒃 ≠𝒄

Angles - 𝜶 = 𝜷 = 𝟗𝟎𝒐 , 𝜸 = 𝟏𝟐𝟎𝒐 Eg - Zn𝑶𝟐 , CdS , HgS

7.Rhombohedral

Edges - 𝐚 = 𝒃 = 𝒄 Angles - 𝜶 = 𝜷 = 𝜸 ≠ 𝟗𝟎𝒐 , Eg - NaN𝑶𝟑 , 𝐈𝐂𝐥

Centred unit cell or Non-primitive unit cell
When a unit cell contains one or more atom / molecules / ions are present corners and other
position of unit cell .
 Types of centered unit cell
1. Body Centred Unit Cells
2. Face Centred Unit Cells:
3. End Centred Unit Cell:
Body Centred Unit Cells
When a unit cell contains one atom / molecules / ions at its center within the body and ones
each corners .

Types of Body Centred Unit Cells :-

1.Cubic Body Centred Unit Cells.
2. Tetragonal Body Centred Unit Cells
3. Orthorhombic Body Centred Unit Cells
Face Centred unit cell
If the unit cell contain one atoms , molecules or ions present at the center of each face
and ones that each corners is known as face centered unit cell .
Types of Face Centred unit cell
1. Cubic Face Centred unit cell
2. Orthorhombic Face centred unit cell
End centred unit cell
If the unit cell contain one atoms , molecules or ions present at the center of two
opposite face and ones that each corners is known as end centered unit cell .
Types of End Centred unit cell
1. Orthorhombic Face Centred unit cell
2. monoclinic end centred unit cell
Contribution of atom in unit cell
𝟏
1. Contribution by a particle on the corner of a unit cell =
𝟖
𝟏
2. Contribution by a particle on the face of a unit cell =
𝟐
3. Contribution by a particle on the body of a unit cell = 1
𝟏
4. Contribution by a particle on the edge of a unit cell =
𝟒
5. Total number of atom per unit cell
𝟏 𝟏
Z = ( × 𝑵𝒄 ) + ( × 𝑵𝒇 ) + ( 𝟏 × 𝑵 𝒃 )
𝟖 𝟐
Calculation of number of atom in unit cell
1. Simple unit cell (primitive unit cell )
𝟏 𝟏
Z=( 𝟖
× 𝑵𝒄 ) + ( 𝟐
× 𝑵𝒇 ) + ( 𝟏 × 𝑵𝒃 )
𝟏 𝟏
=( 𝟖
× 𝟖) + ( 𝟐
× 𝟎) + ( 𝟏 × 𝟎) = 1
2. Body Centered Unit Cells
𝟏 𝟏
Z=( × 𝑵𝒄 ) + ( × 𝑵𝒇 ) + ( 𝟏 × 𝑵𝒃 )
𝟖 𝟐

𝟏 𝟏
=( 𝟖
× 𝟖) + ( 𝟐
× 𝟎) + ( 𝟏 × 𝟏) = 2

3. Face centered unit cell

𝟏 𝟏
Z=( × 𝑵𝒄 ) + ( × 𝑵𝒇 ) + ( 𝟏 × 𝑵𝒃 )
𝟖 𝟐
𝟏 𝟏
=( × 𝟖) + ( × 𝟔) + ( 𝟏 × 𝟎) = 4
𝟖 𝟐
Atomic radius of unit cell

Relation between nearest neighbor distance and edge of unit cell

1. Simple unit cell (primitive unit cell )
x = a = edge length
2. Body Centred Unit Cells
√𝟑
X= 𝒂
𝟐

3. Face centred unit cell

𝒂
X=
√𝟐

Where x = nearest neighbor distance , a = edge length , r = atomic radius

Density of a cubic crystal
𝒁×𝑴 𝒈
• Density of unit cell = 𝟑 ⁄𝒄𝒎𝟑
𝒂 ×𝑵𝒐

Where
Z = Number of atom present per unit cell , M = Atomic mass of the element.
a= edge of unit cell , 𝑵𝒐 = Avogadro’s number = 6.023× 𝟏𝟎𝟐𝟑

1. Simple cubic lattice (Z=1 & a = 2r)

𝟏×𝑴 𝒈
Density of unit cell = ⁄𝒄𝒎𝟑
(𝟐𝒓)𝟑 ×𝑵𝒐
 𝟒𝒓
2. Body centred cubic lattice (z = 2 & a = )
√𝟑

𝟐 ×𝑴 𝒈
Density of unit cell = 𝟒𝒓 ⁄𝒄𝒎𝟑
( )𝟑 ×𝑵𝒐
√𝟑

3. Face centred cubic lattice (z = 4 & a = 2√𝟐 𝐫 )

𝟒 ×𝑴 𝒈
Density of unit cell = 𝟑
⁄𝒄𝒎𝟑
(𝟐√𝟐 𝒓) ×𝑵𝒐
Packing fraction
It is the ratio of volume of unit cell that is occupied by spheres of the unit cell to the total
volume of unit cell .
𝟒
𝒗𝒐𝒍𝒖𝒎𝒆 𝒐𝒄𝒄𝒖𝒑𝒊𝒅 𝒃𝒚 𝒔𝒑𝒉𝒆𝒓𝒆 𝒁 × 𝝅 𝒓𝟑
𝟑
𝒑𝒂𝒄𝒌𝒊𝒏𝒈 𝒇𝒓𝒂𝒄𝒕𝒊𝒐𝒏 = =
𝒗𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒖𝒏𝒊𝒕 𝒄𝒆𝒍𝒍 𝒂𝟑
𝒂
1. Simple cubic lattice (Z = 1 & r = )
𝟐
𝟒 𝟒 𝒂 𝟑
𝒁 × 𝝅 𝒓𝟑 𝟏× 𝝅( )
𝟑 𝟑 𝟐
𝒑𝒂𝒄𝒌𝒊𝒏𝒈 𝒇𝒓𝒂𝒄𝒕𝒊𝒐𝒏 = = = 0.52
𝒂𝟑 𝒂𝟑

It means that 52% of unit cell is occupied by atoms and 48% is empty .
√𝟑𝒂
2. Body centred cubic lattice (Z = 2 & r = )
𝟒
𝟒 𝟒 √𝟑𝒂 𝟑
𝒁 × 𝝅 𝒓𝟑 𝟐× 𝝅( )
𝟑 𝟑 𝟒
𝒑𝒂𝒄𝒌𝒊𝒏𝒈 𝒇𝒓𝒂𝒄𝒕𝒊𝒐𝒏 = = = 0.68
𝒂𝟑 𝒂𝟑

It means that 68% of unit cell is occupied by atoms and 32% is empty .
𝒂
3. face centred cubic lattice (Z = 4 & r = )
𝟐√𝟐
𝟒 𝟒 𝒂 𝟑
𝒁 × 𝝅 𝒓𝟑 𝟒× 𝝅(
𝟑 𝟐√𝟐
)
𝟑
𝒑𝒂𝒄𝒌𝒊𝒏𝒈 𝒇𝒓𝒂𝒄𝒕𝒊𝒐𝒏 = = = 0.74
𝒂𝟑 𝒂𝟑

It means that 74% of unit cell is occupied by atoms and 26% is empty .

Co-ordination number
• Number of nearest neighbors atom .
• It is depends upon structure of unit cell .
1. Simple Unit Cell = 6
2. Body Centered Unit Cells = 8
3. Face Centered Unit Cells = 12
Close packed structures

The packing of spheres takes place in such a way that they occupy the maximum available
space and there is minimum empty space and hence the crystal has maximum density . This
types of packing is called closed packing .
 Types of closed packing
1. Close packing in one dimension
2. Close packing in two dimension
3. Close packing in three dimension
Close packing in one dimension
Each sphere is in contact with two of its neighbours.
Co-ordination number = 2.
Close packing in two dimensions
when the rows are stacked over each other a two dimensional closed packed produced.
The rows of close packed spheres in two ways
(1) Square close packing (2) Hexagonal close packing.
The above those of the first row. This way the spheres are aligned horizontally as well as
vertically.
 The arrangement is AAA type.
 The co-ordination number is 4e spheres of the second row are placed exactly
2-D Hexagonal close packing
• The spheres of the second row are placed above the first one in a staggered manner in
such a way that its spheres fit in the depression of the first row.
• The arrangement is ABAB type.
• Co-ordination number = 6.
Close packing in three dimensions
They can be obtained by stacking the two dimensional layers one above the other.
It can be obtained in two ways
i) Square close packed layers ii) Hexagonal close packed layers.
3-D square close packed layers
The spheres of the upper layer are placed exactly over the first layer such the spheres of the
layers are perfectly aligned horizontally and vertically. It has a AAAA type pattern. The lattice
is simple cubic lattice.
3-D Hexagonal close packed layers
There are two steps involved as
I) Placing the second layer over the first layer
ii) Placing the third layer over the first layer
Void or hole
• There is a always empty space between atom when they are closed pack. The empty space are called
void or hole.
 Types of void or hole
1. Tetrahedral void 2.Octahedral void
1. Tetrahedral void
A simple triangular void in a crystal is surrounded by four sphere of tetrahedral void or
holes.
2. Octahedral void
A double triangular void in a crystal is surrounded by six sphere of octahedral void or holes.

Important point :-
𝑹𝒕𝒆𝒕𝒓𝒂𝒉𝒆𝒅𝒓𝒂𝒍 𝒗𝒐𝒊𝒅
• = 0.225
𝑹𝒔𝒑𝒉𝒆𝒓𝒆
𝑹𝒐𝒄𝒕𝒂𝒉𝒆𝒅𝒓𝒂𝒍 𝒗𝒐𝒊𝒅
• = 0.414
𝑹𝒔𝒑𝒉𝒆𝒓𝒆
• Number of 𝒐𝒄𝒕𝒂𝒉𝒆𝒅𝒓𝒂𝒍 𝒗𝒐𝒊𝒅 = N
• Number of Tetr𝒂𝒉𝒆𝒅𝒓𝒂𝒍 𝒗𝒐𝒊𝒅 = 2N
where N = number of sphere in closed pack lattice .
Defects & impurity in solids
Any irregularities in the arrangement of atom in crystal is called defect in solid .
Types of defect
1. Point defect 2. Crystal defect 3. Line defect
Point defect
When the irregularities exist from the ideal arrangement around a point or an atom in a
crystalline substance .
Types of point defects
1. Vacancy defects 2.Interstitial defects 3. Schottky defects 4. Frenkel defects
Vacancy defects
• When some of the lattice sites are vacant the crystal is said to have vacancy defect .
This defects can also develop when a substance is heated.
Interstitial defects
• When some constituent particles occupy an interstitial site the crystal is said to have
interstitial defects.Couse of this defects increases the density of substance.
Schottky defects
• If in a ionic crystal of the type 𝑨+ 𝑩− equal number of cation and anion are missing from
their lattice sites so that the electrical neutrality is maintained.
• The density is decreases Couse of this defects .
• Cation and anion are almost similar size.
• Eg NaCl, KCl , KBr
Frenkel defect
• If an atom missing from its lattice site and it occupies the interstitial site but electrical
neutrality as well as the stoichiometry of the compound are maintained.
• The density of solid remains unchanged.
• The large difference of size of cation and anion .
• Eg- AgCl , AgBr , AgI

NON – Stoichiometric Defect

• When in any crystal the ratio of action & anion are different or non-stoichiometric ratio
due to defects in their crystal structure is known as non-stoichiometric defects
Types of non – stoichiometric defect .
(1) Metal excess defect (2) Metal deficiency defect
1. Metal excess defect
This defect due to anion vacancies or extra cations at interstitial sites.
𝟏
• Eg:- NaCl , LiCl , ZnO → 𝒁𝒏𝟐+ + 𝑶𝟐 + 2𝒆−
𝟐
2. Metal deficiency defect
• When in any crystal missing of a cation from its lattice site and the presence of the
cation having higher charge in adjacent lattice site.
• This defect occurs when metal show variable valency .
• Eg :- FeS , NiO
Electrical property of solid
Types of solid on the basis of conductivities .
1. Conductor :- Conductivity range 𝟏𝟎𝟒 to 𝟏𝟎𝟕 ohm−𝟏 m−𝟏
2. semiconductor :- Conductivity range 𝟏𝟎−𝟔 to 𝟏𝟎𝟒 ohm−𝟏 m−𝟏
3. insulator :- Conductivity range 𝟏𝟎−𝟐𝟎 to 𝟏𝟎−𝟏𝟎 ohm−𝟏 m−𝟏
Band theory of solid
1. Metal :-
The conductivity of metals depend upon the number of valance electrons available atom.
The atomic orbitals of metal atoms from molecular orbitals which are so closed in energy to
each other as form band.
2. Insulator :-
If the gap between filled valance band and the next conduction band is larger so Electrons
cannot jump to it behaves as an insulator .
3. Semiconductor :-
• If the gap between the valance band and conduction band is small then some
electrons may jump to conduction band and show conductivity.
• Electrical conductivity are increases with rise in temperature & adding an appropriate
amount of impurity (doping) .
Types of Semiconductor :-
1. P – type Semiconductor 2.N – type Semiconductor
Magnetic property of solid
• If the motion of electron on orbit around the nucleus & spin around its own axis.
• Its unit Bohr magneton (𝝁𝑩 ).
• Electrons also spin on their own axis, spins in opposite sides are labelled with + and –
signs. 1 𝝁𝑩 = 9.27 × 𝟏𝟎−𝟐𝟒 A𝒎𝟐
Types of magnetic properties :-
1. Paramagnetic substance
2. Diamagnetic substance
3. Ferromagnetic substance
4. antiferromagnetic substance
5. Ferrimagnetic substance
1. Paramagnetic substance
• Attracted by the external magnetic field .
• Present one or more unpaired electron .
• Eg - 𝑶𝟐 , 𝑪𝒖𝟐+ , 𝑭𝒆𝟑+ , 𝑪𝒓𝟑+
2. Diamagnetic substance
• Weakley repel by the external magnetic field .
• No unpaired electron .
• Eg - 𝑻𝒊𝑶𝟐 , 𝑯𝟐 𝑶 , NaCl
3. Ferromagnetic substance
• Show permanent magnetism even in the absence of magnetic field.
• Strongly Attracted by the magnetic field .
• Eg – Fe , Ni ,Co
4. Anti - Ferromagnetic substance
• Magnetic moment of Domain structure are similar to ferromagnetic substance but
their domains are oppositely oriented and cancel each others magnetic field .
• Eg – MnO
5. Ferrimagnetic substance
• Magnetic moment of Domain in the substance are aligned in parallel and antiparallel
direction in unequal numbers .
• Weakly attracted by magnetic field to compare Ferromagnetic substance
• Eg – 𝑭𝒆𝟑 𝑶𝟒 , Zn𝑭𝒆𝟐 𝑶𝟒