www.sakshieducation.

com

Solid State

Introduction
i. Matter is divided into solids, liquids and Gases.
ii. Random motion and weak intermolecular forces are characteristic of gases.

m
iii. In liquid state, free movement of the molecules is limited due to cohesive
forces.

co
iv. In solid state atoms, ions or molecules are arranged orderly in a three

n.
dimensional manner due to strong binding forces. Thus Solids have generally
high density, low compressibility, very slow or no diffusion. The vapour

io
pressure of solids is generally much less than that of liquids at a definite

at
temperature. uc
I. Types of Solids: Solids are of two types – crystalline and amorphous solids.
ed

A crystalline solid is one in which the component structural units are arranged in a
definite geometrical order which is characteristic of the substances. (Long range order)
hi

Amorphous solids do not have regular and orderly arrangement of the building units of
ks

the substances. (Short range order)

a

II. Properties of solids

.s
w

Sl. Property Crystalline solids Amorphous solids

w

No.
w

1 Condition of Slow cooling without Rapid cooling with

formation disturbing the liquid or churning
disturbance
2 Rigidity and Rigid and hard Rigid and hard
hardness

www.sakshieducation.com
 www.sakshieducation.com

3 Shape Definite geometrical Particles are arranged not in

configuration regular order or arranged in
short range order
4 Melting points Sharp Not sharp and melts over
a range of temperature

m
5 Plane surfaces Possess plane surfaces Not bound by plane

co
surfaces
6 X-ray diffraction Characteristic X– ray Diffraction bands are not

n.
diffraction given experiment

io
bands are given

at
bands are given.
7 Examples KCl; CuSO4. 5H2O; KNO3 Fused silica, glass, pitch,
uc
gelatinous
ed
hi

When Quartz is melted and rapidly cooled an amorphous solid result, in which SiO4
ks

chains are irregular.

I. Amorphous solids can be moulded or blown into articles of different shapes.
a

II. Amorphous solids have a tendency to flow, but very slowly. Hence, they are also
.s

called ‘pseudo solids’ or ‘super cooled liquids’. Amorphous solids are ‘isotropic’ i.e.
w

their physical properties are same in all directions.

w

III. Crystalline solids are ‘anisotropic’ i.e. some of their physical properties like electrical
resistance or refractive index show different values when measured along different
w

directions.
IV. Amorphous solids are used in domestic constructions or appliances like photo voltaic
cells, where the sunlight is transformed into electricity.

www.sakshieducation.com
 www.sakshieducation.com
III. Classification of crystalline Solids: These are classified into ionic, covalent, metallic
and molecular solids according to the nature of the building units, chemical bonding and
the intermolecular forces in the crystal.
The characteristics of various types of solids are given in the table.

Bonding or

m
Constituent Physical Electrical Melting
Type of solid attractive Examples
particles nature conductivity point
forces

co
Molecular solids
(i) Non polar Molecules London or I2,CO2(s), Soft Very low

n.
Dispersion Ar(s)
forces

io
(ii) Polar Dipole - dipole HCl(s), Soft Extremely low Low
interactions SO2(s)

at
(iii) Hydrogen Hydrogen H2O (ice) Soft Low
bonded bonding
uc
Ionic solids Ions Coulombic or NaCl, MgO, Hard but Insulators in solid
electrostatic ZnS, CaF2 brittle state but conductors
ed

in molten state and High

in aqueous solutions
Metallic solids Positive ions Metallic Fe, Cu, Ag, Hard but Conductors in solid Moderate
hi

in a sea of bonding Mg, Sn, Au malleable state as well as in to high

delocalised and molten state
ks

electrons ductile
Covalent or Atoms Covalent SiO2(quartz), Very Insulators, except Very high
a

network solids bonding SiC, AlN,BN, hard, graphite

C (diamond) except
.s

C (graphite) graphite High

w
w

IV. Coordination Number of Crystals: The coordination number of an atom or ion in

w

solid is the number of nearest neighbours for that atom or ion

Eg:
1) In NaCl crystal, coordination number of Na+ ion as well as Cl- ion is 6.
2) Coordination number of C in diamond is 4
3) In Silica, coordination number of ‘Si’ is 4 while that of oxygen atom is 2

www.sakshieducation.com
 www.sakshieducation.com
4) In metal lattices the coordination number of a metal atom is usually 8 or 12.
5) In ZnO, coordination number of Zn+2 ion as well as O-2 ion is 4.
6) In CsCl crystal, coordination number of Cs+ ion as well as Cl- ion is 8.

V. Limiting Radius ratio:

m
The shape of ionic crystal and Co-ordination number depends on cation to anion
radius ratio (i.e. rc/ra value) called ‘Limiting Radius Ratio’

co
Limiting radius Coordination Shape or

n.
ratio number structure

io
< 0.155 2 Linear

0.155 - 0.225 3
at Planar triangle
uc
0.225 - 0.414 4 Tetrahedral
ed

0.414 - 0.732 4 Square planar

hi

0.414 - 0.732 6 Octahedral

ks

0.732 - 0.999 8 Body centred

a

Ex.1.The rc/ra for NaCl is 0.52. Thus NaCl has F.C.C Lattice
.s

2. The rc/ra for CsCl is 0.93. Thus CsCl has b.c.c Lattice
w

VI. Metallic Bonding: Metallic bond is neither ionic nor covalent in nature. Three
w

theories are familiar in explaining bonding in metallic solids.

w

1. Electron sea model of Drude and Lorentz

2. Valence bond theory of Linus Pauling

3. Molecular orbital theory of Hund and Mulliken

www.sakshieducation.com
 www.sakshieducation.com
(1) Electron Sea Model
According to this in a metallic solid all metal atoms lose their valence electrons to
form positive metal ions (called Kernels) and a sea of electrons (called delocalised or
mobile electrons). As a result an electrostatic force of attraction develops between
Kernels and free electrons which is called metallic bond. It explains electrical
conductivity and metallic luster.

m
Defects: Failed to explain quantitative calculations for the lattice energies of ionic

co
compounds.
(2) Valence Bond Theory or Resonance theory: According to this theory,

n.
The metallic bond is essentially a polar or a non polar covalent bond.

io
The covalent bond involves resonance between a number of structures having one

at
electron and electron pair bonds. Resonance occurs due to the possibility of insufficient
valence electrons for the formation of electron pair bonds with each atom of the metal.
uc
Resonance involves both covalent and ionic linkages.
Defects: It does not explain the conduction of heat in solids and their lustre. It does not
ed

explain the retention of metallic properties in liquid state.

hi

VII. Close Packing in Three Dimensions

(i) Simple Cubic Arrangement
ks

In this arrangement the spheres can be arranged in a layer such that each metal
a

atom is in touch with four other atoms. A second layer of spheres is superposed on the
.s

first layer such that the spheres of the second layer are exactly above the spheres of first
w

layer.
* Coordination number of each sphere is 6.
w

*In this structure the percentage space occupied is 52% & the remaining 48%
w

space is void.
Eg: Polonium
(ii) Hexagonal Close Packed (HCP) Arrangement
It is also called as AB AB AB ...... type arrangement.

www.sakshieducation.com
 www.sakshieducation.com
In any layer of spheres every sphere is in contact with six other spheres.
The vacant spaces between the spheres known as holes or voids
If the second layer of spheres is arranged by placing these spheres over the holes in the
first layer, three of the six holes formed are only covered by the spheres. Out of the six
holes; only three are covered by the spheres. Third layer of spheres can be superposed on
the spheres of this layer directly over the spheres of the first layer. i.e. third layer is the

m
repetition of the second layer.

co
In HCP each sphere is in contact with 6 spheres in its own layer. It also touches ‘3’
spheres in the above layer and 3 spheres in the below layer. Thus the co-ordination

n.
number is 12.

io
In this arrangement atoms occupy 74% of the available space and thus have 26% vacant

at
space.
E.g. Be, Mg, Tl, Cd, Co, Zn, Ce, Ti, Os, Ru, etc.
uc
(iii) Body Centered Cubic (BCC) Arrangement
This arrangement is obtained when the spheres in the first layer are slightly
ed

opened up, ie. None of the spheres touches each other. I n the second layer, the spheres
hi

are placed at the top of hollows in the first layer. In the third layer, spheres are placed
exactly above the first layer. Each sphere in this system of packing is in contact with
ks

eight spheres, four in the lower layer and four in the upper layer. Thus the co-ordination
a

number is 8.
.s

In this arrangement atoms occupy 68% of the available space and thus have 32% vacant
w

space.
This lattice is quite common for Alkali metals.
w

Eg. Na, K, Rb, Cs, Ba, Cr, Mo, W

w

(iv) Face Centered Cubic (FCC) Arrangement or Cubic Closed Packing

This type of arrangement is known as ABC ABC ABC ...... arrangement.
In this arrangement, the spheres of the second layer are placed in the holes
formed by the first layer and the spheres in the third layer may be placed in the hollows
of the second layer such that the sphere is not exactly above the sphere in the first layer.

www.sakshieducation.com
 www.sakshieducation.com
* Coordination number of each sphere is 12.
In this arrangement atoms occupy 74% of the available space and thus have 26% vacant
space.

Eg: - Al, Cu, Au, Pb, Pt, Pd, Ni and Ca.

m
VIII. Unit Cell in Two Dimensional &Three Dimensional Lattices

co
(i) Space Lattice: The pattern of points which indicates the arrangement of particles in
the crystal is known as space lattice.

n.
Ex. The space lattice of sodium chloride is obtained by joining the space lattices of Na +

io
and Cl– ions.

at
(ii)Unit Cell: - The smallest three dimensional portion of the space lattice which when
repeated again and again in different directions produces the complete space lattice is
uc
called the unit cell.
ed

Types of unit cells:

i) Primitive or simple unit cell: The unit cell without a point inside is known as
hi

‘primitive unit cell’ i.e., the particles are present only at the corners of the unit cell.
ks

Ii) Centered unit cell: Contains a point inside is known as centered unit cell. Eg.
F.C.C, B.C.C, End face centered unit cell.
a

a) In face-centered unit cell: in addition to the particles at the corners, there is one
.s

particle present at the centre of every face.

w

It has 14 lattice points (8 corners and 6 face centers)

w

b) In End face centered unit cell: in addition to the particles at the corners, there is one
particle in the centre of two opposite faces.
w

It has 10 lattice points (8 corners and 2 face centers)

c) In body-centered unit cell: in addition to the particles at the corners, there is one
particle present within the body of the unit cell.
It has 9 lattice points (8 corners + 1 body centre)

www.sakshieducation.com
 www.sakshieducation.com
IX. Crystal Systems
On the basis of symmetry and set of crystallographic parameters crystals are
classified into 14 types of crystal lattices (Bravais lattices) and 7 different types of crystal
systems.
The intercepts on the X,Y and Z axes are designated as a, b and c respectively.
The angle between the Y and Z axes is, that between X and Z axes is and that between X

m
and Y axes is .

co
Seven primitive cells and their possible variations as centred unit cells
Crystal system Possible Axial Axial angles Examples

n.
variations distances

io
or edge

at
lengths
uc
1. Cubic Primitive, a=b=       90 NaCl, Zinc blend, Cu
f.c.c, c
ed

Body-
centered
hi

2.Tetragonal Primitive, a = b≠ c       90 White tin, SnO2 TiO2,

ks

Body- CaSO4
a

centered
.s

3.Orthorhombic Primitive, a ≠b≠c       90 Rhombic sulphur

w

Body- KNO3, BaSO4

w

centered,
w

Face-centered
End-centered
4.Hexagonal Primitive a = b ≠c     90 Graphite, ZnO, CdS
  120

www.sakshieducation.com
 www.sakshieducation.com

5. Primitive a=b=c       90 Calcite (CaCO3), HgS

Rhombohedral (cinnabar),KMnO4,Bi,As,Sb
or Trigonal

6.Monoclinic Primitive abc     90 Na2SO4.10H2O

End-centered   120 monoclinic sulphur,

m
7.Triclinic Primitive abc       90 K2Cr2O7, CuSO4.5H2O

co
*Ice & Quartz may give hexagonal or trigonal crystals

n.
io
Space lattices of crystal system

at
S.No. Crystal system Number.uc of Common names of the lattices
Bravais lattices
1 Cubic 3 Simple cubic, face centered and body
ed

centered cubes
hi

2 Tetragonal 2 Simple cubic and body centered

ks

tetragonal prisms
a

3 Rhombic 4 Rectangular, body centered, face centered

.s

and end centered rhombic prisms

w

4 Hexagonal 1 Hexagonal prism

w

5 Trigonal 1 Rhombohedral
w

6 Monoclinic 2 Primitive and edge centered

7 Triclinic 1 Triclinic primitive

www.sakshieducation.com
 www.sakshieducation.com
X. characteristics of a crystal lattice
a) Each point in a lattice is called lattice point or lattice site.
b) Each point in a crystal lattice represents one constituent particle which
may be an atom, a molecule or an ion.
c) Lattice points are joined by straight lines to bring out the geometry of the
lattice.

m
co
XI. Position of ions in cubic unit cell and contribution to unit cell
Position of ion Number of Contribution

n.
in unit cell unit cells of ion to each

io
sharing unit cell

at
Centre of the body 1 1
Centre of the face 2 1/2
uc
Edge of a face 4 1/4
ed

Corner of cube 8 1/8

Effective Number of Atoms (Z) In Unit Cell:
hi

IN SIMPLE CUBIC IS 1, B.C.C IS 2 AND F.C.C IS 4

ks

XIII. Interstitial Voids:

a

The empty spaces between the three dimensional layers are known as voids or
.s

holes. There are two types of common voids possible. They are called tetrahedral and
w

octahedral voids. These are also called interstices.

w

Tetrahedral void: A hole formed by three spheres of a layer in contact with each
w

other and also with a sphere on the top or bottom layer is a hole between four spheres.
The spheres are arranged at the vertices of a regular tetrahedron. Such a hole is called
tetrahedral void.

www.sakshieducation.com
 www.sakshieducation.com
*Radius ratio of tetrahedral void= 0.225X Radius of atom

m
co
n.
io
Octahedral void: A hole formed by three spheres of a hexagonal layer and another three

at
spheres of the adjacent layer is a hole between six spheres. The spheres are arranged at
the vertices of a regular octahedron. Such a hole is called octahedral void.
uc
ed
hi
a ks
.s

*Radius ratio of octahedral void,= 0.414X Radius of atom

w
w

If there are ‘n’ atoms present in the unit cell of close packed structure the number of
w

tetrahedral voids are ‘2n’ and the number of octahedral voids are ‘n’.
XIV. Relation between atomic radius and the edge of the Unit cell. (For elements)
i) In simple cubic structure: edge length (a) = 2r
Distance between nearest neighbours (d) = 2r = a
Atomic radius (r) = a/2.

www.sakshieducation.com
 www.sakshieducation.com
ii) In body centered cubic lattice
Body diagonal length = 4r = 3 a
3
Distance between nearest neighbours (d) 2r =  a = 0. 866 a
2

3
Atomic radius (r) =  a = 0. 433 a
4

m
iii) In face centered cubic lattice: - face diagonal length (4r) = 2 a

co
a
Distance between nearest neighbours (d) = 2r = = 0.707 a
2

n.
a
Atomic radius (r) = = 0.3535 a
2 2

io
XV. Packing Efficiency: The percentage of total space filled by the particles in a solid

at
is called packing efficiency.
Packing efficiency = packing fraction X 100.
uc
Volumeoccupied by all the spheres intheunit cell
Packing fraction =
Total volumeof theunitcell
ed

In both H.C.P and C.C.P structures

hi

 2
ks

Packing efficiency = 100 =0.74X 100 = 74%

6

 3
a

In B.C.C structure packing efficiency= 100 = 0.68X 100 = 68%

8
.s


In simple cubic lattice: Packing efficiency = 100 = 0.524 X 100 = 52.4%
6
w

* Hexagonal close – packing and cubic close – packing are more efficient than any
w

other sort of arrangement.

w

www.sakshieducation.com