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Hsslive-XII-Ch-1 - Solid State-Minhad

The document summarizes the classification and properties of solids. It discusses two main classifications: crystalline vs amorphous solids and molecular, ionic, metallic, and covalent solids. Crystalline solids have a defined structure while amorphous solids do not. The bonding and properties differ between the four types of crystalline solids. Unit cells are the smallest repeating units that make up crystal lattices. There are 14 possible crystal lattice structures known as Bravais lattices. The document also provides examples of unit cell calculations.

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0% found this document useful (0 votes)
120 views6 pages

Hsslive-XII-Ch-1 - Solid State-Minhad

The document summarizes the classification and properties of solids. It discusses two main classifications: crystalline vs amorphous solids and molecular, ionic, metallic, and covalent solids. Crystalline solids have a defined structure while amorphous solids do not. The bonding and properties differ between the four types of crystalline solids. Unit cells are the smallest repeating units that make up crystal lattices. There are 14 possible crystal lattice structures known as Bravais lattices. The document also provides examples of unit cell calculations.

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Zonic
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IUHSS

Parappur, Malappuram

CHE-MM: XII 1. SOLID STATE


Solids have definite mass, volume and shape. This is due to the fixed position of their constituent particles, short distances and strong
interactions between them.
Classification of Solids
On the basis of orderly arrangement of particles, solids can be classified into two –
Crystalline solids Amorphous solids
Regarded as pseudo solids or super
Regarded as true solids
cooled liquids
The arrangement of particles is well The arrangement of particles is not
defined (long range order) well defined (short range order).
Have a characteristic shape Irregular shape
They possess a sharp melting point Do not have a sharp m.p On cutting-
Have a definite heat of fusion Do not have definite heat of fusion
Gives a clean cut when cut with a sharp
Gives irregular cut
edged tool
Anisotropic (physical properties like Crystalline solids Amorphous solids
Isotropic (physical properties are
electrical conductance, refractive index
same along any direction)
etc are different in different directions)
E.x.: NaCl, quartz E.x.: Glass, rubber, plastics
Classification of Crystalline Solids
Depending upon the nature of intermolecular forces, solids can be divided into 4 types, namely: molecular, ionic, metallic and covalent
solids. They differ widely in their properties-
Constituent Bonding / Physical Electrical Melting
Type of Solid Examples
particles attractive forces nature conductivity point
1. Molecular solids
i) Non-polar Molecules Dispersion / Ar, CCl4, H2, Soft Insulator Very
London forces I2, CO2 low
ii) Polar ” Dipole-dipole HCl, SO2 Soft Insulator Low
interactions
iii) H-bonded ” H-bonding H2O (ice) Hard Insulator Low
Insulator in solid state
Coulombic / NaCl, MgO, but conductor in
2. Ionic solids Ions Hard but brittle High
electrostatic ZnS, CaF2 molten state and in
aqueous solution
Positive ions Hard, Conductors in solid
Fe, Cu, Ag, Fairly
3. Metallic solids in a sea of Metallic bonding malleable & state as well as in
Mg high
free e- ductile molten state
SiO2 (quartz),
C (diamond), Hard Insulator
AIN
4. Covalent or Very
Atoms Covalent bonding C (graphite) Soft (because Conductor (due to the high
network solids
layers can slide presence of free e-
one over the between layers)
other)

Crystal Lattices and Unit Cells


The 3D arrangements of constituent particles of a crystal in space is called crystal lattice.
Unit cell: It is the smallest repeating unit of a crystal lattice which, when repeated in three dimension
gives a whole crystal. A unit cell is characterised by its edge lengths and three angles between these
edges.

Unit cells can be broadly divided into two -


1. Primitive Unit Cells:
Here the constituent particles are present only at the corners of the unit cell.
2. Centred Unit Cells:
The constituent particles are present at the corners and other positions of the unit cell. These are of 3 types:
i. Body-centred unit cells: The constituent particles are present at the body centre and at the corners of the unit cell.
ii. Face-centred unit cells: The constituent particles are present at the centre of each faces and at the corners of the unit cell.
iii. End-centred unit cells: The constituent particles are present at the centre of any two opposite faces and at the corners of the unit cell.
In all, 14 different types of lattices are possible which are called Bravais lattices.

for www.hsslive.in , by: Minhad. M. Muhiyudeen, #- 9846 29 22 27 1


Bravais lattices -
Crystal Possible variations Examples
Primitive Body-centered Face-centered
Cubic NaCl,
1. a = b = c Zinc Blende,
 = 900 Cu

Primitive Body-centered

Tetragonal White tin,


2. a = b ≠ c SnO2, TiO2,
 = 900 CaSO4

Primitive Body-centered Face-centered End-centered


Orthorhombic
Rhombic
(Rhombic)
3. sulphur,
a≠b≠c
KNO3, BaSO4
 = 900

Primitive

Hexagonal
Graphite, ZnO,
4. a = b ≠ c
CdS
900,  = 1200

Primitive
Rhombohedral /
Trigonal Calcite (CaCO3),
5.
a=b=c HgS (Cinnabar)
 ≠ 900
Primitive End-centered
Monoclinic Monoclinic
6. a ≠ b ≠ c sulphur,
 = 900, ≠ 900 Na2SO4.10 H2O

Primitive
Triclinic K2Cr2O2,
7. a ≠ b ≠ c CuSO4.5H2O,
≠≠ ≠ 900 H3BO3

Calculation of Number of Atoms in a Unit Cell


1. Primitive cubic unit cell (Simple Cubic):
Here atoms are present only at the corners of the cube. Each corner atom is shared by 8 unit cells.
Therefore, contribution to one unit cell = 1/8
Since each unit cell has 8 atoms at the corners, the total number of atoms in one unit cell = 8×1/8 = 1
So for a primitive (simple cubic) unit cell, Z = 1
2. Body-centred cubic (bcc) unit cell:
Here the particles are present at the corners of the cube and also one atom at the body centre.
The number of atoms at the corner = 8×1/8 = 1
The atom present at the centre of the body is not shared by other atoms. So the number of atoms at the body-centre = 1
Therefore, total number of atoms in the unit cell = 1+1=2
So, for a bcc, Z = 2
3. Face-centred cubic (fcc) unit cell:
Here the atoms are present at the corners and also at the centre of each faces. Each corner atom is shared by 8 unit cells and each face
centre atom is shared by 2 unit cells.
Number of corner atoms = 8×1/8 = 1
Number of face-centre atoms = 6×1/2 = 3
Therefore, total number of atoms = 1+3 = 4
So, for an fcc, Z = 4
for www.hsslive.in , by: Minhad. M. Muhiyudeen, #- 9846 29 22 27 2
Packing In Solids
Atoms are space filling entities and structures can be described as resulting from the packing of spheres. The most efficient closest packing
can be achieved in two ways, one of which is called hexagonal close-packing (hcp) and the other, cubic close-packed (ccp).
Place spheres in a row, touching each other (first row). Then spheres of the second row are
placed in the depressions of the first row, the spheres of the third row are placed in the
depressions of the second row and so on. Thus the first layer formed in this manner is in
hexagonal arrangement.
The second layer is placed above the depressions of the first layer. On placing the second
layer there arises two types of voids (empty spaces) above the second layer – tetrahedral
voids and octahedral voids.
 Tetrahedral voids are holes surrounded by 4 spheres present at the corners of
tetrahedron. Number of tetrahedral voids is double the number of spheres (2N)
 Octahedral voids are holes surrounded by 6 spheres located on a regular
octahedron. Number of octahedral voids is equal to the number of spheres (N)

Hexagonal close-packing (hcp)


If the third layer is placed above the tetrahedral voids of the second layer, the first
layer and the third layer are identical. If we call the first layer as ‘A’ and the second
layer as ‘B’, then the third layer will be ‘A’, the fourth layer will be ‘B’ and so on.
This will form the pattern ABAB……
This type of close packing is called Hexagonal close packing (hcp).
 This type of arrangement is found in metals like Mg, Zn etc.

Cubic close-packed (ccp) or Face centred cubic (fcc)


On the other hand, if the third layer is placed above the octahedral voids of the
second layer, the third layer is different from the first or the second layer. If we
call this unique, third layer as ‘C’, it will form the pattern ABCABC…… This
type of close packing is called Cubic close packing (ccp) or face-centred
cubic(fcc) packing.
 This type of arrangement is found in metals like Cu, Ag etc.
Packing Efficiency
Packing efficiency is the percentage of the total space occupied by spheres (particles).
Volume occupied by all the spheres in the unit cell
Packing Efficiency = × 100%
Total volume of the unit cell

Calculation of Packing Efficiency


1) In hcp and ccp structures
Consider a cube with edge length ‘a’ and face diagonal ‘b’
In ΔABC, AC2 = AB2+BC2
i.e. b2 = a2 + a2 = 2a2
or, b = √2a
If ‘r’ is the radius of the sphere, then b = 4r
.
. . 4r = √2a

4r
= 2√2r
Or, a =
√2
We know that, in ccp (fcc) or hcp, there are 4 spheres per unit cell
.
.. Volume of four spheres = 4 × (4/3) πr3
Volume of the cube = a3 = (2√2r )3
. Volume occupied by 4 the spheres in the unit cell
.. Packing Efficiency = × 100%
Total volume of the unit cell
4 × (4/3) πr3
= ×100 % = 74%
(2√2r)3
2) In Body-centred cubic (bcc) structures:
Consider a cube with edge length ‘a’, face diagonal ‘b’ and body
diagonal ‘c’. From the figure it is clear that the atom at the centre
is in contact with the other two atoms diagonally placed.
In ΔEFD, FD2 = EF2 + ED2
i.e. b2 = a2 + a2 = 2a2
or, b = √2a

for www.hsslive.in , by: Minhad. M. Muhiyudeen, #- 9846 29 22 27 3


In ΔAFD, AF2 = AD2 + FD2
i.e. c2 = a2 + b2 = a2 + 2a2 = 3a2
or, c = √3a
We know that, c = 4r (where r is the radius of the particle)
.
. . √3a = 4r

4r
Or, a =
√3
We know that, in a bcc, there are 2 spheres per unit cell
. 3
. . Volume of 2 spheres = 2 × (4/3) πr

Volume of the cube = a3 = (4r/√3)3


. Volume occupied by 2 the spheres in the unit cell
.. Packing Efficiency = × 100%
Total volume of the unit cell
2 × (4/3) πr3
= ×100 % = 68%
(4r/√3)3
3) In simple cubic structures:
Consider a cube with edge length ‘a’ and the radius of the particle ‘r’.
Since particles touch each other along the edge, a = 2r
The volume of the cubic unit cell = a3 = (2r) 3 =8r3
We know, a simple cubic unit cell contains only one particle.
. 3
. . Volume of one sphere = (4/3) πr

. Volume of 1sphere in the unit cell


.. Packing Efficiency = ×100%
Total volume of cubic unit cell
4/3 πr3
= ×100 % = 52.4%
8r3

Density of a Unit Cell


Suppose edge length of a cubic unit cell is ‘a’,‘d’ is the density and ‘M’ is the molar mass (i.e. mass of Avogadro number of atoms).
Mass of unit cell = Number of atom in unit cell x Mass of each atom = z x m
Molar mass (M)
Mass of each atom (m) =
Avogadro number (NA)
M
Mass of unit cell = z x
.
..
NA
Volume of the unit cell = a3.
. Mass of the unit cell
.. Density of the unit cell =
Volume of the unit cell
zxM
d=
a3 x NA

Imperfections in Solids
Solids are not perfect in structure. There are different types of imperfections or defects in them. Point defects and line defects are common
types of defects.
I. Point defect - The irregularity or deviation from the ideal arrangement around a point (an atom) in a crystalline substance.
II. Line defect - The irregularity or deviation from the ideal arrangement along a row.
Types of Point defects
Point defects are of 3 types - stoichiometric defects, impurity defects and non-stoichiometric defects.
A. STOICHIOMETRIC DEFECTS:
The point defects which do not disturb the stoichiometry (the ratio of positive and negative ions) of the solid. They are also called intrinsic
or thermodynamic defects (since these defects can also develop when a substance is heated).
In non-ionic solids, stoichiometric point defects are present as–
i. Vacancy defect: When some of the lattice sites are vacant, the crystal is said to have vacancy defect.
 This defect decreases the density of the solid.
ii. Interstitial defect: When some constituent particles occupy an interstitial site, the crystal is said to
have interstitial defect.
 This defect increases the density of the solid.

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In ionic solids, these defects are present as -
iii. Frenkel defect/ dislocation defect: This defect arises when some of the ions (generally a cation)
misplacing from the lattice site to the interstitial site. This type of defect is found in ionic
crystals where anion is much larger in size than the cation.
E.g. ZnS, AgBr, AgI etc.
 Due to this defect, the density of the solid does not change.
iv. Schottky defect: This defect arises due to the missing of equal number of anions and
cations from the lattice site. It is shown by ionic crystals in which the anionic and cationic
sizes are almost equal.
E.g.: NaCl, KCl, CsCl, etc.
 Due to this defect the density of the solid decreases.
B. IMPURITY DEFECTS:
Impurity defects are caused by the presence of an impurity (foreign particles) in the crystal. If the ionic
impurity has a different valence than the main compound, some vacancies are created.
E.g.: Sr2+ as impurity in NaCl
C. NON-STOICHIOMETRIC DEFECTS:
These are point defects which change the stoichiometry of a solid. These defects are of two types:
i. Metal excess Defect: This arises in two ways:
 Metal excess defect due to anion vacancies: In this defect, some of the anions are missing from the lattice site. The electrical neutrality
is maintained by occupying e- in the anionic sites. These sites are called f-centres, where e- absorb light energy and get excited and
thereby give colour to the crystal
like alkali metal halides.
E.g.: Excess of Na give yellow colour to NaCl crystals
Excess of Li makes LiCl crystals pink
Excess of K makes KCl crystals violet.
 Metal excess defect due to extra cations at interstitial sites: Here some cations
occupy the interstitial sites. The electrical neutrality is maintained by occupying
some e- in adjacent interstitial sites.
E.g. ZnO crystals (which is white in colour) on heating loses oxygen and becomes yellow-
ZnO Zn2+ + ½ O2 + 2e-
The Zn ions now move to the interstitial sites and the e- to neighbouring interstitial sites.
ii. Metal deficiency Defect:
Here the number of cations is smaller than the number of anions. This is mainly arises due to cation vacancies.
This type of defect is commonly shown by transition metal compounds. E.g. FeO

Electrical Properties
Based on the electrical conductivity, solids are classified into 3 types:
(i)Conductors: They are solids which allow the passage of electricity through them. These generally include metals. Their conductivity ranges
from 104 to 107 ohm-1m-1.
Reason:-
A band is formed due to closeness of molecular orbitals. This band is partially filled or it overlaps with a higher energy unoccupied
conduction band. If an electric field is applied, the e- flow and shows conductivity.
(ii) Insulators: They are solids which do not allow electricity through them. Their conductivity ranges from 10-10
to 10-20 ohm-1m-1.
Reason:-
The gap between filled valence band and the unoccupied conduction band is large the e- cannot jump to it.
(iii) Semi-conductors: They are solids which have intermediate conductivity ranging from 104 to 10-6 ohm-1m-1.
Reason:-
The gap between the valence band and the conduction band is small. So some e- may jump from valence band to conduction band and show
some conductivity.

Their conductivity increases with rise in temperature, since more e- can jump to the conduction band. Such semiconductors are also called
intrinsic semiconductors. E.g.: Si, Ge etc.
Dopping: It is the addition of impurities in semiconductors to enhance their conductivity. It creates electronic defects in them. Such
semiconductors are called extrinsic semiconductors.

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Types of extrinsic semiconductors:
1. n-type semiconductor
It is the type obtained by doping of group 14 elements (like Si or Ge) with elements of group 15 (electron rich, like P or As). The excess
e- in crystals increases the conductivity.
2. p-type semiconductors
It is the type obtained by doping of group 14 elements with elements of group 13 (electron deficient, like B, Al or Ga). This creates
an e- hole (vacancy). An e- from a neighbouring atom can come and fill the holes. So the position of the hole is moved in the direction
opposite to that of the e- has moved. Under the influence of electric field, e- would move towards the positively charged plate through
electronic holes. It would appear as if electron holes are positively charged.

Magnetic Properties
Every solid has some magnetic properties associated with it due to the presence of e-. On the basis of magnetic properties, solids can be
classified into five types-
Properties Description Alignment of magnetic dipole Examples

Species weakly repelled by


Diamagnetic Pairing of e- cancels their magnetic H2O, NaCl, C6H6
an external magnetic field.
moments and so they have no net
magnetic moment

Species weakly attracted by


O2, Cu2+, Fe3+,
Paramagnetic an external magnetic field.
Paramagnetism is due to the Cr3+
Temporary magnetism.
presence of at least one unpaired e-.

Species strongly attracted by Fe, Co, Ni,


Ferromagnetic a magnetic field. Ferromagnetism is due to the Gd (Gadolinium),
Permanent magnetism. orientation of all domains in the CrO2
direction of the magnetic field

Anti- Species having no net


This arises when the domains are MnO
ferromagnetic magnetic moment
oppositely oriented and cancel each
other.

Species having a small net Fe3O4, MgFe2O4,


Ferrimagnetic This arises when domains are
magnetic moment ZnFe2O4
arranged in opposite directions but
in unequal numbers.

for www.hsslive.in , by: Minhad. M. Muhiyudeen, #- 9846 29 22 27 6

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