Solid Stat

Solid: - Matter which posses rigidity having

definite shape &volume is called solid.
Types of solid:1.
Crystalline Solid :- Eg:- Metals And Non metals
2.
Amorphous Solid :- Eg:- Rubber ,Glass ,Plastic
Difference
and
Comparison
between
of
characteristics
Crystalline Solid: - Contain regular arrangement
having short range & as well as long range order.
Definite geometric shape, Sharpe melting point,
they have definite heat fusion, they undergo clean
cleavage, and they are true solid.
Amorphous
Solid:
- Containing
irregular
arrangement having short range order only,
irregular shape, melting over range of temp, they do
not have definite heat of fusion they undergo an
irregular cut they are pseudo solid or super cooled
solid.
Classification of crystalline solid:1. Ionic Solid
2. Molecular Solid
3. Covalent of network Solid
4. Metallic Solid
1. Ionic solid: - in these crystalline solids,
constituent particle are positive or negative ion held
together by columbic or electrostatic forces of
attraction.
Eg:-NaCl, MgO
2.
1.

Molecular solids:- These are of three types

Non polar molecular solid: - in these the
constituent particles are atoms of noble gas or non
polar molecules are held by London dispersion
forces.
Eg: - Ar, H2.

2.

Polar molecular solids: - In these solids

constituent particles are held together by dipoledipole attraction forces.
Eg: - Hcl, SO2.

3.

Hydrogen bonded molecular solids: - in these

types of molecular solids constituent particles are
molecule containing hydrogen linked to F, O and N
held by hydrogen bonding.
Eg: - H2O (ice), NH3.

3. Covalent or Network Solids: - Constituent

particles are atoms held together by covalent bonds
Eg: - C (diamond), Sio2 (quartz)
4. Metallic solids: - Constituent particles are
positive ions in a sea of mobile electrons held
together by metallic bonds.
Eg: - All metals and alloys.
Crystal Lattice: - Regular arrangement of
constituent particles in 3-D is called crystal lattice
or space lattice.
Unit cell: - The smallest three dimensional portion
of a complete space lattice which when repeated
over and again in different direction produces the
complete space lattice is called unit cell.
Bravais
lattice:
- The
fourteen
lattices
corresponding to seven crystal system are known as
Bravais Lattice.
Coordination number: - the number of spheres
touching to a particular sphere.
No. of atoms per unit cell:(a) No. of atoms in simple cubic lattice:- 8 atoms are
at corner
8*1/8=1

(b) No. of atoms in BCC:

8 atoms are at corner and one in the body
8*1/8+1=2

Fig.
(c) No. of atoms in FCC:8 atoms are at corner and six atoms are at faces (one
on each face)
8*1/8+6*1/2=4

Close packing in
crystals:-

(a) Close packing in one dimension: - sphere are

touching each other in a row. In this arrangement
coordination no. is 2
(b) Close packing in two dimension:- it is done by
two ways1.
Square close packing: - in this arrangement
spheres of second row are exactly above the first
row.

1.

in a simple cubic unit cell:Suppose radius of sphere is = r

Edge length of unit cell
=a
As sphere are touching each other
a=2r
No. of sphere per unit cell= 8*1/8=1

Volu
2.

me of sphere = 4/3r3
Volume of cube =a3= (2r)3 = 8r3
Packing fraction

Hexagonal close packing: - in this arrangement

the spheres of second row may be placed in the
depression of the first row.

(c)
1.

Close packing in three dimension

Three dimensional close packing from two
dimensional closed packed layer: - starting from the
square close packed layer the second layer and all
further layers will be built up such that they are
horizontally as well as vertically aligned with each
other.

2.

Three dimensional packing from two dimensional

hexagonal close packing:- when spheres are
arranged in hexagonal close packing in 2-Dthe two
types of voids a& b are formed.
a & b voids are triangular when second layer is
placed over the void of first layer (only one void is
full filled) in hexagonal close packing and these
layer form two voids
C Triangular and D Octahedral.
Packing efficiency: - The percentage of the total
space filled by the particles is called packing
efficiency.

Packing fraction: - The fraction of the total space

filled is called packing fraction.
Calculation of spaces occupied

% occupied = 52.4%
2.
in face centred cubic structure (Cubic close
packing):- spheres of the face centre touching the
sphere of the corner,
Then, AC = 4r in ABC

% occupied = 74%
3.

In body centred cubic structure: - Sphere at the

body centred touching the sphere of the corner.
Body diagonal, AD = 4r
Further, face diagonal,

% occupied = 68%

cation from its lattice site and two monovalent

cation is replaced one divalent cation to maintain
electric neutrality.

Radius (r) of the octahedral void =0.414R

Radius (r) of the tetrahedral void = 0.225R
In CCP or HCC. If there are N spheres in the
packing.
No. of octahedral voids = N
No. of Tetrahedral voids = 2N
Imperfection and defects in solids
Types of Defects:1.
Stoichiometric defects
2.
Non-Stoichiometric defects
3.
Impurity defects
1.

a.
b.

c.

d.

2.

a.

b.

Stoichiometric defects:- In these defects the

ratio of anion and cation remains same as the
Stoichiometry of the substance not changed.
These are also classified as:
Vacancy defects: - These arise when some sites
of the crystal lattice are vacant, it decrease density.
Interstitial Defects: - When some constituent
particles present in the interstitial side, it increase
the density of the crystal.
Schottky Defects:- If in a ionic crystal +ve or ve
ions missing their lattice sites so that electric
neutrality is maintained
Ex: NaCl, KCl, CsCl, AgBr.
Frenkel Defect: - If an ion missing their lattice site
(causing vacancy or hole their) and comes in the
interstitial side, so maintain electric neutrality or
Stoichiometry of the crystal is called Frenkel defect.
Ex: ZnS, AgCl, AgBr, AgI.
Non-Stoichiometric Defect: - In this defect ratio
of cation & anion became different from the
original ratio.
It is of two types:
Metal excess: - this may occur in two wayI.
By anion vacancies: A
ve ion may missing their lattice site and leaving a
hole which occupied by an electron there by
maintaining electrical balance.
II.
By the presence of extra
cation in the interstitial site: - it is extra cation (+ve
ion) is occupying the interstitial site.
Anion = -ve ion
Cation = +ve ion
And electric neutrality is maintained by an electron
is present in another interstitial site.
Metal deficiency:- This defect shows variable
vacancy and occurs usually due to the missing of a

III.
Impurity defects :- These
defects arises when foreign atoms are present at the
lattice site in place of host atoms or in the interstitial
sites.
Doping: - The process of adding impurities to a
crystalline substance so as to change its properties is
called doping.
Electrical properties of solids
Conductors:- The solids which have conductivity
in the range of 104 to 107ohm-1m-1 are called
conductors.
2.
Insulators :- The solids which have extremely
low conductivity ranging between 10-20 to 1010
ohm-1m-1 are called insulators.
3.
Semiconductors:- The solids which have
conductivity between the conductors and insulators,
ranging from 10-6 to 104 ohm-1m-1 are called
semiconductors.
1.

1.

2.

3.

Band Theory
In case of metals (conductors), the atomic orbitals
of the metal atom are so close in energy that they
overlap to form a large no. of molecular orbitals
very close in energy. This set of molecular orbitals
is called a band. Two types of band formed then
electron can easily flow by gaining energy and
conduct electricity.
If gap between band is large electron can not jump
from valance band to conduction band, so these
behave as insulator.
If the gap is small then electron may jump and show
some conductivity and act as semiconductor.
Magnetic properties of solids: Diamagnetic Substances: - Substances which are
weakly repelled by the external magnetic field are
called diamagnetic substances.
Ex: TiO2, H2O, NaCl
Paramagnetic Substances: - Substances which
are attracted by the external magnetic field are
called paramagnetic substances.
Ex: O2, Cu2+, Fe3+
Ferromagnetic Substances: - Substances which
show permanent magnetism even in the absence of
magnetic field are called ferromagnetic substances.
Ex: Fe, Ni

4.

Anti- Ferromagnetic Substances: - Substances

which are expected to posses paramagnetism and
ferromagnetism on the basis of magnetic moments
of the domains but actually they posses Zero
magnetic moment are called anti- ferromagnetic
substances.
Ex: MnO
5.
Ferromagnetic Substances: - Substances which
are expected to posses large magnetism on the basis
of magnetic moments of the domains but actually
have small net magnetic moment are called
ferromagnetic substances.
Ex: Fe3O4

SOLUTION
Solution: - A solution is homogeneous mixture of
two or more chemically non-reacting substances,
whose composition can be varied within certain
limits.
Expressing concentration of solutions
1.
Percentage: mass percentage (%) of a component (W/W)
= Mass of the component in
solution*100 / Total mass of the solution
volume percentage (%) of the component (V/V)
= Volume of the component * 100 / Total
volume of the solution
Mass/Volume percentage (%) of the component
(W/V)
=Mass of the component in solution * 100 /
Total volume of the solution
2.
Strength:Strength of the solution ( gl-1 or gdm-3)
= Mass of the solute in grams / Volume of the
solution in litre
3.

Molarity (M) :- No. of moles of the solute /

Volume of the solution in litre
M = strength in gram per litre / Molar mass of the
solute

4.

Mole fraction :- It is obtained by dividing the no.

of moles of the solute or solvent by the total no. of
moles of the solution.
Mole fraction, X1 = n1/n1+n2
X2 = n2/n1+n2
n1 = no. of moles of the solvent
n2 = no. of moles of the solute

X1+X2 = 1
5.
Mass fraction: - Mass of the given component
per unit mass of the solution denoted by X.
XA = WA / WA+WB
XB = WB / WA+WB
WA = Mass of the solvent
WB = Mass of the solute
XA+XB = 1
Solution of solids in liquids
Solubility of a solid in a liquid :- It is defined as
the maximum amount of the solid (solute) in grams
which can dissolve in 100 grams of liquid (solvent)
to form the saturated solution at the particular
temperature.
Factors affecting the solubility of a solid in a
liquid
i.
Nature of the solute & the solvent :- Like
dissolves Like
The polar (ionic) compounds like NaCl dissolve in
polar solvent like water.
The non polar (covalent or organic) compounds
dissolve in non polar compounds like Anthracene
dissolve in Benzene.
ii.
Effect of temperature : The solubility increases with increase of temperature
when the process of dissolution is endothermic.
Solute + Solvent + Heat -> Solution
Ex:- NaNo3, KNO3, NaCl, KCl
The solubility Decreases with increase in
temperature when the process of dissolution is
exothermic.
Solute + Solvent -> Solution + Heat
Ex:- Sodium carbonate mono hydrate
(Na2CO3.H2O).
Those whose solubility does not increases or
decreases continuously
Ex:- CaCl2.6H2O -> CaCl2.4H2O -> CaCl2.2H2O
Solution of Gases in liquids
1) Solubility of a gas in a liquid :- The solubility of
a gas in a particular liquid is the volume of the gas
in CCs (centimetre cubes CM3) that can dissolve in
unit volume of the liquid to form the saturated
solution at the temperature of the experimented
under a pressure of one atmosphere.
Factors affecting the solubility of a liquid in a
gas
i)
Nature of the gas & the solvent:- Gases like
Hydrogen, Oxygen, Nitrogen etc. dissolve in water

only to a small extent but gases like CO2, HCl,

NH3 are highly soluble.
The greater solubility of later gases they react with
solvent. the greater solubility of the gas in a solvent
due to their chemical similarity.
ii)

Nature of temperature:- The solubility of gases

decreases with increase in temperature.
iii) Effect of pressure (Henrys Law):- By
increasing the pressure solubility also increases.
Henrys Law:- The mass of a gas dissolved in the
given volume of liquid at constant temperature is
directly proportional to the pressure of the gas
present in equilibrium with the liquid.
mp
m=KHP
Also,
The partial pressure of gas in vapour phase (P) is
proportional to the mole fraction of gas (x) in the
solution.
P=KHX
Limitations of Henrys law
Henrys law is applicable only if the the following
conditions are satisfied:a) Pressure should be low and temperature should be
high i.e. gas behaves as an ideal gas.
b) The gas should not go under compound formation
with solvent or association or dissociation in the
solvent.
Vapour Pressure of liquid solution:- Vapour
pressure of liquid/solution is the pressure exerted by
the vapour in equilibrium with the liquid/solution at
a particular temperature.
Raoults Law:- it states that for a solution of
volatile liquids, the partial vapour pressure of each
component in the solution is directly proportional to
its mole fraction.
For component A
PA X A
PA = P0AXA
0
Where, P A = Vapour pressure of pure component A
at the same temperature
For component B,
PB = P0BXB
By Daltons law of partial pressure:Ptotal = PA+ PB
Ptotal = P0AXA + P0BXB
= (1-XB) P0A+ P0BXB

= P0A - P0AXB + P0BXB

= P0A+ (P0B- P0A)XB
If YA & YB represents the mole fraction of
component A & B respectively.
In vapour phase,
YA = PA/ PA+ PB = PA/
Ptotal
..(i)
YB = PB/ PA+ PB = PB/
Ptotal
..(ii)
From eq. (i) & (ii)
PA = YA * Ptotal
PB = YB * Ptotal
In general,
Pi = Yi * Ptotal
Raoults Law for non volatile liquid:Vapour pressure of each component is directly
proportional to its mole fraction.
P1 X1
P1 = P01X1
P1/P01 = X1
Ideal solutions:- an ideal is that solution which
obeys raoults law in all conditions of temperature an
concentration.
i.e. Vmixing = 0
Hmixing = 0
Also, forces of attraction between components are
same as in pure state.
A-A = A-B = B-B
Non ideal solutions:- The solutions which not
obeys the Raoults Law is known as non ideal
solutions.
Vmixing 0, Hmixing 0
The force of interaction between solvent/solute is
different than in pure state.
Positive deviation:- in this A-B interaction are
weaker than A-A, B-B
i.e. interaction between solute-solvent is weaker
than solute-solute or solvent-solvent. This means in
such solutions the molecules of A or B (A-B) will
find it easier to escape than in pure state.

For dilute solutions n2<<n1

Hence, neglecting n2 in the denominator we have,

Here, w1 & w2 are the

masses and m1 & m2 are masses of solvent & solute
respectively.

Negative deviation:- Intra molecular attraction

force between A-A and B-B are weaker than those
between A-B. this decreases the escaping tendency
of molecules for each component (A-B) and
consequently the vapour pressure decreases
resulting in Ve deviation from raoults law.

1)
2)
3)
4)

Colligative properties: - Those properties of ideal

solutions which depends only on the no. of particles
of the solute dissolve in the definite amount of
solvent and do not depend upon nature of solute.
The important colligative properties are:Relative lowering of vapour pressure
Osmotic pressure
Elevation in boiling point
Depression in freezing point
Relative lowering of vapour pressure: - from
Raoults law for solutions of solids in liquids.

Where, P0 = vapour pressure of pure solvent

PS = vapour pressure of solution
n2 = no. of moles of solute
n1 = no. of moles of solvent

Osmotic pressure:- The process of the flow of the

solvent molecules from solvent to solution through
semi permeable membrane (SPM) is
called osmosisthe flow of the solvent molecules can
be stopped if some extra pressure is applied on the
solution. This pressure that just stops the flow of
solvent molecules is called osmotic pressure of the
solution.
Osmotic pressure of the solution is directly
proportional to the molar concentration or molarity
(C) of the solution and its temperature (T).
Mathematically,
i.e.
C
T
So,
CT
Or,
= RCT
Where, R is solution constant equal to the gas
constant
= CRT
Hence,
= (n2/v) RT
this equation is called vont hoff equation for dilute
solutions.
Also, v = n2RT

Elevation in boiling point:- It is found that the

boiling point of the solution is always
higher
than that of pure solvent. The
increase is called elevation in boiling point.

Where, T0f = freezing point of pure solvent

Tf = freezing point of solution
Tf = Depression in freezing point
Also,
Tf m
Tf = kfm
Where, kf is molal depression constant or
cryoscopic constant and m is molality of the
solution.
Calculation of molecular mass of solute:Tf = Kf(w2/m2)(1000/W1)
From figure, we known
Tb = Tb - T0b
Where, T0b & Tb is the temperature at which the
vapour pressure of the solvent and solution becomes
equal to the atmospheric pressure and Tb is called
elevation in boiling point.
Also, Tb m
Tb = kbm
Where, kb is called molal elevation constant or
ebullioscopy constant and m is the molality of the
solution.
Calculation of molecular mass of the solute:- As
molality is the no. of moles of the solute dissolve
per 100 gm of the solvent.
If w2 grams of the solute of molecular mass m2 are
dissolve in w1gram of the solvent
m = (W2/M2)(1000/W1)
Tb = Kb(W2/M2)(1000/W1)

Depression in freezing point:- It is observed that

the freezing point of the solution is always lower
than that of pure solvent. And the decrease is called
the depression in freezing point.

From figure,

Tf = T0f Tf

Vant hoff factor:- It is defined as the ratio of the

experimented value to the calculated property of the
colligative property known as vant hoff factor.
12 Class Chapter 3- Electrochemistry

Electrochemistry
Electrolysis: It is the process of decomposition of
an electrolyte by the passage of electricity through
its aqueous solution or molten state.
Faradays first law of electrolysis: In a chemical
reaction, the amount of any substance deposited or
librated is directly proportional to the quantity of
electricity passed through it.
WQ
W = ZQ
W=
Zit
( Q= It )
Where, Z = Electrochemical Equivalent.
Z = atomic weight/nF
(n = no. of
electron, F = 96500 )
Faradays second law of electrolysis: When the
same quantity of electricity is passed through the
different electrolytes connected in series. The
weights of the substance produced at the electrodes
are directly proportional to their equivalent weights.
Ex: AgNO2 and CuSO4 solution connected
in series,
Conductance of electrolytic solution:- Electrolytes
conducts electricity by decomposition.
Electrical resistance:- If voltage v is applied to the
ends of the conductor and currentI floe through
it, then the resistance R of the conductor is V/I
(ohm).

Electrical conductance:- The reciprocal of

electrical resistance is called conductance. And is
represented by G sign
Thus, G = 1/R
[unit of G =
mho]
Specific resistance or Resistivity:- it is observed
that,
R l/a
There is constant and called as resistivity.
Specific conductance or conductivity:- The
reciprocal of resistivity is known as conductivity.
And is denoted by k (kappa).
R=1/G
or,
=
1/k (i)
..(ii)
From eq. (i) and (ii)

Equivalent conductivity:- equivalent conductivity

of a solution at a dilution v is defined as the
conductance of all the ions produced from one gram
equivalent of the electrolyte dissolved in v cm3 of
the solution when the distance between the
electrode is one cm and the area of the electrode is
so large then whole the solution is come between
them. It is represented by eq (lamda).
Equivalent conductivity = Specific
conductivity v
eq = v
Where, Ceq is concentration of solution in
gm. eq/L.
But, for particular cell l/a is constant called
cell constant and is represented by G*
Then, = G G*
since, [G* =
l/a]
Molar conductivity (m):Where, c is molar concentration.
Kohlrausch law: - The limiting molar conductivity
of an electrolyte (i.e. molar conductivity at infinite
dilution) is the sum of the limiting ionic
conductivities of the cation and the anion each
multiplied with the number of ions present in one
formula unit of the electrolyte.
i.e.,
0m for AxBy = x0(A)y+ + y0(B)x0
where, m is the limiting molar conductivity of the
electrolyte 0(A)y+ and 0(B)x- are the limiting ionic
conductivities of the cation (Ay+) and anion (Bx-).

Kohlrausch law in terms of equivalent

conductivity:- The equivalent conductivity of an
electrolyte at infinite dilution is the sum of two
values one depends upon cation and other upon
anion.
0eq = 0c + 0a
Where, 0c & 0a is the limiting ionic conductivity
of the anion and cation.
Electrode potential:- The electrical potential
difference set up between metals and its ions in the
solution is called electrode potential.
Cell potential or EMF of a cell:- The difference
between the electrode potential of the two half cell
is known as cell potential or cell voltage it is
called Electromotive Force or EMF of the cell if
no current is drawn from the cell.
Electrochemical series:- The various electrodes
have been arranged in order of their increasing
value of standard reduction potentials. This
arrangement is called electrochemical series.
Nernst equation for electrode potential:Mn+ + ne- M
Then Nernst equation is,
Where, E = electrode potential under given
concentration of Mn+ ions and temperature T.
E0 = standard electrode potential.
R = gas constant.
T = Temperature in K
F = one Faraday
n = No. of electrons involves in the
electrode reaction.
Also put,
R = 8.314 Jk-1mol-1
F = 96500 coulombs
T = 298 k
Primary cells
Dry cell:- it consist of a cylindrical zinc container
which acts as a anode. A graphite rod is placed
between the centre acts as a cathode. The space
between the cathode and the anode is so packed
with the paste of NH4Cl and ZnCl2 and graphite is
surrounded by MnO2 and carbon.
Reactions,
At Anode: - Zn (s) Zn2+ (aq) + 2eAt cathode: - 2MnO2 (s) + 2NH4+ (aq) + 2e Mn2O3 (s) + 2NH3 (g) +H2O
These cells have voltage in range of 1.25 V to 1.50
V have no long life.

Mercury cell (Ruber Mallory cell) :- It consists of

zinc container as anode, a carbon rod as cathode and
a paste of mercuric oxide mixed with KOH as the
electrolyte a lining of porous paper separate the
electrolyte from zinc container.
Cell reaction:At Anode : - Zn + 2OH- ZnO +
H2O + 2e
At Cathode: - HgO + H2O+2e- Hg
+ 2OH

Secondary cell
Lead storage battery:- cell consist of lead anode
and a grid of lead packed with lead dioxide acts as
lead cathode. These electrodes are arranged
alternatively separated by fibre glass sheet and
suspended in sulphuric acid (dilute) which acts as
electrolyte.
Electrode reaction occurs during discharge
battery:At Anode :- Pb + SO42- PbSO4 + 2eAt Cathode :- PbO2 + SO42- + 4H+ + 2e PbSO4 +2H2O
In above reactions H2SO4 is used hence density of
H2SO4 is decreases so battery will discharge.
During charging:- The electrode reaction is
reserved.
PbSO4 + 2e- Pb + SO42PbSO4 +2H2O PbO2 + SO42- + 4H+ + 2eNickel Cadmium Storage Cell:- It consists of
cadmium electrode (as Anode) and metal grid of
nickel (iv) oxide as cathode immersed in KOH
solution.
Reaction occurs during discharge of cell:At Anode :- Cd + 2OH Cd(OH)2 + 2eAt Cathode :- NiO2 + 2H2O +2e Ni(OH)2 + 2OHHence,
The reaction can be reversed during charging. The
potential of each Ni-Cd cell is approximately 1.4 V
Fuel cell: - It consists of porous carbon electrodes
containing suitable catalyst incorporated in them.
Concentrated KOH or NaOH solution is placed
between the electrodes to act as the electrolyte. The
hydrogen or oxygen gases are bubbled through the
porous electrode into the KOH/NaOH solution.
Reactions:-

At Anode: - 2H2 + 4OH- 4H2O + 4eAt Cathode: - O2 + 2H2O + 4e- 4OHCORROSION

Corrosion:- The process of slowly eating away of
metal due to attack of atmospheric gases on the
surface of metal resulting into the formation of
compounds such as oxides, sulphides, carbonates,
sulphates etc. is called as corrosion.
In corrosion the metal is oxidised by loss of
electrons to oxygen and formation of oxides. The
corrosion of iron occurs in the presence of air &
water.
In iron sheet or object or a particular pot behaves
like a where oxidation takes place.
Anode: - 2Fe (s) 2Fe2+ + 4eAnd these electron moves to another spot where
reduction takes place in the presence of H+ ion
(H2CO3)
At Cathode: - O2(g) + 4H+ (aq) + 4e- 2H2O
(l)
The overall reaction being 2Fe + O2 +
4H+ 2Fe2+ + 2H2O
E0(cell) = 1.67 v
Fe2+ (ferrous ion) oxidised by O2to form ferric ion
(Fe3+) which comes out as Rust