1.

F arada y ' s law of electrolysis :−¿

Faraday ' s 1 st law of electrolysis :-
This law states that, “the mass of substance deposited on an electrode, during electrolysis is
directly proportional to the quantity of electrolysis pass through the electrolyte.”
If W =¿ mass of substance deposited at the electrode
Q=¿ quantity of electricity passed through the electrolyte

Then W α Q
ButQ=It
[Where I =current ∈amperes , T =time∈second ]
 W α I .t
 W =Z . I .t ¿where ‘ Z ’ is a constant which called electro chemical equivalent¿
In the above relation
Then, W =Z [ If I =1 amp , t=1 sec ]
Hence electrochemical equivalent is defined as the mass of substance deposited when 1
ampere of current is passed through the electrolyte for 1 sec.
 A biggest unit of electricity ¿ 1 Faraday
1 Faraday =96500 Coulomb
mass of substance deposited
Electrochemical equivalent =
96500C

Mass of substance ( W )
 Electrochemical equivalent ( Z )= Quantity of electricity (Q )
W
 Z= It
Faraday ’ s 2 nd law of electrolysis :−¿
This law states that “when same quantity of electricity is passed through different electrolytes
connected in series, then the masses of the different substances deposited at the electrodes are
directly proportional to their equivalent masses.”

i. Consider three vessels containing solution of copper sulphate, silver nitrate and sulphuric
acid. Let these electrolytic cells are connected in series and same amount of current be
passed through them for a given time.
ii. If‘ Q ’ is the charge passed through these electrolytes, then according to faradays first law
of electrolysis
W Ag¿ Z AgQ −−−−(i)

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 W Cu¿ Z CuQ −−−−(ii)
W H¿ Z HQ −−−−(iii)
Taking the ratio of (i) and (ii)
W Z
 W Ag = Z Ag
Cu Cu

W Ag Z Ag x 96500 EAg
 = =
W Cu Z Cu x 96500 ECu
Where,
W =mass of the substance deposited
Z=Electrochemical equivalent of substance
E=Equivalent mass of substance
According to the faraday’s 2nd law of electrolysis
mass of copper deposited Eq . mass of copper
deposited ¿= ¿
mass of ¿ Eq . mass of ¿
Also from (ii) and (iii)
mass of hydrogenliberated Eq . mass of hydrogen
=
mass of copper deposited Eq. mass of copper
2. K ohlrausch ’ Law :
It states that, “at infinite dilution, when dissociation of an electrolyte is complete, each
ion of it makes a definite contribution towards the equivalent or molar conductance irrespective
of nature of other ions associated with it and the total molar or equivalent conductance is equal
to the sum of the contributions of cations and anions.”
Mathematically, λ 0=λ0C + λ 0a
Where,
λ 0=¿Equivalent conductance/ molar conductance of electrolyte at infinite dilution
λ 0C =¿Ionic conductance of cation at infinite dilution
λ 0a=¿Ionic conductance of anion at infinite dilution
0
For an electrolyte of type A x B y , λ 0 expressed as λ A B =xλ y+¿ + y λ ¿
x y
0
0
x−¿ ¿

Ex :−¿
−¿¿

HCl ↔ H +¿+Cl ¿

λ 0HCl ↔ λ H +¿ +λ
0
0 ¿
Cl−¿ ¿

Applications of Kohlrausch ’ Law :

i. Calculations of molar∨equivalent conductance at infinite dilutionof weak
Electrolytes :
Weak electrolytes are far from being completely dissociated even at very high dilutions,
their λ ∞ cannot be determined by extrapolation of graph between λ v and √ c to zero
concentration.

Ex :−¿
Molar conductance of acetic acid at infinite dilution can be calculated from the molar
conductance at infinite dilution of hydrochloric acid, sodium chloride and sodium acetate
as illustrated below:-
0 + ¿¿

λ 0 CH 3 COOH → λ 0 CH 3 COO−¿+λ H ¿

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 0 + ¿−−−−(i)¿

λ 0 CH 3 COONa → λ0 CH 3 COO−¿+ λ Na ¿
0 −¿¿

λ 0 HCl → λ 0 H +¿+ λ Cl ¿ −−−−(ii)

0 −¿¿
0 0 +¿+ λ Cl ¿
λ NaCl → λ Na −−−−(iii)

λ 0 CH 3 COONa + λ0 HCl−λ 0 NaCl

0
0 +¿ +λ Cl−¿ −¿ ¿ ¿

0 −¿+ λ 0 Na+ ¿+ λ H ¿
¿
¿ λ CH 3 COO
0
0 +¿ −λ Cl−¿ ¿ ¿
0 +¿ +λ0 Cl−¿ −λ Na ¿¿
0 + ¿+ λ H ¿
0 −¿+ λ Na ¿
¿ λ CH 3 COO
0 +¿ ¿

¿ λ0 CH 3 COO−¿+ λ H ¿
¿ λ0 CH 3 COOH
ii. Calculation of degree of dissociation of weak electrolyte :
The molar conductance of weak electrolyte depends upon the degree of dissociation ( α ).
Greater the value of α higher is the molar conductance. This can be done by the formula:
λC
α=
λ0(m)
Where,
λ C =molar conductance of electrolyte at a given concentration
λ 0=molar conductance at infinte dilution=( λ0C + λ 0a )
This value of α can help in calculating the dissociation constant of weak electrolysis by
applying Ostwald’s dilution law:
a2 C
K=
1−α
Where, K = dissociation constant

3.
Electrochemical cell∨galvanic cell :
It is a device in which the chemical energy of a redox reaction is converted into electrical
energy. Such device is also called electrochemical cell and the redox reaction taking place is
spontaneous one.
The simplest galvanic cell is Daniel cell.
Some examples of galvanic cell :
i. Zn−CuSO 4 cell
ii. Daniel cell
iii. Cu− AgNO3 cell
iv. H 2−CuSO 4 cell
Construction:It consists of two beakers. One of them
contain 1M ZnSO 4 solution in which a zinc rod is dipped
as an electrode and it is called zinc-half cell.
i. In another beaker 1M CuSO 4 solution is taken as
electrolyte and a copper rod is dipped as an
electrode and it is called copper-half cell.
ii. The two terminals of the electrodes are connected
externally by insulated copper wire through a
voltmeter and a key.

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 iii. The electrolytes in the beakers are connected by means of a U-shaped tube containing
semi-solid paste. The two ends of U-tube are sealed with porous plugs or glass wool. The
U-tube is known as salt bridge.

Working :
When electrical contact is established and the voltmeter starts showing deflection, then
the following process takes place:
i. Oxidation occurs at the zinc rod and Zn-rod starts dissolving into Zn2+¿¿ ion. And zinc starts
losing electron. −¿¿

Zn ( s ) → Zn2+¿+2 e ¿
ii. The electrons lost by zinc electrodes flow in copper wires through a voltmeter into
copper-half cell. The Cu2+¿ ¿ions gain these electrons at copper-electrode, undergo
reduction and get deposited over it.
−¿→Cu(deposited )¿

Cu 2+¿ (aq) +2 e ¿

iii. Due to reduction reaction taking place in Cu-half cell, it is called as reduction half cell. The
Cu-electrode is assigned with positive polarity and is electron deficient. In this half cell,
the concentration of Cu2+¿ ¿ ions continuously decreases and the relative concentration of
SO−24 continuously increase.

iv. As electrons continuously flow from Zn-half cell to Cu-half cell, i.e. from anode to
cathode, so the current flows in reverse direction, i.e. from Cu-half cell to Zn-half cell or
cathode to anode.
Salt bridge∧it function:
It is an inverted U-tube that contains solution or semi-solid paste of inert electrolyte ( KCl
, KNO3). It connects the electrolyte solutions of two half-cell.
Substances used as electrolytes in salt bridge must have:
i. It must be inert, i.e. it should not react chemically with the electrolytes of both half
cells.
ii. The cations and anions should have same ionic mobility.
iii. It should not interfere with overall cell reactions.
Function of salt bridge:
i. It internally connects the two electrolytic solutions, i.e. it completes the circuit.
ii. It reduces the liquid junction potential.
iii. It maintains the electrical neutrality of the electrolytic solutions of two half cells.
Cell diagram∨representation of an electrochemical cell :
The Daniel cell is represented as:
2+ ¿ ( C 2 )∨Cu(s )¿
2 +¿ (C 1 )∨¿Cu ¿
Zn(s )∨Zn
a. Anode half-cell is written on left had side while cathode half-cell on right hand side.
b. A single vertical line separates the metal from aqueous solution of its own ions.
Zn(s )∨Zn2 +¿ (aq ) ¿ Cu 2+¿ (aq)∨Cu(s)¿
anodic chamber cathodic chamber
c. A double vertical line represents salt bridge which allows the passage of ions through it
but prevents the mixing of two solutions.
d. The molar concentration (C) or activity (a) is paled in brackets after the formula of the
corresponding ion.

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 e. The value of e.m.f of the cell is written on the extreme right of cell.
2 +¿ ( 1 M )∨Cu( s)¿

Zn(s )∨Zn2 +¿ (1 M )∨¿Cu EMF=+1.1 V

¿

f. If an inert electrode like platinum is involved in the construction of the cell. It may be
written along the working electrode in bracket.
+ ¿ ( C2 )∨H 2 (Pt )¿
2 +¿ (C 1 )∨¿ H ¿
Zn(s )∨Zn

Conclusion:
i. An electrochemical cell converts chemical energy into electrical energy.
ii. In an electrochemical cell, anode is that electrode at which oxidation half reaction takes
place.
iii. Cathode is that electrode at which reduction half reaction takes place.
iv. Electrons in the external circuit flow anode to cathode.
v. Representation of electrochemical cell:
Anode salt bridge cathode
Zn∨Zn2+¿¿ kNO 3 Cu2+¿∨Cu¿

Electrochemical series:
The series of electrodes arranged in the increasing order of their standard reduction
potential is called electrochemical series.
Applications:
i. Predicting relative reactivity of elements.
ii. Constructing galvanic cell.
iii. Determining feasibility of a reaction.
iv. Calculating EMF of a cell.
v. Extraction of metals by using the principle of ‘Hydrometallurgy’.
NERNST EQUATION :
The value of electrode potential at different concentration and temperature can be obtained
by using Nernst equation.
 Nernst gave a relation between the reduction potential of an electrode and the
concentration of the ions in the electrode reaction. For this purpose the electrode reaction
is written as reduction, i.e.
−¿→ M( s) ¿

M n+¿ (aq )+n e ¿

−¿ Zn¿
2 +¿+2 e ¿
e . g . Zn
Then the Nernst equation is applied as follows,
0 RT [ M ]
E=E − ln ¿
nf ¿¿
Where, E=¿ electrode potential under given concentration of M n+¿ ¿, ion and temperature ‘T ’.
E0 =¿Standard electrode potential
R=¿ Real gas constant
T =¿Temperature in Kelvin
F=¿ 1 Faraday
n=¿Number of electrons involved in the electrode reaction

When concentration of solid ‘ M ’ is taken as unity,

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 RT 1
E=E0− ln ¿
nf ¿¿
0 RT 1
 E=E − nf x 2.303 log ¿ ¿ ¿
Putting,
R=8.314 J K −1 mol−1
F=96500 coulombs
T =298 K
We get,
0 8.314 x 298 1
 E=E − n 96500 x 2.303 log ¿ ¿ ¿
0 0.0591 1
 E=E − n x log ¿ ¿ ¿
While applying Nernst equation, electrode potential is always taken as reduction potential.

Applications:
Nernst equation for emf of a cell:
Let’s consider an example of a Denial cell in which the cell reaction is
2+ ¿ ( aq )+ Cu(s )¿

Zn ( s ) +Cu2+¿ (aq )→ Zn ¿

For cathode:
E¿
For anode:
E¿
The cell potential:
 Ecell =E ¿
 Ecell =¿
 Ecell =E0 ¿
 Ecell =E0 ¿
0 RT
 Ecell =E cell − 2 F ln ¿ ¿

It can be seen that Ecell depends on the concentration of both Cu2+¿ ¿ and Zn2+¿¿ions. It
increases with increase in the concentration of Cu2+¿ ¿ions and decreases in the concentration of
Zn2+¿¿ions.
By converting the natural logarithm in equation to the base 10 and substituting the
values of R,F and T it reduces to
0.0591
E=E0− x log ¿ ¿
n
−¿
Taking a general electro chemical reaction of the type: aA +bB ne
→
cC +dD ¿
Nernst equation can be written as
c d
0 RT [ C ] [ D ]
 Ecell =E cell − nF ln a b
[ A] [B]
SHORT
1. R elation between Gibb ’ s energy∧emf of a cell :

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 It is known that Gibb’s energy is a measure of chemical useful work that is available from a
chemical reaction.
We write ∆ G=maximum work
 If the potential of two electrodes differ by Ecell then the maximum work done is given as,
maximum work =nf Ecell
Where, n is the number of moles of electrons transferred in them and F is the faraday
constant.
 In a denial cell, the work is done on the surroundings because electrical energy flows
through the external circuit.

 Such a work is given a negative sign (by convention)

∴ Maximumwork =−nf Ecell =∆ G
 For comparing cell voltage, standard electrode potentials ( E 0 ) are used.
 Thus, ∆ G=−nf E0cell
Where,
∆ G 0 =standard gib b' s energy of a reaction
Significance :
The above reaction is used to predict feasibility of a reaction. If ∆ G0 is negative, the
above reaction is spontaneous or feasible otherwise not.
mass of substance deposited
2. E lectrochemical equivalent =
96500 C

Mass of substance ( W )
Electrochemical equivalent ( Z )=
Quantity of electricity (Q )
W
Z=
It
3. C ell constant :
The cell constant is a fixed quantity for a particular cell and may be defined as the
distances two parallel electrodes of a cell divided by the area of cross section of each electrode.
l
 Cell constant =
a
Unit :
m
 Cell constant = 2
=m−1
m
specific conductance
Cell constant = =specific conductance x resistance
conductance
Equivalent conductance :
It is defined as the conducting power of all the ions produced by one gram equivalent of an
electrolyte in a given volume of solution at a constant temperature.
 It is represented by λ eq.
Unit ohm−1 cm2( gram equivalent ¿¿−1)¿
Molar conductance:
It is defined as ‘the conducting power of all the ions produced by 1 gm mole of an electrolyte
in a given volume of solution at constant temperature’.
It is represented by the symbol λ mand μ.
Unit ohm−1 cm2( gram mol e ¿¿−1) ¿

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