Unit:9

ELECTRO CHEMISTRY

 Define Resistivity (ρ) (or) Define specific resistance.

Resistivity is defined as the resistance of an electrolyte confined between two electrodes
having unit cross sectional area and are separated by a unit distance.
l l Ra
R α  R = ρ   ρ =
a a l
If a =1m2 and 𝑙=1m then ρ=R
Unit of resistivity is ohm metre (Ωm).
l
The ratio   is called the cell constant.
a
 Define Conductivity (  ) (or) Define specific conductance.
The reciprocal of the specific resistance is called the specific conductance(or) conductivity.

1 1 l  l
( ) =   =   = C 
ρ Ra a
If 𝑎 =1m2 and 𝑙=1m then 𝜅=C.
The specific conductance is defined as the conductance of a cube of an electrolytic
solution of unit dimensions.
The SI unit of specific conductance is Sm -1 .
 Define Molar conductivity (Λ m)

Molar conductance is defined as the conductance of 'V' m3 of electrolytic solution

containing one mole of electrolyte in a conductivity cell in which the electrodes are one
metre apart.
Λm =   V

number of moles of electrolyte(n)

Molarity ( M ) =
volume of the solution(V in L)
1 -1
Volume of the solution containing 1 mole of solute =   mol L
M
 10-3  -1 3
Volume of the solution containing 1 mole of solute =   mol m
 M 
  10-3
Hence Λ m = Smol-1m2
M

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 Define equivalent conductance (Λ )
Equivalent conductance is defined as the conductance of 'V' m3 of electrolytic solution
containing one-gram equivalent of electrolyte in a conductivity cell in which the
electrodes are one metre apart.
  10-3
equivalent conductance( Λ ) = S (gram.equ ) m2
-1

N
Where  the specific conductance and N is the normality electrolytic solution.
 List the factors affecting electrolytic conductance.
• If the interionic attraction between the oppositely charged ions increases, the
conductance will decrease.
• Solvent of higher dielectric constant show high conductance in solution.
• Conductivity increases with the decrease in viscosity.
• Increase in temperature increases the kinetic energy of the ions and decreases the
attractive force between the oppositely charged ions and hence conductivity
increases.
• Molar conductance increases with increase in dilution. This is because, for a strong
electrolyte, interionic forces of attraction decrease with dilution. For a weak
electrolyte, degree of dissociation increases with dilution.
 Explain the measurement of conductivity of ionic solutions

 The conductivity of an electrolytic solution is determined by using a Wheatstone

bridge, in which one resistance is replaced by a conductivity cell filled with the
electrolytic solution.
 AC current is used for this measurement to prevent electrolysis.

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  A Wheatstone bridge is constructed using known resistances P, Q, a variable resistance
S and conductivity cell (Let the resistance of the electrolytic solution taken in it be R).
 An AC source is connected between the junctions A and C. Connect a suitable detector
(Telephone ear piece-G) between the junctions ‘B’ and ‘D’
 The variable resistance ‘S’ is adjusted until the bridge is balanced and in this conditions
there is no current flow through the detector.
 Under balanced condition,
P R PS
=  R =
Q S Q
 The resistance of the electrolytic solution (R) is calculated from the known resistance
values P, Q and ‘S’ value under balanced condition.
Conductivity calculation:
Specific conductance or conductivity of an electrolytic solution can be calculated using the
following expression.
1 l 
 =  
Ra
l
The value of the cell constant   is usually provided by the cell manufacturer.
a
Variation of molar conductivity with concentration

Kohlraush deduced the following empirical relationship between the molar conductance
(  m ) and the concentration ( C ) of the electrolyte.
 m = m - k C
the plot of  m Vs C gives a straight line with a negative slope of –k and the y intercept,
 m . Where  m is called the limiting molar conductivity.

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 What is limiting molar conductivity?
The molar conductivity of an electrolytic solution when its concentration approaches zero
is known as limiting molar conductivity m . ( )
 State Kohlrausch’s law
At infinite dilution, the limiting molar conductivity of an electrolyte is equal to the sum of
the limiting molar conductivities of its constituent ions.
For an electrolyte Ax By , the molar conductivity at infinite dilution

( ) 0
m AB
x y
( )
= x m0
Ay +
( )
+ y m0
Bx−
For a uni – univalent electrolyte such as NaCl

( ) 0
m NaCl ( )
= m0
Na +
( )
+ m0
Cl −

Applications of Kohlrausch's Law

 State Kohlrausch Law. How is it useful to determine the molar conductivity of weak
electrolyte at infinite dilution?
At infinite dilution, the limiting molar conductivity of an electrolyte is equal to the sum of
the limiting molar conductivities of its constituent ions.
The molar conductance of CH3COOH, can be calculated using the experimentally
determined molar conductivities of strong electrolytes HCl, NaCl and CH3COONa.

( 0m )CH COONa = ( m0 )Na + ( m0 )CH COO − − − − − (1)

3
+
3
−

( 0m )HCl = ( m0 )H + ( m0 )Cl − − − − − (2)

+ −

( 0m )NaCl = ( m0 )Na + ( m0 )Cl − − − − − (3)

+ −

(1) + (2) − (3)

( 0m )CH COONa + ( 0m )HCl − ( 0m )NaCl
3
( )CH COO + ( m0 )H
= m0
3
− +

= ( 0m )
CH COOH
3

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 State Kohlrausch Law. How is it useful to determine degree of dissociation of weak
electrolytes?
The degree of dissociation of weak electrolyte can be calculated from the molar
conductivity at a given concentration and the molar conductivity at infinite dilution.
m
=
 0m
According to Ostwald dilution Law,
 2C
Ka =
(1 −  )
(  ) C
2
m
Ka =
(  ) 1 − 0m 

0 2 
m
 m 
( )
2
m C
Ka =
( ) − (  )
0 2
m
0
m m

(  ) C
2
m
Ka =
 ( −  )
0
m
0
m m

 Write a note on Galvanic cell notation

The galvanic cell is represented by a cell diagram, for example, Daniel cell is represented
as

Zn | Zn 2+ (aq) || Cu 2+ (aq) | Cu E 0 = +1.1V

 In the above notation, a single vertical bar (|) represents a phase boundary and the
double vertical bar (||) represents the salt bridge.
 The anode half-cell is written on the left side of the salt bridge and the cathode half-
cell on the right side.
 The anode and cathode are written on the extreme left and extreme right,
respectively.
 The emf of the cell is written on the right side after cell diagram.

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 Measurement of electrode potential
The emf of a cell can be considered as the sum of the electrode potentials of cathode and
anode.
Ecell = ( Eox )anode + ( Ered )cathode
It is impossible to measure the emf of a single electrode, but we can measure Ecell using a
voltmeter. If we know the emf of any one of the electrodes, we can calculate the emf of the
other electrode from the measured Ecell . Hence, we need a reference electrode whose emf
is known.
 Write a note of SHE.
• Standard Hydrogen Electrode (SHE) is used as the reference electrode.
• It consists of a platinum electrode in contact with 1M HCl solution and 1 atm hydrogen
gas. The hydrogen gas is bubbled through the solution at 25°C .
• emf of SHE has been assigned arbitrarily as zero volt.
• SHE can act as a cathode as well as an anode.
If SHE is used as an anode, the oxidation reaction is
0
H2(1atm)⎯⎯→ 2H+(aq)+ 2e- ESHE = 0V
If SHE is used as a cathode, the reduction reactions is
0
2H+(aq)+ 2e- ⎯⎯→ H2(1atm) ESHE = 0V
 How is half-cell potential of zinc electrode calculated?
The reduction potential of zinc electrode is calculated by combining it with SHE.
Step : 1
The following galvanic cell is constructed using SHE
Zn(s) | Zn 2+ (aq,1M) || H + (aq,1M), H 2 (1atm) | Pt(s)
Step : 2
The measured emf of the above galvanic cell is Ecell = +0.76V
Calculation:
Ecell = ( Eox )Zn/Zn2+ + ( Ered )SHE
0.76V = ( Eox )Zn/Zn2+ + OV
( Eox )Zn/Zn
2+ = 0.76V
This is the oxidation potential zinc electrode.
Zn ⎯⎯→ Zn2+ + 2e- ( Eox )Zn/Zn 2+ = 0.76V
The emf for the reverse reaction will give the reduction potential
Zn2+ + 2e- ⎯⎯→ Zn ( Ered )Zn2+
/Zn
= -0.76V

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 Is it possible to store copper sulphate in an iron vessel for a long time?
Given : ECu2+/Cu = 0.34V and EFe2+/Fe = -0.44V
The reduction potential of copper is greater than the reduction potential of iron. Hence
when the copper sulphate solution is stored in iron vessel, the vessel dissolves and copper
get precipitated, so it is not possible to store copper sulphate in iron vessel.
 Can Fe3+ oxidises Bromide to bromine under standard conditions?
Given: E0Fe3+ /Fe2+ = 0.771V and E0Br /Br- = 1.09V
2

Solution:
2Br- ⎯⎯→ Br2 + 2e- ( Eox )Br /Br = -1.09V
-
2

2Fe + 2e ⎯⎯→ 2Fe

3+ - 2+
( ERed )Fe /Fe = +0.771V
3+ 2+

2Br- + 2Fe3+ ⎯⎯→ Br2 + 2Fe2+ Ecell = ?

E0cell = ( Eox ) + ( Ered )
E0cell = -1.09 + 0.771V
E0cell = -0.319V
E0cell is – ve; G is +ve and the cell reaction is non spontaneous. Hence Fe 3+ cannot
oxidises Br- to Br2
 Define Electrode potential (E)
Electromotive force of a cell in which the standard hydrogen electrode (SHE) is on the left
and the electrode on the right is the electrode in question.
 Define Standard electrode potential (E0)
The value of the standard emf of a cell in which molecular hydrogen under standard
pressure is oxidised to solvated protons at the anode left hand electrode.
 Explain the thermodynamics of cell reactions
• The electrical energy produced by the galvanic cell is equal to the product of the total
charge of electrons and the emf of the cell.
• If ‘n’ moles of electrons are exchanged in the overall cell reaction, then the electrical
energy produced by the cell is

elec tric a l energ y = ( c ha rg e of n moles of elec trons) ª Ec ell

elec tric a l energ y = nFEc ell − − − − − (1)

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 • This energy is used to do the electric work. Therefore, the maximum work that can be
obtained from a galvanic cell is
( Wma x )c ell = - nFEc ell − − − − − (2)
• Here the ( − ) sign is introduced to indicate that the work is done by the system on the
surroundings.
• From the Second Law of thermodynamics that the maximum work done by the system
is equal to the change in the Gibbs free energy of the system.
Wm a x = G − − − − − (3)
From (2) and (3)
G = - nFEc e ll − − − − − (4)
For a spontaneous cell reactions, G should be negative. The above expression (4)
indicates that Ec e ll should be positive to get a negative G value.
• When all the cell components are in their standard state,
G  = - nFEc ell
• The standard free energy change is related to the equilibrium constant as
G  = - RT lnKe q − − − − − (5)
- nFEc e ll = - RT lnKe q
RT
Ec e ll = lnKe q
nF
2.303 RT
Ec e ll = lo g Ke q
nF
 Derive an expression for Nernst equation
Nernst equation relates the cell potential and the concentration of the species involved in
an electrochemical reaction.
xA + yB lC + mD

The reaction quotient Q =

 C  D 
l m
- - - - - (1)
A x By
We know that G = G ° + RT lnQ - - - - - (2)
The Gibbs free energy can be related to the cell emf as follows
°
G° = - nFECell G = - nFECell - - - - - (3)
From (2 ) 

- nFECell = °
- nFECell + RTln
 C  D 
l m

A x By
Divide the above equation by (-nF)

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 RT C  D 
l m
°
ECell = ECell - ln
nF  A x By

°
ECell = ECell -
2.303RT
log
C  D  - - - - - (4)
l m

nF A x By
The above equation is called the Nernst equation.
At 298K, the above equation becomes,

°
ECe ll = ECe -
0.0591
lo g
C  D 
l m

A x By
ll
n
Electrolytic cell and electrolysis
 Describe the electrolysis of molten NaCl using inert electrodes
 The electrolytic cell consists of two iron electrodes dipped in molten NaCl and they are
connected to an external DC power supply via a key.
 The electrode attached to the negative terminal of the power supply is called the
cathode, and the one which attached to the positive end is called the anode.
 Once the key is closed, the external DC power supply drives the electrons to the
cathode and at the same time pull the electrons from the anode.
 Cell reactions
At cathode: Na+ ions are reduced to liquid sodium.
Na+ + e- ⎯⎯→ Na E0 = -2.71V
At anode : Cl– ions are oxidised to chlorine gas.
2Cl- ⎯⎯→ Cl2 + 2e- E0 = -1.36V
The overall reaction is,
2Na+ + 2Cl- ⎯⎯→ 2Na + Cl2 E0 = -6.78V
The negative E0 value shows that the above reaction is a non-spontaneous. Hence, a
voltage greater than 6.78 V can cause the electrolysis of molten NaCl.
 State Faraday’s Laws of electrolysis
First Law:
The mass of the substance (m) liberated at the electrode during electrolysis is directly
proportional to the quantity of charge (Q) passed through the cell.
m α Q
m α It
m = ZIt
Where is Z is known as the electro chemical equivalent of the substance.

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 Second Law:
When the same quantity of charge is passed through the solutions of different
electrolytes, the amount of substances liberated at the respective electrodes are directly
proportional to their electrochemical equivalents.
When Q coulomb charge is passed through the electrolytic cells containing AgNO 3, ZnSO4
and CuSO4 solutions, the masses of silver, zinc and copper deposited at the respective
electrodes be m Ag, mZn and mCu respectively.
According to faraday’s second law.
m Agα ZAg ; mZnα ZZn and m Cuα ZCu
m Ag mZn mCu
= =
ZAg ZZn ZCu
 Define electrochemical equivalent of the substance.
The electrochemical equivalent is defined as the amount of substance liberated at the
electrode by a charge of 1 coulomb.
m = ZIt
if I = 1amp ; t = 1 sec ; Q = 1C
m = Z
 A solution of silver nitrate is electrolysed for 20 minutes with a current of 2 amperes.
Calculate the mass of silver deposited at the cathode.
Solution:
Electrochemical reaction at cathode is Ag + + e - ⎯⎯→ Ag (reduction)
eq.mass of Ag 108 m = ZIT
Z= = gC-1
96500 96500 108g
I = 2A m = ª 2A ª 1200s
96500C
t = 20  60 = 1200sec m = 2.68g
 A solution of a salt of metal was electrolysed for 15 minutes with a current of 0.15
amperes. The mass of the metal deposited at the cathode is 0.783g. Calculate the
equivalent mass of the metal.
Solution:
m
Z=
m = 0.783g It
0.783 g
I = 0.15 A Z=
0.15A ª 900 s
t = 15  60 = 900sec
Z = 5.8 ª 10 - 3 g C - 1

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