Electrochemistry

GANAPATI G
(IIT BOMBAY Alumnus)
Senior Chemistry Faculty
 Session Objectives

1. Introduction

2. Electrolysis

3. Faraday’s first law of electrolysis

4. Faraday’s second law of electrolysis

5. Electrochemical cell

6. Concentration cell

7. Conductance

8. Kohlrausch’s Law

9. Secondary Cell
 Electrolysis :
The process in which discharge of ions takes place at respective electrodes
by passage of electricity through an electrolyte.
Electrolytic cell cell that drives a non-spontaneous redox reaction
through the application of electrical energy
Electrolysis of Water:
At cathode: Reduction takes place e.g.

2 H+(aq) + 2e− → H2(g)

At anode: Oxidation takes place e.g.

4 OH--(aq) → O2(g) + H2O + 4e−

 Electrolysis of Molten NaCl by using pt
electrodes

At cathode: Reduction takes place e.g.

Na  e  Na (S)

At anode: Oxidation takes place e.g.

 1
Cl  Cl2 (g)  e
2

Electrolysis of fused NaOH by using pt electrodes

preferential discharge theory
This is explained by preferential discharge theory. It
states that if more than one type of ions are attracted
towards a particular electrode, then the one discharged is
the ion which require least energy
Electrolysis of aq NaCl by using pt
electrodes
 Faraday’s first law of electrolysis
The mass of substance deposited or liberated at an electrode during
electrolysis is directly proportional to the amount of charge passed
through the electrolyte
WQ

But Q = it, Where Z is a constant of

proportionality and is known as
or W = Z it electrochemical equivalent.
E
By definition Z 
96500

Eit
or W 
96500
 Illustrative example

How many atoms of calcium will be deposited from

a solution of CaCl2 by a current of 25 milliamperes
flowing for 60 s?
 Solution

Number of Faraday of electricity passed

3
25  10  60

96500

25  103  60
 moles of Ca atoms
96500  2

25  103  60
  6.023  1023 atoms of Ca
96500  2

= 4.68 × 1018 atoms of calcium.

Calculate the amounts of Na and
chlorine gas produced during the
electrolysis of fused NaCl by the passage
of 1 ampere current for 25 minutes.
ANSWER
For Na, we have
w=(23 ∗1 ∗25∗60​)/96500

w=0.357g

for chlorine, we have

w=(71/2)∗1∗25∗60​/96500

w=0.55g
 Faraday’s Second law of electrolysis
The amount of different substances deposited or liberated by passing
same amount of charge through different electrolytic solutions is
directly proportional to their equivalent weights.

W1 E1 W1 Z1I t
 But 
W2 E2 W2 Z2I t

Z1 E1
Hence 
Z2 E2
 Illustrative Example

The electrolytic cells, one containing acidified ferrous

chloride and another acidified ferric chloride are
connected in series. What will be the ratio of iron
deposited at cathodes in the two cells when electricity
is passed through the cells ?
Solution

Ratio of iron deposited at cathode will be in

their ratio of equivalents

Equivalent of iron from ferrous salt


Equivalent of iron from ferric salt

M
3
=2 
M 2
3
Calculate the amounts of products
formed during the electrolysis of aq .
CuSO4 by the passage of 965 ampere
current for 5 minutes by using Pt
electrodes.
Electrochemical cell
Chemical energy electrical energy.
 Reactions involved in
electrochemical cell
At anode: Oxidation takes place

2 –
Zn(s)  Zn (aq)  2e
At cathode: Reduction takes place

2 –
Cu (aq)  2e  Cu(s)
Cell reaction

2 2
Zn(s)  Cu (aq)  Zn (aq)  Cu(s)
 Salt Bridge

Salt bridge : Agar—agar mixed with KCl or KNO3 or NH4NO3 etc.

• Minimizes liquid junction potential

• Maintains the electrical neutrality of solutions.

• Completes the circuit.

Cell representation:

Zn(s) | Zn2(C1M) || Cu2(C2M) | Cu(s)

 Standard hydrogen electrode

When the ions are at unit activity at 1 bar pressure and

the temperature is 25°C (298 K), the potential is called
the standard electrode potential (E°).
It is measured with reference to Standard Hydrogen Electrode(SHE)

2 H+(aq) + 2 e–  H2(g); E° = 0 V

Pt|H2(g, 1 bar)|H+(a = 1)
 Standard electrode potential

According to international convention standard reduction

potential are now called standard electrode potentials.

Standard Reduction Potential (SRP) gives a measure

of tendency of species to get reduced in solution.

Greater the SRP greater the tendency to get reduced

and greater is the oxidizing power.
Electrochemical series

When elements are arranged in increasing order

of standard electrode potential as compared to
that of standard hydrogen electrode,

It is called electrochemical series.

Note: Oxidation Potential-Reduction Potential of an element

Have same magnitude and different sign
 Electromotive force (emf)
It is the difference of potential between the two electrodes

o o o
Ecell  Ecathode  Eanode

(Both are reduction

potential )
 Electrochemical cell

Galvanic cell:-

Chemical energy electrical energy.

Daniel cell
Cell Representation
Writing the cell Reaction from the Cell Notation
a) Write the cell reaction for the voltaic cell
Tl(s) | Tl+(aq) || Sn2(aq) | Sn(s)

b) Write the cell reaction for the voltaic cell

Zn(z) | Zn2+(aq) || Fe3+(aq), Fe2+(aq) | Pt
Solution: a) The half-cell reactions are
Tl(s)  Tl+(aq) + e–, Sn2+(aa) + 2e–  Sn(s)
Multiplying the anode reaction by 2 and then summing the
half-cell reactions gives

2Tl(s) + Sn2+(aq)  2Tl+(aq) + Sn(s)

b) The half cell reactions are

Zn(s)  Zn2+(aq) + 2e–. Fe3+(aq) + e–  Fe2+(aq) and the cell
reaction is
Zn(s) + 2Fe3+(aq)  Zn2+(aq) + 2Fe2+(aq)
Electrode potential of the metals in their respective
solution are provided.
Arrange the metals in their increasing order of
reducing power.
K+/K = – 2.93V, Ag+/Ag = + 0.80V
Hg+/Hg = +0.79V, Mg2+/Mg = – 2.37V
Cr3+/Cr = –0.74V
Solution: We know that the reducing
power of a metal depends upon its
tendency to lose electrons. Thus lower the
reduction potential, more the tendency to
get oxidized and thus more will be the
reducing power. Hence increasing order
of reducing power is:
Ag < Hg < Cr < Mg < K
Nernst Equation
 Illustrative Example

E0 values of Mg+2/Mg is –2.37V,

Zn+2/Zn is –0.76V, Fe+2/Fe
is –0.44V. Using this information
predict whether Zn will reduce iron or
not?
 Solution

Zinc has lower reduction potential than

iron. Therefore, it can reduce iron.

Hence, the answer is (a).

 Illustrative example

Saturated solution of KNO3 is used to make ‘salt bridge’ because

(a) velocity of K+ is greater than

(b) velocity of is greater than K+
(c) velocity of both K+ and NO3— are nearly the same
(d) KNO3 is highly soluble in water
 Solution

The velocity of cation and anion used in salt bridge should be same.

Hence answer is (c).

Solution:
Solution:
Solution:
Solution:
Concentration cells

Electrochemical cells for which Eocell = 0 and which

work due to concentration gradient.

Concentration cells are of two types:

(a)Electrolyte concentration cells

(b)Electrode concentration cells

M/Mn+ (Cl) // Mn+(C2)/M
 Electrolyte concentration cell

Pt(H2 ) | HCl | HCl | (H2 )Pt

1 atm C1 M C2 M 1 atm

Cell reaction
 
H2 (a)  2H (c2 ) 
 2H (c1 )  H2 (c)

0.0591 P H2 (c) [c1]2

E log
2 PH2 (a) c 2
 2

For spontaneous cell reaction C2 > C1

 Electrode concentration cell

Na | Hg | NaCl | Hg | Na
[Na]  C1 [Na]  C2

o [Na]c
 Ecell  Ecell  0.0591log
[Na]a

 C1 
 E  0.0591log  
 C2 

Condition for spontaneity

C1 > C2
 Applications of Electrochemical Series

Higher the standard reduction potential, the lesser will be its

reducing strength.
Li is strongest reducing agent in aqueous solution.
The lesser the standard reduction potential of an element, greater
will be its activity.
A more active metal displaces a less active one from its salt
solution.
Those metals which have positive oxidation potential will displace
hydrogen from acids.
The metals above hydrogen are easily rusted and those situated
below are not rusted.
 Conductance

The reciprocal of the resistance is called conductance.

For a conductor of uniform cross section(a)

and length(l);
a
Resistance R
l
1 l
R  l and R  R  
a a

Where  is called resistivity or

specific resistance.
 Specific Conductance
Conductivity of a material in Sm-1 is its conductance when
it is 1m long and its area of cross section is 1 m2.

1
Specific conductance  

l 
K    x Conductance
 a

Unit of specific conductance is

ohm–1cm–1

SI Unit of specific conductance is

ohm–1m–1 (or)

Sm–1 where S is Siemen

 Molar Conductance

It is the conductance of all the ions produced by dissolving

1 mole of an electrolyte in solution.

Molar Conductance
m    V
  1000
m  M=molarity
M

Unit Ω−1 cm2 mol−1.

 Equivalent Conductance

It is the conductance of all the ions produced by dissolving

1 gram equivalent of an electrolyte in solution.

  V
Equivalent conductance

  1000
eq  N = Normality
N

Ω−1 cm2 equi−1.

Effect of Dilution on Conductivity
 Effect of Dilution on Conductivity
Specific conductivity decreases on dilution.

Equivalent and molar conductance both increase with dilution

and reaches a maximum value.

The conductance of all electrolytes increases with temperature.

KCl (strong electrolyte)

CH3COOH (weak electrolyte)

–1 1/2
concentration, (mole L )
 Kohlrausch Law

The limiting molar conductivity of an electrolyte can be represented

as the sum of individual contributions of cations and anions of
the electrolyte at infinite dilution.

m  a   c

Where a and  c are known as ionic

conductance of anion and cation at infinite dilution

respectively.

It is used for determination of degree of

dissociation of a weak electrolyte.
c
m
 
m
 Illustrative problem
The equivalent conductance's of two strong electrolytes at infinite
dilution in H2O (where ions move freely through a solution) at 25°C are
given below
oCH  91.0 cm2 / equiv, oHCl  426.2 cm2 / equiv
3COONa

What additional information/quantity one needs to

calculate Λ° of an aqueous solution of acetic acid?
(a) Λ° of chloroacetic acid (ClCH2COOH)
(b) Λ° of NaCl
(c) Λ° of CH3COOK
(d) The limiting equivalent conductance of H (Ho  )

Solution: b According to Kohlrausch’ law

  
mCH COOH  m  m  mNaCl
3 CH3COONa HCl


m of NaCl is required.
From the given molar conductivities at infinite
dilution,
calculate for NH4OH.
for Ba(OH)2 = 457.6 ohm-1 cm2mol-1.
for Ba(Cl)2 = 240.6 ohm-1 cm2mol-1.
for NH4Cl = 129.8 ohm-1 cm2mol-1.
= 238.3 ohm-1 cm2 mol-1
 Illustrative example

A decinormal solution of NaCl has specific conductivity equal to

0.0092. If ionic conductance of Na+ and Cl– ions are 43.0 and 65.0
ohm–1 respectively. Calculate the degree of dissociation of NaCl
solution.
Solution:

Equivalent conductance of NaCl

  1000 0.0092  1000

m    92 ohm1
M 0.1

     –  43  65  108 ohm1
Na Cl

v 92
    0.85
 108
 Secondary Cell
Famous lead storage cell is an example of secondary
cell
Pb | H2SO4 | PbO2 | Pb

Cell reaction:

Pb  PbO2  s   4H  2Pb2  2H2O

o 0.0591 [Pb2 ]
Ecell  Ecell  log  4
2 [H ]

At cathode:
PbO 2  2e  4H

Pb  2  2 H2O
At anode:

Pb  Pb2  2e
 Corrosion
Process of slowly eating away of the metal
due to attack of atmospheric gases on the
surface of the metal.

Examples of corrosion

• Rusting of iron
• Tarnishing of silver
• Development of green coating on copper and bronze, etc.
 Illustrative Example
The standard reduction potentials of Sn+2/Sn and
Zn+2/Zn are respectively –0.14V, -0.76V. Predict
whether the corrosion of tin can be prevented by
coating with zinc or not.

Solution :

Zinc lies above tin in the electrochemical series, therefore

it has a lower reduction potential than [Link] property is
employed to prevent corrosion of tin by coating it with zinc
as zinc acts as a sacrificial electrode.
Illustrative Example

Given : E0  0.036 V,E0  0.439 V

Fe3 /Fe Fe2  /Fe
The value of standard electrode potential for the change,

 aq  e  Fe  aq
Fe3   2 will be

(1) – 0.072 (2) 0.385 V

(3) 0.770 V (4) – 0.270 V
 Solution

Fe3+ + 3e–  Fe; E° = – 0.036 V, DG°1 = 3 × 0.036 F

Fe  Fe2+ + 2e–, E° = 0.439 V; DG°2 = – 2 × 0.439F
_________________________________________
Fe3+ + e–  Fe2+; E° = ?, DG°3 = – 1 × E° × F
– E°F = 0.108F – 0.878F
or E° = 0.77 V
 Illustrative example

The standard reduction potentials of Cu2+/Cu and

Cu2+/Cu+ are 0.337 V and 0.153 V respectively. The
standard electrode potential of Cu+/Cu half-cell is

(a) 0.184 V (b) 0.827 V

(c) 0.521 V (d) 0.490 V

 Solution

Cu   2e 

 Cu o
DG1
Cu   e 
 Cu o
DG2
___________________
Cu  e 
 Cu o
DG3

o o o
DG3  DG1  DG2
o
1  E3F  2  0.337 F  0.153  1 F
o
E3  0.674  0.153
o
E3  0.521 V

Hence answer is (c)

CAN YOU CONCLUDE WHETHER Cu+ WILL GET DISPROPORTIONATED?

Q.1
Solution:
Q.2
Solution:
Q.3
Solution: B
Q.4
Solution: C
Q.5
Solution: A
Q.6
Solution:
Q.7
Solution:
Q.8
Solution:
Q.9
Solution:
Q.10
Solution:
Q.11
Solution:
Q.12
Solution: B
Q.13
Solution:
Q.14
Solution:
Q.15
Solution: A
Q.16
Solution:
Q.17
Solution: C
Q.18
Solution:
Q.19
Solution:
Q.20
Solution:
Q.21
Solution:
Q.22
Solution:
Q.23
Solution:
Q.24
Solution:
Q.26
Solution:
Q.27
Solution:
Thank You