CHAPTER THREE

KINETICS OF ELECTROCHEMICAL CELLS

 Faraday’s Laws of Electrolysis
2

 First Law: The amount of chemical reaction which

occurs at any electrode during electrolysis by a
current is proportional to the quantity of electricity
passed through the electrolyte solution.
 Second Law: The amounts of different substances
liberated by the same quantity of electricity passing
through the electrolytic solution are proportional to
their chemical equivalent weights.
 Faraday’s law
3

Faraday first law :

Mass of primary product ,g is proportional with quantity of
electricity passed.

(1)

Where :

m: Mass of primary product(g)

Z: Proportionality constant (mass /A.s)
I: Current (A)
t: Time (s)
 Faraday’s law
4

Faraday second law :

Mass of products are proportional with their molecular weight
(2) (3)
Where:
m: Mass of primary product(g)
K: Stoichiometry constant
Mwt.: Molecular weight (g/mol)
I : Current (A)
F : Faraday constant (A.S/ mol)
n No. of exchanged electrons
t: Time (s)
 Faraday’s law
5

 Example:
A solution of CuSO4 is electrolyzed for 10 minute with a
current of 1.5 A. What is the mass of copper deposited at the
cathode? Mwt. of Cu= 63g/mol.

 According to the reaction: Cu2+ (aq) + 2e– → Cu(s)

m= [63 (g/mol) x 1.5 (A)x 600(s)] /[96500 (A.S/ mol) x 2

= 0.2938 g
 Faraday’s law
6

 Example : A medal was plated with 0.86 g of Cr

metal by electrolysis of aqueous Cr2(SO4)3 . If 12.5
min is allowed for the plating, what current is
needed?
 Sol.

By applying equation (3)

 Faraday’s law
7

0.86(g) x 96500 (A.S/mol) x 3 = I X (12.5 x 60 S) x 52

(g/mol)

I= 6.4 A
 Faraday’s law
8

Example:
 If one kilogram of copper is to be deposited by

means of the electrochemical reaction

Cu2+ + 2e- → Cu
 Calculate how many coulombs will be required?

 If a constant current of 10 A is used to carry out this

deposition, we can calculate how long it will take.
 Faraday’s law
9

 Solution
Coulombs = A.S
By applying equation (3)

m = 1 Kg =1000 g
Mwt. Of Cu= 63.456 g/mol
I = 10 A
F = 96500 A.S/mol
n =2
 Faraday’s law
10

1000(g) x 96500 (A.S/mol) x 2 =63.45 (g/mole) x It

It = 3.04 x10^6 A.S

If 10 A passes then
t = 3.04 X10^ 5 S
= 84.5 hr
 Cell efficiency
11

 In many electrochemical reactions, the actual amount

of product is less than the theoretical amount
calculated according to Faraday’s laws.

 The percentage ratio between the actually produced

and the theoretically calculated amounts is known as
“current efficiency”.
 Cell efficiency
12

 The electrochemical parameters we have explored so far

are linked with the Gibbs' Free Energy to establish the
thermodynamic model of galvanic cells. Work is the
negative of charge times potential:
w = – Q.E
where
Q = nF
F is the Faraday constant (96500 C/mol).
We are interested in the maximum work since this can
be related to the thermodynamic parameter ΔG.
 Cell efficiency
13

Example
 A cell with a maximum cell potential of 2.50 V. If 1.33 mol of

electrons passes through the cell at an average potential E =

2.10 V. What is the cell efficiency?
 Solution:

w= –Q E = –nFE= 1.33 mol ×96500 C/mol ×2.10 V (V = J/C)

w= –2.69 ×10^5 J = –269 kJ
wmax= –nFEmax= 1.33 mol ×96500 C/mol ×2.50 V =
w max = –321 kJ
Efficiency =w/wmax×100% = –269/–321 ×100% = 83.8 %
 Cell efficiency
14

 Current efficiency

Example :
It is required to plate 20 g of copper from CuSO4 solution with a
passage current of 25 A.h
How much theoretical mass of copper produced and what will be the
efficiency of the process.
Cu+2 +2e-→Cu
Q = 25 A.hr
F = 26.8 A.hr/mol
Mwt. of Cu= 63.6 g/mol
 Cell efficiency
15

By using equ.(3) :
 Deviations from Faraday’s Laws

16

1. Current Inefficiency

2. Polarization (Over potential):

A) Concentration Polarization:
B) Activation Polarization
 Cell Inefficiency
17

The major causes of current inefficiency are:

a- Occurrence of secondary reactions along with the
main reaction: For example, in the deposition of zinc,
hydrogen gas evolves simultaneously with zinc
deposition:
Zn2+ + 2e- → Zn (main)

2 H+ + 2e- → H2 (secondary)
 Cell Inefficiency
18

b-Mixing of cathodic products with anodic products:

• In electrolysis of brine to produce NaOH and Cl2
using graphite electrodes (for example), chlorine gas
which is an anodic product dissolve in water and
diffuse to the cathode where it reacts with the formed
NaOH.
• Thus, undesirable products are obtained resulting in a
loss in the yield of Cl2 and NaOH:
 Cell Inefficiency
19

NaCl → Na+ + Cl-

H2O → OH- + H+
2C1- → Cl2 + 2e-
2H+ + 2e- → H2
Na+ +OH- → NaOH
• The desired products of NaOH and Cl2 are lost by the
reaction:
2NaOH + Cl2 → NaOCl + NaCl + H2O
 Cell Inefficiency
20

 To prevent the mixing of NaOH and chlorine, a

porous diaphragm or membrane is used to divide the
cell into separated anode and cathode compartments
(see Figure 1 a & b).
 Cell Inefficiency
21

Fig(1) : separation of anode and cathode by a) diaphragm b) membrane

 Polarization (Over-potential):
22

 This is the difference between the actual potential

and the theoretical (reversible) potential required to
complete an electrolysis process.
 It can also be defined as the extra voltage that should
be added to the theoretical potential in order to
complete an electrolysis process.
 The main types of polarization are the concentration
polarization and the activation (or chemical)
polarization.