C7-Electrochemical Processes

SC-EPC

Process Engineering and Energy Technolgy (PEET)-2

Felicitas Berger
Lecture 5: Electrolysis
1 4. Electrolysis

4. Electrolysis
4.1 Principle

Michael Faraday 1791-1867

Electrolysis is the passing of a direct current through an electrolyte,

producing chemical reactions at the electrodes. In this process,
electrical energy is converted into chemical energy.
2 4. Electrolysis

4. Electrolysis
4.1 Principle

graphite electrode platinum electrode ruthenium electrode

Nobel metals like gold, platinum, iridium, ruthenium or graphite and

sometimes steel are used as electrode materials. The electrolyse must
contain the substance that should be produced or analysed and an
external power source is needed.
3 4. Electrolysis

4. Electrolysis
4.1 Principle

Water electrolysis Fused salt electrolysis

Sometimes very complex partition materials are used to increase the

efficiency of electrolysis in some applications no partition is needed.
4 4. Electrolysis

4. Electrolysis
4.2 Electrolysis of water

When two electrodes are put into water and an external power supply
is connected, Protons are attracted by the cathode, get reduced and
form Hydrogen. At the anode, electrones are removed from the water
and oxygen is formed.
5 4. Electrolysis

4. Electrolysis
4.2 Electrolysis of water

Cathode: Anode:
2 H 2O + 2 e - H2 + 2 OH- 2 H 2O O2 + 4 H+ + 4 e-

Overall reaction:
2 H 2O O2 + 2 H2
6 4. Electrolysis

4. Electrolysis
4.2 Electrolysis of water: Faraday`s laws

n≈Q
Q /mol = e x NA = F

To form one mole of a single charged ion by

electrolysis the amount of charge Q is needed

1. The amount of substance that is deposited at one electrode is

proportional to the quantitiy of the transmitted electricity .

2. The mass of different elements obtained at an electrode by using a

certain amount of electricity is proportional to the atomic weight of
that element and the charges per ion of the element.
7 4. Electrolysis

4. Electrolysis
4.2 Electrolysis of water: Faraday`s laws

Q=nxzxF and n=Q/zxF

since m = M x n

m = M x Q /z x F
Q=mxzxF/M

Q= charge
n = amount of substance
e= elementary charge
NA = Avogardo constant
F = Faraday constant
M = atomic/molecular weight
m = mass
8 4. Electrolysis

4. Electrolysis
4.2 Electrolysis of water, Faraday`s laws

Since at a constant current I the charge is

proportional to the time of the electrolysis:

Q=Ixt

m = M x Q /z x F can be converted to
m=MxIxt/zxF

t = time I = current
Q= charge n = amount of substance
e= elementary charge NA = Avogardo constant
F = Faraday constant M = atomic/molecular weight
m = mass
What time is needed, to produce 1 l H2
at a constant current of 4 A ?

m=MxIxt/zxF

The molar volume of an ideal gas

(under normal conditions) is 22,4 l/mol.
m=MxIxt/zxF
1. t = m x z x F / M x I (or 2. n x z x F/ I)

2 H2O + 2 e- H2 + 2 OH-
22,4 l = 1 mol, 1 l = 0,044643 mol
MH2 = 2,01568 g/mol, m = 0,089986 g

1.
t = 2 x 0,089986 g x 96485 C/mol / 4 A x 2,01568 g/mol
t = 2153,6 g x mol x C / A x g x mol
t = 2153,6 C/A, since A = C/s, C/A= s = 35,9 min
2.
t = 0,44643 mol x 2 x 96485 C/mol /4 A
t = 2153,6 s
9 4. Electrolysis

4. Electrolysis
4.2 Electrolysis of water
Acidic conditions:
Anode:
2 H 2O O2 + 4 H+ + 4 e-

Cathode:
2 H+ + 2 e- H2
Basic conditions:
Anode:
4 OH- O2 + 2 H2O + 4 e-

Cathode:
2 H 2O + 2 e - H2 + 2 OH-

Electrolysis of water can be carried out under acidic and basic

conditions.
10 4. Electrolysis

4. Electrolysis
4.2 Electrolysis of water, decomposition potential

The decomposition potential is the minimum voltage that has to be

applied on an electrolytical cell in order to induce a reaction turnover.
It is proportional to the Gibb´s free enthalpie of the system.
11 4. Electrolysis

4. Electrolysis
4.2 Electrolysis of water, decomposition potential

∆G = ∆H –T ∆S
∆H°R = ∑ ∆ HF° (∑ ∆ HF° products - ∑ ∆ HF° reactants)
∆S°R = ∑ ∆ SF° (∑ ∆ SF° products - ∑ ∆ SF° reactants)

soichiometric factors for each reactant and product must be

considered

For the electrolysis of 1 mol of water: H2O H2 +1/2 O2

One mole hydrogen and a half mole of oxigen are produced

∆H°R = 1 ∆H°F (H2) + 1/2 ∆H°F (O2) - ∆H°F (H2O)

∆H°F of elements is 0, ∆H°F of water is -285,9 kJ/mol

∆H°R = 0 + 0 – (-285,9 kJ/mol) = 285,9 kJ/mol (endothermic)

12 4. Electrolysis

4. Electrolysis
4.2 Electrolysis of water, decomposition potential

∆G = ∆H –T ∆S
∆H°R = ∑ ∆ HF° (∑ ∆ HF° products - ∑ ∆ HF° reactants)
∆S°R = ∑ ∆ SF° (∑ ∆ SF° products - ∑ ∆ SF° reactants)

soichiometric factors for each reactant and product must be

considered

∆S°R = 130,6 J/mol x K + 1/2 x 205,03 J/mol x K – 69,96 J/mol x K

∆S°R = 163,16 J/mol x K = 0,16316 kJ / mol x K

∆G°R = 285,9 kJ/mol – 298,15 K x 0,16316 kJ / mol x K =

∆G°R = 237,25 kJ / mol (endergonic)
13 4. Electrolysis

4. Electrolysis
4.2 Electrolysis of water, decomposition potential

The decomposition potential E° is proportional to the Gibb´s free

enthalpie ∆G°R of a system:

E° = ∆G°R / z x F
E° = 237,25 kJ/mol / 2 x 96485 C/mol
E° = 0,001229 kJ/ C = 1,229 V

The decomposition potential of the electrolysis of water is 1,229 V.

14 4. Electrolysis

4. Electrolysis
4.2 Electrolysis of water,
overpotential

The decomposition potential is a theoretical value. Due to kinetic

inhibition it does not match the voltage that actually causes depletion
of water. Reasons for the differences are mosty transport barriers
(electron, reactant, product transfer, diffusion and adsorption).
15 4. Electrolysis

4. Electrolysis
4.2 Electrolysis of water, overpotential

The overpotential is the extra

potential, which must be applied
to an electrode to initiate the
electrode reaction in an
electrochemical cell.
16 4. Electrolysis

4. Electrolysis
4.2 Electrolysis of water, faraday efficiency

h= faradaic efficiency, loss or yield

h= Eusable/Einput or h= Eproduct/Eelectrical

Eproduct is the amount of the product produced by the cell x the caloric
value of the product.
The caloric value of a substance is the amount of energy that can be
released by the complete combustion of the material.

For Hydrogen, the caloric value is 141 MJ/kg or 286 kJ/mol or 12,745 x
106 J/m3
17 4. Electrolysis

4. Electrolysis
4.2 Electrolysis of water, faraday efficiency

Eelectrical (electrical power) is the overall rate of electrical energy that is

transferred by an electrical curcuit during the whole time that the cell
was running:

Power (P) = V x Q/ t or V x I with the unit Watt (W) or J/s

Eelectrical = P x t with the unit W or J

h= amount, of substance, mass, volume x caloric value/V x I x t

In an experiment 0,03 l Hydrogen were produced
by applying a voltage of 1,95 V
with a current of 1 A over
a time of 300 s. Calculate the energy efficiency