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SC-EPC
Felicitas Berger
Lecture 5: Electrolysis
1 4. Electrolysis
4. Electrolysis
4.1 Principle
4. Electrolysis
4.1 Principle
4. Electrolysis
4.1 Principle
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
4. Electrolysis
4.2 Electrolysis of water: Faraday`s laws
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
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
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-
4. Electrolysis
4.2 Electrolysis of water, decomposition potential
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)
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)
4. Electrolysis
4.2 Electrolysis of water, decomposition potential
E° = ∆G°R / z x F
E° = 237,25 kJ/mol / 2 x 96485 C/mol
E° = 0,001229 kJ/ C = 1,229 V
4. Electrolysis
4.2 Electrolysis of water,
overpotential
4. Electrolysis
4.2 Electrolysis of water, overpotential
4. Electrolysis
4.2 Electrolysis of water, faraday efficiency
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