C7-Electrochemical Processes Sc-Epc: Process Engineering and Energy Technolgy (PEET) - 2

C7-Electrochemical Processes
SC-EPC
Process Engineering and Energy Technolgy (PEET)-2
Felicitas Berger
What is the force that repels two electrons
at a distance of 100 pm?
erratum
F = Kc x q 1 x q 2
r 2
r = 10-10 m
Q = 1,602 x 10 -19 C
Kc = 8,98755 x 109 Vm/As
F = 8,98755 x 109 x (1,602 x 10 -19)2 / (10-10 )2

F = 23,066 x 109 x 10 -38 / 10-10
F = 23,066 x 10-9
F = 2,3066 x 10-9 C2 x V x m / As x m2 = 2,3066 x 10-8 N

The left tube is filled with a copper
sulfate solution and a zinc rod.
Name the metal in the right tube!
The metal has a higher redox
poten1al (Eo) than copper. It is
either silver or pla1num.
Calculate the cell potential of a cell
with electrodes out of Magnesium
and Silver!
The cell potential of a cell with
electrodes out of Magnesium and
Silver is 3,16 V.
Ecell = Ecathode – E anode
Ecell = 0,8 V – (- 2,36 V) = 3,16 V

Setup the equation for the reaction
with aluminium and lead oxide. Do
you think that this reaction is
exergonic, why?
Alo + PbO Al2O3 + Pbo
Alo Al3+ + 3 e- Oxidation (double)
PbO + 2 e- Pbo + O2- Reduction (triple)
2 Alo + 3PbO + 6 e- 2 Al3+ + 6e- + 3O2- +3 Pbo
2 Alo + 3 PbO Al2O3 + 3 Pb0 Redox reaction

Lecture 3: Electrochemical cells
1 3. Electrochemical cells
3. Electrochemical cells
3.1 Oxidation and reduction
Oxidation: loss of electrones (gain of weight), anode reaction
Reduction: gain of electrones (loss of weight), cathode reaction

If Nickel forms the anode, the

following reaction takes place:
Ni Ni2+ + 2e-
If Nickel forms the cathode, the
following reaction takes place:
Ni2+ + 2e- Ni
3.1 Oxida4on and reduc4on
The free enthalpy from a galvanic

cell is given by:
∆G0 = - z x F x ∆ Eo
z = number of exchanged
electrons
F= Faraday constant = e x NA
e= 1,602176634 x 10 -19 C
NA = 6,02214076 x 1023 /mol
F= 96485,332 C/mol
∆E0 = Ecell = Ecathode – E anode
3.1 Oxida4on and reduc4on
The free enthalpy of the Daniell element is given by:
∆G0=-2 x 96485,332 C/mol x (0,35 V - (- 0,76 V))

∆G0= - 212267 C x V/mol
The work that is performed, to transport
the amount of 1 C over a potential
difference of 1 V is defined as Joule.
CxV=J
∆G0= - 212, 267 kJ/mol

What is the free enthalpy of a
galvanic cell consisting of
Aluminium (anode) and lead
oxide (cathode)?
∆G0=-6 x 96485,332 C/mol x (0,13 V - (- 1,66 V))
∆G0= - 885, 735 kJ/mol
The free enthalpy of a galvanic cell out of

Aluminium (anode) and lead oxide (cathode) is
886 kJ/mol.
3.2 Proper3es of electrochemical cells
At a given voltage the current flow

increases with decreasing resistance.
Ohm`s law:
V=RxI
3.2 Properties of electrochemical cells Ohm`s law: V=RxI
The voltage of an electrochemical cell
is given by the difference of the
electrode (or redox) potentials, the
cell potential.
The unit is Volt (V) V = W/A or J/C
One Volt is defined as the electrical

potential difference between two
points in a conductor, when an
electrical current of 1 A produces 1 W
of power. Or where one Joule of
energy per Coulomb of charge is
consumed/released when transported
between these two points.
The current represents the amount of

of electrical charges that flows across
an area or cross-section per time.
The unit is Ampere (A) A = C/s
One Ampere is defined as the flow of

one C per second through a cross
section.
1 A =6,2 x 10 18 e- / s
The resistance of an electrochemical

cell is inversely proportional to the
cross section of the conductor and the
proportional to ist length. It is material
specific.
The unit is Ohm (W) W = V/A
One Ohm is defined as the reistance

between two points of a conductor
with a potential difference of 1 V that
produces 1 A.
3.2 Properties of electrochemical
9.1 Daniell-Element cells 401
Abb. 9.1 Schematische

Darstellung eines
Daniell-Elements
The zink-ion concentration

increases, while the
eqillibrium is reached.
The copper concentration

decreases, while the
eqillibrium is reached.
Die Frage der maximalen Last kann durch die folgende Betrachtung beantwortet werden.
In Abb. 9.2 ist eine Verschaltung einer idealen Spannungsquelle der Quellspannung U0 mit
einem Innenwiderstand Ri und einem Lastwiderstand R1 dargestellt. Aus
3.2 Proper3es of electrochemical
9.1 Daniell-Element cells 401
Abb. 9.1 Schematische

Darstellung eines
Daniell-Elements
External curcuit
Does not contribute to

the resistance of an
electrochemical cell.
Internal curcuit
Migration of ions
determine the
resistance of an
electrochemical cell.
Die Frage der maximalen Last kann durch die folgende Betrachtung beantwortet werden.
In Abb. 9.2 ist eine Verschaltung einer idealen Spannungsquelle der Quellspannung U0 mit
einem Innenwiderstand Ri und einem Lastwiderstand R1 dargestellt. Aus
3.2 Properties of electrochemical cells
A self driven cell is a galvanic cell, where chemical energy is converted

into electrical energy. An external driven cell is an electrolytic cell,
which stores chemical energy, which can be converted into electrical
energy.
3.3 Examples of electrochemical cells
Ag Pt
AgNO3
AgNO3
A galvanic cell consisting of a silver an a platinum electrode and a

AgNO3 electrolyte is set up. A current can be observed and after some
time the weight of the two electrodes reveals, that the platinum
electrode gained weight during the process.
Ag Pt
AgNO3
AgNO3
Anode reaction: Ago Ag+ + e-

Cathode reaction: Ag+ + e- Ago
Solid silver is formed at the cathode which explains the weight gain.
Chlorine and Hydrogen are formed at the

electrodes.
In the internal curcuit the chloride anions migrate to the anode and
Protons migrate to the cathode.
Two identical lead electrodes are placed into an electrolyte of diluted

sulfuric acid. E0Pb/Pb2+ = -0,126 V
Pb Pb2+ + 2e-
2 H + + 2 e- H2
A thin layer of white lead sulfate is formed at both of the electrodes.
An external voltage of 20 V is applied to the cell. On one electrode the

white pracipitate disappears and a metallic glance is formed, on the
other electrode, the formation of a brown substance can be observed.
At the cathode of the electrolytic cell, the reduction takes place: The
lead of the lead sulfate is reduced to metallic lead. Cathode reactions:
PbSO4 + 2e- Pbo + SO42

2 H + + 2 e- H2
At the anode of the electrolytic cell, the oxidation takes place: The lead
of the lead sulfate is oxidized to Pb4+. Anode reaction 1:
PbSO4 Pb(SO4)2 + 2 e-
Pb(SO4)2 + 2H2O PbO2 + 2H2SO4
Sulfate-Ions are oxidized, electrons are removed and Sulfate radicals

are formed. Oxygen is formed. Anode reaction 2:
2 SO42- 2 SO4* + 4 e-
2 SO4* + 2H2O 2H2SO4 + O2
When the external voltage is removed, a current flow can be observed.

The cell potential of the galvanic cell is 2 V. At the cathode, the
reduction of the Pb4+ to lead sulfate takes place and at the anode lead
is oxidized to lead sulfate, they both form a layer of white lead sulfate.
loaded unloaded
The lead accumulator is a rechargable electrochemical cell, in its
galvanic state (lead/lead oxide) it can release energy to perform work.
In ist unloaded state (lead sulfate) it can be charged by an external
voltage. In this electrolytic state it is reloaded and becomes, once
again, a galvanic cell.

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C7-Electrochemical Processes

Process Engineering and Energy Technolgy (PEET)-2

F = 8,98755 x 109 x (1,602 x 10 -19)2 / (10-10 )2

F = 2,3066 x 10-9 C2 x V x m / As x m2 = 2,3066 x 10-8 N

Ecell = Ecathode – E anode

Ecell = 0,8 V – (- 2,36 V) = 3,16 V

2 Alo + 3 PbO Al2O3 + 3 Pb0 Redox reaction

Oxidation: loss of electrones (gain of weight), anode reaction

Reduction: gain of electrones (loss of weight), cathode reaction

If Nickel forms the anode, the

The free enthalpy from a galvanic

The free enthalpy of the Daniell element is given by:

∆G0=-2 x 96485,332 C/mol x (0,35 V - (- 0,76 V))

∆G0= - 212, 267 kJ/mol

The free enthalpy of a galvanic cell out of

At a given voltage the current flow

The unit is Volt (V) V = W/A or J/C

One Volt is defined as the electrical

The current represents the amount of

The unit is Ampere (A) A = C/s

One Ampere is defined as the flow of

The resistance of an electrochemical

The unit is Ohm (W) W = V/A

One Ohm is defined as the reistance

Abb. 9.1 Schematische

The zink-ion concentration

The copper concentration

Abb. 9.1 Schematische

Does not contribute to

A self driven cell is a galvanic cell, where chemical energy is converted

A galvanic cell consisting of a silver an a platinum electrode and a

Anode reaction: Ago Ag+ + e-

Chlorine and Hydrogen are formed at the

Two identical lead electrodes are placed into an electrolyte of diluted

An external voltage of 20 V is applied to the cell. On one electrode the

PbSO4 + 2e- Pbo + SO42

Sulfate-Ions are oxidized, electrons are removed and Sulfate radicals

When the external voltage is removed, a current flow can be observed.

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