CHAPTER 3.

10

Thermodynamic Basis of Electrolysis

and Electrochemistry
Tetsuji Hirato
Department of Energy Science and Technology, Kyoto University, Kyoto, Japan

3.10.1. ZINC ELECTROWINNING

The thermodynamic basis of zinc electrowinning can be understood from the
potentialpH diagram shown in Figure 1 of Chapter 3.9. In the process, the anode reaction is oxygen evolution, which is shown as line b in the potentialpH diagram. The reaction proceeds at potentials higher than line b. The cathode reaction is deposition of metal
zinc, which is shown as line 1 in the potentialpH diagram because the concentration of
Zn2(aq) is relatively high in solutions used in this process.
The reaction proceeds at potentials lower than line 1. Since this potential region is
lower than line a, it is easily understood that hydrogen evolution cannot be avoided
in this process.
The voltage required in this process is the difference between lines b and 1. The voltage increases with decreasing pH value, and at pH 0, a voltage of at least 1.99 V is required
for progression of the zinc electrowinning process. Of course, more voltage is required to
operate the real process, including overpotential of zinc deposition, and an IR drop in a
circuit with an electric current.
This diagram can also be used to consider the removal of Zn2 from waste solutions as
Zn(OH)2. In the pH area between lines 4 and 5, the concentration of zinc in the solution
can be reduced to less than 105.

3.10.2. COPPER ELECTROWINNING

The thermodynamic basis of copper electrorefining can be understood from the
potentialpH diagram shown in Figure 3.10.1. In this process, the anode reaction is
oxygen evolution, which is shown as line b in the potentialpH diagram. The reaction
proceeds at potentials higher than line b. The cathode reaction is deposition of metal copper shown as line 1 in Figure 3.10.1. The reaction proceeds at potentials lower than line
1. The potential indicated by line 1 is higher than line a, and thus hydrogen evolution
does not need to be considered in this process. The voltage required in this process is the
Treatise on Process Metallurgy, Volume 1
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653

654

Tetsuji Hirato

Figure 3.10.1 PotentialpH diagram for the CuH2O system at 298 K.

difference between lines b and 1. The voltage increases with decreasing pH value, and at
pH 0, a voltage of at least 0.899 V is required for progression of the copper electrowinning process, which is much lower than that in zinc electrowinning process.

3.10.3. COPPER ELECTROREFINING

The thermodynamic basis of copper electrorefining can also be understood from
the potentialpH diagram shown in Figure 3.10.1. In this process, anode and cathode
reactions are expressed as follows:
at anode : Cu Cu2 2e
at cathode : Cu2 2e Cu
Both reactions are indicated by line 1 in Figure 3.10.1 and the required voltage is
0 from a thermodynamic understanding. More strictly, the activity of anode copper is
less than 1 because of impurities, so the voltage is a little bit more than 0.

3.10.4. ELECTROCHEMISTRY IN LEACHING

The electrochemistry in acid leaching or dissolution of copper oxides and hydroxides can also be understood by the potentialpH diagram shown in Figure 3.10.1. The
dissolution reactions of copper oxides and hydroxides are as follows:
CuOH2 s 2H Cu2 aq 2H2 Ol

3:10:1

655

Thermodynamic Basis of Electrolysis and Electrochemistry

Cu2 Os 2H aq 2Cu2 aq H2 Ol 2e

3:10:2

Reactions (3.10.1) and (3.10.2) are indicated by lines 2 and 3 in the diagram, respectively. Reaction (3.10.2) is a redox reaction as well as an acidbase reaction. For the dissolution of Cu2O to proceed, oxidant is required. When powders of Cu2O are put into
an aqueous sulfuric acid solution from which oxygen is purged, the following disproportionation reaction occurs:
Cu2 Os 2H aq Cus Cu2 aq H2 Ol

3:10:3

The thermodynamic properties of sulfide minerals in an aqueous environment can

also be described by means of potentialpH diagrams. Such diagrams are as useful to
hydrometallurgists as are Ellingham diagrams to pyrometallurgists [1]. For example,
Figure 3.10.2 shows the potentialpH diagram for the ZnSH2O system. This diagram
is constructed by considering that zinc in zinc sulfide is decomposed to Zn2, Zn, and Zn

(OH)2 and sulfur to H2S, S, HSO
4 , or HS . As can be seen from this figure, zinc sulfide
can be decomposed by oxidation, acidification, or reduction. The decomposition of zinc
sulfide is represented by the following reactions:
Oxidation
ZnS Zn2 S 2e


ZnS 4H2 O Zn2 HSO
4 7H 8e


ZnS 4H2 O Zn2 SO2
4 8H 8e

HSO4- SO42-

0.8

E / V vs. SHE

S
0

Zn2+

Zn(OH)2

H 2S
Zn2+

ZnS

-0.8
Zn
-1.6
-4

H2S
0

HS8

pH

Figure 3.10.2 PotentialpH diagram for the ZnSH2O system at 298 K.

12

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Tetsuji Hirato

Acidification
ZnS 2H Zn2 H2 S
Reduction
ZnS 2H 2e Zn H2 S
ZnS 2e Zn S2
In oxidative leaching, oxygen or Fe3 is used as an oxidant. In real oxidative leaching of
sulfides, the stable area of elemental sulfur seems larger than shown in Figure 3.10.2. This
is caused by the slow reaction of oxidation from elemental sulfur to sulfate. This diagram
can also be used to consider the removal of Zn2 from waste solutions as ZnS. In this case,
the activity of Zn2(aq) should be set at 106.

REFERENCES
[1] E. Peters, Metall. Trans. B 7B (1976) 505517.