0765162_AppF_Roberge 9/1/99 8:29 Page 1101

APPENDIX

F
Thermodynamic Data
and E-pH Diagrams

The tables and graphics in this appendix describe the thermodynam-

ic behavior of the following metals when exposed to pure water at 25
and 60°C:
■ Chromium1,2
■ Copper3,4
■ Iron5–8
■ Manganese9,10
■ Nickel11–13
■ Zinc9,14

Tables F.1 to F.6 contain the basic thermodynamic values for each
species, solid or ionic, considered for the construction of the E-pH dia-
grams. The graphics were obtained with a publicly available software
system that has been used throughout the book to calculate different
equilibrium systems.15 The basic calculations were detailed in Sec. D.2,
Chemical Thermodynamics. The relations between the free energy of
the species considered and the associated equations are evaluated with
the data presented in Tables F.1 to F.6 and the following equations. The
free energy (G0) of a substance for which heat capacity data are avail-
able can be calculated as a function of temperature using Eq. (F.1).

G(T2)  G(T1)  S(T1) (T2  T1)  T2

0 0 0 
T1
T1
T2

T2
C

0
p

T dT 

T1
T1
T2

T2
C 0p dT (F.1)

1101
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1102 Appendix F

TABLE F.1Species Considered for the Cr-H2O System and Their

Thermodynamic Data
G0(298 K), S0(298 K),
Species Jmol1 Jmol1 A B  103 C  105
O2 0 205 29.96 4.184 1.674
H2 0 131 27.28 3.263 0.502
H2O 237,000 69.9 75.27 0 0
Cr 0 23.77 17.41 15.15 1.26
CrO 350,661 44.77 46.48 8.12 3.68
Cr2O3 1,058,134 81.17 119.37 9.2 15.65
CrO2 539,740 48.12 67.49 12.55 12.55
CrO3 502,080 73.22 75.86 16.78 8.37
Cr(OH)3 900,815 80.33 0 0 0
CrOOH 672,955 25.1 0 0 0
Š0(298 K,
Jmol1 a b
H 0 0 20.9 0.065 0.005
Cr2 176,146 104.6 146.44 0.13 0.00166
Cr3 215,476 307.52 370.28 0.13 0.00166
Cr(OH)2 430,950 68.62 110.46 0.13 0.00166
Cr(OH)2 632,663 144.77 165.69 0.13 0.00166
CrO42 727,849 50.21 92.05 0.37 0.0055
HCrO4 764,835 184.1 205.02 0.37 0.0055
CrO2 535,929 96.23 117.15 0.37 0.0055
CrO33 603,416 238.49 175.73 0.37 0.0055

TABLE F.2 Pure Species Considered for the Cu-H2O System and
Their Thermodynamic Data
G0(298 K), S0(298 K),
Species Jmol1 Jmol1 A B  103 C 105
O2 0 205 29.96 4.184 1.674
H2 0 131 27.28 3.263 0.502
H2O 237,000 69.9 75.27 0 0
Cu 0 33.2 22.635 6.276 0
Cu2O 147,904 92.4 62.62 0 0
CuO 127,905 42.6 42.32 0 0
Cu(OH)2 358,987 87 87.91 0 0
Š0(298 K),
Jmol1 a b
H 0 0 20.9 0.065 0.005
Cu 50,626 12.6 33.52 0.13 0.00166
Cu2  65,689 207.2 249.04 0.13 0.00166
Cu(OH) 129,704 41.89 20.97 0.13 0.00166
Cu2(OH)22  280,328 98.22 140.06 0.13 0.00166
Cu3 303,340 401.8 464.56 0.13 0.00166
HCuO2 258,571 96.38 117.3 0.37 0.0055
CuO22 183,678 98.22 56.38 0.37 0.0055
CuO2 112,550 96.38 117.3 0.37 0.0055
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Thermodynamic Data and E-pH Diagrams 1103

TABLE F.3Pure Species Considered for the Fe-H2O System and Their
Thermodynamic Data
G0(298 K), S0(298 K),
Species Jmol1 Jmol1 A B  103 C  105
O2 0 205 29.96 4.184 1.674
H2 0 131 27.28 3.263 0.502
H2O 237,000 69.9 75.27 0 0
Fe 0 27.1 12.72 31.71 2.51
Fe3O4 1,020,000 146 91.55 201.67 0
Fe2O3 742,000 87.3 98.28 77.82 14.85
Fe(OH)2 493,000 92.4 96.3 0 0
Fe(OH)3 714,000 96.1 105 0 0
Š0(298 K),
Jmol1 a b
H 0 0 20.9 0.065 0.005
Fe(OH)2(sln) 449,000 38 38 0.13 0.00166
Fe(OH)3(sln) 661,000 75.2 75.2 0.13 0.00166
FeOH  274,000 29.3 50.2 0.13 0.00166
Fe(OH)2 459,000 29.3 50.2 0.13 0.00166
Fe2 92,200 107 149 0.13 0.00166
FeOH2  242,000 105 147 0.13 0.00166
Fe3 17,800 279 342 0.13 0.00166
Fe(OH)3 621,000 41.8 62.7 0.37 0.0055
Fe(OH)4 843,000 25.1 46 0.37 0.0055
FeO42 467,000 37.6 79.5 0.37 0.0055

TABLE F.4Pure Species Considered for the Mn-H2O System and Their
Thermodynamic Data
G0(298 K), S 0(298 K),
Species Jmol1 Jmol1 A B  103 C  105
O2 0 205 29.96 4.184 1.674
H2 0 131 27.28 3.263 0.502
H2O 237,000 69.9 75.27 0 0
Mn 0 32.0076 23.8488 14.14192 1.54808
MnO 362,920 59.70568 46.48424 8.11696 3.68192
Mn3O4 1,283,233 155.6448 144.9338 45.27088 9.2048
Mn2O3 881,150 110.4576 103.4703 35.06192 13.5143
MnO2 465,177 53.05312 69.4544 10.20896 16.2339
Š 0(298 K),
Jmol1 a b
H 0 0 20.9 0.065 0.005
Mn2 228,028 115.478 157.34 0.13 0.00166
Mn(OH) 405,011 37.656 58.576 0.13 0.00166
Mn3 82,006.4 378.652 441.41 0.13 0.00166
HMnO2 507,101 62.76 83.68 0.37 0.0055
MnO4 447,270 212.1288 233.05 0.37 0.0055
MnO42 500,825 100.416 142.256 0.37 0.0055
0765162_AppF_Roberge 9/1/99 8:29 Page 1104

1104 Appendix F

TABLE F.5 Pure Species Considered for the Ni-H2O System and Their
Thermodynamic Data
G0(298 K), S0(298 K),
Species Jmol1 Jmol1 A B  103 C  105
O2 0 205 29.96 4.184 1.674
H2 0 131 27.28 3.263 0.502
H2O 237,000 69.9 75.27 0 0
Ni 0 30.12 16.99 294.55 0
Ni(OH)2 453,130 79.5 0 0 0
NiO 215,940 38.58 20.88 157.23 16.28
Ni3O4 711,910 146.44 129.03 71.46 23.93
Ni2O3 469,740 94.14 98.28 77.82 14.85
NiO2 215,140 52.3 69.45 10.21 16.23
Š0(298 K),
Jmol1 a b
H 0 0 20.9 0.07 0.01
Ni2 46,442 201.3 243.14 0.13 0
HNiO2 349,218 62.76 41.84 0.37 0.01

TABLE F.6 Pure Species Considered for the Ni-H2O System and Their
Thermodynamic Data
G0(298 K), S0(298 K),
Species Jmol1 Jmol1 A B  103 C  105
O2 0 205 29.96 4.184 1.674
H2 0 131 27.28 3.263 0.502
H2O 237,000 69.9 75.27 0 0
Zn 0 41.63 25.4 0 0
Zn(OH)2 559,358 81.6 72.4 0 0
Š0(298 K),
Jmol1 a b
H 0 0 20.9 0.065 0.005
Zn2  147,280 207.2 249.04 0.13 0.00166
Zn(OH) 329,438 41.89 20.97 0.13 0.00166
HZnO2 464,227 96.38 117.3 0.37 0.0055
ZnO22 389,424 98.22 56.38 0.37 0.0055
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Thermodynamic Data and E-pH Diagrams 1105

For pure substances, i.e., solids, liquids, and gases, the heat capacity
Cp0 is expressed as an empirical function of the absolute temperature
[Eq. (F.2)].

Cp0  A  BT  CT 2 (F.2)

For ionic substances, one has to use another method, such as that
proposed by Criss and Cobble in 1964,16 to obtain the heat capacity, pro-
vided that the temperature does not rise above 200°C. The expression of
the ionic capacity [Eq. (F.3)] makes use of absolute entropy values and
the parameters a and b contained in Tables F.1 to F.6.

 
T2
Cp0  (4.186a  bŠ0(298 K)) (T2  298.16) / ln  (F.3)
298.16
By combining Eq. (F.2) or (F.3) with Eq. (F.1), one can obtain the free
energy [Eq. (F.4)] at a given temperature by using the fundamental
data contained in Tables F.1 to F.6.

Gt0  G0(298 K)  (Cp0  S0(298 K)) (T2  298.16)

 T2 ln T2
298.16
Cp0  (F.4)

Table F.7 provides an index for the thermodynamic data of the species
considered, the equations possible, and associated E-pH diagrams at
two temperatures, 25 and 60°C.

References
1. Silverman, D.C., Absence of Cr(IV) in the EMF-PH Diagram for Chromium,
Corrosion, 39:488–491 (1983).
2. Lee, J. B., Elevated Temperature Potential-pH Diagrams for the Cr-H2O, Mo-H2O,
and Pt-H2O Systems, Corrosion, 37:467 (1981).
3. Bianchi, G., and Longhi, P., Copper in Sea-Water, Potential-pH Diagrams, Corrosion
Science, 13:853–864 (1973).
4. Duby, P., The Thermodynamic Properties of Aqueous Inorganic Copper Systems,
INCRA Monograph IV, New York, The International Copper Research Association,
1977.
5. Le, H. H., and Ghali, E., Interpretation des diagrammes E-pH du système Fe-H2O
en relation avec la fragilisation caustique des aciers, Journal of Applied
Electrochemistry, 23:72–77 (1993).
6. Silverman, D. C., Presence of Solid Fe(OH)2 in EMF-pH Diagram for Iron,
Corrosion, 38:453–455 (1982).
7. Townsend, H. E., Potential-pH Diagrams at Elevated Temperature for the System
Fe-H2O, Corrosion Science, 10:343–358 (1970).
8. Biernat, R. J., and Robins, R. G., High-Temperature Potential/pH Diagrams for the
Iron-Water and Iron-Water-Sulphur Systems, Electrochimica Acta, 17:1261–1283
(1972).
9. Pourbaix, M., Atlas of Electrochemical Equilibria in Aqueous Solutions, Houston,
Tex., NACE International, 1974.
0765162_AppF_Roberge 9/1/99 8:29 Page 1106

1106 Appendix F

TABLE F.7 Index to Thermodynamic Data, Equilibrium, and

Associated E-pH Diagrams for Important Engineering Metals
Element Equations Temperature, °C Figure
Chromium (Data Table F.1)
Hydrated state Table F.8 25 F.1
60 F.2
Dry state Table F.9 25 F.3
60 F.4
Copper (Data Table F.2)
Hydrated state Table F.10 25 F.5
60 F.6
Dry state Table F.11 25 F.7
60 F.8
Iron (Data Table F.3)
Hydrated state Table F.12 25 F.9
60 F.10
Dry state Table F.13 25 F.11
60 F.12
Manganese (Data Table F.4)
Table F.14 25 F.13
60 F.14
Nickel (Data Table F.5)
Hydrated state Table F.15 25 F.15
60 F.16
Dry state Table F.16 25 F.17
60 F.18
Zinc (Data Table F.6)
Table F.17 25 F.19
60 F.20

10. Macdonald, D. D., The Thermodynamics and Theoretical Corrosion Behavior of

Manganese in Aqueous Systems at Elevated Temperatures, Corrosion Science,
16:482 (1976).
11. Macdonald, D. D., The Thermodynamics of Metal-Water Systems at Elevated
Temperatures, Part 4, The Nickel-Water System, AECL-4139, Pinawa, Canada,
Whiteshell Nuclear Research Establishment, 1972.
12. Chen, C. M., and Theus, G. J., Chemistry of Corrosion-Producing Salts in Light
Water Reactors, NP-2298, Palo Alto, Calif., Electric Power Research Institute, 1982.
13. Cowan, R. L., and Staehle, R. W., The Thermodynamics and Electrode Kinetic
Behavior of Nickel in Acid Solution in the Temperature Range 25° to 300°C, Journal
of the Electrochemical Society, 118:557–568 (1971).
14. Pan, P., and Tremaine, P. R., Thermodynamics of Aqueous Zinc: Standard Partial
Molar Heat Capacities and Volumes of Zn2 (aq) from 10 to 55°C, Geochimica et
Cosmochimica Acta, 58:4867–4874 (1994).
15. Roberge, P. R., KTS-Thermo (2.01), Kingston, Canada, Kingston Technical Software,
1998.
16. Criss, C. M., and Cobble, J. W., The Thermodynamic Properties of High
Temperature Aqueous Solutions, Journal of the American Chemical Society,
86:5385–5393 (1964).
0765162_AppF_Roberge 9/1/99 8:29 Page 1107

Thermodynamic Data and E-pH Diagrams 1107

TABLE F.8 Possible Reaction in the Cr-H2O System

between the Species Most Stable in Wet Conditions
Equilibria
1. 2e  1CrO  2H   1Cr  1H2O
2. 1 e  1Cr(OH)3  1H   1CrO  2H2O


3. 3 e  1Cr(OH)3  3H   1Cr  3H2O

4. 1 e  1CrO2  1H2O  1H   1Cr(OH)3
5. 1 e  1CrO2  1H   1Cr(OH)3
6. 3 e  1CrO3  3H   1CrO2  1H2O
7. 2 e  1Cr2  1Cr
8. 3 e  1CrO2  4H   1Cr  2H2O
9. 6 e  1HCrO4  7H   1Cr  4H2O
10. 6 e  1CrO42  8H   1Cr  4H2O
11. 1 e  1CrO2  2H   1CrO1H2O
12. 1CrO2  1H2O1H   1Cr(OH)3
13. 1CrO3  1H2O  1CrO42  2H 
14. 1CrO3  1H2O  1HCrO4  1H 
15. 1CrO2H   1Cr2   1H2O
16. 3 e  1Cr3  1Cr
17. 3 e  1CrO33  6H   1Cr  3H2O
18. 1 e  1CrO33  4H   1CrO2H2O
19. 1 e  1CrO2  4H   1Cr3  2H2O
20. 2 e  1HCrO4  3H   1CrO2  2H2O
21. 2 e  1CrO42  4H   1CrO2  2H2O
22. 1Cr(OH)3  3H   1Cr3  3H2O
23. 1Cr(OH)3  1CrO33  3H 
24. 1 e  1Cr(OH)3  3H   1Cr2  3H2O
25. 3 e  1HCrO4  4H   1Cr(OH)3  1H2O
26. 3 e  1CrO42  5H   1Cr(OH)3  1H2O
27. 3 e  1CrO42  4H   1CrO2  2H2O
28. 3 e  1CrO42  2H   1CrO33  1H2O
29. 1CrO2  4H   1Cr3  2H2O
30. 1CrO33  2H   1CrO2  1H2O
31. 1CrO42  1H   1HCrO4
32. 1 e  1Cr3  1Cr2 
33. 1 e  1CrO2  4H   1Cr2  2H2O
34. 3 e  1HCrO4  7H   1Cr3  4H2O
35. 3 e  1CrO42  8H   1Cr3  4H2O
36. 3 e  1HCrO4  3H   1CrO2  2H2O
37. 1Cr(OH)3  2H   1Cr(OH)2   2H2O
38. 1Cr(OH)3  1H   1Cr(OH)2  1H2O
39. 1 e  1CrO2  3H   1Cr(OH)2  1H2O
40. 1Cr(OH)2   1H   1Cr3  1H2O
41. 1Cr(OH)2  1H   1Cr(OH)2  1H2O
42. 1CrO2  2H   1Cr(OH)2
43. 1 e  1Cr(OH)2  1H   1Cr2   1H2O
44. 1 e  1Cr(OH)2  2H   1Cr2   2H2O
45. 3 e  1CrO42  7H   1Cr(OH)2   3H2O
46. 3 e  1CrO42  7H   1Cr(OH)2   3H2O
47. 3 e  1HCrO4  5H   1Cr(OH)2  2H2O
48. 3 e  1CrO42  6H   1Cr(OH)2  2H2O
49. 1CrO2  3H   1Cr(OH)2   1H2O
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1108 Appendix F

TABLE F.9 Possible Reactions in the Cr-H2O System

between the Species Most Stable in Dry Conditions
Equilibria
1. 2e  1CrO2H   1Cr  1H2O
2. 2 e  1Cr2O3  2H   2CrO1H2O


3. 6 e  1Cr2O3  6H   2Cr  3H2O

4. 2 e  2CrO2  2H   1Cr2O3  1H2O
5. 6 e  2CrO3  6H   1Cr2O3  3H2O
6. 2 e  1CrO3  2H   1CrO2  1H2O
7. 2 e  1Cr2  1Cr
8. 3 e  1CrO2  4H   1Cr  2H2O
9. 6 e  1HCrO4  7H   1Cr  4H2O
10. 6 e  1CrO42  8H   1Cr  4H2O
11. 1 e  1CrO2  2H   1CrO1H2O
12. 2CrO2  2H   1Cr2O3  1H2O
13. 1CrO3  1H2O  1CrO42  2H 
14. 1CrO3  1H2O  1HCrO4  1H 
15. 1CrO2H   1Cr2   1H2O
16. 3 e  1Cr3  1Cr
17. 3 e  1CrO33 r  3H2O
18. 1 e  1CrO33  4H   1CrO2H2O
19. 1 e  1CrO2  4H   1Cr3  2H2O
20. 2 e  1HCrO4  3H   1CrO2  2H2O
21. 2 e  1CrO42  4H   1CrO2  2H2O
22. 1Cr2O3  6H   2Cr3  3H2O
23. 1Cr2O3  3H2O  2CrO33  6H 
24. 2 e  1Cr2O3  6H   2Cr2  3H2O
25. 6 e  2HCrO4  8H   1Cr2O3  5H2O
26. 6 e  2CrO42  10H   1Cr2O3  5H2O
27. 3 e  1CrO42  4H   1CrO2  2H2O
28. 3 e  1CrO42  2H   1CrO33  1H2O
29. 1CrO2  4H   1Cr3  2H2O
30. 1CrO33  2H   1CrO2  1H2O
31. 1CrO4 2  1H   1HCrO4
32. 1 e  1Cr3  1Cr2 
33. 1 e  1CrO2  4H   1Cr2  2H2O
34. 3 e  1HCrO4  7H   1Cr3  4H2O
35. 3 e  1CrO42  8H   1Cr3  4H2O
36. 3 e  1HCrO4  3H   1CrO2  2H2O
37. 1Cr2O3  4H   2Cr(OH)2   1H2O
38. 1Cr2O3  1H2O2H   2Cr(OH)2
39. 1 e  1CrO2  3H   1Cr(OH)2  1H2O
40. 1Cr(OH)2   1H   1Cr3  1H2O
41. 1Cr(OH)2  1H   1Cr(OH)2  1H2O
42. 1CrO2  2H   1Cr(OH)2
43. 1 e  1Cr(OH)2  1H   1Cr2   1H2O
44. 1 e  1Cr(OH)2  2H   1Cr2   2H2O
45. 3 e  1CrO42  7H   1Cr(OH)2   3H2O
46. 3 e  1CrO42  7H   1Cr(OH)2   3H2O
47. 3 e  1HCrO4  5H   1Cr(OH)2  2H2O
48. 3 e  1CrO42  6H   1Cr(OH)2  2H2O
49. 1CrO2  3H   1Cr(OH)2   1H2O
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Thermodynamic Data and E-pH Diagrams 1109

TABLE F.10 Possible Reactions in the Cu-H2O

System between the Species Most Stable in Wet
Conditions
Equilibria
1. 3H   1HCuO2  2H2O1Cu2 
2. 4H   1CuO22  2H2O1Cu2 
3. 1H   1CuO22  1HCuO2
4. 1 e  1Cu2  1Cu
5. 1 e  3H   1HCuO2  1Cu  2H2O
6. 1 e  4H   1CuO22  2H2O1Cu
7. 2 e  2H   1Cu2O  1H2O2Cu
8. 2 e  2H   1Cu(OH)2  2H2O1Cu
9. 2 e  2H   2Cu(OH)2  3H2O1Cu2O
10. 2H   1Cu2O  1H2O2Cu
11. 2H   1Cu(OH)2  2H2O1Cu2
12. 2H   1CuO22  1Cu(OH)2
13. 1 e  1Cu  1Cu
14. 2 e  1Cu2  1Cu
15. 2 e  3H   1HCuO2  2H2O1Cu
16. 2 e  4H   1CuO22  2H2O1Cu
17. 2 e  1H2O  2Cu2   2H   1Cu2O
18. 2 e  4H   2HCuO2  3H2O1Cu2O
19. 2 e  6H   2CuO22  3H2O1Cu2O
20. 1 e  2H   1Cu(OH)2  2H2O1Cu

TABLE F.11 Possible Reactions in the Cu-H2O System

between the Species Most Stable in Dry conditions
Equilibria
1. 3H   1HCuO2  2H2O1Cu2
2. 4H   1CuO22  2H2O1Cu2
3. 1H   1CuO22  1HCuO2
4. 1 e  1Cu2   1Cu
5. 1 e  3H   1HCuO2  1Cu  2H2O
6. 1 e  4H   1CuO22  2H2O1Cu
7. 2 e  2H   1Cu2O  1H2O2Cu
8. 2 e  2H   1CuO  1H2O1Cu
9. 2 e  2H   2CuO  1H2O1Cu2O
10. 2H   1Cu2O  1H2O2Cu
11. 2H   1CuO  1H2O1Cu2 
12. 1H   1HCuO2  1H2O1CuO
13. 1 e  1Cu  1Cu
14. 2 e  1Cu2   1Cu
15. 2 e  3H   1HCuO2  2H2O1Cu
16. 2 e  4H   1CuO22  2H2O1Cu
17. 2 e  1H2O2Cu2   2H   1Cu2O
18. 2 e  4H   2HCuO2  3H2O1Cu2O
19. 2 e  6H   2CuO22  3H2O1Cu2O
20. 1 e  2H   1CuO  1H2O1Cu
0765162_AppF_Roberge 9/1/99 8:29 Page 1110

TABLE F.12 Possible Reactions in the Fe-H2O System

between the Species Most Stable in Wet Conditions
Equilibria
1. 2 e  2H   1H2
2. 4 e  1O2  4H   2H2O
3. 2 e  1Fe(OH)2  2H   1Fe2H2O
4. 2 e  1Fe2  1Fe
5. 2 e  1Fe(OH)3  3H   1Fe3H2O
6. 1 e  1Fe(OH)3  1H   1Fe(OH)2  1H2O
7. 1 e  1Fe(OH)3  3H   1Fe2  3H2O
8. 1Fe(OH)3  1H   1Fe(OH)2  1H2O
9. 1 e  1Fe(OH)3  1Fe(OH)3
10. 1Fe3  3H2O  1Fe(OH)3  3H 
11. 1Fe2   2H2O  1Fe(OH)2  2H 
12. 1 e  1Fe3  1Fe2 
13. 1Fe2   1H2O  1FeOH   1H 
14. 1FeOH   1H2O  1Fe(OH)2(sln)  1H 
15. 1Fe(OH)2(sln)  1H2O  1Fe(OH)3  1H 
16. 1Fe3  1H2O  1FeOH2   1H 
17. 1FeOH2  1H2O  1Fe(OH)2  1H 
18. 1Fe(OH)2  1H2O  1Fe(OH)3(sln)  1H 
19. 1 e  1FeOH2   1H   1Fe2  1H2O
20. 1 e  1Fe(OH)2  2H   1Fe2   2H2O
21. 1 e  1Fe(OH)3(sln)  1H   1Fe(OH)2(sln)  1H2O
22. 1 e  1Fe(OH)3(sln)  2H   1FeOH   2H2O
23. 1 e  1Fe(OH)3(sln)  3H   1Fe2   3H2O

TABLE F.13 Possible Reactions in the Fe-H2O System

between the Species Most Stable in Dry Conditions
Equilibria
1. 2e  2H   1H2
2. 4 e  1O2  4H   2H2O
3. 8 e  1Fe3O4  8H   3Fe4H2O
4. 2 e  1Fe2   1Fe
5. 2 e  1Fe(OH)3  3H   1Fe3H2O
6. 2 e  3Fe2O3  2H   2Fe3O4  1H2O
7. 2 e  1Fe3O4  8H   3Fe2   4H2O
8. 2 e  1Fe2O3  6H   2Fe2   3H2O
9. 2 e  1Fe3O4  5H2O  3Fe(OH)3  1H 
10. 2Fe3  3H2O  1Fe2O3  6H 
11. 1 e  1Fe3  1Fe2 
12. 1Fe2  1H2O  1FeOH   1H 
13. 1FeOH   1H2O  1Fe(OH)2(sln)  1H 
14. 1Fe(OH)2(sln)  1H2O  1Fe(OH)3  1H 
15. 1Fe3  1H2O  1FeOH2   1H 
16. 1FeOH2   1H2O  1Fe(OH)2  1H 
17. 1Fe(OH)2  1H2O  1Fe(OH)3(sln)  1H 
18. 1FeOH2   1H   1Fe2  1H2O
19. 1 e  1Fe(OH)2  2H   1Fe2  2H2O
20. 1 e  1Fe(OH)3(sln)  1H   1Fe(OH)2(sln)  1H2O
21. 1 e  1Fe(OH)3(sln)  2H   1FeOH   2H2O
22. 1 e  1Fe(OH)3(sln)  3H   1Fe2  3H2O
0765162_AppF_Roberge 9/1/99 8:29 Page 1111

Thermodynamic Data and E-pH Diagrams 1111

TABLE F.14 Possible Reactions in the Mn-H2O System

Equilibria
1. 2e  2H  1H2
2. 4 e  1O2  4H   2H2O
3. 1Mn(OH)  1H   1Mn2  1H2O
4. 1HMnO2  3H   1Mn2  2H2O
5. 1HMnO2  2H   1Mn(OH)  1H2O
6. 1MnO2H   1Mn2  1H2O
7. 1MnO1H   1Mn(OH)
8. 1HMnO2  1H   1MnO1H2O
9. 2 e  1Mn3O4  8H   3Mn2  4H2O
10. 2 e  1Mn3O4  5H   3Mn(OH)  1H2O
11. 2 e  1Mn3O4  2H2O  3HMnO2  1H 
12. 2 e  1Mn2O3  6H   2Mn2  3H2O
13. 2 e  1MN2O3  4H   2Mn(OH)  1H2O
14. 2 e  1Mn2O3  1H2O  2HMnO2
15. 2 e  1MnO2  4H   1Mn2   2H2O
16. 2 e  1MnO2  3H   1Mn(OH)  1H2O
17. 2 e  1MnO2  1H   1HMnO2
18. 1 e  1MnO2  4H   1Mn3  2H2O
19. 3 e  1MnO4  4H   1MnO2  2H2O
20. 2 e  1MnO42  4H   1MnO2  2H2O
21. 2 e  1MnO2H   1Mn1H2O
22. 2 e  1Mn3O4  2H   3MnO1H2O
23. 2 e  3Mn2O3  2H   2Mn3O4  1H2O
24. 2 e  2MnO2  2H   1Mn2O3  1H2O
25. 2 e  1Mn2  1Mn
26. 2 e  1Mn(OH)  1H   1Mn1H2O
27. 2 e  1HMnO2  3H   1Mn2H2O
28. 3 e  1Mn3  1Mn
29. 7 e  1MnO4  8H   1Mn4H2O
30. 6 e  1MnO42  8H   1Mn4H2O
31. 1 e  1Mn3  1Mn2 
32. 4 e  1MnO42  8H   1Mn2   4H2O
33. 4 e  1MnO42  7H   1Mn(OH)  3H2O
34. 4 e  1MnO42  5H   1HMnO2  2H2O
35. 5 e  1MnO4  8H   1Mn2  4H2O
36. 5 e  1MnO4  7H   1Mn(OH)  3H2O
37. 4 e  1MnO4  8H   1Mn3  4H2O
38. 1 e  1MnO4  1MnO42
0765162_AppF_Roberge 9/1/99 8:29 Page 1112

1112 Appendix F

TABLE F.15 Possible Reactions in the Ni-H2O

System between the Species Most Stable in Wet
Conditions
Equilibria
1. 1Ni(OH)2  2H   1Ni2  2H2O
2. 2 e  8H   1Ni3O4  3Ni2   4H2O
3. 2 e  6H   1Ni2O3  3H2O2Ni2 
4. 2 e  4H   1NiO2  2H2O1Ni2
5. 2 e  1Ni2   1Ni
6. 2 e  3H   1HNiO2  2H2O1Ni
7. 2 e  2H   1Ni(OH)2  2H2O1Ni
8. 2 e  2H   2H2O1Ni3O4  3Ni(OH)2
9. 1H   1HNiO2  1Ni(OH)2
10. 2 e  1Ni3O4  2H2O  1H   3HNiO2
11. 2 e  2H   3Ni2O3  1H2O2Ni3O4
12. 2 e  2H   2NiO2  1H2O1Ni2O3
13. 3H   1HNiO2  2H2O1Ni2 
14. 2 e  1H2O1Ni2O3  2HNiO2
15. 2 e  1H   1NiO2  1HNiO2

TABLE F.16 Possible Reactions in the Ni-H2O System

between the Species Most Stable in Dry Conditions
Equilibria
1. 2e 8H   1Ni3O4  3Ni2   4H2O
2. 2 e  6H  1Ni2O3  3H2O2Ni2 
 

3. 2 e  4H   1NiO2  2H2O1Ni2
4. 2 e  1Ni2   1Ni
5. 2 e  2H   1NiO  1Ni1H2O
6. 2 e  3H   1HNiO2  2H2O1Ni
7. 2 e  2H   1Ni3O4  1H2O3NiO
8. 2H   1NiO  1H2O1Ni2
9. 1H   1HNiO2  1H2O1NiO
10. 2 e  1Ni3O4  2H2O  1H   3HNiO2
11. 2 e  2H   3Ni2O3  1H2O2Ni3O4
12. 2 e  2H   2NiO2  1H2O1Ni2O3
13. 3H   1HNiO2  2H2O1Ni2
14. 2 e  1H2O1Ni2O3  2HNiO2
15. 2 e  1H   1NiO2  1HNiO2
0765162_AppF_Roberge 9/1/99 8:29 Page 1113

Thermodynamic Data and E-pH Diagrams 1113

TABLE F.17 Possible Reactions in the Zn-H2O System

Equilibria
1. 2 e
  1H2 2H 
2. 4 e  1O2  4H   2H2O
3. 3H   1HZnO2  2H2O1Zn2
4. 1H   1Zn(OH)  1H2O1Zn2
5. 2H   1HZnO2  2H2O1Zn(OH)
6. 4H   1ZnO22  2H2O1Zn2 
7. 1H   1ZnO22  1HZnO2
8. 2 e  2H   1Zn(OH)2  2H2O1Zn
9. 2H   1Zn(OH)2  2H2O1Zn2
10. 1H   1HZnO2  1Zn(OH)2
11. 2H 1ZnO22  1Zn(OH)2
12. 2 e  1Zn2  1Zn
13. 2 e  3H   1HZnO2  2H2O1Zn
14. 2 e  4H   1ZnO22  2H2O1Zn

2
H2CrO4
2-
Cr2O7
1.5
CrO42-
b HCrO4-

1 3+
100
Cr
10-2
Potential (V vs. SHE)

0.5 10-4
10-6 CrO3
3-

0 a

Cr(OH)3
-0.5
Cr2+

-1

-1.5 Cr

-2
-2 0 2 4 6 8 10 12 14 16
pH
Figure F.1 Potential-pH equilibrium diagram for the chromium-water sys-
tem at 25°C considering the hydrated oxide forms.
0765162_AppF_Roberge 9/1/99 8:29 Page 1114

1114 Appendix F

2
H2CrO4
Cr2O72-
1.5
CrO42-
HCrO4-
b
1 100
10-2
Potential (V vs. SHE)

0.5 10-4
10-6
0 a
Cr3+ Cr(OH)3
-0.5
Cr2+ CrO33-
-1

-1.5 Cr

-2
-2 0 2 4 6 8 10 12 14 16
pH
Figure F.2 Potential-pH equilibrium diagram for the chromium-water
system at 60°C considering the hydrated oxide forms.

2
H2CrO4
Cr2O72-
1.5
CrO42-
b HCrO4-

1
Cr3+ 100
10-2
Potential (V vs. SHE)

0.5
10-4
10-6
0 a

Cr2O3
-0.5
Cr2+
CrO33-
-1

-1.5 Cr

-2
-2 0 2 4 6 8 10 12 14 16
pH
Figure F.3 Potential-pH equilibrium diagram for the chromium-water sys-
tem at 25°C considering the dry oxide forms.
0765162_AppF_Roberge 9/1/99 8:29 Page 1115

Thermodynamic Data and E-pH Diagrams 1115

2
H2CrO4
Cr2O72-
1.5
CrO42-
b HCrO4-

1
100
-2
10
Potential (V vs. SHE)

0.5 -4
10
10-6
0 a

Cr2O3
-0.5
Cr2+
CrO33-
-1

-1.5 Cr

-2
-2 0 2 4 6 8 10 12 14 16
pH
Figure F.4 Potential-pH equilibrium diagram for the chromium-water sys-
tem at 60°C considering the dry oxide forms.

0
1.5 10
b -2
10 Cu(OH)2
-4
1 10
-6 CuO22-
Cu2+ 10
Potential (V vs. SHE)

0.5

Cu2O
0 a

-0.5

-1
Cu

-1.5

-2
-2 0 2 4 6 8 10 12 14 16
pH
Figure F.5 Potential-pH equilibrium diagram for the copper-water system
at 25°C considering the hydrated oxide forms.
0765162_AppF_Roberge 9/1/99 8:29 Page 1116

1116 Appendix F

0
10
1.5 -2
10
b -4
10 Cu(OH)2
1 -6
10
CuO22-
Cu2+
Potential (V vs. SHE)

0.5

Cu2O
0 a

-0.5

-1
Cu

-1.5

-2
-2 0 2 4 6 8 10 12 14 16
pH
Figure F.6 Potential-pH equilibrium diagram for the copper-water system
at 60°C considering the hydrated oxide forms.

0
1.5 10
b -2
10 CuO
-4
1 10 2-
-6 CuO2
Cu2+ 10
Potential (V vs. SHE)

0.5

Cu2O
0 a

-0.5

-1
Cu

-1.5

-2
-2 0 2 4 6 8 10 12 14 16
pH
Figure F.7 Potential-pH equilibrium diagram for the copper-water system
at 25°C considering the dry oxide forms.
0765162_AppF_Roberge 9/1/99 8:29 Page 1117

Thermodynamic Data and E-pH Diagrams 1117

0
10
1.5 -2
10
b -4
10 CuO
1 -6
10
CuO22-
Cu2+
Potential (V vs. SHE)

0.5

Cu2O
0 a

-0.5

-1
Cu

-1.5

-2
-2 0 2 4 6 8 10 12 14 16
pH
Figure F.8 Potential-pH equilibrium diagram for the copper-water system
at 60°C considering the dry oxide forms.

1.5
b
Fe(OH)3
1
Fe3+
Potential (V vs. SHE)

0.5 Fe2+ 0
10
-2
10
a 10
-4
HFeO2
-
0
-6
10
HFeO2-
-0.5 Fe(OH)2

-1

Fe
-1.5

-2
-2 0 2 4 6 8 10 12 14 16
pH
Figure F.9 Potential-pH equilibrium diagram for the iron-water system at
25°C considering the hydrated oxide forms.
0765162_AppF_Roberge 9/1/99 8:29 Page 1118

1118 Appendix F

1.5
b
Fe(OH)3
1
Fe3+
Potential (V vs. SHE)

0.5 Fe2+ 0
10
-2
10
-
a 10
-4
HFeO2
0
-6
10

-0.5 Fe(OH)2

-1

Fe
-1.5

-2
-2 0 2 4 6 8 10 12 14 16
pH
Figure F.10Potential-pH equilibrium diagram for the iron-water system
at 60°C considering the hydrated oxide forms.

1.5
b

1
Fe3+ Fe2O3
Potential (V vs. SHE)

0.5 Fe2+ 0
10
-2
10
a 10
-4
0 HFeO2-
-6
10

-0.5 Fe3O4

-1

Fe
-1.5

-2
-2 0 2 4 6 8 10 12 14 16
pH
Figure F.11 Potential-pH equilibrium diagram for the iron-water system at
25°C considering the dry oxide forms.
0765162_AppF_Roberge 9/1/99 8:29 Page 1119

Thermodynamic Data and E-pH Diagrams 1119

1.5
b

1
Fe3+ Fe2O3
Potential (V vs. SHE)

0.5 Fe2 0
10
-2
10
a 10
-4
HFeO2-
0
-6
10

-0.5 Fe3O4

-1

Fe
-1.5

-2
-2 0 2 4 6 8 10 12 14 16
pH
Figure F.12 Potential-pH equilibrium diagram for the iron-water system
at 60°C considering the dry oxide forms.

MnO4-
1.5
b

1
0
10
10
-2 MnO2
Potential (V vs. SHE)

0.5 -4
10
-6 Mn2O3
10
a
0
Mn3O4

-0.5
MnO
Mn2+

-1
HMnO2-

-1.5
Mn

-2
-2 0 2 4 6 8 10 12 14 16
pH

Figure F.13Potential-pH equilibrium diagram for the manganese-water

system at 25°C.
0765162_AppF_Roberge 9/1/99 8:29 Page 1120

1120 Appendix F

2
-
MnO4
1.5
b

1
0
10
10
-2 MnO2
Potential (V vs. SHE)

0.5 -4
10
-6
Mn2O3
10
a
0 Mn3O4

-0.5
Mn2+ MnO

-1
HMnO2-

-1.5
Mn

-2
-2 0 2 4 6 8 10 12 14 16
pH
Figure F.14 Potential-pH equilibrium diagram for the manganese-water
system at 60°C.

1.5 NiO2
b

1
Ni2O3
Potential (V vs. SHE)

0
0.5 10 Ni3O4
2+ -2
Ni 10
-4
10
a
0 10
-6
Ni(OH)2
HNiO2-
-0.5

-1

Ni
-1.5

-2
-2 0 2 4 6 8 10 12 14 16
pH
Figure F.15Potential-pH equilibrium diagram for the nickel-water sys-
tem at 25°C considering the hydrated oxide forms.
0765162_AppF_Roberge 9/1/99 8:29 Page 1121

Thermodynamic Data and E-pH Diagrams 1121

1.5 NiO2
b

1
Ni2O3
Potential (V vs. SHE)

0
0.5 10 Ni3O4
2+ -2
Ni 10
-4
10
a
0 10
-6 Ni(OH)2
HNiO2-
-0.5

-1

Ni
-1.5

-2
-2 0 2 4 6 8 10 12 14 16
pH
Figure F.16Potential-pH equilibrium diagram for the nickel-water sys-
tem at 60°C considering the hydrated oxide forms.

1.5 NiO2
b

1
Ni2O3
Potential (V vs. SHE)

0
0.5 10 Ni3O4
Ni2+ 10
-2

-4
10
a
0 10
-6
NiO
HNiO2-
-0.5

-1

Ni
-1.5

-2
-2 0 2 4 6 8 10 12 14 16
pH
Figure F.17Potential-pH equilibrium diagram for the nickel-water system
at 25°C considering the dry oxide forms.
0765162_AppF_Roberge 9/1/99 8:29 Page 1122

1122 Appendix F

1.5 NiO2
b

1
Ni2O3
Potential (V vs. SHE)

0
0.5 10 Ni3O4
Ni2+ 10
-2

-4
10
a
0 10
-6 NiO
-
HNiO2
-0.5

-1

Ni
-1.5

-2
-2 0 2 4 6 8 10 12 14 16
pH
Figure F.18Potential-pH equilibrium diagram for the nickel-water system
at 60°C considering the dry oxide forms.

1.5 ZnO2
b

0
Potential (V vs. SHE)

10
0.5
-2
Zn2+ 10
-4
10
a
0 10
-6
Zn(OH)2 ZnO22-

-0.5

-1

Zn
-1.5

-2
-2 0 2 4 6 8 10 12 14 16
pH
Figure F.19 Potential-pH equilibrium diagram for the zinc-water system
at 25°C.
0765162_AppF_Roberge 9/1/99 8:29 Page 1123

Thermodynamic Data and E-pH Diagrams 1123

1.5 ZnO2
b

1
0
10
Potential (V vs. SHE)

-2
0.5 10
-4
10
-6
a 10 Zn(OH)2
0
ZnO22-
Zn2+
-0.5

-1

Zn
-1.5

-2
-2 0 2 4 6 8 10 12 14 16
pH
Figure F.20 Potential-pH equilibrium diagram for the zinc-water system
at 60°C.