thermodynamic data and e ph diagrams
TRANSCRIPT
1101
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 25and 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 eachspecies, solid or ionic, considered for the construction of the E-pH dia-grams. The graphics were obtained with a publicly available softwaresystem that has been used throughout the book to calculate differentequilibrium systems.15 The basic calculations were detailed in Sec. D.2,Chemical Thermodynamics. The relations between the free energy ofthe species considered and the associated equations are evaluated withthe data presented in Tables F.1 to F.6 and the following equations. Thefree 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)0 � G(T1)
0 � S(T1)0 (T2 � T1) � T2
� T2
T1
dT � � T2
T1
C0p dT (F.1)
C0p
�
T
APPENDIX
F
T1
T2
T1
T2
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1102 Appendix F
TABLE F.1 Species Considered for the Cr-H2O System and TheirThermodynamic Data
G0(298 K), S0
(298 K), Species J�mol�1 J�mol�1 A B � 103 C � 10�5
O2 0 205 29.96 4.184 �1.674H2 0 131 27.28 3.263 0.502H2O �237,000 69.9 75.27 0 0Cr 0 23.77 17.41 15.15 1.26CrO �350,661 44.77 46.48 8.12 �3.68Cr2O3 �1,058,134 81.17 119.37 9.2 �15.65CrO2 �539,740 48.12 67.49 12.55 �12.55CrO3 �502,080 73.22 75.86 16.78 �8.37Cr(OH)3 �900,815 80.33 0 0 0CrOOH �672,955 25.1 0 0 0
S0(298 K,
J�mol�1 a b
H� 0 0 �20.9 0.065 �0.005Cr2� �176,146 �104.6 �146.44 0.13� 0.00166Cr3� �215,476 �307.52 �370.28 0.13 �0.00166Cr(OH)2� �430,950 �68.62 �110.46 0.13 �0.00166Cr(OH)2
� �632,663 �144.77 �165.69 0.13 �0.00166CrO4
2� �727,849 50.21 92.05 �0.37 0.0055HCrO4
� �764,835 184.1 205.02 �0.37 0.0055CrO2
� �535,929 96.23 117.15 �0.37 0.0055CrO3
3� �603,416 �238.49 �175.73 �0.37 0.0055
TABLE F.2 Pure Species Considered for the Cu-H2O System andTheir Thermodynamic Data
G0(298 K), S0
(298 K), Species J�mol�1 J�mol�1 A B � 103 C� 10�5
O2 0 205 29.96 4.184 �1.674H2 0 131 27.28 3.263 0.502H2O �237,000 69.9 75.27 0 0Cu 0 33.2 22.635 6.276 0Cu2O �147,904 92.4 62.62 0 0CuO �127,905 42.6 42.32 0 0Cu(OH)2 �358,987 87 87.91 0 0
S0(298 K),
J�mol�1 a b
H� 0 0 �20.9 0.065 �0.005Cu� 50,626 �12.6 �33.52 0.13 �0.00166Cu2� 65,689 �207.2 �249.04 0.13 �0.00166Cu(OH)� �129,704 41.89 20.97 0.13 �0.00166Cu2(OH)2
2� �280,328 �98.22 �140.06 0.13 �0.00166Cu3� 303,340 �401.8 �464.56 0.13 �0.00166HCuO2
� �258,571 96.38 117.3 �0.37 0.0055CuO2
2� �183,678 �98.22 �56.38 �0.37 0.0055CuO2
� �112,550 96.38 117.3 �0.37 0.0055
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Thermodynamic Data and E-pH Diagrams 1103
TABLE F.3 Pure Species Considered for the Fe-H2O System and TheirThermodynamic Data
G0(298 K), S0
(298 K), Species J�mol�1 J�mol�1 A B � 103 C � 10�5
O2 0 205 29.96 4.184 �1.674H2 0 131 27.28 3.263 0.502H2O �237,000 69.9 75.27 0 0Fe 0 27.1 12.72 31.71 �2.51Fe3O4 �1,020,000 146 91.55 201.67 0Fe2O3 �742,000 87.3 98.28 77.82 �14.85Fe(OH)2 �493,000 92.4 96.3 0 0Fe(OH)3 �714,000 96.1 105 0 0
S0(298 K),
J�mol�1 a b
H� 0 0 �20.9 0.065 �0.005Fe(OH)2(sln) �449,000 38 38 0.13 �0.00166Fe(OH)3(sln) �661,000 75.2 75.2 0.13 �0.00166FeOH� �274,000 �29.3 �50.2 0.13 �0.00166Fe(OH)2
� �459,000 �29.3 �50.2 0.13 �0.00166Fe2� �92,200 �107 �149 0.13 �0.00166FeOH2� �242,000 �105 �147 0.13 �0.00166Fe3� �17,800 �279 �342 0.13 �0.00166Fe(OH)3
� �621,000 41.8 62.7 �0.37 0.0055Fe(OH)4
� �843,000 25.1 46 �0.37 0.0055FeO4
2� �467,000 37.6 79.5 �0.37 0.0055
TABLE F.4 Pure Species Considered for the Mn-H2O System and TheirThermodynamic Data
G0(298 K), S0
(298 K), Species J�mol�1 J�mol�1 A B � 103 C � 10�5
O2 0 205 29.96 4.184 �1.674H2 0 131 27.28 3.263 0.502H2O �237,000 69.9 75.27 0 0Mn 0 32.0076 23.8488 14.14192 �1.54808MnO �362,920 59.70568 46.48424 8.11696 �3.68192Mn3O4 �1,283,233 155.6448 144.9338 45.27088 �9.2048Mn2O3 �881,150 110.4576 103.4703 35.06192 �13.5143MnO2 �465,177 53.05312 69.4544 10.20896 �16.2339
S0(298 K),
J�mol�1 a b
H� 0 0 �20.9 0.065 �0.005Mn2� �228,028 �115.478 �157.34 0.13 �0.00166Mn(OH)� �405,011 �37.656 �58.576 0.13 �0.00166Mn3� �82,006.4 �378.652 �441.41 0.13 �0.00166HMnO2
� �507,101 62.76 83.68 �0.37 0.0055MnO4
� �447,270 212.1288 233.05 �0.37 0.0055MnO4
2� �500,825 100.416 142.256 �0.37 0.0055
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1104 Appendix F
TABLE F.5 Pure Species Considered for the Ni-H2O System and TheirThermodynamic Data
G0(298 K), S0
(298 K), Species J�mol�1 J�mol�1 A B � 103 C � 10�5
O2 0 205 29.96 4.184 �1.674H2 0 131 27.28 3.263 0.502H2O �237,000 69.9 75.27 0 0Ni 0 30.12 16.99 294.55 0Ni(OH)2 �453,130 79.5 0 0 0NiO �215,940 38.58 �20.88 157.23 16.28Ni3O4 �711,910 146.44 129.03 71.46 �23.93Ni2O3 �469,740 94.14 98.28 77.82 �14.85NiO2 �215,140 52.3 69.45 10.21 �16.23
S0(298 K),
J�mol�1 a b
H� 0 0 �20.9 0.07 �0.01Ni2� �46,442 �201.3 �243.14 0.13 0HNiO2
� �349,218 62.76 41.84 �0.37 0.01
TABLE F.6 Pure Species Considered for the Ni-H2O System and TheirThermodynamic Data
G0(298 K), S0
(298 K), Species J�mol�1 J�mol�1 A B � 103 C � 10�5
O2 0 205 29.96 4.184 �1.674H2 0 131 27.28 3.263 0.502H2O �237,000 69.9 75.27 0 0Zn 0 41.63 25.4 0 0Zn(OH)2 �559,358 81.6 72.4 0 0
S0(298 K),
J�mol�1 a b
H� 0 0 �20.9 0.065 �0.005Zn2� �147,280 �207.2 �249.04 0.13 �0.00166Zn(OH)� �329,438 41.89 20.97 0.13 �0.00166HZnO2
� �464,227 96.38 117.3 �0.37 0.0055ZnO2
2� �389,424 �98.22 �56.38 �0.37 0.0055
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For pure substances, i.e., solids, liquids, and gases, the heat capacityCp
0 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 ofthe ionic capacity [Eq. (F.3)] makes use of absolute entropy values andthe parameters a and b contained in Tables F.1 to F.6.
Cp0 � (4.186a � bS0
(298 K)) (T2 � 298.16) / ln � � (F.3)
By combining Eq. (F.2) or (F.3) with Eq. (F.1), one can obtain the freeenergy [Eq. (F.4)] at a given temperature by using the fundamentaldata contained in Tables F.1 to F.6.
Gt0 � G0
(298 K) � (Cp0 � S0
(298 K)) (T2 � 298.16)
� T2 ln � � Cp0 (F.4)
Table F.7 provides an index for the thermodynamic data of the speciesconsidered, the equations possible, and associated E-pH diagrams attwo 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, CorrosionScience, 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-H2Oen relation avec la fragilisation caustique des aciers, Journal of AppliedElectrochemistry, 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 SystemFe-H2O, Corrosion Science, 10:343–358 (1970).
8. Biernat, R. J., and Robins, R. G., High-Temperature Potential/pH Diagrams for theIron-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.
T2�298.16
T2�298.16
Thermodynamic Data and E-pH Diagrams 1105
0765162_AppF_Roberge 9/1/99 8:29 Page 1105
10. Macdonald, D. D., The Thermodynamics and Theoretical Corrosion Behavior ofManganese in Aqueous Systems at Elevated Temperatures, Corrosion Science,16:482 (1976).
11. Macdonald, D. D., The Thermodynamics of Metal-Water Systems at ElevatedTemperatures, 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 LightWater Reactors, NP-2298, Palo Alto, Calif., Electric Power Research Institute, 1982.
13. Cowan, R. L., and Staehle, R. W., The Thermodynamics and Electrode KineticBehavior of Nickel in Acid Solution in the Temperature Range 25° to 300°C, Journalof the Electrochemical Society, 118:557–568 (1971).
14. Pan, P., and Tremaine, P. R., Thermodynamics of Aqueous Zinc: Standard PartialMolar Heat Capacities and Volumes of Zn2� (aq) from 10 to 55°C, Geochimica etCosmochimica 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 HighTemperature Aqueous Solutions, Journal of the American Chemical Society,86:5385–5393 (1964).
1106 Appendix F
TABLE F.7 Index to Thermodynamic Data, Equilibrium, andAssociated 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.2Dry state Table F.9 25 F.3
60 F.4Copper (Data Table F.2)
Hydrated state Table F.10 25 F.560 F.6
Dry state Table F.11 25 F.760 F.8
Iron (Data Table F.3)Hydrated state Table F.12 25 F.9
60 F.10Dry state Table F.13 25 F.11
60 F.12Manganese (Data Table F.4)
Table F.14 25 F.1360 F.14
Nickel (Data Table F.5)Hydrated state Table F.15 25 F.15
60 F.16Dry state Table F.16 25 F.17
60 F.18Zinc (Data Table F.6)
Table F.17 25 F.1960 F.20
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Thermodynamic Data and E-pH Diagrams 1107
TABLE F.8 Possible Reaction in the Cr-H2O Systembetween the Species Most Stable in Wet Conditions
Equilibria
1. 2 e� � 1CrO � 2H� � 1Cr � 1H2O2. 1 e� � 1Cr(OH)3 � 1H� � 1CrO � 2H2O3. 3 e� � 1Cr(OH)3 � 3H� � 1Cr � 3H2O4. 1 e� � 1CrO2 � 1H2O � 1H� � 1Cr(OH)35. 1 e� � 1CrO2 � 1H� � 1Cr(OH)36. 3 e� � 1CrO3 � 3H� � 1CrO2 � 1H2O7. 2 e� � 1Cr2� � 1Cr8. 3 e� � 1CrO2
� � 4H� � 1Cr � 2H2O9. 6 e� � 1HCrO4
� � 7H� � 1Cr � 4H2O10. 6 e� � 1CrO4
2� � 8H� � 1Cr � 4H2O11. 1 e� � 1CrO2
� � 2H� � 1CrO�1H2O12. 1CrO2
� � 1H2O�1H� � 1Cr(OH)313. 1CrO3 � 1H2O � 1CrO4
2� � 2H�
14. 1CrO3 � 1H2O � 1HCrO4� � 1H�
15. 1CrO�2H� � 1Cr2� � 1H2O16. 3 e� � 1Cr3� � 1Cr17. 3 e� � 1CrO3
3� � 6H� � 1Cr � 3H2O18. 1 e� � 1CrO3
3� � 4H� � 1CrO�2H2O19. 1 e� � 1CrO2 � 4H� � 1Cr3� � 2H2O20. 2 e� � 1HCrO4
� � 3H� � 1CrO2 � 2H2O21. 2 e� � 1CrO4
2� � 4H� � 1CrO2 � 2H2O22. 1Cr(OH)3 � 3H� � 1Cr3� � 3H2O23. 1Cr(OH)3 � 1CrO3
3� � 3H�
24. 1 e� � 1Cr(OH)3 � 3H� � 1Cr2� � 3H2O25. 3 e� � 1HCrO4
� � 4H� � 1Cr(OH)3 � 1H2O26. 3 e� � 1CrO4
2� � 5H� � 1Cr(OH)3 � 1H2O27. 3 e� � 1CrO4
2� � 4H� � 1CrO2� � 2H2O
28. 3 e� � 1CrO42� � 2H� � 1CrO3
3� � 1H2O29. 1CrO2
� � 4H� � 1Cr3� � 2H2O30. 1CrO3
3� � 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
� � 2H2O37. 1Cr(OH)3 � 2H� � 1Cr(OH)2� � 2H2O38. 1Cr(OH)3 � 1H� � 1Cr(OH)2
� � 1H2O39. 1 e� � 1CrO2 � 3H� � 1Cr(OH)2� � 1H2O40. 1Cr(OH)2� � 1H� � 1Cr3� � 1H2O41. 1Cr(OH)2
� � 1H� � 1Cr(OH)2� � 1H2O42. 1CrO2
� � 2H� � 1Cr(OH)2�
43. 1 e� � 1Cr(OH)2� � 1H� � 1Cr2� � 1H2O44. 1 e� � 1Cr(OH)2
� � 2H� � 1Cr2� � 2H2O45. 3 e� � 1CrO4
2� � 7H� � 1Cr(OH)2� � 3H2O46. 3 e� � 1CrO4
2� � 7H� � 1Cr(OH)2� � 3H2O47. 3 e� � 1HCrO4
� � 5H� � 1Cr(OH)2� � 2H2O
48. 3 e� � 1CrO42� � 6H� � 1Cr(OH)2
� � 2H2O49. 1CrO2
� � 3H� � 1Cr(OH)2� � 1H2O
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1108 Appendix F
TABLE F.9 Possible Reactions in the Cr-H2O Systembetween the Species Most Stable in Dry Conditions
Equilibria
1. 2 e� � 1CrO�2H� � 1Cr � 1H2O2. 2 e� � 1Cr2O3 � 2H� � 2CrO�1H2O3. 6 e� � 1Cr2O3 � 6H� � 2Cr � 3H2O4. 2 e� � 2CrO2 � 2H� � 1Cr2O3 � 1H2O5. 6 e� � 2CrO3 � 6H� � 1Cr2O3 � 3H2O6. 2 e� � 1CrO3 � 2H� � 1CrO2 � 1H2O7. 2 e� � 1Cr2� � 1Cr8. 3 e� � 1CrO2
� � 4H� � 1Cr � 2H2O9. 6 e� � 1HCrO4
� � 7H� � 1Cr � 4H2O10. 6 e� � 1CrO4
2� � 8H� � 1Cr � 4H2O11. 1 e� � 1CrO2
� � 2H� � 1CrO�1H2O12. 2CrO2
� � 2H� � 1Cr2O3 � 1H2O13. 1CrO3 � 1H2O � 1CrO4
2� � 2H�
14. 1CrO3 � 1H2O � 1HCrO4� � 1H�
15. 1CrO�2H� � 1Cr2� � 1H2O16. 3 e� � 1Cr3� � 1Cr17. 3 e� � 1CrO3
3� �r � 3H2O18. 1 e� � 1CrO3
3� � 4H� � 1CrO�2H2O19. 1 e� � 1CrO2 � 4H� � 1Cr3� � 2H2O20. 2 e� � 1HCrO4
� � 3H� � 1CrO2 � 2H2O21. 2 e� � 1CrO4
2� � 4H� � 1CrO2 � 2H2O22. 1Cr2O3 � 6H� � 2Cr3� � 3H2O23. 1Cr2O3 � 3H2O � 2CrO3
3� � 6H�
24. 2 e� � 1Cr2O3 � 6H� � 2Cr2� � 3H2O25. 6 e� � 2HCrO4
� � 8H� � 1Cr2O3 � 5H2O26. 6 e� � 2CrO4
2� � 10H� � 1Cr2O3 � 5H2O27. 3 e� � 1CrO4
2� � 4H� � 1CrO2� � 2H2O
28. 3 e� � 1CrO42� � 2H� � 1CrO3
3� � 1H2O29. 1CrO2
� � 4H� � 1Cr3� � 2H2O30. 1CrO3
3� � 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
� � 2H2O37. 1Cr2O3 � 4H� � 2Cr(OH)2� � 1H2O38. 1Cr2O3 � 1H2O�2H� � 2Cr(OH)2
�
39. 1 e� � 1CrO2 � 3H� � 1Cr(OH)2� � 1H2O40. 1Cr(OH)2� � 1H� � 1Cr3� � 1H2O41. 1Cr(OH)2
� � 1H� � 1Cr(OH)2� � 1H2O42. 1CrO2
� � 2H� � 1Cr(OH)2�
43. 1 e� � 1Cr(OH)2� � 1H� � 1Cr2� � 1H2O44. 1 e� � 1Cr(OH)2
� � 2H� � 1Cr2� � 2H2O45. 3 e� � 1CrO4
2� � 7H� � 1Cr(OH)2� � 3H2O46. 3 e� � 1CrO4
2� � 7H� � 1Cr(OH)2� � 3H2O47. 3 e� � 1HCrO4
� � 5H� � 1Cr(OH)2� � 2H2O
48. 3 e� � 1CrO42� � 6H� � 1Cr(OH)2
� � 2H2O49. 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-H2OSystem between the Species Most Stable in WetConditions
Equilibria
1. 3H� � 1HCuO2� � 2H2O�1Cu2�
2. 4H� � 1CuO22� � 2H2O�1Cu2�
3. 1H� � 1CuO22� � 1HCuO2
�
4. 1 e� � 1Cu2� � 1Cu�
5. 1 e� � 3H� � 1HCuO2� � 1Cu� � 2H2O
6. 1 e� � 4H� � 1CuO22� � 2H2O�1Cu�
7. 2 e� � 2H� � 1Cu2O � 1H2O�2Cu8. 2 e� � 2H� � 1Cu(OH)2 � 2H2O�1Cu9. 2 e� � 2H� � 2Cu(OH)2 � 3H2O�1Cu2O
10. 2H� � 1Cu2O � 1H2O�2Cu�
11. 2H� � 1Cu(OH)2 � 2H2O�1Cu2�
12. 2H� � 1CuO22� � 1Cu(OH)2
13. 1 e� � 1Cu� � 1Cu14. 2 e� � 1Cu2� � 1Cu15. 2 e� � 3H� � 1HCuO2
� � 2H2O�1Cu16. 2 e� � 4H� � 1CuO2
2� � 2H2O�1Cu17. 2 e� � 1H2O � 2Cu2� � 2H� � 1Cu2O18. 2 e� � 4H� � 2HCuO2
� � 3H2O�1Cu2O19. 2 e� � 6H� � 2CuO2
2� � 3H2O�1Cu2O20. 1 e� � 2H� � 1Cu(OH)2 � 2H2O�1Cu�
TABLE F.11 Possible Reactions in the Cu-H2O Systembetween the Species Most Stable in Dry conditions
Equilibria
1. 3H� � 1HCuO2� � 2H2O�1Cu2�
2. 4H� � 1CuO22� � 2H2O�1Cu2�
3. 1H� � 1CuO22� � 1HCuO2
�
4. 1 e� � 1Cu2� � 1Cu�
5. 1 e� � 3H� � 1HCuO2� � 1Cu� � 2H2O
6. 1 e� � 4H� � 1CuO22� � 2H2O�1Cu�
7. 2 e� � 2H� � 1Cu2O � 1H2O�2Cu8. 2 e� � 2H� � 1CuO � 1H2O�1Cu9. 2 e� � 2H� � 2CuO � 1H2O�1Cu2O
10. 2H� � 1Cu2O � 1H2O�2Cu�
11. 2H� � 1CuO � 1H2O�1Cu2�
12. 1H� � 1HCuO2� � 1H2O�1CuO
13. 1 e� � 1Cu� � 1Cu14. 2 e� � 1Cu2� � 1Cu15. 2 e� � 3H� � 1HCuO2
� � 2H2O�1Cu16. 2 e� � 4H� � 1CuO2
2� � 2H2O�1Cu17. 2 e� � 1H2O�2Cu2� � 2H� � 1Cu2O18. 2 e� � 4H� � 2HCuO2
� � 3H2O�1Cu2O19. 2 e� � 6H� � 2CuO2
2� � 3H2O�1Cu2O20. 1 e� � 2H� � 1CuO � 1H2O�1Cu�
0765162_AppF_Roberge 9/1/99 8:29 Page 1109
TABLE F.12 Possible Reactions in the Fe-H2O Systembetween the Species Most Stable in Wet Conditions
Equilibria
1. 2 e� � 2H� � 1H22. 4 e� � 1O2 � 4H� � 2H2O3. 2 e� � 1Fe(OH)2 � 2H� � 1Fe�2H2O4. 2 e� � 1Fe2� � 1Fe5. 2 e� � 1Fe(OH)3
� � 3H� � 1Fe�3H2O6. 1 e� � 1Fe(OH)3 � 1H� � 1Fe(OH)2 � 1H2O7. 1 e� � 1Fe(OH)3 � 3H� � 1Fe2� � 3H2O8. 1Fe(OH)3
� � 1H� � 1Fe(OH)2 � 1H2O9. 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� � 1H2O20. 1 e� � 1Fe(OH)2
� � 2H� � 1Fe2� � 2H2O21. 1 e� � 1Fe(OH)3(sln) � 1H� � 1Fe(OH)2(sln) � 1H2O22. 1 e� � 1Fe(OH)3(sln) � 2H� � 1FeOH� � 2H2O23. 1 e� � 1Fe(OH)3(sln) � 3H� � 1Fe2� � 3H2O
TABLE F.13 Possible Reactions in the Fe-H2O Systembetween the Species Most Stable in Dry Conditions
Equilibria
1. 2 e� � 2H� � 1H22. 4 e� � 1O2 � 4H� � 2H2O3. 8 e� � 1Fe3O4 � 8H� � 3Fe�4H2O4. 2 e� � 1Fe2� � 1Fe5. 2 e� � 1Fe(OH)3
� � 3H� � 1Fe�3H2O6. 2 e� � 3Fe2O3 � 2H� � 2Fe3O4 � 1H2O7. 2 e� � 1Fe3O4 � 8H� � 3Fe2� � 4H2O8. 2 e� � 1Fe2O3 � 6H� � 2Fe2� � 3H2O9. 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� � 1H2O19. 1 e� � 1Fe(OH)2
� � 2H� � 1Fe2� � 2H2O20. 1 e� � 1Fe(OH)3(sln) � 1H� � 1Fe(OH)2(sln) � 1H2O21. 1 e� � 1Fe(OH)3(sln) � 2H� � 1FeOH� � 2H2O22. 1 e� � 1Fe(OH)3(sln) � 3H� � 1Fe2� � 3H2O
0765162_AppF_Roberge 9/1/99 8:29 Page 1110
Thermodynamic Data and E-pH Diagrams 1111
TABLE F.14 Possible Reactions in the Mn-H2O System
Equilibria
1. 2 e� � 2H� � 1H22. 4 e� � 1O2 � 4H� � 2H2O3. 1Mn(OH)� � 1H� � 1Mn2� � 1H2O4. 1HMnO2
� � 3H� � 1Mn2� � 2H2O5. 1HMnO2
� � 2H� � 1Mn(OH)� � 1H2O6. 1MnO�2H� � 1Mn2� � 1H2O7. 1MnO�1H� � 1Mn(OH)�
8. 1HMnO2� � 1H� � 1MnO�1H2O
9. 2 e� � 1Mn3O4 � 8H� � 3Mn2� � 4H2O10. 2 e� � 1Mn3O4 � 5H� � 3Mn(OH)� � 1H2O11. 2 e� � 1Mn3O4 � 2H2O � 3HMnO2
� � 1H�
12. 2 e� � 1Mn2O3 � 6H� � 2Mn2� � 3H2O13. 2 e� � 1MN2O3 � 4H� � 2Mn(OH)� � 1H2O14. 2 e� � 1Mn2O3 � 1H2O � 2HMnO2
�
15. 2 e� � 1MnO2 � 4H� � 1Mn2� � 2H2O16. 2 e� � 1MnO2 � 3H� � 1Mn(OH)� � 1H2O17. 2 e� � 1MnO2 � 1H� � 1HMnO2
�
18. 1 e� � 1MnO2 � 4H� � 1Mn3� � 2H2O19. 3 e� � 1MnO4
� � 4H� � 1MnO2 � 2H2O20. 2 e� � 1MnO4
2� � 4H� � 1MnO2 � 2H2O21. 2 e� � 1MnO�2H� � 1Mn�1H2O22. 2 e� � 1Mn3O4 � 2H� � 3MnO�1H2O23. 2 e� � 3Mn2O3 � 2H� � 2Mn3O4 � 1H2O24. 2 e� � 2MnO2 � 2H� � 1Mn2O3 � 1H2O25. 2 e� � 1Mn2� � 1Mn26. 2 e� � 1Mn(OH)� � 1H� � 1Mn�1H2O27. 2 e� � 1HMnO2
� � 3H� � 1Mn�2H2O28. 3 e� � 1Mn3� � 1Mn29. 7 e� � 1MnO4
� � 8H� � 1Mn�4H2O30. 6 e� � 1MnO4
2� � 8H� � 1Mn�4H2O31. 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
� � 2H2O35. 5 e� � 1MnO4
� � 8H� � 1Mn2� � 4H2O36. 5 e� � 1MnO4
� � 7H� � 1Mn(OH)� � 3H2O37. 4 e� � 1MnO4
� � 8H� � 1Mn3� � 4H2O38. 1 e� � 1MnO4
� � 1MnO42�
0765162_AppF_Roberge 9/1/99 8:29 Page 1111
1112 Appendix F
TABLE F.15 Possible Reactions in the Ni-H2OSystem between the Species Most Stable in WetConditions
Equilibria
1. 1Ni(OH)2 � 2H� � 1Ni2� � 2H2O2. 2 e� � 8H� � 1Ni3O4 � 3Ni2� � 4H2O3. 2 e� � 6H� � 1Ni2O3 � 3H2O�2Ni2�
4. 2 e� � 4H� � 1NiO2 � 2H2O�1Ni2�
5. 2 e� � 1Ni2� � 1Ni6. 2 e� � 3H� � 1HNiO2
� � 2H2O�1Ni7. 2 e� � 2H� � 1Ni(OH)2 � 2H2O�1Ni8. 2 e� � 2H� � 2H2O�1Ni3O4 � 3Ni(OH)29. 1H� � 1HNiO2
� � 1Ni(OH)210. 2 e� � 1Ni3O4 � 2H2O � 1H� � 3HNiO2
�
11. 2 e� � 2H� � 3Ni2O3 � 1H2O�2Ni3O412. 2 e� � 2H� � 2NiO2 � 1H2O�1Ni2O313. 3H� � 1HNiO2
� � 2H2O�1Ni2�
14. 2 e� � 1H2O�1Ni2O3 � 2HNiO2�
15. 2 e� � 1H� � 1NiO2 � 1HNiO2�
TABLE F.16 Possible Reactions in the Ni-H2O Systembetween the Species Most Stable in Dry Conditions
Equilibria
1. 2 e� � 8H� � 1Ni3O4 � 3Ni2� � 4H2O2. 2 e� � 6H� � 1Ni2O3 � 3H2O�2Ni2�
3. 2 e� � 4H� � 1NiO2 � 2H2O�1Ni2�
4. 2 e� � 1Ni2� � 1Ni5. 2 e� � 2H� � 1NiO � 1Ni�1H2O6. 2 e� � 3H� � 1HNiO2
� � 2H2O�1Ni7. 2 e� � 2H� � 1Ni3O4 � 1H2O�3NiO8. 2H� � 1NiO � 1H2O�1Ni2�
9. 1H� � 1HNiO2� � 1H2O�1NiO
10. 2 e� � 1Ni3O4 � 2H2O � 1H� � 3HNiO2�
11. 2 e� � 2H� � 3Ni2O3 � 1H2O�2Ni3O412. 2 e� � 2H� � 2NiO2 � 1H2O�1Ni2O313. 3H� � 1HNiO2
� � 2H2O�1Ni2�
14. 2 e� � 1H2O�1Ni2O3 � 2HNiO2�
15. 2 e� � 1H� � 1NiO2 � 1HNiO2�
0765162_AppF_Roberge 9/1/99 8:29 Page 1112
Thermodynamic Data and E-pH Diagrams 1113
TABLE F.17 Possible Reactions in the Zn-H2O System
Equilibria
1. 2 e� � 2H� � 1H22. 4 e� � 1O2 � 4H� � 2H2O3. 3H� � 1HZnO2
� � 2H2O�1Zn2�
4. 1H� � 1Zn(OH)� � 1H2O�1Zn2�
5. 2H� � 1HZnO2� � 2H2O�1Zn(OH)�
6. 4H� � 1ZnO22� � 2H2O�1Zn2�
7. 1H� � 1ZnO22� � 1HZnO2
�
8. 2 e� � 2H� � 1Zn(OH)2 � 2H2O�1Zn9. 2H� � 1Zn(OH)2 � 2H2O�1Zn2�
10. 1H� � 1HZnO2� � 1Zn(OH)2
11. 2H�1ZnO22� � 1Zn(OH)2
12. 2 e� � 1Zn2� � 1Zn13. 2 e� � 3H� � 1HZnO2
� � 2H2O�1Zn14. 2 e� � 4H� � 1ZnO2
2� � 2H2O�1Zn
-2
-2 0 2 4 6 8 10 12 14 16
-1.5
-1
-0.5
0
0.5
1
1.5
2
Po
ten
tial
(V
vs.
SH
E)
pH
b
a
Cr(OH)3
Cr
HCrO4-
Cr2O72-
H2CrO4
Cr3+
Cr2+
CrO42-
CrO33-
100
10-2
10-4
10-6
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 1113
1114 Appendix F
-2
-2 0 2 4 6 8 10 12 14 16
-1.5
-1
-0.5
0
0.5
1
1.5
2
Po
ten
tia
l (V
vs
. S
HE
)
pH
b
a
Cr(OH)3
HCrO4-
Cr2O72-
H2CrO4
Cr3+
Cr2+
CrO42-
CrO33-
100
10-2
10-4
10-6
Cr
Figure F.2 Potential-pH equilibrium diagram for the chromium-watersystem at 60°C considering the hydrated oxide forms.
-2
-2 0 2 4 6 8 10 12 14 16
-1.5
-1
-0.5
0
0.5
1
1.5
2
Po
ten
tial
(V
vs.
SH
E)
pH
b
a
Cr2O3
HCrO4-
Cr2O72-
H2CrO4
Cr3+
Cr2+
CrO42-
CrO33-
100
10-2
10-4
10-6
Cr
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 1114
Thermodynamic Data and E-pH Diagrams 1115
-2
-2 0 2 4 6 8 10 12 14 16
-1.5
-1
-0.5
0
0.5
1
1.5
2
Po
ten
tial
(V
vs.
SH
E)
pH
b
a
Cr2O3
HCrO4-
Cr2O72-
H2CrO4
Cr2+
CrO42-
100
10-2
10-4
10-6
Cr
CrO33-
Figure F.4 Potential-pH equilibrium diagram for the chromium-water sys-tem at 60°C considering the dry oxide forms.
-2
-2 0 2 4 6 8 10 12 14 16
-1.5
-1
-0.5
0
0.5
1
1.5
2
Po
ten
tial
(V
vs.
SH
E)
pH
b
Cu2+
100
10-2
10-4
10-6
Cu(OH)2
CuO22-
Cu2Oa
Cu
Figure F.5 Potential-pH equilibrium diagram for the copper-water systemat 25°C considering the hydrated oxide forms.
0765162_AppF_Roberge 9/1/99 8:29 Page 1115
1116 Appendix F
-2
-2 0 2 4 6 8 10 12 14 16
-1.5
-1
-0.5
0
0.5
1
1.5
2
Po
ten
tial
(V
vs.
SH
E)
pH
b
Cu2+
Cu(OH)2
CuO22-
Cu2Oa
Cu
100
10-2
10-4
10-6
Figure F.6 Potential-pH equilibrium diagram for the copper-water systemat 60°C considering the hydrated oxide forms.
-2
-2 0 2 4 6 8 10 12 14 16
-1.5
-1
-0.5
0
0.5
1
1.5
2
Po
ten
tial
(V
vs.
SH
E)
pH
b
Cu2+
100
10-2
10-4
10-6
CuO
Cu2Oa
Cu
CuO22-
Figure F.7 Potential-pH equilibrium diagram for the copper-water systemat 25°C considering the dry oxide forms.
0765162_AppF_Roberge 9/1/99 8:29 Page 1116
Thermodynamic Data and E-pH Diagrams 1117
-2
-2 0 2 4 6 8 10 12 14 16
-1.5
-1
-0.5
0
0.5
1
1.5
2
Po
ten
tial
(V
vs.
SH
E)
pH
b
Cu2+
CuO
CuO22-
Cu2Oa
Cu
100
10-2
10-4
10-6
Figure F.8 Potential-pH equilibrium diagram for the copper-water systemat 60°C considering the dry oxide forms.
-2
-2 0 2 4 6 8 10 12 14 16
-1.5
-1
-0.5
0
0.5
1
1.5
2
Po
ten
tial
(V
vs.
SH
E)
pH
b
Fe2+
Fe3+
HFeO2-
a
100
10-2
10-4
10-6
Fe(OH)2
Fe(OH)3
HFeO2-
Fe
Figure F.9 Potential-pH equilibrium diagram for the iron-water system at25°C considering the hydrated oxide forms.
0765162_AppF_Roberge 9/1/99 8:29 Page 1117
1118 Appendix F
-2
-2 0 2 4 6 8 10 12 14 16
-1.5
-1
-0.5
0
0.5
1
1.5
2
Po
ten
tial
(V
vs.
SH
E)
pH
b
Fe2+
Fe3+
a
100
10-2
10-4
10-6
Fe(OH)2
Fe(OH)3
HFeO2-
Fe
Figure F.10 Potential-pH equilibrium diagram for the iron-water systemat 60°C considering the hydrated oxide forms.
-2
-2 0 2 4 6 8 10 12 14 16
-1.5
-1
-0.5
0
0.5
1
1.5
2
Po
ten
tial
(V
vs.
SH
E)
pH
b
Fe2+
Fe3+
a
100
10-2
10-4
10-6
Fe
HFeO2-
Fe3O4
Fe2O3
Figure F.11 Potential-pH equilibrium diagram for the iron-water system at25°C considering the dry oxide forms.
0765162_AppF_Roberge 9/1/99 8:29 Page 1118
Thermodynamic Data and E-pH Diagrams 1119
-2
-2 0 2 4 6 8 10 12 14 16
-1.5
-1
-0.5
0
0.5
1
1.5
2
Po
ten
tial
(V
vs.
SH
E)
pH
Fe2
Fe3+
a
100
10-2
10-4
10-6
Fe
HFeO2-
Fe3O4
Fe2O3
b
Figure F.12 Potential-pH equilibrium diagram for the iron-water systemat 60°C considering the dry oxide forms.
-2
-2 0 2 4 6 8 10 12 14 16
-1.5
-1
-0.5
0
0.5
1
1.5
2
Po
ten
tial
(V
vs.
SH
E)
pH
Mn2+
100
10-2
10-4
10-6
MnO4-
Mn
MnO
a
HMnO2-
Mn3O4
b
MnO2
Mn2O3
Figure F.13 Potential-pH equilibrium diagram for the manganese-watersystem at 25°C.
0765162_AppF_Roberge 9/1/99 8:29 Page 1119
-2
-2 0 2 4 6 8 10 12 14 16
-1.5
-1
-0.5
0
0.5
1
1.5
2
Po
ten
tial
(V
vs.
SH
E)
pH
Ni2+100
10-2
10-4
10-6
Ni
Ni(OH)2
a
HNiO2-
b
NiO2
Ni2O3
Ni3O4
Figure F.15 Potential-pH equilibrium diagram for the nickel-water sys-tem at 25°C considering the hydrated oxide forms.
1120 Appendix F
-2
-2 0 2 4 6 8 10 12 14 16
-1.5
-1
-0.5
0
0.5
1
1.5
2
Po
ten
tial
(V
vs.
SH
E)
pH
Mn2+
100
10-2
10-4
10-6
MnO4-
Mn
MnO
a
HMnO2-
Mn3O4
b
MnO2
Mn2O3
Figure F.14 Potential-pH equilibrium diagram for the manganese-watersystem at 60°C.
0765162_AppF_Roberge 9/1/99 8:29 Page 1120
Thermodynamic Data and E-pH Diagrams 1121
-2
-2 0 2 4 6 8 10 12 14 16
-1.5
-1
-0.5
0
0.5
1
1.5
2
Po
ten
tial
(V
vs.
SH
E)
pH
Ni2+100
10-2
10-4
10-6
Ni
Ni(OH)2a
HNiO2-
b
NiO2
Ni2O3
Ni3O4
Figure F.16 Potential-pH equilibrium diagram for the nickel-water sys-tem at 60°C considering the hydrated oxide forms.
-2
-2 0 2 4 6 8 10 12 14 16
-1.5
-1
-0.5
0
0.5
1
1.5
2
Po
ten
tial
(V
vs.
SH
E)
pH
Ni2+100
10-2
10-4
10-6
Ni
NiOa
HNiO2-
b
NiO2
Ni2O3
Ni3O4
Figure F.17 Potential-pH equilibrium diagram for the nickel-water systemat 25°C considering the dry oxide forms.
0765162_AppF_Roberge 9/1/99 8:29 Page 1121
1122 Appendix F
-2
-2 0 2 4 6 8 10 12 14 16
-1.5
-1
-0.5
0
0.5
1
1.5
2
Po
ten
tial
(V
vs.
SH
E)
pH
Zn2+
Zn
100
10-2
10-4
10-6a
b
Zn(OH)2
ZnO2
ZnO22-
Figure F.19 Potential-pH equilibrium diagram for the zinc-water systemat 25°C.
-2
-2 0 2 4 6 8 10 12 14 16
-1.5
-1
-0.5
0
0.5
1
1.5
2
Po
ten
tial
(V
vs.
SH
E)
pH
Ni2+100
10-2
10-4
10-6
Ni
NiOa
HNiO2-
b
NiO2
Ni2O3
Ni3O4
Figure F.18 Potential-pH equilibrium diagram for the nickel-water systemat 60°C considering the dry oxide forms.
0765162_AppF_Roberge 9/1/99 8:29 Page 1122
Thermodynamic Data and E-pH Diagrams 1123
Figure F.20 Potential-pH equilibrium diagram for the zinc-water systemat 60°C.
-2
-2 0 2 4 6 8 10 12 14 16
-1.5
-1
-0.5
0
0.5
1
1.5
2
Po
ten
tial
(V
vs.
SH
E)
pH
Zn2+
Zn
100
10-2
10-4
10-6a
b
ZnO2
ZnO22-
Zn(OH)2
0765162_AppF_Roberge 9/1/99 8:29 Page 1123