| Preface |
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xi | |
| Notations and Symbols |
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xv | |
Part
1. Ionic Equilibria |
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1 | (162) |
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Chapter 1 Dissociation of Electrolytes in Solution |
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3 | (28) |
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1.1 Strong electrolytes — weak electrolytes |
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3 | (2) |
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3 | (1) |
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4 | (1) |
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4 | (1) |
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1.2 Mean concentration and mean activity coefficient of ions |
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5 | (1) |
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1.3 Dissociation coefficient of a weak electrolyte |
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6 | (3) |
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1.4 Conduction of electrical current by electrolytes |
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9 | (11) |
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1.4.1 Transport numbers and electrical conductivity of an electrolyte |
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9 | (1) |
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1.4.2 Equivalent conductivity and limiting equivalent conductivity of an electrolyte |
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10 | (1) |
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11 | (3) |
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1.4.4 Relation between equivalent conductivity and mobility — Kohlrausch's law |
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14 | (2) |
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1.4.5 Apparent dissociation coefficient and equivalent conductivity |
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16 | (1) |
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1.4.6 Variations of equivalent conductivities with the concentrations |
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16 | (4) |
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1.5 Determination of the dissociation coefficient |
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20 | (3) |
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1.5.1 Determination of the dissociation coefficient by the cryometric method |
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21 | (1) |
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1.5.2 Determination of the dissociation coefficient on the basis of the conductivity values |
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22 | (1) |
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1.6 Determination of the number of ions produced by dissociation |
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23 | (4) |
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1.6.1 Use of limiting molar conductivity |
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23 | (1) |
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24 | (3) |
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1.7 Thermodynamic values relative to the ions |
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27 | (4) |
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1.7.1 The standard molar Gibbs energy of formation of an ion |
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27 | (2) |
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1.7.2 Standard enthalpy of formation of ions |
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29 | (1) |
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1.7.3 Absolute standard molar entropy of an ion |
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29 | (1) |
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1.7.4 Determination of the mean activity of a weak electrolyte on the basis of the dissociation equilibrium |
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30 | (1) |
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Chapter 2 Solvents and Solvation |
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31 | (30) |
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31 | (2) |
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2.2 Solvation and structure of the solvated ion |
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33 | (2) |
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2.3 Thermodynamics of solvation |
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35 | (9) |
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2.3.1 Thermodynamic values of solvation |
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36 | (1) |
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2.3.2 Gibbs energy of salvation — Born's model |
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37 | (7) |
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2.4 Transfer of a solute from one solvent to another |
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44 | (4) |
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2.5 Mean transfer activity coefficient of solvation of an electrolyte |
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48 | (1) |
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2.6 Experimentally determining the transfer activity coefficient of solvation |
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49 | (6) |
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2.6.1 Determining the activity coefficient of a molecular solute |
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50 | (1) |
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2.6.2 Determination of the mean transfer activity coefficient of a strong electrolyte |
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51 | (1) |
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2.6.3 Evaluation of the individual transfer activity coefficient of an ion. |
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51 | (4) |
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2.7 Relation between the constants of the same equilibrium achieved in two different solvents |
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55 | (6) |
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2.7.1 General relation of solvent change on an equilibrium constant |
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55 | (1) |
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2.7.2 Influence of the dielectric constant of the solvent on the equilibrium constant of an ionic reaction |
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56 | (5) |
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Chapter 3 Acid/Base Equilibria |
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61 | (40) |
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3.1 Definition of acids and bases and acid—base reactions |
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62 | (1) |
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3.2 Ion product of an amphiprotic solvent |
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63 | (1) |
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3.3 Relative strengths of acids and bases |
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64 | (5) |
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3.3.1 Definition of the acidity constant of an acid |
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64 | (3) |
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3.3.2 Protic activity in a solvent |
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67 | (2) |
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3.4 Direction of acid—base reactions, and domain of predominance |
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69 | (2) |
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3.5 Leveling effect of a solvent |
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71 | (4) |
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3.6 Modeling of the strength of an acid |
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75 | (9) |
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3.6.1 Model of the strength of an acid |
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75 | (3) |
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3.6.2 Comparison of an acid's behavior in two solvents |
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78 | (3) |
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3.6.3 Construction of activity zones for solvents |
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81 | (3) |
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3.7 Acidity functions and acidity scales |
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84 | (4) |
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3.8 Applications of the acidity function |
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88 | (3) |
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3.8.1 Measuring the pKa of an indicator |
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89 | (1) |
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3.8.2 Measuring the ion products of solvents |
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89 | (2) |
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3.9 Acidity in non-protic molecular solvents |
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91 | (1) |
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3.10 Protolysis in ionic solvents (molten salts) |
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92 | (1) |
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3.11 Other ionic exchanges in solution |
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93 | (3) |
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93 | (1) |
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3.11.2 Acidity in molten salts: definition given by Lux and Flood |
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94 | (2) |
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3.12 Franklin and Gutmann's solvo-acidity and solvo-basicity |
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96 | (4) |
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3.12.1 Definition of solvo-acidity |
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96 | (1) |
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3.12.2 Solvo-acidity in molecular solvents |
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96 | (2) |
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3.12.3 Solvo-acidity in molten salts |
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98 | (2) |
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3.13 Acidity as understood by Lewis |
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100 | (1) |
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Chapter 4 Complexations and Redox Equilibria |
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101 | (34) |
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4.1 Complexation reactions |
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101 | (16) |
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4.1.1 Stability of complexes |
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101 | (5) |
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4.1.2 Competition between two ligands on the same acceptor |
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106 | (2) |
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4.1.3 Method for studying perfect complexes |
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108 | (2) |
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4.1.4 Methods for studying imperfect complexes |
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110 | (5) |
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4.1.5 Study of successive complexes |
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115 | (2) |
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117 | (18) |
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4.2.1 Electronegativity — electronegativity scale |
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117 | (7) |
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4.2.2 Degrees of oxidation |
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124 | (4) |
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4.2.3 Definition of redox reactions |
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128 | (1) |
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4.2.4 The two families of redox reactions |
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128 | (2) |
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4.2.5 Dismutation and antidismutation |
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130 | (1) |
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4.2.6 Redox reactions, and calculation of the stoichiometric numbers |
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131 | (1) |
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4.2.7 Concept of a redox couple |
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132 | (3) |
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Chapter 5 Precipitation Reactions and Equilibria |
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135 | (28) |
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5.1 Solubility of electrolytes in water — solubility product |
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135 | (1) |
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5.2 Influence of complex formation on the solubility of a salt |
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136 | (1) |
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5.3 Application of the solubility product in determining the stability constant of complex ions |
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137 | (1) |
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5.4 Solution with multiple electrolytes at equilibrium with pure solid phases |
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138 | (9) |
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5.4.1 Influence of a salt with non-common ions on the solubility of a salt |
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139 | (2) |
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5.4.2 Influence of a salt with a common ion on the solubility of a salt |
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141 | (1) |
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5.4.3 Crystallization phase diagram for a mixture of two salts in solution |
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141 | (1) |
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5.4.4 Formation of double salts or chemical combinations in the solid state |
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142 | (2) |
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5.4.5 Reciprocal quaternary systems — square diagrams |
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144 | (3) |
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5.5 Electrolytic aqueous solution and solid solution |
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147 | (8) |
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5.5.1 Thermodynamic equilibrium between a liquid ionic solution and a solid solution |
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147 | (3) |
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5.5.2 Solubility product of a solid solution |
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150 | (5) |
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155 | (3) |
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155 | (1) |
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5.6.2 Solubility of oxides in molten alkali hydroxides |
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156 | (1) |
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5.6.3 Solubility in oxo-acids and oxo-bases (see section 3.12.2) |
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157 | (1) |
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5.7 Calculation of equilibria in ionic solutions |
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158 | (5) |
Part
2. Electrochemical Thermodynamics |
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163 | (104) |
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Chapter 6 Thermodynamics of the Electrode |
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165 | (44) |
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6.1 Electrochemical systems |
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165 | (8) |
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6.1.1 The electrochemical system |
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166 | (1) |
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6.1.2 Electrochemical functions of state |
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167 | (1) |
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6.1.3 Electrochemical potential |
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167 | (2) |
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6.1.4 Gibbs—Duhem relation for electrochemical systems |
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169 | (1) |
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6.1.5 Chemical system associated with an electrochemical system |
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170 | (1) |
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6.1.6 General conditions of an equilibrium of an electrochemical system |
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171 | (2) |
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173 | (11) |
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6.2.1 Definition and reaction of the electrode |
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173 | (1) |
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6.2.2 Equilibrium of an insulated metal electrode — electrode absolute voltage |
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174 | (1) |
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6.2.3 Voltage relative to a metal electrode — Nernst's relation |
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175 | (3) |
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6.2.4 Chemical and electrochemical Gibbs energy of the electrode reaction |
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178 | (1) |
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6.2.5 Influence of pH on the electrode voltage |
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179 | (2) |
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6.2.6 Influence of the solvent and of the dissolved species on the electrode voltage |
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181 | (2) |
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6.2.7 Influence of temperature on the normal potentials |
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183 | (1) |
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6.3 The different types of electrodes |
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184 | (9) |
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184 | (5) |
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189 | (3) |
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192 | (1) |
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6.4 Equilibrium of two ionic conductors in contact |
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193 | (3) |
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6.4.1 Junction potential with a semi-permeable membrane |
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193 | (1) |
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6.4.2 Junction potential of two electrolytes with a permeable membrane |
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194 | (2) |
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6.5 Applications of Nernst's relation to the study of various reactions |
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196 | (7) |
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6.5.1 Prediction of redox reactions |
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196 | (1) |
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6.5.2 Relations between the redox voltages of different systems of the same element |
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197 | (4) |
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6.5.3 Predicting the dismutation and anti-dismutation reactions |
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201 | (1) |
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202 | (1) |
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6.6 Redox potential in a non-aqueous solvent |
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203 | (6) |
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6.6.1 Scale of redox potential in a non-aqueous medium |
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203 | (3) |
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6.6.2 Oxidation and reduction of the solvent |
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206 | (1) |
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6.6.3 Influence of solvent on redox systems in a non-aqueous solvent |
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207 | (2) |
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Chapter 7 Thermodynamics of Electrochemical Cells |
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209 | (36) |
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7.1 Electrochemical chains — batteries and electrolyzer cells |
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209 | (1) |
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7.2 Electrical voltage of an electrochemical cell |
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210 | (2) |
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212 | (1) |
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7.4 Influence of temperature on the cell voltage; Gibbs—Helmholtz formula |
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213 | (1) |
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7.5 Influence of activity on the cell voltage |
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214 | (1) |
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7.6 Dissymmetry of cells, chemical cells and concentration cells |
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215 | (1) |
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7.7 Applications to the thermodynamics of electrochemical cells |
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216 | (29) |
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7.7.1 Determining the standard potentials of cells |
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216 | (2) |
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7.7.2 Determination of the dissociation constant of a weak electrolyte on the basis of the potential of a cell |
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218 | (3) |
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7.7.3 Measuring the activity of a component in a strong electrolyte |
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221 | (3) |
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7.7.4 Influence of complex formation on the redox potential |
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224 | (2) |
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7.7.5 Electrochemical methods for studying complexes |
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226 | (8) |
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7.7.6 Determining the ion product of a solvent |
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234 | (1) |
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7.7.7 Determining a solubility product |
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235 | (1) |
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7.7.8 Determining the enthalpies, entropies and Gibbs energies of reactions |
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236 | (1) |
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7.7.9 Determining the standard Gibbs energies of the ions |
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237 | (1) |
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7.7.10 Determining the standard entropies of the ions |
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238 | (1) |
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7.7.11 Measuring the activity of a component of a non-ionic conductive solution (metal solution) |
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238 | (3) |
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7.7.12 Measuring the activity coefficient of transfer of a strong electrolyte |
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241 | (1) |
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7.7.13 Evaluating the individual activity coefficient of transport for an ion |
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242 | (3) |
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Chapter 8 Potential/Acidity Diagrams |
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245 | (22) |
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245 | (4) |
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8.1.1 Plotting conventions |
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245 | (1) |
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246 | (3) |
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8.2 Intersections of lines in the diagram |
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249 | (7) |
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8.2.1 Relative disposition of the lines in the vicinity of a triple point |
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249 | (1) |
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8.2.2 Shape of equi-concentration lines in the vicinity of a triple point |
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250 | (6) |
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8.3 Plotting a diagram: example of copper |
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256 | (6) |
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8.3.1 Step 1: list of species and thermodynamic data |
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256 | (1) |
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8.3.2 Step 2: choice of hydrated forms |
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256 | (1) |
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8.3.3 Step 3: study by degrees of oxidation of acid—base reactions; construction of the situation diagram |
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257 | (2) |
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8.3.4 Step 4: elimination of unstable species by dismutation |
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259 | (2) |
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8.3.5 Step 5: plotting the e/pH diagram |
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261 | (1) |
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8.4 Diagram for water superposed on the diagram for an element |
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262 | (1) |
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8.5 Immunity, corrosion and passivation |
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263 | (1) |
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8.6 Potential/pX (e/pX) diagrams |
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264 | (1) |
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8.7 Potential/acidity diagrams in a molten salt |
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265 | (2) |
| Appendix |
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267 | (8) |
| Bibliography |
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275 | (4) |
| Index |
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279 | |
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