| Preface |
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xi | |
| Notations And Symbols |
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xv | |
| Chapter 1 Pure Liquids |
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1 | (36) |
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1.1 Macroscopic modeling of liquids |
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1 | (1) |
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1.2 Distribution of molecules in a liquid |
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2 | (7) |
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1.2.1 Molecular structure of a non- associated liquid |
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3 | (1) |
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1.2.2 The radial distribution function |
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4 | (2) |
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1.2.3 The curve representative of the radial distribution function |
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6 | (2) |
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1.2.4 Calculation of the macroscopic thermodynamic values |
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8 | (1) |
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1.3 Models extrapolated from gases or solids |
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9 | (7) |
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1.3.1 Guggenheim's smoothed potential model |
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10 | (3) |
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1.3.2 Mie's harmonic oscillator model |
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13 | (2) |
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1.3.3 Determination of the free volume on the basis of the dilation and the compressibility |
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15 | (1) |
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1.4 Lennard-Jones and Devonshire cellular model |
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16 | (9) |
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1.5 Cellular and vacancies model |
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25 | (4) |
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1.6 Eyring's semi-microscopic formulation of the vacancy model |
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29 | (3) |
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1.7 Comparison between the different microscopic models and experimental results |
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32 | (5) |
| Chapter 2 Macroscopic Modeling Of Liquid Molecular Solutions |
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37 | (24) |
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2.1 Macroscopic modeling of the Margules expansion |
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38 | (1) |
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2.2 General representation of a solution with several components |
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39 | (1) |
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2.3 Macroscopic modeling of the Wagner expansions |
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40 | (3) |
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2.3.1 Definition of the Wagner interaction coefficients |
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40 | (1) |
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2.3.2 Example of a ternary solution: experimental determination of Wagner's interaction coefficients |
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41 | (2) |
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2.4 Dilute ideal solutions |
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43 | (3) |
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2.4.1 Thermodynamic definition of a dilute ideal solution |
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43 | (1) |
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2.4.2 Activity coefficients of a component with a pure-substance reference |
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44 | (1) |
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2.4.3 Excess Gibbs energy of an ideal dilute solution |
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44 | (1) |
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2.4.4 Enthalpy of mixing for an ideal dilute solution |
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45 | (1) |
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2.4.5 Excess entropy of a dilute ideal solution |
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46 | (1) |
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2.4.6 Molar heat capacity of an ideal dilute solution at constant pressure |
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46 | (1) |
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46 | (11) |
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2.5.1 Example of the study of an associated solution |
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47 | (2) |
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2.5.2 Relations between the chemical potentials of the associated solution |
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49 | (1) |
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2.5.3 Calculating the extent of the equilibrium in an associated solution |
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50 | (1) |
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2.5.4 Calculating the activity coefficients in an associated solution |
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50 | (1) |
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2.5.5 Definition of a regular solution |
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51 | (1) |
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2.5.6 Strictly-regular solutions |
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52 | (1) |
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2.5.7 Macroscopic modeling of strictly-regular binary solutions |
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53 | (3) |
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2.5.8 Extension of the model of a strictly-regular solution to solutions with more than two components |
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56 | (1) |
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57 | (4) |
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2.6.1 Thermodynamic definition of an athermic solution |
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58 | (1) |
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2.6.2 Variation of the activity coefficients with temperature in an athermic solution |
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58 | (1) |
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2.6.3 Molar entropy and Gibbs energy of mixing for an athermic solution |
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58 | (1) |
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2.6.4 Molar heat capacity of an athermic solution |
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59 | (2) |
| Chapter 3 Microscopic Modeling Of Liquid Molecular Solutions |
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61 | (56) |
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3.1 Models of binary solutions with molecules of similar dimensions |
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62 | (12) |
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3.1.1 The microscopic model of a perfect solution |
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68 | (2) |
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3.1.2 Microscopic description of strictly-regular solutions |
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70 | (2) |
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3.1.3 Microscopic modeling of an ideal dilute solution |
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72 | (2) |
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3.2 The concept of local composition |
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74 | (13) |
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3.2.1 The concept of local composition in a solution |
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74 | (2) |
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3.2.2 Energy balance of the mixture |
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76 | (2) |
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3.2.3 Warren and Cowley's order parameter |
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78 | (2) |
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3.2.4 Model of Fowler & Guggenheim's quasi-chemical solution |
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80 | (7) |
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3.3 The quasi-chemical method of modeling solutions |
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87 | (5) |
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3.4 Difference of the molar volumes: the combination term |
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92 | (9) |
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3.4.1 Combinatorial excess entropy |
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92 | (5) |
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3.4.2 Flory's athermic solution model |
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97 | (1) |
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3.4.3 Staverman's corrective factor |
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98 | (3) |
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3.5 Combination of the different concepts: the UNIQUAC model |
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101 | (6) |
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3.6 The concept of contribution of groups: the UNIFAC model |
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107 | (10) |
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3.6.1 The concept of the contribution of groups |
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108 | (1) |
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108 | (6) |
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3.6.3 The modified UNIFAC model (Dortmund) |
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114 | (1) |
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3.6.4 Use of the UNIFAC system in the UNIQUAC model |
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114 | (3) |
| Chapter 4 Ionic Solutions |
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117 | (42) |
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4.1 Reference state, unit of composition and activity coefficients of ionic solutions |
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119 | (2) |
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4.2 Debye and Hiickel's electrostatic model |
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121 | (29) |
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4.2.1 Presentation of the problem |
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122 | (1) |
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123 | (1) |
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124 | (1) |
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4.2.4 Electrical potential due to the ionic atmosphere |
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125 | (2) |
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4.2.5 Debye and Mickel's hypotheses |
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127 | (5) |
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4.2.6 Debye and Hiickel's solution for the potential due to the ionic atmosphere |
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132 | (2) |
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4.2.7 Charge and radius of the ionic atmosphere of an ion |
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134 | (2) |
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4.2.8 Excess Helmholtz energy and excess Gibbs energy due to charges |
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136 | (2) |
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4.2.9 Activity coefficients of the ions and mean activity coefficient of the solution |
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138 | (3) |
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4.2.10 Self-consistency of Debye and Hilckel's model |
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141 | (3) |
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4.2.11 Switching from concentrations to molalities |
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144 | (2) |
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4.2.12 Debye and HtIckel's law: validity and comparison with experimental data |
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146 | (1) |
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4.2.13 Debye and Mickel's limit law |
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147 | (1) |
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4.2.14 Extensions of Debye and Mickel's law |
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148 | (2) |
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150 | (5) |
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4.4 UNIQUAC model extended to ionic solutions |
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155 | (4) |
| Chapter 5 Determination Of The Activity Of A Component Of A Solution |
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159 | (22) |
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5.1 Calculation of an activity coefficient when we know other coefficients |
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160 | (4) |
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5.1.1 Calculation of the activity of a component when we know that of the other components in the solution |
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160 | (2) |
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5.1.2 Determination of the activity of a component at one temperature if we know its activity at another temperature |
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162 | (2) |
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5.2 Determination of the activity on the basis of the measured vapor pressure |
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164 | (4) |
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5.2.1 Measurement by the direct method |
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165 | (1) |
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5.2.2 Method using the vaporization constant in reference 11 |
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166 | (2) |
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5.3 Measurement of the activity of the solvent of the basis of the colligative properties |
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168 | (5) |
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5.3.1 Use of measuring of the depression of the boiling point - ebullioscopy |
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168 | (2) |
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5.3.2 Use of measuring of the depression of the freezing point - cryoscopy |
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170 | (2) |
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5.3.3 Use of the measurement of osmotic pressure |
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172 | (1) |
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5.4 Measuring the activity on the basis of solubility measurements |
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173 | (3) |
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5.4.1 Measuring the solubilities in molecular solutions |
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174 | (1) |
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5.4.2 Measuring the solubilities in ionic solutions |
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174 | (2) |
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5.5 Measuring the activity by measuring the distribution of a solute between two immiscible solvents |
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176 | (1) |
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5.6 Activity in a conductive solution |
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176 | (5) |
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5.6.1 Measuring the activity in a strong electrolyte |
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176 | (4) |
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5.6.2 Determination of the mean activity of a weak electrolyte on the basis of the dissociation equilibrium |
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180 | (1) |
| Appendices |
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181 | (40) |
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183 | (10) |
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193 | (14) |
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207 | (14) |
| Bibliography |
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221 | (4) |
| Index |
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225 | |
