Chapter 1. Definition of thermodynamic terms .................... 1
1.1. Systems ................................................. 1
1.2. Phase ................................................... 2
1.3. Components .............................................. 3
1.4. Functions and variables of state ........................ 5
1.5. The concept of thermodynamic equilibrium ................ 7
1.6. Temperature ............................................. 7
1.7. Pressure ............................................... 10
1.8. Composition ............................................ 10
1.8.1. Graphic representation of composition ........... 11
1.9. Problems ............................................... 21
Chapter 2. Volume as a state function .......................... 23
2.1. Volume of pure phases .................................. 23
2.1.1. Thermal expansion and compressibility ........... 25
Examples of calculated thermal expansion and
compressibility .................................... 28
2.1.2. Volume of ideal gases as a state function ....... 34
2.1.3. Volume of real gases ............................ 37
2.1.4. Volume of solid phases .......................... 43
Calculation of molar volume using x-ray
diffraction data ................................... 46
2.2. Volume of solutions .................................... 47
2.2.1. Partial molar volume ............................ 48
2.2.2. Volume relationships in binary solutions ........ 51
2.2.3. Volume changes on mixing ........................ 56
2.2.4. Examples for the volumes of binary solutions .... 60
2.2.5. Volume of reaction .............................. 73
2.3. Problems ............................................... 75
Chapter 3. The first law of thermodynamics ..................... 78
3.1. The relationship between heat and work ................. 78
3.2. Internal Energy ........................................ 78
3.2.1. Work ............................................ 79
3.2.2. Enthalpy ........................................ 83
3.3. Application of the first law of thermodynamics to
pure phases ............................................ 84
3.3.1. Heat capacities Cv and Сp ....................... 86
The temperature dependence of heat capacity ........ 91
The empirical representation of heat capacities .... 98
3.3.2. Enthalpy, H, of pure phases as a function of
temperature .................................... 101
3.4. Enthalpy of solutions ................................. 106
3.4.1. Enthalpy of binary solution .................... 107
3.4.2. Examples of enthalpy of mixing in binary
solutions ...................................... 110
3.5. Enthalpy of reaction .................................. 116
3.5.1. Temperature dependence of the enthalpy of
reaction ....................................... 119
3.5.2. Hess's law ..................................... 122
3.6. Problems .............................................. 124
Chapter 4. Second law of thermodynamics ....................... 129
4.1. Entropy ............................................... 130
4.2. Classical definition of entropy ....................... 130
4.2.1. Entropy of pure phases ......................... 131
4.2.2. Adiabatic changes .............................. 136
4.2.3. Temperature dependence of entropy .............. 137
4.2.4. Entropy changes associated with irreversible
processes ...................................... 140
4.3. Statistical interpretation of entropy ................. 144
4.3.1. Thermal entropy ................................ 145
4.3.2. Configurational entropy (entropy of mixing) .... 149
4.4. Entropy of reaction ................................... 160
4.4.1 Temperature dependence of the entropy of
reaction ........................................ 160
4.5. Problems .............................................. 163
Chapter 5. Gibbs free energy and Helmholtz free energy ........ 165
5.1. Chemical potential of pure phases ..................... 168
5.1.1. Chemical potential of ideal gases .............. 168
5.1.2. Chemical potential of non-ideal gases .......... 169
5.2. The chemical potential of components in solutions ..... 173
5.2.1. Chemical potential of an ideal gas in an
ideal solution ................................. 176
5.2.2. Chemical potential of a real gas in ideal and
non-ideal gas mixtures ......................... 177
5.2.3. Chemical potential of components in ideal
solid solutions ................................ 181
5.2.4. Chemical potential of components in non-ideal
solid solutions ................................ 183
Activity and activity coefficient as a function
of composition .................................... 184
5.2.5. The standard state ............................. 186
The activity coefficient as a function of
temperature and pressure .......................... 189
5.3. Gibbs free energy of mixing ........................... 191
5.3.1. Mixing and activity models ..................... 194
5.4. Gibbs free energy of reaction ......................... 214
5.4.1 Standard Gibbs free energy of reaction .......... 215
5.5. Problems .............................................. 216
Chapter 6. Thermal equilibrium ................................ 218
6.1. Stability conditions for phases in one-component
systems ............................................... 220
6.1.1. Phase equilibria in one-component systems ...... 223
6.1.2. Classification of phase transformations ........ 227
6.2. Stability conditions for solutions .................... 237
6.2.1. Coherent exsolution ............................ 244
6.3. Gibbs free energy and phase diagrams of binary
systems ............................................... 249
6.3.1. Calculation of phase diagrams from
thermodynamic data ............................. 253
Critical mixing conditions, binodal, spinodal ..... 253
Simple eutectic system ............................ 259
Binary system with complete miscibility of
components in two phases .......................... 265
6.4. Gibbs phase rule ...................................... 272
6.5. Problems .............................................. 275
Chapter 7. Chemical reactions ................................. 277
7.1. Phase equilibria in reacting systems .................. 277
7.1.1. Reactions in systems containing pure solid
phases ......................................... 278
7.1.2. Reactions in systems containing solid
solutions ...................................... 288
7.1.3. Reactions in systems containing solid and
gas phases ..................................... 291
7.1.4. Distribution coefficient, KD ................... 306
Reciprocal solutions .............................. 313
Energetics of order-disorder ...................... 325
7.2. Problems .............................................. 339
Chapter 8. Geothermometry and geobarometry .................... 343
8.1. Exchange geothermometers .............................. 345
8.2. Solvus thermometry .................................... 349
8.3. Solid-solid reactions ................................. 354
8.3.1. Reactions in one-component system .............. 354
8.3.2. Reactions in multicomponent systems ............ 355
8.4. Reactions involving gaseous phases .................... 358
Solutions to problems ......................................... 365
References .................................................... 371
Subject Index ................................................. 381
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