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Tables of Contents for Chemical Thermodynamics
Chapter/Section Title
Page #
Page Count
Preface to the Two-Volume Series
xiii
Preface to the Second Volume
xix
Summary of Thermodynamic Relationships
1
42
Thermodynamic Relationships
2
5
The Gibbs Equations
3
1
Differential Relationships
4
3
Phase Equilibria Relationships
7
3
Fugacity
10
3
Effect of Temperature and Pressure on the Fugacity
10
2
Raoult's Law, Henry's Law, and the Ideal Solution
12
1
Activity and Standard States
13
7
Effect of Pressure and Temperature on the Activity
14
1
Choice of Standard States
14
2
Choice of Standard States for Strong Electrolyte Solutes
16
1
Debye-Huckel Predictions of the Thermodynamic Properties of Strong Electrolyte Solutions
16
4
Thermodynamics of Mixtures
20
4
Change in the Thermodynamic Properties in Forming Nonelectrolyte Mixtures
20
1
Thermodynamic Properties of Ideal Solutions
21
1
Effect of Temperature and Pressure on (Solid + Liquid) Equilibrium in an Ideal Solution
21
1
Excess Thermodynamic Functions
22
1
Relative Partial Molar Thermal Properties
23
1
Relative Apparent Molar Properties
24
1
Chemical Equilibrium
24
5
The Equilibrium Constant
25
1
Alternate Forms of the Equilibrium Constant
25
2
Effect of Pressure and Temperature on the Equilibrium Constant
27
1
The Effect of Pressure
27
1
The Effect of Temperature
27
2
Enthalpies and Gibbs Free Energies of Formation
29
1
Electrochemical Cells
29
2
Calculations from Statistical Thermodynamics
31
12
The Boltzmann Distribution Equation
31
1
The Partition Function
31
1
Relationships for Calculating the Thermodynamic Functions of the Ideal Gas
32
1
Contributions of Internal Rotation to the Thermodynamic Functions of the Ideal Gas
32
3
The Debye Heat Capacity Equation
35
6
References
41
2
Thermodynamics of Other Variables
43
32
Effect of Gravitational Fields
47
4
Effect of Height on Atmospheric Pressure
47
1
Effect of Gravity on Composition
48
3
Effect of Centrifugal Fields
51
2
Density-Gradient Centrifugation
52
1
Thermodynamics of Surfaces
53
22
A One-Component System
54
5
The Effect of Curvature On Surface Properties
59
3
Surface Effects for Mixtures
62
1
Surface Concentration
62
2
Thermodynamic Properties of the Surface
64
10
References
74
1
Applications of Thermodynamics to Phase Equilibria Studies of Pure Substances
75
40
Classification of Phase Transitions in Pure Materials
75
27
First- and Second-Order Transitions
76
4
First-Order Phase Transitions
80
5
Continuous Phase Transitions and Related Thermodynamic Information
85
1
(Liquid + Gas) Critical Phase Transition
86
1
Order--Disorder Transitions Involving Position, Orientation and Magnetic Moments
86
1
Position Disorder
86
2
Rotational Disorder
88
1
Magnetic Effects
89
1
Helium-4 Normal-superfluid Transition
90
3
Helium-3 Phase Properties
93
3
Conductor--Superconductor Transition
96
4
Effect of Pressure on Superconducting Transitions
100
2
Modern Theories of Phase Transformations
102
13
References
114
1
Applications of Thermodynamics to Phase Equilibria Studies of Mixtures
115
46
Phase Changes for Mixtures
115
1
(Vapor + Liquid) Equilibria
116
4
(Liquid + Liquid) Equilibrium
120
5
Combination of (Liquid + Liquid) and (Vapor + Liquid) Equilibrium
123
2
(Fluid + Fluid) Equilibrium
125
9
Type I Systems
126
2
Retrograde Condensation
128
2
Type II Systems
130
1
Type III Systems
131
2
Type IV and Type V Systems
133
1
(Solid + Liquid) Phase Equilibrium
134
27
Simple Eutectic Systems with Large Deviations from Ideal Solution Behavior
137
1
(Liquid + Liquid) with (Solid + Liquid) Equilibria
138
2
A Quadruple Point
140
2
(Solid + Solid) with (Solid + Liquid) Equilibria
142
2
Metastable Equilibrium
144
1
Congruently Melting Solid Addition Compounds
144
3
Incongruently Melting Solid Addition Compounds
147
3
Solid Solution Formation
150
1
Partial Miscibility in the Solid State
150
1
Complete Miscibility in the Solid State
151
1
Variable Composition in a Molecular Addition Compound
152
1
The (Solid + Liquid) Equilibrium Curve for a Dissociable Solute
153
5
References
158
3
Applications of Thermodynamics to Chemical Processes
161
52
The Haber Cycle: Application to an Industrial Process
161
13
The Synthesis of Diamond: Application to Phase Changes
174
7
Applications of Thermodynamics to Geological Systems
181
12
Effect of Temperature on the Solubility of Calcite
181
3
Thermodynamic Insights into the Energetics of Ternary Oxides with Mineralogical Significance
184
1
Formation of Ternary Oxides
184
3
Enthalpies of Formation from the Oxides
187
1
Entropies of Formation from the Oxides
188
1
Enthalpies of Formation of Orthosilicates
189
1
Enthalpies of Mixing of (Metal Oxide + Silica) Systems
189
2
Enthalpies of Solution of Metal Oxides into a Molten ``Oxide-buffered'' Solution
191
1
Conclusions
192
1
Thermodynamics of Complexation with Macrocyclic Ligands
193
20
Thermodynamic Properties of Macrocycle---Metal Ion Complexes
197
1
Complexes with Oxygen Macrocycles
197
3
Complexes with Macrocycles Containing Heteroatoms other than Oxygen
200
4
Interpretation of the Results to Explain Complex Stability Involving ``Hard'' and ``Soft'' Metal Ions
204
1
Hard Ions
204
1
Soft Ions
205
1
(Hard Ion + Soft Ligand Complexes)
205
1
(Soft Ion + Soft Ligand Complexes)
206
4
References
210
3
Applications of Thermodynamics to Biological Processes
213
58
Metabolism and Work
214
16
Phosphorylation of Glucose
217
1
The Isomerization of Glucose-6-Phosphate into Fructose-6-Phosphate
218
1
Phosphorylation of Fructose-6-Phosphate
219
1
Cleavage of Fructose-1,6-Bisphosphate into Three-Carbon Phosphates
219
1
Oxidative Phosphorylation of Glyceraldehyde-3-Phosphate
220
6
Historical Perspective on Metabolic Energy and the Thermodynamics of Phosphate Compounds
226
4
Biopolymer Stabilities
230
41
The Thermodynamics of the Two-State Model
233
2
Optical Methods and the van't Hoff Enthalpy
235
2
Calorimetric Studies
237
2
Thermodynamic Studies of Protein Stabilities
239
1
The Calorimetrically Obtained van't Hoff Enthalpy
240
6
Thermodynamic and Spectroscopic Studies of Synthetic Oligonucleotides as Model Compounds for DNA
246
4
Description of Procedures and Techniques Associated with Duplex Melting
250
5
Observance of Equilibria Between Two Oligonucleotide Conformations
255
2
Studies of Synthetic Oligonucleotides to Generate Information About the Energetics of Structural Features
257
1
The d(GCGCGC)2 Duplex
257
1
The d(ATGCAT)2 Duplex
257
2
The d(CGCGAATTCGCG)2 Duplex
259
1
The d(GGAATTCC)2 and d(GAATTCGCG)2 Duplexes
259
1
Wobble Base-Pairs
260
1
Generation of a Thermodynamic Database to Estimate Melting Parameters of Oligonucleotides and Portions of Nucleic Acids
261
1
Estimation of a Duplex Melting Enthalpy
262
1
Ligand Binding of Cisplatin
263
6
References
269
2
Applications of Thermodynamics to Nonelectrolyte Solutions
271
38
Excess Thermodynamic Properties
272
19
Thermodynamic Properties of Ideal Solutions
272
2
Thermodynamic Properties of Regular Solutions
274
4
Examples of Thermodynamic Properties of Real Solutions
278
1
Nonpolar + Nonpolar mixtures
278
5
Polar + Nonpolar Mixtures
283
4
Polar + Polar Mixtures
287
1
Mixtures With Complex Formation
288
1
Hydrogen-Bonded Systems
289
2
The Excess Thermodynamic Properties and (Liquid + Liquid) Phase Equilibrium
291
8
The Excess Thermodynamic Properties and (Fluid + Fluid) Phase Equilibrium
299
10
References
306
3
Applications of Thermodynamics to Solutions Containing Electrolyte Solutes
309
50
Electrolyte Solutions
309
22
Thermodynamics of More Concentrated Electrolyte Solutions
312
1
Guggenheim's Equations
313
2
Pitzer and Brewer Tabulations
315
1
Pitzer's Equations
316
1
The Osmotic Coefficient and Activity Coefficient
317
2
Thermal Properties
319
5
Volumetric Properties
324
1
Pitzer's Equations at Elevated Temperatures
324
1
Generalized Equations
325
6
Ion Association
331
10
Ion Association at High Temperatures
335
2
Ion Association from Flow Calorimetry
337
4
Surfactant Solutions
341
18
Thermodynamic Properties of Surfactant Solutions
341
2
Theoretical Description of Surfactant Solutions
343
1
The Pseudo-Phase Model
343
6
The Mass Action Model
349
7
References
356
3
Appendix 5: Thermodynamic Properties of Selected Chemical Substances
359
22
Table A5.1 Thermodynamic Functions
361
7
Table A5.2 Standard Heat Capacities, Entropies, Enthalpies, and Gibbs Free Energies of Formation of Selected Substances at T = 298.15 K
368
5
Table A5.3 Standard Heat Capacities, Entropies, Enthalpies, and Gibbs Free Energies of Formation of Some Common Ions at T = 298.15 K
373
1
Table A5.4 Enthalpies and Temperatures of Fusion and Vaporization
374
2
Table A5.5 Coefficients at p = 0.1 MPa for the Heat Capacity Equation
376
3
Table A5.6 Standard Reduction Potentials at T = 298.15 K
379
2
Appendix 6: Calculations from Statistical Thermodynamics
381
24
A6.1 Atomic and Molecular Energy Levels
381
5
A6.1a Translational Energy Levels
381
1
A6.1b Rotational Energy Levels
382
2
A6.1c Vibrational Energy Levels
384
1
A6.1d Internal Rotational Energy Levels
385
1
A6.1e Electronic Energy Levels
386
1
A6.2 The Partition Function
386
1
A6.3 Relationship Between the Partition Function and the Thermodynamic Functions for the Ideal Gas
387
1
A6.4 Partition Functions for the Ideal Gas
388
2
A6.5 Calculation of the Thermodynamic Properties from the Energy Levels
390
1
Table A6.1 Thermodynamic Functions of an Ideal Gas
391
2
Table A6.2 Moments of Inertia and Rotational Constants of Some Common Molecules
393
2
Table A6.3 Fundamental Vibrational Frequencies of some Common Molecules
395
2
Table A6.4 Electronic Energy Levels of Some Common Molecules or Atoms with Unpaired Electrons
397
1
Table A6.5 Anharmonic Oscillator and Nonrigid Rotator Corrections
397
2
Table A6.6 Contributions to the Thermodynamic Properties Due to Internal Rotation
399
3
Table A6.7 The Debye Thermodynamic Functions Expressed in Terms of &thetas;D/T
402
3
Appendix 7: Coefficients for Pitzer's Equations
405
19
Table A7.1 Debye-Huckel Parameters for the Osmotic Coefficient, Volume, Enthalpy, and Heat Capacity
406
2
Table A7.2 Pitzer Coefficients for 1:1 Electrolytes
408
3
Table A7.3 Pitzer Coefficients for 2:1 Electrolytes
411
2
Table A7.4 Pitzer Coefficients for 3:1 Electrolytes
413
1
Table A7.5 Pitzer Coefficients for 4:1 and 5:1 Electrolytes
414
1
Table A7.6 Pitzer Coefficients for 2:2 Electrolytes
415
1
Table A7.7 Temperature Derivatives of Pitzer Coefficients for 1:1 Electrolytes
415
7
Table A7.8 Temperature Derivatives of Pitzer Coefficients for 2:1 and 1:2 Electrolytes
422
1
Table A7.9 Temperature Derivatives of Pitzer Coefficients for 3:1, 2:2, 3:2, and 4:2 Electrolytes
423
1
Table A7.10 Volumetric Properties and the Pressure Derivatives of Pitzer Coefficients for Salts
424