viii
Contents
3.2
The Mathematical Statement of the Second Law:
Entropy
114
3.3
The Calculation of Entropy Changes
121
3.4
Statistical Entropy
133
3.5
The Third Law of Thermodynamics and Absolute
Entropies
139
Chapter 4
The Thermodynamics of Real Systems
151
4.1
Criteria for Spontaneous Processes and for Equilibrium:
The Gibbs and Helmholtz Energies
152
4.2
Fundamental Relations for Closed Simple Systems
158
4.3 Additional Useful Thermodynamic Identities
167
4.4
Gibbs Energy Calculations
175
4.5
Multicomponent Systems
182
4.6
Euler’s Theorem and the Gibbs–Duhem Relation
188
Chapter 5
Phase Equilibrium
199
5.1
The Fundamental Fact of Phase Equilibrium
200
5.2
The Gibbs Phase Rule
202
5.3
Phase Equilibria in One-Component Systems
205
5.4
The Gibbs Energy and Phase Transitions
215
5.5
Surfaces in One-Component Systems
222
5.6
Surfaces in Multicomponent Systems
230
Chapter 6
The Thermodynamics of Solutions
237
6.1
Ideal Solutions
238
6.2
Henry’s Law and Dilute Nonelectrolyte Solutions
248
6.3 Activity and Activity Coefficients
258
6.4
The Activities of Nonvolatile Solutes
267
6.5
Thermodynamic Functions of Nonideal Solutions
275
6.6
Phase Diagrams of Nonideal Mixtures
282
6.7
Colligative Properties
292
Chapter 7
Chemical Equilibrium
303
7.1
Gibbs Energy Changes and the Equilibrium
Constant
304
7.2
Reactions Involving Gases and Pure Solids or Liquids
310
7.3
Chemical Equilibrium in Solutions
315
7.4
Equilibria in Solutions of Strong Electrolytes
328
7.5
Buffer Solutions
331
7.6
The Temperature Dependence of Chemical Equilibrium.
The Principle of Le Châtelier
335
7.7
Chemical Equilibrium and Biological Systems
343
Chapter 8
The Thermodynamics of Electrochemical Systems
351
8.1
The Chemical Potential and the Electric Potential
352
8.2
Electrochemical Cells
354
8.3
Half-Cell Potentials and Cell Potentials
361
8.4
The Determination of Activities and Activity Coefficients
of Electrolytes
371
8.5
Thermodynamic Information from Electrochemistry
374
Contents
3.2
The Mathematical Statement of the Second Law:
Entropy
114
3.3
The Calculation of Entropy Changes
121
3.4
Statistical Entropy
133
3.5
The Third Law of Thermodynamics and Absolute
Entropies
139
Chapter 4
The Thermodynamics of Real Systems
151
4.1
Criteria for Spontaneous Processes and for Equilibrium:
The Gibbs and Helmholtz Energies
152
4.2
Fundamental Relations for Closed Simple Systems
158
4.3 Additional Useful Thermodynamic Identities
167
4.4
Gibbs Energy Calculations
175
4.5
Multicomponent Systems
182
4.6
Euler’s Theorem and the Gibbs–Duhem Relation
188
Chapter 5
Phase Equilibrium
199
5.1
The Fundamental Fact of Phase Equilibrium
200
5.2
The Gibbs Phase Rule
202
5.3
Phase Equilibria in One-Component Systems
205
5.4
The Gibbs Energy and Phase Transitions
215
5.5
Surfaces in One-Component Systems
222
5.6
Surfaces in Multicomponent Systems
230
Chapter 6
The Thermodynamics of Solutions
237
6.1
Ideal Solutions
238
6.2
Henry’s Law and Dilute Nonelectrolyte Solutions
248
6.3 Activity and Activity Coefficients
258
6.4
The Activities of Nonvolatile Solutes
267
6.5
Thermodynamic Functions of Nonideal Solutions
275
6.6
Phase Diagrams of Nonideal Mixtures
282
6.7
Colligative Properties
292
Chapter 7
Chemical Equilibrium
303
7.1
Gibbs Energy Changes and the Equilibrium
Constant
304
7.2
Reactions Involving Gases and Pure Solids or Liquids
310
7.3
Chemical Equilibrium in Solutions
315
7.4
Equilibria in Solutions of Strong Electrolytes
328
7.5
Buffer Solutions
331
7.6
The Temperature Dependence of Chemical Equilibrium.
The Principle of Le Châtelier
335
7.7
Chemical Equilibrium and Biological Systems
343
Chapter 8
The Thermodynamics of Electrochemical Systems
351
8.1
The Chemical Potential and the Electric Potential
352
8.2
Electrochemical Cells
354
8.3
Half-Cell Potentials and Cell Potentials
361
8.4
The Determination of Activities and Activity Coefficients
of Electrolytes
371
8.5
Thermodynamic Information from Electrochemistry
374