Preface ........................................................ ix
1 Definitions .................................................. 1
1.1 Thermodynamics .......................................... 1
1.2 System .................................................. 1
1.3 Boundary, Environment, and Interactions ................. 2
1.4 States and State Variables .............................. 2
1.5 Equations of State ...................................... 3
1.6 Work .................................................... 3
1.7 Heat 5 Problems ......................................... 6
2 Equilibrium .................................................. 8
2.1 Equilibrium ............................................. 8
2.2 Zeroth Law of Thermodynamics ............................ 9
2.3 Empirical Temperature .................................. 10
2.4 Traditional Temperature Scales ......................... 11
2.5 Equilibrium Processes .................................. 12
Problems .................................................... 13
3 Heat ........................................................ 14
3.1 Quantifying Heat ....................................... 14
3.2 Calorimetry ............................................ 15
3.3 What is Heat? .......................................... 17
Problems .................................................... 18
4 The First Law ............................................... 19
4.1 Count Rumford .......................................... 19
4.2 Joule's Experiments .................................... 21
4.3 The First Law of Thermodynamics ........................ 22
4.4 Thermodynamic Cycles ................................... 23
4.5 Cycle Adjustment ....................................... 26
Problems .................................................... 27
5 The Second Law .............................................. 30
5.1 Sadi Carnot ............................................ 30
5.2 Statements of the Second Law ........................... 31
5.3 Equivalence and Inequivalence .......................... 34
5.4 Reversible Heat Engines ................................ 38
5.5 Refrigerators and Heat Pumps ........................... 42
Problems .................................................... 43
6 The First and Second Laws ................................... 45
6.1 Rudolph Clausius ....................................... 45
6.2 Thermodynamic Temperature .............................. 46
6.3 Clausius's Theorem ..................................... 50
Problems .................................................... 54
7 Entropy ..................................................... 57
7.1 The Meaning of Reversibility ........................... 57
7.2 Entropy ................................................ 58
7.3 Entropy Generation in Irreversible Processes ........... 61
7.4 The Entropy Generator .................................. 62
7.5 Entropy Corollaries .................................... 64
7.6 Thermodynamic Arrow of Time ............................ 68
Problems .................................................... 70
8 Fluid Variables ............................................. 73
8.1 What Is a Fluid? ....................................... 73
8.2 Reversible Work ........................................ 75
8.3 Fundamental Constraint ................................. 77
8.1 Enthalpy ............................................... 79
8.5 Helmholtz and Gibbs Free Energies ...................... 82
8.6 Partial Derivative Rules ............................... 83
8.7 Thermodynamic Coefficients ............................. 86
8.8 Heat Capacities ........................................ 87
Problems .................................................... 88
9 Simple Fluid Systems ........................................ 94
9.1 The Ideal Gas .......................................... 94
9.2 Room-Temperature Elastic Solid ......................... 98
9.3 Cavity Radiation ...................................... 101
Problems ................................................... 104
10 Nonfluid Systems ........................................... 110
10.1 Nonfluid Variables .................................... 110
10.2 The Theoretician's Rubber Band ........................ 111
10.3 Paramagnetism ......................................... 113
10.4 Surfaces .............................................. 116
10.5 Chemical Potential .................................... 120
10.6 Multivariate Systems .................................. 125
Problems ................................................... 126
11 Equilibrium and Stability .................................. 129
11.1 Mechanical and Thermal Systems ........................ 129
11.2 Principle of Maximum Entropy .......................... 131
11.3 Other Stability Criteria .............................. 134
11.4 Intrinsic Stability of a Fluid ........................ 138
Problems ................................................... 140
12 Two-Phase Systems .......................................... 142
12.1 Phase Diagrams ........................................ 142
12.2 Van der Waals Equation of State ....................... 146
12.3 Two-Phase Transition .................................. 149
12.4 Maxwell Construction .................................. 153
12.5 Clausius-Clapeyron Equation ........................... 155
12.6 Critical Point ........................................ 160
Problems ................................................... 161
13 The Third Law .............................................. 164
13.1 The Principle of Thomsen and Berthelot ................ 164
13.2 Entropy Change ........................................ 165
13.3 Unattainability ....................................... 167
13.4 Absolute Entropy ...................................... 171
Problem .................................................... 173
Appendixes
A Physical Constants and Standard Definitions ............. 175
B Catalog of 21 Simple Cycles ............................. 176
C Glossary of Terms ....................................... 181
D Selected Worked Problems ................................ 184
E Answers to Problems ..................................... 194
Annotated Bibliography ........................................ 199
Index ......................................................... 203
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