Heat and thermodynamics

Front cover......Page 1
Title page......Page 3
Date-line......Page 4
Dedication......Page 5
About the authors......Page 7
CONTENTS......Page 9
Preface......Page 15
Notation......Page 17
Part I Fundamental Concepts......Page 23
1.1 Macroscopic Point of View......Page 25
1.2 Microscopic Point of View......Page 26
1.3 Macroscopic vs. Microscopic Points of View......Page 27
1.4 Scope of Thermodynamics......Page 28
1.5 Thermal Equilibrium and the Zeroth Law......Page 29
1.6 Concept of Temperature......Page 32
1.7 Thermometers and Measurement of Temperature......Page 34
1.8 Comparison of Thermometers......Page 37
1.9 Gas Thermometer......Page 38
1.10 Ideal-Gas Temperature......Page 40
1.11 Celsius Temperature Scale......Page 42
1.12 Platinum Resistance Thermometry......Page 43
1.13 Radiation Thermometry......Page 44
1.15 Thermocouple......Page 45
1.16 International Temperature Scale of 1990 (ITS-90)......Page 46
1.17 Rankine and Fahrenheit Temperature Scales......Page 48
2.1 Thermodynamic Equilibrium......Page 51
2.2 Equation of State......Page 53
2.3 Hydrostatic Systems......Page 54
2.4 Mathematical Theorems......Page 57
2.5 Stretched Wire......Page 60
2.6 Surfaces......Page 62
2.7 Electrochemical Cell......Page 63
2.8 Dielectric Slab......Page 65
2.9 Paramagnetic Rod......Page 66
2.10 Intensive and Extensive Coordinates......Page 68
3.1 Work......Page 71
3.2 Quasi-Static Process......Page 72
3.3 Work in Changing the Volume of a Hydrostatic System......Page 74
3.4 $PV$ Diagram......Page 76
3.5 Hydrostatic Work Depends on the Path......Page 77
3.6 Calculation of $\int P dV$ for Quasi-Static Processes......Page 79
3.8 Work in Changing the Area of a Surface Film......Page 81
3.9 Work in Moving Charge with an Electrochemical Cell......Page 82
3.10 Work in Changing the Total Polarization of a Dielectric Solid......Page 84
3.11 Work in Changing the Total Magnetization of a Paramagnetic Solid......Page 85
3.13 Composite Systems......Page 88
4.1 Work and Heat......Page 94
4.2 Adiabatic Work......Page 96
4.3 Internal-Energy Function......Page 99
4.4 Mathematical Formulation of the First Law......Page 100
4.5 Concept of Heat......Page 102
4.6 Differential Form of the First Law......Page 103
4.7 Heat Capacity and its Measurement......Page 105
4.8 Specific Heat of Water; the Calorie......Page 109
4.9 Equations for a Hydrostatic System......Page 110
4.10 Quasi-Static Flow of Heat; Heat Reservoir......Page 111
4.11 Heat Conduction......Page 112
4.12 Thermal Conductivity and its Measurement......Page 113
4.13 Heat Convection......Page 115
4.14 Thermal Radiation; Blackbody......Page 116
4.15 Kirchhoff's Law; Radiated Heat......Page 119
4.16 Stefan-Boltzmann Law......Page 121
5.1 Equation of State of a Gas......Page 128
5.2 Internal Energy of a Real Gas......Page 130
5.3 Ideal Gas......Page 134
5.4 Experimental Determination of Heat Capacities......Page 136
5.5 Quasi-Static Adiabatic Process......Page 138
5.6 Ruchhardt's Method of Measuring $\gamma$......Page 140
5.7 Velocity of a Longitudinal Wave......Page 143
5.8 The Microscopic Point of View......Page 148
5.9 Kinetic Theory of the Ideal Gas......Page 149
6.1 Conversion of Work into Heat and Vice Versa......Page 162
6.2 The Gasoline Engine......Page 164
6.3 The Diesel Engine......Page 168
6.4 The Steam Engine......Page 170
6.5 The Stirling Engine......Page 172
6.6 Heat Engine; Kelvin-Planck Statement of the Second Law......Page 175
6.7 Refrigerator; Clausius' Statement of the Second Law......Page 176
6.8 Equivalence of the Kelvin-Planck and Clausius Statements......Page 178
6.9 Reversibility and Irreversibility......Page 180
6.10 External Mechanical Irreversibility......Page 181
6.12 External and Internal Thermal Irreversibility......Page 183
6.13 Chemical Irreversibility......Page 184
6.14 Conditions for Reversibility......Page 185
7.1 Carnot Cycle......Page 190
7.2 Examples of Carnot Cycles......Page 192
7.3 Carnot Refrigerator......Page 195
7.4 Carnot's Theorem and Corollary......Page 196
7.5 The Thermodynamic Temperature Scale......Page 198
7.7 Equality of Ideal-Gas and Thermodynamic Temperatures......Page 202
8.1 Reversible Part of the Second Law......Page 208
8.2 Entropy......Page 211
8.3 Principle of Caratheodory......Page 214
8.4 Entropy of the Ideal Gas......Page 216
8.5 $TS$ Diagram......Page 218
8.6 Entropy and Reversibility......Page 220
8.7 Entropy and Irreversibility......Page 221
8.8 Irreversible Part of the Second Law......Page 226
8.9 Heat and Entropy in Irreversible Processes......Page 228
8.10 Entropy and Nonequilibrium States......Page 230
8.11 Principle of Increase of Entropy......Page 232
8.12 Application of the Entropy Principle......Page 235
8.13 Entropy and Disorder......Page 236
8.14 Exact Differentials......Page 239
9.1 $PV$ Diagram for a Pure Substance......Page 244
9.2 $PT$ Diagram for a Pure Substance; Phase Diagram......Page 248
9.3 $PVT$ Surface......Page 250
9.4 Equations of State......Page 254
9.5 Molar Heat Capacity at Constant Pressure......Page 255
9.6 Volume Expansivity; Cubic Expansion Coefficient......Page 258
9.7 Compressibility......Page 261
9.8 Molar Heat Capacity at Constant Volume......Page 265
9.9 $TS$ Diagram for a Pure Substance......Page 266
10.1 Characteristic Functions......Page 271
10.2 Enthalpy......Page 274
10.3 Helmholtz and Gibbs Functions......Page 280
10.4 Two Mathematical Theorems......Page 282
10.5 Maxwell's Relations......Page 283
10.6 $T dS$ Equations......Page 285
10.7 Internal-Energy Equations......Page 289
10.8 Heat-Capacity Equations......Page 291
11.1 Joule-Thomson Expansion......Page 299
11.2 Liquefaction of Gases by the Joule-Thomson Expansion......Page 302
11.3 First-Order Phase Transitions; Clausius-Clapeyron Equation......Page 308
11.4 Clausius-Clapeyron Equation and Phase Diagrams......Page 311
11.5 Clausius-Clapeyron Equation and the Carnot Engine......Page 314
11.6 Chemical Potential......Page 315
11.7 Open Hydrostatic Systems in Thermodynamic Equilibrium......Page 319
Part II Applications of Fundamental Concepts......Page 327
12.1 Fundamental Principles......Page 329
12.2 Equilibrium Distribution......Page 333
12.3 Significance of Lagrangian Multipliers $\lambda$ and $\beta$......Page 336
12.4 Partition Function for Canonical Ensemble......Page 339
12.5 Partition Function of an Ideal Monatomic Gas......Page 341
12.6 Equipartition of Energy......Page 344
12.7 Distribution of Speeds in an Ideal Monatomic Gas......Page 346
12.8 Statistical Interpretation of Work and Heat......Page 350
12.9 Entropy and Information......Page 352
13.1 Statistical Mechanics of a Nonmetallic Crystal......Page 359
13.2 Frequency Spectrum of Crystals......Page 364
13.3 Thermal Properties of Nonmetals......Page 367
13.4 Thermal Properties of Metals......Page 370
14.1 Critical State......Page 381
14.2 Critical-Point Exponents of a Hydrostatic System......Page 385
14.3 Critical-Point Exponents of a Magnetic System......Page 390
14.4 Higher-Order Phase Transitions......Page 394
14.5 Lambda Transitions in $^4$He......Page 396
14.6 Liquid and Solid Helium......Page 400
15.1 Dalton's Law......Page 408
15.2 Semipermeable Membrane......Page 409
15.3 Gibbs' Theorem......Page 410
15.4 Entropy of a Mixture of Inert Ideal Gases......Page 412
15.5 Gibbs Function of a Mixture of Inert Ideal Gases......Page 414
15.6 Chemical Equilibrium......Page 415
15.7 Thermodynamic Description of Nonequilibrium States......Page 417
15.8 Conditions for Chemical Equilibrium......Page 419
15.9 Condition for Mechanical Stability......Page 420
15.10 Thermodynamic Equations for a Phase......Page 422
15.11 Chemical Potentials......Page 425
15.12 Degree of Reaction......Page 426
15.13 Equation of Reaction Equilibrium......Page 429
16.1 Law of Mass Action......Page 435
16.2 Experimental Determination of Equilibrium Constants......Page 436
16.3 Heat of Reaction......Page 439
16.4 Nernst's Equation......Page 442
16.5 Affinity......Page 445
16.6 Displacement of Equilibrium......Page 448
16.7 Heat Capacity of Reacting Gases in Equilibrium......Page 450
17.1 Thermodynamic Equations for a Heterogeneous System......Page 455
17.2 Phase Rule without Chemical Reaction......Page 457
17.3 Simple Applications of the Phase Rule......Page 461
17.4 Phase Rule with Chemical Reaction......Page 465
17.5 Determination of the Number of Components......Page 469
17.6 Displacement of Equilibrium......Page 472
A Physical Constants......Page 481
B Method of Lagrangian Multipliers......Page 482
C Evaluation of the Integral $\int\limits_0^\infty e^{-ax^2} dx$......Page 484
D Riemann Zeta Functions......Page 486
E Thermodynamic Definitions and Formulas......Page 488
Bibliography......Page 493
Answers to Selected Problems......Page 495
Index......Page 499
Back cover......Page 510