Elementary General Thermodynamics
| Date: 21 April 2011, 10:56
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CONTENTS
Symbols Used in This Book xvii
Section 1 Introduction
1 Introduction 2
2 Temperature and the zeroth law 3
Section 2 Energy Conservation: the First Law of Thermodynamics
1 Energy forms 8
2 Accumulated energy 8
3 Transitory energy forms 11
4 Graphical representation of work 17
5 Reversible work processes 18
6 Efficiency 19
7 Reversible expansion and compression 19
8 Equivalence of all energy forms 21
9 Equivalence of heat and work energy 21
10 Equivalence of mass and energy 23
11 System 23
12 Surroundings 25
13 First law or the conservation of energy 27
14 The sign convention 28
15 Accumulated internal energy and the thermodynamic state ... 29
16 U: a state property 30
17 Enthalpy 33
18 General procedure for analyzing problems 35
19 Specific heat 37
20 Phase change 41
21 Ideal gas 42
22 Reversible work: ideal-gas systems 44
23 Exact and inexact differentials; thermodynamic surfaces .... 50
24 Exact and inexact differentials: some mathematical characteristics . 53
25 Cyclical process 56
26 Steam: a nonideal gas 56
27 Application of the first law to irreversible processes: the free expansion
process 61
28 The infinitesimal free expansion process 62
29 Flow processes: open systems 63
30 Steady-flow processes 65
31 Frictionless, reversible steady-flow processes 66
32 Engineering applications 67
33 Nuclear energy 75
34 Thermochemistry 76
35 Standard enthalpies of formation 79
36 Standard enthalpy of combustion 86
37 Standard enthalpy change for any chemical reaction process at 25°C,
1 atm 91
38 Enthalpy of solution 95
39 Enthalpy of atomization 95
40 Enthalpy change of a chemical process at any temperature ... 96
41 Adiabatic chemical processes: flame temperatures 100
Section 3 Entropy and the Second Law of Thermodynamics
1 Work from heat 114
2 The second law of thermodynamics (and spontaneous change) . 114
3 Heat reservoirs 115
4 Reversibility 115
5 Characteristics of reversible and irreversible processes 116
6 Converting heat into work: noncyclical process 117
7 Converting heat into work: Carnot cycle 118
8 Thermal efficiency of a heat engine 121
9 Refrigeration cycle 121
10 Maximum thermal efficiency 123
11 Temperature and the efficiency of a reversible engine 125
12 The thermodynamic temperature scale . 126
13 Entropy 128
14 Entropy and integrating factors 131
15 Computing changes in entropy 132
16 Temperature-entropy diagram: Carnot cycle 136
17 Free expansion: entropy increase for an irreversible process . 137
18 Other irreversible processes 138
19 Entropy change during chemical reactions . 140
20 Entropy of phase change 141
21 Trouton's law 141
22 Third law of thermodynamics: absolute entropy 141
23 Absolute entropy and molecular structure 142
24 Work functions 142
25 Gibbs free energy 143
26 dG for any system 144
27 Applications of free-energy equations 145
28 Effect of total pressure on vapor pressure: the Poynting effect 149
29 The Helmholtz function 150
30 Equilibrium and spontaneous change 151
31 Work functions and equilibrium 154
32 Equilibrium criteria for systems that do work other than expansion
work 156
33 Carnot engine and the measurement of available work energy 157
34 Supplementary remarks on reversible work, energy and entropy
change, lost work, and the Clausius inequality 158
Section 4 Power and Refrigeration Cycles
1 Gasoline engines: the Otto cycle 168
2 The Diesel engine cycle 170
3 Steam engines: the Rankine cycle 171
4 Gas turbine: the Joule cycle 174
5 Refrigeration cycles 176
6 Properties of refrigerants 176
7 Vapor-compression cycle 177
8 Air conditioners and heat pumps 178
9 Absorption refrigeration 179
10 Steam jet refrigeration 181
11 Air liquefaction 181
Section 5 Statistical Thermodynamics
1 Connecting the microscopic and macroscopic 188
2 Allowed energies 188
3 Multiparticle quantum states 191
4 Additional hypothesis 195
5 Maximizing uncertainty 195
6 Partition functions 199
7 Changing 0 and \jj 200
8 The nature of 0 200
9 Negative temperatures 204
10 Probability and partition function for single-particle quantum states. 204
11 N-particle partition function from single-particle partition functions . 205
12 Reversible work 207
13 Work and heat 209
14 Entropy 210
15 The meaning of entropy 211
16 The Clausius inequality 211
17 Increase in entropy when heat is added to a system 212
18 Maxwell's distribution 213
19 Other distributions: open systems 215
20 The nature of a 217
21 Bose-Einstein and Fermi-Dirac distribution 219
22 Other approaches to statistical thermodynamics 220
23 Statement of basic problems 220
24 Ensemble of states 221
25 Ergodic hypothesis 222
26 Equal a priori probabilities 222
27 True ensemble average 223
^Lxiv Contents
28 Most likely condition 223
29 Mathematical necessity 225
30 Information-theory approach 226
Section 6 Relations Among Thermodynamic Properties
1 Combined first and second law 236
2 The state principle 237
3 Relations among thermodynamic properties 238
4 Differential property relationships 238
5 The Maxwell relations 239
6 The Clapeyron equation 242
7 Jacobians 244
8 Specific heats and expansion coefficients 245
9 Thermodynamic properties as functions of measurable properties 246
10 Evaluation of changes in thermodynamic properties 249
Section 7 Equations of State
1 Deviation from ideal-gas behavior; compressibility factor 256
2 Real gases 257
3 The van der Waals equation 258
4 Other two-constant equations of state 259
5 Benedict-Webb-Rubin equation 260
6 Virial equations of state 261
7 The generalized equation of state 261
8 Improved generalized correlation 263
9 Thermodynamic properties from equations of state 268
10 Effect of different equations of state on property computation 269
11 Departure functions 274
12 Generalized equation of state: departure functions 277
13 The need for experimental data 282
14 Presentation of thermodynamic data 283
15 Thermodynamic properties of liquids and solids 283
Section 8 Fugacity and Activity
1 Fugacity 294
2 Fugacities computed from the generalized equation of state . 295
3 Fugacity of liquids and solids 298
4 The effect of pressure on fugacity of liquids and solids .... 299
5 Activity 301
6 Activity of liquids and solids 302
7 General dependence of fugacity and activity on pressure and
temperature 303
^LContents xv
Section 9 Thermodynamics of Mixing and Composition Change
1 Ideal solutions y 308
2 Ideal solutions of ideal gases; Dalton's and Amagat's laws 309
3 Ideal solutions of liquids; Raoult's law 312
4 Entropy of mixing ideal solutions: statistical approach .314
5 Entropy of mixing ideal solutions: macroscopic approach . 316
6 Entropy, free energy, and Helmholtz function of mixing ideal gases 317
7 Free energy of mixing: ideal liquid solutions 319
8 Composition change and chemical work 322
9 Minimum work of separation 323
10 Ideal solutions of real materials 324
11 Compressibility and fugacity of real gas solutions: pseudocritical
properties 324
12 Ideal solution of real gases 325
13 Solutions of real liquids; Henry's law 326
14 Ideal solutions of real liquids 327
15 K factors; composition of vapor and liquid phases in equilibrium 327
16 Real liquid solutions: activity coefficients 328
17 Partial molar properties 329
18 Partial molar volume 332
19 Partial molar enthalpies of a nonideal binary solution 334
20 Graphical computation of partial molar properties 335
21 Energy-conservation equation for variable work systems 336
22 Differential relations in chemical work systems 337
23 Gibbs-Duhem equation 339
24 Equilibrium in multiphase systems: constancy of Mi 345
25 Phase rule 346
Section 10 Chemical Equilibrium
1 The chemical-equilibrium state 356
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