Principles of Thermodynamics

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CRC Press, Aug 27, 2002 - Science - 408 pages
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Ideal for one- or two-semester courses that assume elementary knowledge of calculus, This text presents the fundamental concepts of thermodynamics and applies these to problems dealing with properties of materials, phase transformations, chemical reactions, solutions and surfaces. The author utilizes principles of statistical mechanics to illustrate key concepts from a microscopic perspective, as well as develop equations of kinetic theory. The book provides end-of-chapter question and problem sets, some using MathcadTM and MathematicaTM; a useful glossary containing important symbols, definitions, and units; and appendices covering multivariable calculus and valuable numerical methods.
 

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Contents

Introduction and Background
1
11 Introduction
2
12 The Ideal Gas
4
13 Thermal Expansion Coefficient and Isothermal Compressibility
6
14 A Simple Model of the Ideal Gas
8
The van der Waals Equation
12
Other Equations
15
17 Condensation and the Critical Point
19
76 Direction of Chemical Reactions 77 Concentration Dependence of Free Energy
192
78 Equilibrium Constants
193
The Gibbs Phase Rule
196
710 Concentrations at Equilibrium
199
711 Temperature Dependence of the Equilibrium Constant
204
712 Equilibrium Constant in Terms of Partition Function
206
Questions
207
Problems
209

18 Gas Mixtures
24
19 Equations of State of Condensed Phases
26
110 Pressure Variations in Fluids
30
Questions
31
Problems
32
Notes
34
Thermodynamics The Zeroth and First Laws
36
21 The Nature of Thermodynamics
37
23 Equilibrium
38
24 Properties
39
25 Processes 26 Heat and the Zeroth Law of Thermodynamics
40
27 Work
43
28 Internal Energy 29 The First Law
49
210 Heat Capacities
51
211 The Joule Process
58
212 The JouleThomson Process
59
213 Reversible Adiabatic Expansion of an Ideal Gas
62
214 A Simple Heat Engine
64
Questions
67
Problems
69
Notes
70
The Second Law of Thermodynamics 31 The Second Law
71
32 Entropy Changes in Some Simple Processes
79
33 Heat Diagrams
84
34 General Analysis of Thermal Devices
85
Questions
88
Problems
90
Notes
92
The Third Law and Free Energies
93
41 Absolute Zero and the Third Law of Thermodynamics
94
42 Absolute Entropies
97
43 Helmholtz and Gibbs Free Energies
98
44 Partial Derivatives of Energylike Quantities
101
45 Heat Capacities 46 Generalization to Additional Displacements
106
47 Standard States
107
48 Entropy of Mixing of Ideal Gases
109
49 Thermodynamics of Stretching Rubbers
110
Questions
112
Problems
114
Notes
116
Statistical Mechanics
117
51 The Microscopic World
118
52 The Joule Process
119
53 Distribution Among Energy States
124
54 Thermodynamic Functions from the Partition Function
128
55 System Partition Functions
130
56 Velocity Distributions
132
57 A SteadyState Example
135
58 Thermodynamic Functions of the Monatomic Ideal Gas
136
59 Energy of Polyatomic Ideal Gases
138
510 Configurations of a Polymer Chain
141
511 Theory of Ideal Rubber Elasticity
144
Questions Problems
146
Notes
148
Phase Transformations in Single Component Systems
150
61 Thermodynamics of Open Systems
151
62 Entropy Change for Open Systems
153
63 Phases and Phase Transformations
154
64 General Criterion for Equilibrium in a Multiphase System
155
65 Phase Equilibrium Conditions
161
66 Vapor Pressure When a Gas Is Not Ideal
164
67 Equation of State for the TwoPhase Region
166
68 Effect of Inert Gas on Phase Equilibria
168
69 CondensedPhase Equilibria
169
610 Equilibrium Between Three Phases
170
611 Phase Diagrams
171
612 Mesomorphic Phases
173
Questions
175
Problems
176
Notes
178
Chemical Reactions
179
71 Nomenclature
180
72 Thermochemistry
181
73 Calorimetry
185
74 Estimating the Thermodynamics of Reactions
187
75 Chemical Equilibrium
190
Notes
211
Ideal Solutions
212
81 Measures of Concentration
213
82 Partial Molar Quantities
214
83 Measurement of Partial Molar Quantities
217
84 The Ideal Solution
220
85 The Ideally Dilute Solution
222
86 FreezingPoint Depression BoilingPoint Elevation and Osmotic Pressure
226
87 Distribution of a Solute Between Two Solvents
231
88 Phase Diagram of a Binary Ideal Solution
232
Questions
240
Problems
242
Notes
244
Nonideal Solutions 91 Activity Coefficients
245
92 Excess Thermodynamic Functions
248
93 Determining Activity Coefficients
249
94 Equilibrium Constants
257
95 Phase Diagrams of Binary Nonideal Systems
258
96 Phase Diagrams of Ternary Systems
266
Questions
269
Problems
270
Notes
272
Ionized Systems
273
101 Ionic Solutions
274
102 Mean Ionic Activity Coefficients
275
103 Mean Ionic Activity Coefficients from Experimental Data
276
104 Calculation of Mean Ionic Activity Coefficient
277
105 Ionic Equilibrium
282
106 Ion Pairs and Ion Solvation
284
107 Electrochemical Systems
286
108 Types of Electrodes
288
109 Electrochemical Cells
291
1010 Thermodynamics of Electrochemical Cells
293
1011 Standard Electrode Potentials
296
1012 Applications of Electrochemical Cells
300
Questions
303
Problems
304
Notes
306
Surfaces
308
111 The Surface Region 112 The Surface of the SingleComponent Condensed Phase
309
113 Surface Tension of Single Components
311
114 Processes Involving One Interface
313
115 Processes Involving More Than One Interface
316
116 Thermodynamics of Immersion 117 Effect of Surface Curvature on Vapor Pressure
320
118 Thermodynamics of Solution Surfaces
322
119 Properties of Surface Films
325
1110 Adsorption on Solids
328
1111 Statistical Mechanics of Adsorption
334
1112 Colloids
337
Questions
340
Problems
341
Notes
342
SteadyState Systems
343
121 SteadyState Systems 122 Conservative and Nonconservative Properties
344
123 Entropy Generation in Some Simple Processes in SteadyState Systems
346
124 The Phenomenological Equations Relating Flows and Forces
353
125 Fluxes Produced by Nonconjugate Forces
356
126 Thermal Diffusion
357
127 Thermoelectric Effects
360
Questions
361
Problems
362
Notes
363
Multivariable Calculus A1 Differentials
365
A2 Integrals
368
A3 Second Derivatives
369
Problems
370
Note
371
Numerical Methods B1 Solving Equations
372
B2 Fitting Data
374
B3 Numerical Integration
375
Problems
376
Table of Thermodynamic Data
377
Glossary of Symbols
381
Index
387
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