The present textbook is a study aid to the course in chemical thermodynamics.

The examples and problems contained in it cover the most essential and characteristic sections of the course, which should assist students in mastering the elementary methods of both general thermodynamic calculations and special calculations connected with separate processes of chemical technology.

The topics of the examples and problems mainly reflect questions concerning the technology of inorganic production processes and the chemical processing and refining of fuel. In this connection, the main attention has been devoted to gaseous systems.

Each chapter of the book begins with a brief theoretical introduction containing the equations and formulas needed for calculations. This is followed by examples with detailed solutions and problems.

The examples contain all the data necessary for calculations and can be used for independent solution. In compiling the book, the author tried to avoid identical examples and problems (using the same formulas and quantities, but describing different objects).

For a greater approximation to practical calculations, the book acquaints students with approximate methods of computation, graphical methods of calculation, and with some semi-empirical and empirical laws. The results of the calculations, when possible, are compared with experimental data or with calculations by other methods, which makes it possible to assess the accuracy of different methods and the limits of their application.

A considerable part of the examples and problems have been drawn up according to the published works of Soviet investigators. The experimental data are also taken from reference books and monographs. Some problems have been taken from different textbooks.

Translated from the Russian by G. Leib

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Preface 5
List of Symbols 9
Chapter One. The First Law of Thermodynamics 11
Chapter Two. Heats, Heat Capacity and Enthalpy 19
2.1. Hess’s Law 19
2.2. Thermochemical Laws 26
2.3. Heat Capacity and Enthalpy 31
2.4. Theoretical Temperature of Combustion 45
2.5. Influence of Temperature on Heat Reaction 49
Chapter Three. The Second Law of Thermodynamics 58
3.1. Entropy 58
3.2. Thermodynamic Potentials 76
Chapter Four. Real Gases 82
4.1. Pressure-Volume-Temperature-Composition Relationships 82
4.2. Fugacity 94
4.3. Heat Capacity 100
4.4. Enthalpy 104
4.5. Joule-Thomson Effect 109
Chapter Five. One-Component Heterogeneous Systems 114
5.1. Clapeyron-Clausius Equation 114
5.2. Methods for Comparative Calculation of the Temperature Dependence of Saturated Vapour Pressure 127
5.3. Critical Parameters 132
5.4. Heat Capacities of Coexisting Phases and Heats of Phase Transitions 137
Chapter Six. Generalized Methods of Calculation 145
6.1. Gases 145
6.2. Liquid-Vapour Equilibrium 156
Chapter Seven. Solubility 160
7.1. Influence of Temperature 160
7.2. Influence of Pressure 173
7.3. Mutual Solubility of Liquids 183
Chapter Eight. Vapour Pressure of Solutions 191
8.1. Completely Miscible Liquids 191
8.2. Incompletely Miscible and Immiscible Liquids 200
Chapter Nine. Equilibrium Constant and Change in Standard Gibbs Energy 209
9.1. Calculation of K and AG° According to Equilibrium Data 209
9.2. Calculation of K and AG° According to Thermal Data 225
Chapter Ten. Equilibrium Transition 243
10.1. Calculation of Equilibrium Transition 243
10.2. Influence of Various Factors on the Extent of a Reaction 252
10.3. Calculating the Equilibrium of Complex Processes 261
Answers to Problems 271
Chapter One 271
Chapter Two 271
Chapter Three 273
Chapter Four 275
Chapter Five 276
Chapter Six 279
Chapter Seven 280
Chapter Eight 282
Chapter Nine 283
Chapter Ten 285
Appendices 288