The book is primarily aimed at students in higher education specialising in chemistry, particularly future engineers. The author has avoided unnecessary abstraction and overly complex mathematics to ensure the material remains practical and accessible, while still providing a solid theoretical foundation. The content includes approximate laws that allow for quick, practical problem-solving, even when precise values are unavailable. The author integrates empirical thermodynamics with the periodic table to make thermodynamic concepts more comprehensible, particularly entropy, which students often find difficult to grasp.

The book also addresses the importance of connecting thermodynamics with other branches of chemistry, such as general and inorganic chemistry, to enhance students’ understanding for later courses. The primary focus is on the thermodynamics of gaseous systems, with less emphasis on solutions and electrolytes. Numerous examples, mainly related to inorganic substances and chemical processing, help students apply theory to practical problems, with calculations that can be compared to experimental data. The book also includes many tables and figures derived from various sources to support these applications.

Translated from the Russian by G. Leib

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Contents

List of Tables 11
Preface 13
Chapter 1. INTRODUCTION 15
1.1. The Subject and Method of Thermodynamics 15
1.2. Basic Concepts and Definitions 17
1.2.1. Systems and Their Classification 17
1.2.2. Thermodynamic Parameters 18
1.2.3. Work and Heat 22
1.2.4. Reversible and Irreversible Processes 23
1.2.5. Mathematical Relations Between the Parameters of State 28
1.3. Terms and Symbols 33
Chapter 2. THE FIRST LAW OF THERMODYNAMICS 35
2.1. Content of the First Law 35
2.1.1. Cyclic Processes 35
2.1.2. Non-Cyclic Processes. Internal Energy 36
2.2. Enthalpy 41
Chapter 3. HEAT EFFECTS AND HEAT CAPACITIES 45
3.1. Hess’s Law 45
3.2. Standard Heat Effects 49
3.3. Some Methods of Calculating Heat Effects 53
3.3.1. Heats of Formation 53
3.3.2. Heats of Combustion 57
3.3.3. Comparative Calculation of Heat Effects 58
3.4. Heat Capacity 58
3.4.1. Heat Capacity in Different Processes 58
3.4.2. Temperature Dependence of Heat Capacity 61
3.4.3. Certain Laws 71
3.5. Temperature Dependence of Heat Effect 73
3.5.1. Kirchhoff Equation 73
3.5.2. Equation AH = <p(T) in Its Final Form 77
3.5.3. Heat Balance 84
Chapter 4. THE SECOND LAW OF THERMODYNAMICS 87
4.1. Content of the Second Law 87
4.1.1. The Carnot Cycle 87
4.1.2. Thermodynamic Temperature Scale 91
4.1.3. Impossibility of a Perpetual Motion Machine 92
4.2. Entropy 94
4.2.1. Change in Entropy in Reversible Processes 95
4.2.2. Change in Entropy in Irreversible Processes 97
4.2.3. Change in Entropy as a Criterion of the Equilibrium and Spontaneity of Processes 98
4.2.4. Relation Between Entropy and Other Thermodynamic Parameters and Some Relationships Between Derived Functions 102
4.3. Substantiation of the Second Law 106
4.3.1. Thermodynamic Probability of a State 106
4.3.2. Phase Space 106
4.3.3. Relationship Between Entropy and Thermodynamic Probability 108
4.3.4. Fluctuations 110
4.3.5. The Invalidity of the “Theory of Heat Death” of the Universe 112
Chapter 5. THERMODYNAMIC AND CHEMICAL POTENTIALS. THE GENERAL CONDITIONS OF EQUILIBRIUM 114
5.1. Thermodynamic Potentials 114
5.1.1. Change in Thermodynamic Potential as a Criterion of the Equilibrium and Spontaneous Nature of a Process 119
5.1.2. Various Thermodynamic Relationships 121
5.2. Characteristic Functions 123
5.3. Chemical Potential 128
5.4. General Conditions of Equilibrium 131
5.4.1. Stable and Unstable Equilibria 132
5.4.2. Equilibrium Coexistence of Phases. The Gibbs Phase Rule 134
5.4.3. Principle of Displacement of Equilibrium 139
Chapter 6. ONE-COMPONENT HOMOGENEOUS SYSTEMS 141
6.1. Ideal Gas 141
6.2. Equations of State of a Real Gas 150
6.3. Fugacity 159
6.3.1. Standard State 160
6.3.2. Temperature Dependence of Fugacity 162
6.3.3. Methods of Calculating Fugacity 163
6.4. Throttling 168
6.5. Calculation of Properties of Gases According to Experimental Data 175
6.5.1. Calculations Using the Relationships p-V-T and Cp = q>(T) 175
6.5.2. Calculations Using the Relationships Cp = <p(p, T) or H = q(p, T) and VT> = 9 (p) 184
6.5.3. Calculations Using (ij and C9 185
6.5.4. Influence of Pressure on the Heat Effect of a Reaction 185
6.6. A Generalized Method of Calculating Selected Properties of Gases and Liquids at Pressures above Atmospheric 186
6.6.1. Gases 186
6.6.2. Liquids 199
Chapter 7. ONE-COMPONENT HETEROGENEOUS SYSTEMS 205
7.1. Relationship Between Temperature and Pressure with Coexisting Phases 205
7.1.1. Clapeyron-Clausius Equation 205
7.1.2. Approximate Relationships 209
7.2. Methods for the Comparative Calculation of the Temperature Dependence of the Saturated Vapour Pressure 214
7.2.1. Straight Line Method 215
7.2.2. Method of Comparing Boiling Points of Given and Standard Substances at Equal Vapour Pressures 216
7.2.3. Method of Comparing Vapour Pressures of Various Substances at Equal Boiling Points 218
7.2.4. Method of Comparing Vapour Pressures of Various Substances at Equal Reduced Boiling Points 220
7.3. Critical State 221
7.4. Heat Capacities of Coexisting Phases and Heats of Phase Transitions 227
7.4.1. Heat Capacities of Coexisting Phases 227
7.4.2. Heats of Phase Transitions 232
7.5. Influence of Total Pressure on Saturated Vapour Pressure 244
7.6. Influence of Surface Curvature on Saturated Vapour Pressure 247
7.7. Second-Order Phase Transitions 249
Chapter 8. SOLUTIONS 251
8.1. Fundamental Concepts and Definitions 251
8.2. Partial Molar Quantities 255
8.2.1. Basic Equations 257
8.2.2. Methods of Calculation 260
8.3. Heat Capacities and Enthalpies of Solutions 264
8.3.1. Partial Molar Heat Capacities 264
8.3.2. Partial Molar Enthalpies 265
8.4. Ideal Solutions 272
8.5. Infinitely Dilute Solutions 278
8.5.1. Partial Molar Quantities 279
8.5.2. Henry’s Law 281
Chapter 9. BINARY SOLUTION-PURE COMPONENT EQUILIBRIUM 285
9.1. Relationship Between Temperature and Concentration 285
9.1.1. Solution-Solid Component Equilibrium 287
9.1.2. Analysis of Solubility Diagrams 292
9.1.3. Solution-Gas Equilibrium 304
9.2. Relationship Between Pressure and Concentration 305
9.2.1. Solution-Solid Component Equilibrium 306
9.2.2. Solution-Gas Equilibrium 307
9.3. Gas Mixture-Pure Component Equilibrium 317
9.4. Influence of Dispersion on Solubility 318
Chapter 10. SOLUTION-SOLUTION EQUILIBRIUM IN BINARY MIXTURES 319
10.1. Liquid-Gas Equilibrium for Completely Miscible Liquids at Low Pressures 319
10.1.1. Ideal Solution-Mixture of Ideal Gases 319
10.1.2. Non-Ideal Solution-Mixture of Ideal Gases 322
10.1.3. Separation of Solution Components 332
10.2. Liquid-Gas Equilibrium for Completely Miscible Liquids at High Pressures 334
10.2.1. Critical Phenomena 341
10.3. Equilibrium in Systems with Incompletely Miscible Liquids 349
10.3.1. Liquid-Gas Equilibrium 349
10.3.2. Liquid-Liquid Equilibrium 351
10.3.3. Gas-Gas Equilibrium 352
10.4. Liquid-Gas Equilibrium for Immiscible Liquids 355
Chapter 11. EQUILIBRIUM IN THREE- AND FOUR-COMPONENT SYSTEMS 359
11.1. Depicting Composition 359
11.1.1. Three-Component Systems 359
11.1.2. Four-Component Systems 361
11.2. Liquid-Solid Equilibrium in Three-Component Systems 362
11.2.1. Substances Forming No Compounds 362
11.2.2. Substances Forming Compounds 366
11.2.3. Isotherms of Aqueous Solutions of Two Common-Ion Salts 367
11.3. Mutual Solubility of Three Liquids 385
11.4. Liquid-Gas Equilibrium in Ternary Systems 391
11.4.1. Isotherm 391
11.4.2. Is

obaric Systems 399
Chapter 12. THE PRINCIPLE OF MAXIMUM ENTROPY 405
12.1. Entropy as a Thermodynamic Function 405
12.2. Method of Maximum Entropy 410
12.3. Application of the Maximum Entropy Principle in Thermodynamics 414
Chapter 13. MODERN CONCEPTS OF THERMODYNAMICS 419
13.1. Thermodynamic Models 419
13.2. Relations with Other Areas of Science 421
13.3. Role of Thermodynamics in Physical Chemistry 424
13.4. Applications of Thermodynamics in Industry 427
13.5. Advanced Topics in Thermodynamics 430

Chapter 14. EQUILIBRIUM TRANSFORMATION 518

14.1. Direction of a Process 518

14.2. Calculation of Equilibrium Transformation 527

14.2.1. Reactions in the Gaseous Phase 528

14.2.2. Reactions in Solutions 531

14.2.3. Heterogeneous Reactions 533

14.2.4. Electrochemical Reactions 537

14.3. Influence of Various Factors on the Extent of a Reaction 541

14.3.1. Temperature 541

14.3.2. Pressure 545

14.3.3. Presence of an Inert Gas 548

14.3.4. Ratio of Reactants 549

14.3.5. Change in Surface Area 550

14.3.6. Kind of Reaction 552

14.4. Equilibrium in Complex Chemical Systems 553

14.5. Sources of Errors in Calculating Equilibrium 562

14.5.1. Errors Due to Inaccuracy of Experimental Data 562

14.5.2. Errors Connected with the Processing of Experimental Data 564

14.6. Theoretical and Practical Extents of a Reaction 566

Chapter 15. FUNDAMENTALS OF QUANTUM STATISTICAL CALCULATIONS OF THERMODYNAMIC FUNCTIONS AND CHEMICAL EQUILIBRIUM FROM SPECTROSCOPIC DATA 568

15.1. Introduction 568

15.2. Thermodynamic Properties of Gases Due to Translational Degrees of Freedom 572

15.3. Thermodynamic Properties of Gases Due to Intramolecular Degrees of Freedom 575

15.3.1. Rotational Partition Function 577

15.3.2. Vibrational Partition Function 583

15.3.3. Partition Function for Electronic Excitation 587

15.3.4. Nuclear Spin 588

15.3.5. Effect of Isotopic Composition 589

15.3.6. Group of Properties 589

15.4. Calculation of Chemical Equilibrium 592

APPENDICES 599

List of Symbols 599

Heat Capacities, Standard Enthalpies and Gibbs Energies of