Thermodynamics: Principles Characterizing Physical and Chemical Processes
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Table of contents
- Prefacev
- Preface to the Second Editionvii
- Preface to the First Editionix
- Contentsxi
- Chapter 1. Fundamentals1
- 1.0 Introductory Remarks1
- 1.1 Introductory Definitions2
- 1.2 The Zeroth Law of Thermodynamics5
- 1.3 Mathematical Apparatus9
- 1.4 Thermodynamic Forces18
- 1.5 Elements of Work19
- 1.6 The Element of Work for a System Subjected to Electromagnetic Fields29
- 1.7 The First Law of Thermodynamics31
- 1.8 The First Law of Thermodynamics as a Parable37
- 1.9 The Second Law of Thermodynamics38
- 1.10 Cyclic processes in relation to reversibility and irreversibility42
- 1.11 An Entropy Analogy47
- 1.12 Constraints, Equilibrium, Functions of State48
- 1.13 Systematics of Thermodynamic Functions of State58
- 1.14 Interrelations Involving Heat Capacities73
- 1.15 The Joule-Thomson Experiment75
- 1.16 Heat Measurements and Calorimetry80
- 1.17 Determination of Enthalpies and Entropies of Materials82
- 1.18 The Third Law of Thermodynamics86
- 1.19 The Gibbs-Duhem Relation and Its Analogs88
- 1.20 Thermodynamics of Open Systems93
- 1.21 Effect of Chemical Changes on Composition103
- 1.22 Legendre Transforms and Stability of a System106
- Chapter 2. Equilibrium in Ideal Systems111
- 2.0 Thermodynamics of Ideal Systems with Several Components and Phases111
- 2.1 Coexistence of Phases: The Gibbs Phase Rule111
- 2.2 Achievement of Equilibrium114
- 2.3 System of one component and several phases120
- 2.4 Properties of Ideal Gases126
- 2.5 Properties of Ideal Solutions in Condensed Phases130
- 2.6 The Duhem-Margules Equation and its Consequences136
- 2.7 Temperature Dependence of Composition of Solutions138
- 2.8 Lowering of the freezing point and elevation of the boiling point139
- 2.9 Chemical Equilibrium: General Principles and Application to Ideal Gases143
- 2.10 Chemical Equilibrium in Homogeneous Condensed Ideal Solutions150
- 2.11 Chemical Equilibrium in Ideal Heterogeneous Systems153
- 2.12 Equilibrium Between Two Ideal Phases156
- 2.13 Chemical Irreversibility in Chemical Reactions; The Affinity156
- Chapter 3. Characterization of Nonideal Solutions159
- 3.0 Introductory Remarks159
- 3.1 Thermodynamic Treatment of Nonideal Gas Mixtures159
- 3.2 Temperature and Pressure Dependence of the Fugacity of a Gas162
- 3.3 Thermodynamic Description of Real Solutions in the Condensed State163
- 3.4 Characterization of Nonideal Solutions; Preliminaries165
- 3.5 Standardization of Thermodynamic Analysis for Nonideal Solutions170
- 3.6 Reformulation of the Thermodynamic Description of Nonideal Solutions176
- 3.7 Characterization of Equilibrium in Nonideal Solutions178
- 3.8 Variation of Activity, Activity Coefficients with Temperature and Presssure188
- 3.9 Calorimetric Functions of State in Chemical Processes189
- 3.10 Equilibrium Calculations197
- 3.11 Determination of Activity Coefficients201
- 3.12 Oxidation Boundary for Magnetite-Zinc Ferrite Solid Solutions208
- 3.13 Activity of Solvent and Solute210
- 3.14 Mixing in Nonideal Solutions214
- 3.15 Phase Stability: General Consequences of Deviations from Ideality224
- 3.16 Discussion of Several Types of Phase Diagrams230
- 3.17 Variation of Mutual Solubility with Temperature239
- Chapter 4. Thermodynamic Properties of Electrolytes249
- 4.0 Introductory Comments249
- 4.1 Activities of Strong Electrolytes249
- 4.2 Theoretical Determination of Activities in Electrolyte Solutions256
- 4.3 Experimental Determination of Activities and Activity Coefficients258
- 4.4 Equilibrium Properties of Weak Electrolytes261
- 4.5 Galvanic Cells267
- 4.6 Operation of Galvanic Cells269
- 4.7 Galvanic Cells; Operational Analysis272
- 4.8 Liquid Junction Potentials278
- 4.9 EMF Dependence on Activities279
- 4.10 Types of Operating Cells282
- 4.11 Thermodynamic Information from Galvanic Cell Measurements284
- Chapter 5. Thermodynamic Properties of Materials in Externally Applied Fields287
- 5.0 Introductory Comments287
- 5.1 Thermodynamics of Gravitational Fields287
- 5.2 Thermodynamics of Adsorption Processes294
- 5.3 Heats of Adsorption303
- 5.4 Surface vs. Bulk Effects; Thermodynamics of Self-Assembly310
- 5.5 Pressure of Electromagnetic Radiation320
- 5.6 Thermodynamic Characterization of Electromagnetic Radiation323
- 5.7 Effects of Electric Fields on Thermodynamic Properties of Matter327
- 5.8 Systematization of Electromagnetic Field Effects in Thermodynamics333
- 5.9 Adiabatic Demagnetization and Transitions to Superconductivity343
- Chapter 6. Irreversible Thermodynamics347
- 6.0 Introductory Comments347
- 6.1 Generalities347
- 6.2 Shock Phenomena357
- 6.3 Linear Phenomenological Equations364
- 6.4 Steady State Conditions and Prigogine's Theorem366
- 6.5 Onsager Reciprocity Conditions367
- 6.6 Thermomolecular Mechanical Effects369
- 6.7 Electrokinetic Phenomena372
- 6.8 The Soret Effect377
- 6.9 Thermoelectric Effects379
- 6.10 Irreversible Thermomagnetic Phenomena in Two Dimensions383
- 6.11 Chemical Processes389
- 6.12 Coupled Reactions: Special Example392
- 6.13 Coupled Reactions, General Case394
- Chapter 7. Critical Phenomena397
- 7.0 Introductory Remarks397
- 7.1 Properties of Materials Near Their Critical Point397
- 7.2 Homogeneity Requirements, Correlation Lengths, Scaling Properties404
- 7.3 Derivation of Griffith's and Rushbrooke's Inequality407
- 7.4 Scaled Equation of State415
- 7.5 Landau Theory of Critical Phenomena and Phase Transitions415
- Chapter 8. A Final Speculation About Ultimate Temperatures-A Fourth Law of Thermodynamics?425
- Chapter 9. Mathematical Proof of the Carathéodory Theorem and Resulting Interpretations; Derivation427
- 9.1 Fundamentals427
- 9.2 Proof of Holonomicity429
- 9.3 Necessary Condition for Establishing the Carathéodory Theorem433
- 9.4 Relevance to Thermodynamics436
- 9.5 Derivation of the Limiting Form for the Debye-Hückel Equation437
- Index445
Thermodynamics is a self-contained analysis of physical and chemical processes, based on classical thermodynamic principles. Emphasis is placed on the fundamental principles, with a conbination of theory and practice, and demonstrating their application to a variety of disciplines.
Included in this work are new approaches to irreversible processes, electromagnetic effects, adsorption phenomena, self-assembly, the origin of phase diagrams, critical phenomena, and Carathéodory's treatment of the second law. This book will appeal to graduate students and professional chemists and physicists who wish to acquire a more sophisticated overview of thermodynamics and related subject matter.
· Easy-to-understand style appeals to both chemists and physicists
· Discusses treatment of electromagnetic phenomena and adsorption of surface gases surfaces
· Extensively revised to cater for advanced courses in thermodynamics
Included in this work are new approaches to irreversible processes, electromagnetic effects, adsorption phenomena, self-assembly, the origin of phase diagrams, critical phenomena, and Carathéodory's treatment of the second law. This book will appeal to graduate students and professional chemists and physicists who wish to acquire a more sophisticated overview of thermodynamics and related subject matter.
· Easy-to-understand style appeals to both chemists and physicists
· Discusses treatment of electromagnetic phenomena and adsorption of surface gases surfaces
· Extensively revised to cater for advanced courses in thermodynamics