Classical and Geometrical Theory of Chemical and Phase Thermodynamics2025|PDF|Epub|mobi|kindle电子书版本百度云盘下载

Classical and Geometrical Theory of Chemical and Phase ThermodynamicsPDF格式电子书版下载

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PART Ⅰ INDUCTIVE FOUNDATIONS OF CLASSICAL THERMODYNAMICS1

1.Mathematical Preliminaries：Functions and Differentials3

1.1 Physical Conception of Mathematical Functions and Differentials3

1.2 Four Useful Identities7

1.3 Exact and Inexact Differentials10

1.4 Taylor Series15

2.Thermodynamic Description of Simple Fluids17

2.1 The Logic of Thermodynamics17

2.2 Mechanical and Thermal Properties of Gases：Equations of State18

2.3 Thermometry and the Temperature Concept24

2.4 Real and Ideal Gases30

2.4.1 Compressibility Factor and Ideal Gas Deviations31

2.4.2 Van der Waals and Other Model Equations of State36

2.4.3 The Virial Equation of State44

2.5 Condensation and the Gas-Liquid Critical Point47

2.6 Van der Waals Model of Condensation and Critical Behavior50

2.7 The Principle of Corresponding States54

2.8 Newtonian Dynamics in the Absence of Frictional Forces56

2.9 Mechanical Energy and the Conservation Principle58

2.10 Fundamental Definitions：System，Property，Macroscopic，State60

2.10.1 System60

2.10.2 Property61

2.10.3 Macroscopic63

2.10.4 State64

2.11 The Nature of the Equilibrium Limit65

3.General Energy Concept and the First Law67

3.1 Historical Background of the First Law67

3.2 Reversible and Irreversible Work71

3.3 General Forms of Work76

3.3.1 Pressure-Volume Work76

3.3.2 Surface Tension Work78

3.3.3 Elastic Work79

3.3.4 Electrical（emf）Work80

3.3.5 Electric Polarization Work81

3.3.6 Magnetic Polarization Work83

3.3.7 Overview of General Work Forms84

3.4 Characterization and Measurement of Heat85

3.5 General Statements of the First Law87

3.6 Thermochemical Consequences of the First Law89

3.6.1 Heat Capacity and the Enthalpy Function89

3.6.2 Joule’s Experiment91

3.6.3 Joule-Thomson Porous Plug Experiment93

3.6.4 Ideal Gas Thermodynamics95

3.6.5 Thermochemistry：Enthalpies of Chemical Reactions101

3.6.6 Temperature Dependence of Reaction Enthalpies107

3.6.7 Heats of Solution108

3.6.8 Other Aspects of Enthalpy Decompositions112

4.Engine Efficiency，Entropy，and the Second Law117

4.1 Introduction：Heat Flow，Spontaneity，and Irreversibility117

4.2 Heat Engines：Conversion of Heat to Work122

4.3 Carnot’s Analysis of Optimal Heat-Engine Efficiency123

4.4 Theoretical Limits on Perpetual Motion：Kelvin’s and Clausius’Principles128

4.5 Kelvin’s Temperature Scale130

4.6 Carnot’s Theorem and the Entropy of Clausius134

4.7 Clausius’Formulation of the Second Law139

4.8 Summary of the Inductive Basis of Thermodynamics145

PART Ⅱ GIBBSIAN THERMODYNAMICS OF CHEMICAL AND PHASE EQUILIBRIA147

5.Analytical Criteria for Thermodynamic Equilibrium149

5.1 The Gibbs Perspective149

5.2 Analytical Formulation of the Gibbs Criterion for a System in Equilibrium152

5.3 Alternative Expressions of the Gibbs Criterion157

5.4 Duality of Fundamental Equations：Entropy Maximization versus Energy Minimization160

5.5 Other Thermodynamic Potentials：Gibbs and Helmholtz Free Energy162

5.6 Maxwell Relations164

5.7 Gibbs Free Energy Changes in Laboratory Conditions170

5.8 Post-Gibbsian Developments180

5.8.1 The Fugacity Concept181

5.8.2 The “Third Law” of Thermodynamics：A Critical Assessment183

6.Thermodynamics of Homogeneous Chemical Mixtures195

6.1 Chemical Potential in Multicomponent Systems195

6.2 Partial Molar Quantities197

6.3 The Gibbs-Duhem Equation201

6.4 Physical Nature of Chemical Potential in Ideal and Real Gas Mixtures204

7.Thermodynamics of Phase Equilibria209

7.1 The Gibbs Phase Rule211

7.2 Single-Component Systems216

7.2.1 The Phase Diagram of Water217

7.2.2 Clapeyron and Clausius-Clapeyron Equations for Phase Boundaries219

7.2.3 Illustrative Phase Diagrams for Pure Substances224

7.3 Binary Fluid Systems233

7.3.1 Vapor-Pressure（P-x）Diagrams：Raoult and Henry Limits237

7.3.2 The Lever Rule241

7.3.3 Positive and Negative Deviations243

7.3.4 Boiling-Point Diagrams：Theory of Distillation247

7.3.5 Immiscibility and Consolute Behavior250

7.3.6 Colligative Properties and Van’t Hoff Osmotic Equation253

7.3.7 Activity and Activity Coefficients260

7.4 Binary Solid-Liquid Equilibria263

7.4.1 Eutectic Behavior264

7.4.2 Congruent Melting265

7.4.3 Incongruent Melting and Peritectics266

7.4.4 Alloys and Partial Miscibility266

7.4.5 Phase Boundaries and Gibbs Free Energy of Mixing267

7.5 Ternary and Higher Systems273

8.Thermodynamics of Chemical Reaction Equilibria281

8.1 Analytical Formulation of Chemical Reactions in Terms of the Advancement Coordinate281

8.2 Criterion of Chemical Equilibrium：The Equilibrium Constant282

8.3 General Free Energy Changes：de Donder’s Affinity285

8.4 Standard Free Energy of Formation286

8.5 Temperature and Pressure Dependence of the Equilibrium Constant288

8.5.1 Temperature Dependence：Van’t Hoff Equation288

8.5.2 Pressure Dependence289

8.6 Le Chatelier’s Principle290

8.7 Thermodynamics of Electrochemical Cells292

8.8 Ion Activities in Electrolyte Solutions296

8.9 Concluding Synopsis of Gibbs’Theory305

PART Ⅲ METRIC GEOMETRY OF EQUILIBRIUM THERMODYNAMICS311

9.Introduction to Vector Geometry and Metric Spaces313

9.1 Vector and Matrix Algebra315

9.2 Dirac Notation323

9.3 Metric Spaces328

10.Metric Geometry of Thermodynamic Responses331

10.1 The Space of Thermodynamic Response Vectors331

10.2 The Metric of Thermodynamic Response Space333

10.3 Linear Dependence，Dimensionality，and Gibbs-Duhem Equations337

11.Geometrical Representation of Equilibrium Thermodynamics345

11.1 Thermodynamic Vectors and Geometry345

11.2 Conjugate Variables and Conjugate Vectors348

11.3 Metric of a Homogeneous Fluid353

11.4 General Transformation Theory in Thermodynamic Metric Space357

11.5 Saturation Properties Along the Vapor-Pressure Curve360

11.6 Self-Conjugate and Normal Response Modes363

11.7 Geometrical Characterization of Common Fluids366

11.8 Stability Conditions and the “Third Law” for Homogeneous Phases376

11.9 The Critical Instability Limit379

11.10 Critical Divergence and Exponents384

11.11 Phase Heterogeneity and Criticality386

12.Geometrical Evaluation of Thermodynamic Derivatives393

12.1 Thermodynamic Vectors and Derivatives394

12.2 General Solution for Two Degrees of Freedom and Relationship to Jacobian Methods401

12.3 General Partial Derivatives in Higher-Dimensional Systems405

12.4 Phase-Boundary Derivatives in Multicomponent Systems408

12.5 Stationary Points of Phase Diagrams：Gibbs-Konowalow Laws414

12.6 Higher-Order Derivatives and State Changes417

13.Further Aspects of Thermodynamic Geometry421

13.1 Reversible Changes of State：Riemannian Geometry424

13.2 Near-Equilibrium Irreversible Thermodynamics：Diffusional Geometry429

13.3 Quantum Statistical Thermodynamic Origins of Chemical and Phase Thermodynamics439

13.3.1 Nonequilibrium Displacement Variables of Mayer and Co-workers442

13.3.2 Quantum Statistical Thermodynamics and the Statistical Origins of Metric Geometry445

13.3.3 Evaluation of Molecular Partition Functions for Reactive Mixtures452

13.3.4 Quantum Cluster Equilibrium Theory of Phase Thermodynamics455

Appendix：Units and Conversion Factors465

AUTHOR INDEX469

SUBJECT INDEX473