THE PRINCIPLES OF CHEMICAL EQUILIBRIUM FOURTH EDITION【2025|PDF下载-Epub版本|mobi电子书|kindle百度云盘下载】

THE PRINCIPLES OF CHEMICAL EQUILIBRIUM FOURTH EDITIONPDF格式电子书版下载

注意：本站所有压缩包均有解压码： 点击下载压缩包解压工具

PART Ⅰ：THE PRINCIPLES OF THERMODYNAMICS3

Chapter 1： First and Second Laws3

1.1 Introduction3

1.2 Thermodynamic systems5

1.3 Thermodynamic variables6

1.4 Temperature and the zeroth law9

1.5 Work14

1.6 Internal energy and the first law15

1.7 Heat18

1.8 Expression of the first law for an infinitesimal process19

1.9 Adiabatically impossible processes21

1.10 Natural and reversible processes23

1.11 Systematic treatment of the second law25

1.12 Final statement of the second law39

1.13 A criterion of equilibrium.Reversible processes40

1.14 Maximum work43

1.15 The fundamental equation for a closed system45

1.16 Summary of the basic laws46

1.17 Natural processes as mixing processes48

1.18 The molecular interpretation of the second law56

Problems60

Chapter 2：Auxiliary Functions and Conditions of Equilibrium63

2.1 The functions H， A and G63

2.2 Properties of the enthalpy63

2.3 Properties of the Helmholtz free energy66

2.4 Properties of the Gibbs function67

2.5a Availability70

2.5b Digression on the useful work of chemical reaction72

2.6 The fundamental equations for a closed system in terms of H，A and G76

2.7 The chemical potential76

2.8 Criteria of equilibrium in terms of extensive properties82

2.9 Criteria of equilibrium in terms of intensive properties85

2.10 Mathematical relations between the various functions of state89

2.11 Measurable quantities in thermodynamics94

2.12 Calculation of changes in the thermodynamic functions over ranges of temperature and pressure98

2.13 Molar and partial molar quantities99

2.14 Calculation of partial molar quantities from experimental data104

Problems106

PART Ⅱ： REACTION AND PHASE EQUILIBRIA111

Chapter 3： Thermodynamics of Gases111

3.1 Models111

3.2 The single perfect gas111

3.3 The perfect gas mixture114

3.4 Imperfect gases119

3.5 The Joule-Thomson effect120

3.6 The fugacity of a single imperfect gas122

3.7 Fugacities in an imperfect gas mixture125

3.8 Temperature coefficient of the fugacity and standard chemical potential127

3.9 Ideal gaseous solutions and the Lewis and Randall rule128

Problems130

Chapter 4： Equilibria of Reactions Involving Gases133

4.1 Introduction133

4.2 The stoichiometry of chemical reaction133

4.3 Preliminary discussion on reaction equilibrium135

4.4 Concise discussion on reaction equilibrium139

4.5 The equilibrium constant for a gas reaction140

4.6 The temperature dependence of the equilibrium constant143

4.7 Other forms of equilibrium constant for perfect gas mixtures146

4.8 Free energies and enthalpies of formation from the elements148

4.9 Some examples149

4.10 Free energies of formation of non-gaseous substances or from non-gaseous elements153

4.11 Preliminary discussion on reaction equilibria involving gases together with immiscible liquids and solids156

4.12 Concise discussion on reaction equilibria involving gases together with immiscible liquids and solids159

4.13 Example on the roasting of galena161

4.14 Measurement of the free energy of reaction by use of galvanic cells163

4.15 Alternative discussion of the galvanic cell167

4.16 Number of independent reactions169

4.17 Conditions of equilibrium for several independent reactions172

4.18 General remarks on simultaneous reactions173

4.19 General remarks on maximum attainable yield175

problems177

Chapter 5：Phase Rule182

5.1 Introduction182

5.2 The phase rule for non-reactive components184

5.3 The phase rule for reactive components187

5.4 Additional restrictions188

5.5 Example of the application of the phase rule188

5.6 Alternative approach191

5.7 Two examples from the zinc smelting industry191

Problems194

Chapter 6：Phase Equilibria in Single Component Systems196

6.1 Introduction196

6.2 The Clausius-Clapeyron equation197

6.3 The enthalpy of vaporization and its temperature coefficient200

6.4 Integration of the Clausius-Clapeyron equation202

6.5 The effect of a second gas on the vapour pressure of a liquid or solid203

6.6 Lambda transitions207

Problems213

Chapter 7：General Properties of Solutions and the Gibbs-Duhem Equation215

7.1 The Gibbs-Duhem equation215

7.2 Pressure-temperature relations216

7.3 Partial pressure-composition relations221

7.4 The empirical partial pressure curves of binary solutions222

7.5 Application of the Gibbs-Duhem equation to the partial pressure curves232

7.6 Application of the Gibbs-Duhem equation to the total pressure curve235

7.7 The Gibbs-Duhem equation in relation to Raoult’s and Henry’s laws236

7.8 The Gibbs-Duhem equation in relation to the Margules and van Laar equations240

Problems242

Chapter 8：Ideal Solutions244

8.1 Molecular aspects of solutions244

8.2 Definition of the ideal solution249

8.3 Raoult’s and Henry’s laws249

8.4 Imperfect vapour phase252

8.5 The mixing properties of ideal solutions252

8.6 The dependence of vapour-solution equilibria on temperature and pressure255

8.7 Nernst’s law256

8.8 Equilibrium between an ideal solution and a pure crystalline component257

8.9 Depression of the freezing-point260

8.10 Elevation of the boiling-point261

8.11 The osmotic pressure of an ideal solution262

8.12 The ideal solubility of gases in liquids264

8.13 The ideal solubility of solids in liquids266

Problems267

Chapter 9：Non-Ideal Solutions270

9.1 Conventions for the activity coefficient on the mole fraction scale270

9.2 The activity coefficient in relation to Raoult’s and Henry’s laws271

9.3 The use of molality and concentration scales274

9.4 Convention for the activity-coefficient on the molality scale276

9.5 The effect of temperature and pressure278

9.6 The determination of activity coefiicients281

9.7 The Gibbs-Duhem equation applied to activity coefficients284

9.8 The calculation of the activity coefficient of the solute284

9.9 Excess functions of non-ideal solutions285

9.10 The activity287

9.11 The osmotic coefficient288

Problems288

Chapter 10： Reaction Equilibrium in Solution.Electrolytes292

10.1 Reaction equilibrium in solution292

10.2 Free energy of formation in solution.Convention concerning hydrates295

10.3 Equilibrium constants expressed on the molality and volume concentration scales298

10.4 Temperature and pressure dependence of the equilibrium constant299

10.5 Ratio of an equilibrium constant in the gas phase and in solution301

10.6 Notation for electrolytes302

10.7 Lack of significance of certain quantities303

10.8 Dissociation equilibrium and the chemical potential of the electrolyte304

10.9 Activity coefficients305

10.10 Phase equilibrium of an electrolyte.Solubility product307

10.11 Equilibrium constant for ionic reactions309

10.12 Magnitude of activity coefficients of charged and uncharged species310

10.13 Free energy of dissociation312

10.14 The hydrogen ion convention and the free energies and enthalpies of formation of individual ions314

10.15 Activity coefficients and free energies as measured by the use of the galvanic cell316

10.16 Activity coefficients by use of the Gibbs-Duhem equation322

10.17 Partial pressure of a volatile electrolyte324

10.18 Limiting behaviour at high dilution325

Problems327

PART Ⅲ：THERMODYNAMICS IN RELATION TO THE EXISTENCE OF MOLECULES333

Chapter 11： Statistical Analogues of Entropy and Free Energy333

11.1 Thermodynamics and molecular reality333

11.2 The quantum states of macroscopic systems333

11.3 Quantum states， energy states and thermodynamic states334

11.4 Fluctuations335

11.5 Averaging and the statistical postulate336

11.6 Accessibility337

11.7 The equilibrium state338

11.8 Statistical methods339

11.9 The ensemble and the averaging process340

11.10 Statistical analogues of the entropy and Helmholtz free energy345

11.11 Comparison of statistical analogues with thermodynamic functions350

11.12 Thermal and configurational entropy353

11.13 Appendix Ⅰ.Origin of the canonical distribution356

11.14 Appendix Ⅱ.Entropy analogues359

Problem360

Chapter 12： Partition Function of a Perfect Gas361

12.1 Distinguishable states of a gas and the molecular partition function361

12.2 Schrodinger’s equation365

12.3 Separability of the wave equation367

12.4 Factorization of the molecular partition function371

12.5 The translational partition function372

12.6 The internal partition function376

12.7 Thermodynamic properties of the perfect gas377

12.8 The Maxwell-Boltzmann distribution383

12.9 Distribution over translational and internal states386

12.10 Number of translational sates of a given energy387

12.11 The Maxwell velocity distribution390

12.12 Principle of equipartition392

12.13 Appendix.Some definite integrals394

Problems396

Chapter 13： Perfect Crystals and the Third Law397

13.1 Normal co-ordinates397

13.2 The Schrodinger equation for the crystal400

13.3 The energy levels of the harmonic oscillator401

13.4 The partition function402

13.5 The Maxwell-Boltzmann distribution405

13.6 The high temperature approximation406

13.7 The Einstein approximation408

13.8 The Debye approximation409

13.9 Comparison with experiment411

13.10 Vapour pressure at high temperature414

13.11 The third law—preliminary416

13.12 Statement of the third law421

13.13 Tests and applications of the third law424

Problems427

Chapter 14：Configurational Energy and Entropy429

14.1 Introduction429

14.2 Example 1：the lattice model of mixtures432

14.3 Example 2：the Langmuir isotherm436

Chapter 15：Chemical Equilibrium in Relation to Chemical Kinetics439

15.1 Introduction439

15.2 Kinetic species440

15.3 Variables determining reaction rate441

15.4 Forward and backward processes442

15.5 Thermodynamic restrictions on the form of the kinetic equations444

15.6 The temperature coefficient in relation to thermodynamic quantities449

15.7 Transition-state theory450

15.8 The equilibrium assumption453

15.9 The reaction rate455

Appendix.Answers to Problems and Comments460

Index487