THE PRINCIPLES OF CHEMICAL EQUILIBRIUM FOURTH EDITIONPDF电子书下载

PART Ⅰ：THE PRINCIPLES OF THERMODYNAMICS 3

Chapter 1： First and Second Laws 3

1.1 Introduction 3

1.2 Thermodynamic systems 5

1.3 Thermodynamic variables 6

1.4 Temperature and the zeroth law 9

1.5 Work 14

1.6 Internal energy and the first law 15

1.7 Heat 18

1.8 Expression of the first law for an infinitesimal process 19

1.9 Adiabatically impossible processes 21

1.10 Natural and reversible processes 23

1.11 Systematic treatment of the second law 25

1.12 Final statement of the second law 39

1.13 A criterion of equilibrium.Reversible processes 40

1.14 Maximum work 43

1.15 The fundamental equation for a closed system 45

1.16 Summary of the basic laws 46

1.17 Natural processes as mixing processes 48

1.18 The molecular interpretation of the second law 56

Problems 60

Chapter 2：Auxiliary Functions and Conditions of Equilibrium 63

2.1 The functions H， A and G 63

2.2 Properties of the enthalpy 63

2.3 Properties of the Helmholtz free energy 66

2.4 Properties of the Gibbs function 67

2.5a Availability 70

2.5b Digression on the useful work of chemical reaction 72

2.6 The fundamental equations for a closed system in terms of H，A and G 76

2.7 The chemical potential 76

2.8 Criteria of equilibrium in terms of extensive properties 82

2.9 Criteria of equilibrium in terms of intensive properties 85

2.10 Mathematical relations between the various functions of state 89

2.11 Measurable quantities in thermodynamics 94

2.12 Calculation of changes in the thermodynamic functions over ranges of temperature and pressure 98

2.13 Molar and partial molar quantities 99

2.14 Calculation of partial molar quantities from experimental data 104

Problems 106

PART Ⅱ： REACTION AND PHASE EQUILIBRIA 111

Chapter 3： Thermodynamics of Gases 111

3.1 Models 111

3.2 The single perfect gas 111

3.3 The perfect gas mixture 114

3.4 Imperfect gases 119

3.5 The Joule-Thomson effect 120

3.6 The fugacity of a single imperfect gas 122

3.7 Fugacities in an imperfect gas mixture 125

3.8 Temperature coefficient of the fugacity and standard chemical potential 127

3.9 Ideal gaseous solutions and the Lewis and Randall rule 128

Problems 130

Chapter 4： Equilibria of Reactions Involving Gases 133

4.1 Introduction 133

4.2 The stoichiometry of chemical reaction 133

4.3 Preliminary discussion on reaction equilibrium 135

4.4 Concise discussion on reaction equilibrium 139

4.5 The equilibrium constant for a gas reaction 140

4.6 The temperature dependence of the equilibrium constant 143

4.7 Other forms of equilibrium constant for perfect gas mixtures 146

4.8 Free energies and enthalpies of formation from the elements 148

4.9 Some examples 149

4.10 Free energies of formation of non-gaseous substances or from non-gaseous elements 153

4.11 Preliminary discussion on reaction equilibria involving gases together with immiscible liquids and solids 156

4.12 Concise discussion on reaction equilibria involving gases together with immiscible liquids and solids 159

4.13 Example on the roasting of galena 161

4.14 Measurement of the free energy of reaction by use of galvanic cells 163

4.15 Alternative discussion of the galvanic cell 167

4.16 Number of independent reactions 169

4.17 Conditions of equilibrium for several independent reactions 172

4.18 General remarks on simultaneous reactions 173

4.19 General remarks on maximum attainable yield 175

problems 177

Chapter 5：Phase Rule 182

5.1 Introduction 182

5.2 The phase rule for non-reactive components 184

5.3 The phase rule for reactive components 187

5.4 Additional restrictions 188

5.5 Example of the application of the phase rule 188

5.6 Alternative approach 191

5.7 Two examples from the zinc smelting industry 191

Problems 194

Chapter 6：Phase Equilibria in Single Component Systems 196

6.1 Introduction 196

6.2 The Clausius-Clapeyron equation 197

6.3 The enthalpy of vaporization and its temperature coefficient 200

6.4 Integration of the Clausius-Clapeyron equation 202

6.5 The effect of a second gas on the vapour pressure of a liquid or solid 203

6.6 Lambda transitions 207

Problems 213

Chapter 7：General Properties of Solutions and the Gibbs-Duhem Equation 215

7.1 The Gibbs-Duhem equation 215

7.2 Pressure-temperature relations 216

7.3 Partial pressure-composition relations 221

7.4 The empirical partial pressure curves of binary solutions 222

7.5 Application of the Gibbs-Duhem equation to the partial pressure curves 232

7.6 Application of the Gibbs-Duhem equation to the total pressure curve 235

7.7 The Gibbs-Duhem equation in relation to Raoult’s and Henry’s laws 236

7.8 The Gibbs-Duhem equation in relation to the Margules and van Laar equations 240

Problems 242

Chapter 8：Ideal Solutions 244

8.1 Molecular aspects of solutions 244

8.2 Definition of the ideal solution 249

8.3 Raoult’s and Henry’s laws 249

8.4 Imperfect vapour phase 252

8.5 The mixing properties of ideal solutions 252

8.6 The dependence of vapour-solution equilibria on temperature and pressure 255

8.7 Nernst’s law 256

8.8 Equilibrium between an ideal solution and a pure crystalline component 257

8.9 Depression of the freezing-point 260

8.10 Elevation of the boiling-point 261

8.11 The osmotic pressure of an ideal solution 262

8.12 The ideal solubility of gases in liquids 264

8.13 The ideal solubility of solids in liquids 266

Problems 267

Chapter 9：Non-Ideal Solutions 270

9.1 Conventions for the activity coefficient on the mole fraction scale 270

9.2 The activity coefficient in relation to Raoult’s and Henry’s laws 271

9.3 The use of molality and concentration scales 274

9.4 Convention for the activity-coefficient on the molality scale 276

9.5 The effect of temperature and pressure 278

9.6 The determination of activity coefiicients 281

9.7 The Gibbs-Duhem equation applied to activity coefficients 284

9.8 The calculation of the activity coefficient of the solute 284

9.9 Excess functions of non-ideal solutions 285

9.10 The activity 287

9.11 The osmotic coefficient 288

Problems 288

Chapter 10： Reaction Equilibrium in Solution.Electrolytes 292

10.1 Reaction equilibrium in solution 292

10.2 Free energy of formation in solution.Convention concerning hydrates 295

10.3 Equilibrium constants expressed on the molality and volume concentration scales 298

10.4 Temperature and pressure dependence of the equilibrium constant 299

10.5 Ratio of an equilibrium constant in the gas phase and in solution 301

10.6 Notation for electrolytes 302

10.7 Lack of significance of certain quantities 303

10.8 Dissociation equilibrium and the chemical potential of the electrolyte 304

10.9 Activity coefficients 305

10.10 Phase equilibrium of an electrolyte.Solubility product 307

10.11 Equilibrium constant for ionic reactions 309

10.12 Magnitude of activity coefficients of charged and uncharged species 310

10.13 Free energy of dissociation 312

10.14 The hydrogen ion convention and the free energies and enthalpies of formation of individual ions 314

10.15 Activity coefficients and free energies as measured by the use of the galvanic cell 316

10.16 Activity coefficients by use of the Gibbs-Duhem equation 322

10.17 Partial pressure of a volatile electrolyte 324

10.18 Limiting behaviour at high dilution 325

Problems 327

PART Ⅲ：THERMODYNAMICS IN RELATION TO THE EXISTENCE OF MOLECULES 333

Chapter 11： Statistical Analogues of Entropy and Free Energy 333

11.1 Thermodynamics and molecular reality 333

11.2 The quantum states of macroscopic systems 333

11.3 Quantum states， energy states and thermodynamic states 334

11.4 Fluctuations 335

11.5 Averaging and the statistical postulate 336

11.6 Accessibility 337

11.7 The equilibrium state 338

11.8 Statistical methods 339

11.9 The ensemble and the averaging process 340

11.10 Statistical analogues of the entropy and Helmholtz free energy 345

11.11 Comparison of statistical analogues with thermodynamic functions 350

11.12 Thermal and configurational entropy 353

11.13 Appendix Ⅰ.Origin of the canonical distribution 356

11.14 Appendix Ⅱ.Entropy analogues 359

Problem 360

Chapter 12： Partition Function of a Perfect Gas 361

12.1 Distinguishable states of a gas and the molecular partition function 361

12.2 Schrodinger’s equation 365

12.3 Separability of the wave equation 367

12.4 Factorization of the molecular partition function 371

12.5 The translational partition function 372

12.6 The internal partition function 376

12.7 Thermodynamic properties of the perfect gas 377

12.8 The Maxwell-Boltzmann distribution 383

12.9 Distribution over translational and internal states 386

12.10 Number of translational sates of a given energy 387

12.11 The Maxwell velocity distribution 390

12.12 Principle of equipartition 392

12.13 Appendix.Some definite integrals 394

Problems 396

Chapter 13： Perfect Crystals and the Third Law 397

13.1 Normal co-ordinates 397

13.2 The Schrodinger equation for the crystal 400

13.3 The energy levels of the harmonic oscillator 401

13.4 The partition function 402

13.5 The Maxwell-Boltzmann distribution 405

13.6 The high temperature approximation 406

13.7 The Einstein approximation 408

13.8 The Debye approximation 409

13.9 Comparison with experiment 411

13.10 Vapour pressure at high temperature 414

13.11 The third law—preliminary 416

13.12 Statement of the third law 421

13.13 Tests and applications of the third law 424

Problems 427

Chapter 14：Configurational Energy and Entropy 429

14.1 Introduction 429

14.2 Example 1：the lattice model of mixtures 432

14.3 Example 2：the Langmuir isotherm 436

Chapter 15：Chemical Equilibrium in Relation to Chemical Kinetics 439

15.1 Introduction 439

15.2 Kinetic species 440

15.3 Variables determining reaction rate 441

15.4 Forward and backward processes 442

15.5 Thermodynamic restrictions on the form of the kinetic equations 444

15.6 The temperature coefficient in relation to thermodynamic quantities 449

15.7 Transition-state theory 450

15.8 The equilibrium assumption 453

15.9 The reaction rate 455

Appendix.Answers to Problems and Comments 460

Index 487