Chemical Thermodynamics: Principles and Applications (eBook)

Cover 1
Contents 6
Preface to the Two-Volume Series 16
Preface to the First Volume 22
Chapter 1. Introduction 26
1.1 Thermodynamics „ A Pre-eminent Example of an Exact Science 26
1.2 The Language of Thermodynamics 28
1.3 Thermodynamic Variables 33
1.4 The Mathematics of Thermodynamics 47
1.5 Derivation of Thermodynamic Equations using the Properties of the Exact Differential 53
1.6 Calculation of Changes in the Thermodynamic Variable 57
1.7 Use of Units 58
References 61
Chapter 2. The First and Second Laws of Thermodynamics 62
2.1 The First Law of Thermodynamics 62
2.2 The Second Law of Thermodynamics 81
2.3 Implications of the Laws 115
References 127
Chapter 3. Thermodynamic Relationships and Applications 130
3.1 The Gibbs Equations 131
3.2 Partial Differential Relationships 132
3.3 Applications of the Differential Relationships 143
3.4 Relationship Between Free Energy and Work 170
References 178
Chapter 4. The Third Law and Absolute Entropy Measurements 180
4.1 Verification of the Third Law 188
4.2 Exceptions to the Third Law 192
4.3 Implications and Applications of the Third Law 202
4.4 Production of Low Temperatures and the Inaccessibility of Absolute 209
4.5 Thermodynamic Functions 214
References 225
Chapter 5. The Chemical Potential and Equilibrium 228
5.1 Composition as a Variable 228
5.2 The Chemical Potential 229
5.3 Partial Molar Properties 233
5.4 The Gibbs–Duhem Equation 238
5.5 Determination of Partial Molar Properties 239
5.6 Criteria for Equilibrium 250
References 271
Chapter 6. Fugacity, Activity, and Standard States 272
6.1 Fugacity 272
6.2 The Activity 304
6.3 Standard States 307
6.4 Activities of Electrolyte Solutions 319
6.5 Determination of Activity 329
References 347
Chapter 7. The Thermodynamic Properties of Solutions 350
7.1 Change in the Thermodynamic Properties of Nonelectrolyte Solutions due to the Mixing Process 350
7.2 Calculation of the Thermodynamic Properties of Strong Electrolyte Solutes: The Debye – Hückel Theory 358
7.3 Relative Partial Molar and Apparent Relative Partial Molar Thermal Properties 375
7.4 The Osmotic Pressure 392
References 407
Chapter 8. The Equilibrium Condition Applied to Phase Equilibria 408
8.1 Phase Equilibria for Pure Substances 410
8.2 Phase Equilibria for Mixtures 430
References 458
Chapter 9. The Equilibrium Condition Applied to Chemical Processes 460
9.1 The Equilibrium Constant 460
9.2 Enthalpies and Gibbs Free Energies of Formation 473
9.3 Examples of Chemical Equilibrium Calculations 489
9.4 Electrochemical Cells 500
References 521
Chapter 10. Statistical Thermodynamics 522
10.1 Energy Levels of an Ideal Gas Molecule 522
10.2 Distribution of Energy Among Energy Levels 532
10.3 The Boltzmann Distribution Law 539
10.4 The Partition Function 548
10.5 Relationship Between the Partition Function and the Thermodynamic Properties 553
10.6 Evaluation of the Partition Function for the Ideal Gas 559
10.7 Calculation of the Thermodynamic Properties of the Ideal Gas 568
10.8 Calculation of the Thermodynamic Properties of Solids 594
References 617
Appendix 1. Mathematics for Thermodynamics 618
A l.1 Operations with Derivatives and Integrals 618
A 1.2 Total Differentials and Relationships Between Partial Derivatives 619
A1.3 Intensive and Extensive Variables 623
A 1.4 State Functions and Exact Differentials Inexact Differentials and Line Integrals
Al.5 Pfaffian Differentials 633
A1.6 Euler's Theorem 637
A1.7 Graphical Integrations 638
A.8 Stirling's Approximation 640
Appendix 2. The International Temperature Scale of 19901 642
A2.1 Fixed Points 644
A2.2 Choice of Thermometer 644
A2.3 The Deviation Function 647
A2.4 Measurement of Temperatures Above 1234.93 K 649
A2.5 Correction of Existing Data to ITS-90 649
Appendix 3. Equations of State for Gases 652
A3.1 The Ideal Gas 652
A3.2 The Virial Equation 652
A3.3 The Virial Equation Explicit in Pressure 654
A3.4 Other Equations of State 654
A3.5 Cubic Equations of State 656
Appendix 4. Calculations from Statistical Thermodynamics 664
Table A4.1 Thermodynamic Functions of an Ideal Gas 665
Table A4.2 Moments of Inertia and Rotational Constants of Some Common Molecules 667
Table A4.3 Fundamental Vibrational Frequencies of Some Common Molecules 669
Table A4.4 Electronic Energy Levels of some Common Molecules or Atoms With Unpaired Electrons 671
Table A4.5 Anharmonic Oscillator and Nonrigid Rotator Corrections 671
Table A4.6 Contributions to the Thermodynamic Properties Due to Internal Rotation 673
Table A4.7 The Debye Thermodynamic Functions Expressed in Terms of 0o/T 676
Index 680