Basic chemical thermodynamics / E. Brian Smith.

Format:

Book

Author/Creator:

Smith, E. Brian (Eric Brian), 1933-

Language:

English

Subjects (All):

Thermodynamics.

Physical Description:

xiii unnumbered pages, 166 pages : illustrations ; 24 cm

Edition:

Fifth edition.

Place of Publication:

London : Imperial College Press, 2004.

Contents:

1.1 The scope and nature of chemical thermodynamics 1

1.2 Equilibrium in mechanical systems 2

1.3 Reversibility and equilibrium 4

1.4 Why we need thermodynamics 6

1.5 The mole 8

1.6 The perfect gas 9

2 Energy 10

2.1 Work 10

2.2 Heat and temperature 12

2.3 Measurement of temperature 12

2.4 Heat and molecular motion 13

2.5 Conservation of energy 14

2.6 State functions: a digression 16

2.7 Enthalpy 18

2.8 Heat capacity 19

3 Entropy and equilibrium 21

3.1 Reversibility and equilibrium: a recapitulation 21

3.2 Condition of equilibrium 21

3.3 Entropy 23

3.4 Entropy as a state function 25

3.5 Entropy of expansion of a gas 26

3.6 Entropy changes accompanying heat flow 27

3.7 Entropy and equilibrium 27

3.8 A cosmological aside 28

3.9 Entropy as a function of pressure and temperature 28

3.10 Molecular basis of entropy 30

3.11 Statistical basis of the Second Law 32

3.12 Magnitudes of entropy changes 32

3.13 Heat engines 33

4 Equilibrium in chemical systems 36

4.1 Free energy 36

4.2 Gibbs free energy 37

4.3 Pressure-dependence of free energy 40

4.4 Temperature variation of free energy 41

4.5 Phase equilibria 42

4.6 Clapeyron equation 44

4.7 Clausius-Clapeyron equation 45

4.8 The vapour pressure of liquids 46

4.9 Chemical potential 48

4.10 Chemical potential and free energy 49

4.11 Equilibrium between gaseous reactants 51

4.12 Temperature-dependence of equilibrium constants 55

4.13 Effect of pressure on equilibrium constants 57

4.14 Basic results of chemical thermodynamics 59

4.15 Le Chatelier's Principle 61

5 Determination of thermodynamic quantities 63

5.1 Hess's Law 63

5.2 Standard enthalpies of formation 64

5.3 Average bond energies 65

5.4 Temperature dependence of enthalpy changes 66

5.5 Standard free energies of formation 67

5.6 Determination of free-energy changes 68

5.7 Determination of entropies of substances 69

5.8 Example of the determination of thermodynamic quantities 70

5.9 Calculation of thermodynamic quantities at temperatures other than 298 K 76

5.10 Ellingham diagrams 77

5.11 Free-energy functions 79

6 Ideal solutions 82

6.1 The ideal solution 82

6.2 Properties of truly ideal solutions 85

6.3 Mixtures of liquids 86

6.4 Ideal solutions of solids in liquids 88

6.5 Ideal dilute solutions 90

6.6 Colligative properties 91

6.7 Freezing-point depression 92

6.8 Elevation of boiling point 96

6.9 Osmotic pressure 99

6.10 Properties of the solute in dilute solutions 100

6.11 Solubility of solids 102

7 Non-ideal solutions 104

7.1 The concept of activity 104

7.2 Activity of solids in liquids 106

7.3 Activity in aqueous solutions 107

7.4 Chemical equilibria in solution 110

7.5 Electrochemical cells 112

7.6 Standard electrode potentials 115

8 Thermodynamics of gases 120

8.1 Expansion of a perfect gas 120

8.2 Irreversible expansion 121

8.3 Equation of state of gases 123

8.4 Joule-Thomson experiment 125

8.5 Imperfect gases: fugacity 126

8.6 Calculation of fugacities 128

9 Molecular basis of thermodynamics 130

9.1 Energy levels 130

9.2 Microstates 133

9.3 The Boltzmann factor 134

9.4 Behaviour of heat capacity 137

9.5 Partition functions 140

9.6 Entropy and the partition function 141

9.7 Calculation of the translational partition function 145

9.8 The rotational partition function 147

9.9 Vibrational partition function 148

9.10 Evaluation of the properties of gaseous nitrogen 149

9.11 Chemical equilibrium 150

Appendix 1 Thermochemical data at 298.15 K 156

Appendix 2 Thermodynamic data for ions in aqueous solution at 298.15 K 159.

Notes:

Includes bibliographical references (page [160]) and index.

ISBN:

1860944450

1860944469

OCLC:

55692889