Chemical Equilibria E-Book

Michel Soustelle

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 216

Veröffentlichungsjahr: 2015

Beschreibung

The book offers advanced students, in 7 volumes, successively characterization tools phases, the study of all types of phase, liquid, gas and solid, pure or multi-component, process engineering, chemical and electrochemical equilibria, the properties of surfaces and phases of small sizes. Macroscopic and microscopic models are in turn covered with a constant correlation between the two scales. Particular attention was given to the rigor of mathematical developments.

Besides some very specialized books, the vast majority of existing works are intended for beginners and therefore limited in scope. There is no obvious connection between the two categories of books, general books does not go far enough in generalizing concepts to enable easy reading of advanced literature. The proposed project aims to give readers the ability to read highly specialized publications based on a more general presentation of the different fields of chemical thermodynamics. Consistency is ensured between the basic concepts and applications. So we find, in the same work, the tools, their use and comparison, for a more general macroscopic description and a microscopic description of a phase.

Leseprobe

Table of Contents

Cover

Title

Copyright

Preface

Notations and Symbols

1: Physico-Chemical Transformations and Equilibria

1.1. Characteristic parameters of physico-chemical transformations

1.2. Entropy production during the course of a transformation in a closed system

1.3. Affinity of a transformation

1.4. De Donder’s inequality – direction of the transformations and equilibrium conditions

1.5. Heats of transformation

1.6. Set of points representing the equilibrium states of a transformation

1.7. Closed systems accommodating multiple reactions

1.8. Direction of evolution and equilibrium conditions in an open system

1.9. Azeotropic transformations

2: Properties of States of Physico-Chemical Equilibrium

2.1. Laws of displacement of an equilibrium

2.2. Properties of all the equilibria in a system

2.3. Phase laws

2.4. Indifferent states

2.5. Thermodynamically-equivalent systems

2.6. Stability of equilibria

3: Molecular Chemical Equilibria

3.1. Law of mass action – equilibrium constants

3.2. Graphical representations of equilibria – pole diagrams

3.3. Representation of the evolution of an equilibrium with the temperature

3.4. Binary diagrams for chemical equilibrium

3.5. Ternary diagrams of chemical equilibria

3.6. Quaternary diagrams of chemical equilibria

4: Determination of the Values Associated with Reactions – Equilibrium Calculations

4.1. Reminders of a few thermodynamic relations

4.2. Enthalpies of reaction – thermochemistry

4.3. Reaction entropies

4.4. Specific heat capacities

4.5. Experimental determination of the equilibrium constants

4.6. Calculation of the equilibrium constants on the basis of other thermodynamic data

4.7. Determination of the equilibrium constants on the basis of spectral data and statistical thermodynamics

4.8. Thermodynamic tables and databanks

4.9. Estimation of thermodynamic data

4.10. Thermodynamic calculations for complex systems

APPENDICES

Appendix 1: Recap on the Reference States of Solutions

A1.1. Concentration and molar fraction

A1.2. Chemical potentials and activity coefficients

A1.3. Characterization of the imperfection of a real solution by the excess Gibbs energy

Appendix 2: Recap of statistical thermodynamics

A2.1. The three branches of statistics

A2.2. Partition functions of a molecule object

A2.3. Canonical partition function

A2.4. Canonical partition functions and thermodynamic functions

A2.5. Equilibrium constants and molecular partition functions

Bibliography

Index

End User License Agreement

Guide

Cover

Table of Contents

Begin Reading

List of Illustrations

3: Molecular Chemical Equilibria

Figure 3.1

Isothermal of pressure to composition for dissolution of hydrogen in palladium. Curves calculated by Larcher; [FOW 49]

Figure 3.2

Pole diagram of a reaction

Figure 3.3

Influence of temperature with conservation of the same pole

Figure 3.4

Influence of temperature on the pole diagram in the case of changing poles

Figure 3.5

Representation of the evolution of an equilibrium with temperature as a van ’t Hoff diagram

Figure 3.6

a) Generalized Ellingham diagram; b) Ellingham diagram for the CO

2

+C=2CO equilibrium

Figure 3.7

Ellingham diagram and oxygen pressure at equilibrium

Figure 3.8

Consequences of state changes of a component on an Ellingham diagram

Figure 3.9

a) Possibilities of reactions between metal–oxide couples; b) case where the Ellingham lines intersect one another

Figure 3.10

Diagrams of the stability of iron oxides

Figure 3.11

Reduction of zinc oxide by the CO/CO

2

mixture

Figure 3.12

Ellingham diagrams for the oxidations by gaseous oxygen (www.google.com/patents/EP1218556B1?cl=fr,2004)

Figure 3.13

Boudouard diagram for a total pressure of 1 atmosphere

Figure 3.14

Ternary representation of a chemical equilibrium between three gases or three components of a solution

Figure 3.15

Iso-Q curves: a) in the case of three reagents; b) in the case of two reagents and an inert component [SOU 68]

Figure 3.16

Plot of the iso-composition line and the equilibrium point [SOU 68]

Figure 3.17

Square diagram for chemical equilibrium between four gases [SOU 68]

4: Determination of the Values Associated with Reactions – Equilibrium Calculations

Figure 4.1.

Energy of a bond as a function of the inter-atomic distance

Figure 4.2.

Limit of a spectral series

Figure 4.3.

Drop calorimeter

Figure 4.4.

Differential scanning calorimetry

List of Tables

1: Physico-Chemical Transformations and Equilibria

Table 1.1.

Symbolic representation of the phases of components in balance equations

3: Molecular Chemical Equilibria

Table 3.1.

Meaning of each of the corners of the square diagram

4: Determination of the Values Associated with Reactions – Equilibrium Calculations

Table 4.1.

Enthalpy values of combustion in kJ/mol at 25°C. Data from the National Bureau of Standards

Table 4.2.

Comparison of the energies of dissociation of thermal origin and spectral origin for halogens (in kJ/mol) [EMS 51]

Table 4.3.

A few values of bond energies (kJ.mol

−1

)

Table 4.4.

Comparisons of the standard entropies of reactions at 25°C

, Δ

r

S

0

298

(in Jmol

−1

.deg

−1

), measured on the basis of the equilibrium constants, by calorimetry [EMS 51]

Table 4.5.

Calorimetric and spectral values of the entropies at 298K for certain substances (expressed in J.mol

−1

.deg

−1

), and zero entropies, found experimentally and calculated [EMS 51]

Table 4.6.

Examples of contributions of substitutions of a methyl group with one hydrogen on the methane and cyclopentane bases

Table 4.7.

Characterized carbon atoms

Table 4.8.

Thermodynamic data on the base groups in the group-substitution evaluation method

Pages

cover

contents

iii

iv

xi

xii

xiii

xv

xvi

xvii

xviii

xix

xx

xxi

xxii

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

18

19

20

21

22

23

24

25

26

27

28

29

30

31

32

33

34

35

36

37

38

39

40

41

42

43

44

45

46

47

48

49

50

51

52

53

55

56

57

58

59

60

61

62

63

64

65

66

67

68

69

70

71

72

73

74

75

76

77

78

79

80

81

82

83

84

85

86

87

88

89

90

91

92

93

94

95

96

97

98

99

100

101

102

103

104

105

106

107

108

109

110

111

112

113

114

115

116

117

118

119

120

121

122

123

124

125

126

127

128

129

130

131

132

133

134

135

136

137

138

139

140

141

142

143

144

145

146

147

148

149

150

151

153

154

155

156

157

158

159

160

161

162

163

164

165

166

167

168

169

170

171

172

173

174

175

176

177

178

179

181

182

183

185

186

Chemical Thermodynamics Set

coordinated byMichel Soustelle

Volume 4

Chemical Equilibria

Michel Soustelle

First published 2015 in Great Britain and the United States by ISTE Ltd and John Wiley & Sons, Inc.

Apart from any fair dealing for the purposes of research or private study, or criticism or review, as permitted under the Copyright, Designs and Patents Act 1988, this publication may only be reproduced, stored or transmitted, in any form or by any means, with the prior permission in writing of the publishers, or in the case of reprographic reproduction in accordance with the terms and licenses issued by the CLA. Enquiries concerning reproduction outside these terms should be sent to the publishers at the undermentioned address:

ISTE Ltd27-37 St George’s RoadLondon SW19 4EUUK

www.iste.co.uk

John Wiley & Sons, Inc.111 River StreetHoboken, NJ 07030USA

www.wiley.com

© ISTE Ltd 2015

The rights of Michel Soustelle to be identified as the author of this work have been asserted by him in accordance with the Copyright, Designs and Patents Act 1988.

Library of Congress Control Number: 2015951442

British Library Cataloguing-in-Publication DataA CIP record for this book is available from the British LibraryISBN 978-1-84821-867-3

Preface

This book – an in-depth examination of chemical thermodynamics – is written for an audience of engineering undergraduates and Masters students in the disciplines of chemistry, physical chemistry, process engineering, materials, etc., and doctoral candidates in those disciplines. It will also be useful for researchers at fundamental- or applied-research labs dealing with issues in thermodynamics during the course of their work.

These audiences will, during their undergraduate degree, have received a grounding in general thermodynamics and chemical thermodynamics, which all science students are normally taught, and will therefore be familiar with the fundamentals, such as the principles and the basic functions of thermodynamics, and the handling of phase and chemical equilibrium states, essentially in an ideal medium, usually for fluid phases, in the absence of electrical fields and independently of any surface effects.