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E-raamat: Chemical Thermodynamics: Theory and Applications [Taylor & Francis e-raamat]

  • Formaat: 320 pages, 34 Tables, black and white; 123 Illustrations, black and white
  • Ilmumisaeg: 07-Nov-2019
  • Kirjastus: CRC Press
  • ISBN-13: 9780429277252
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  • Taylor & Francis e-raamat
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Chemical Thermodynamics: Theory and ApplicationsSuurem pilt
  • Formaat: 320 pages, 34 Tables, black and white; 123 Illustrations, black and white
  • Ilmumisaeg: 07-Nov-2019
  • Kirjastus: CRC Press
  • ISBN-13: 9780429277252
Teised raamatud teemal:
Taylor & Francis e-raamatudRohkem infot Taylor & Francis e-raamatute kohta
Raamatu kodulehekülg: https://www.taylorfrancis.com/books/9780429277252
This book develops the theory of chemical thermodynamics from first principles, demonstrates its relevance across scientific and engineering disciplines, and shows how thermodynamics can be used as a practical tool for understanding natural phenomena and developing and improving technologies and products.

Concepts such as internal energy, enthalpy, entropy, and Gibbs energy are explained using ideas and experiences familiar to students, and realistic examples are given so the usefulness and pervasiveness of thermodynamics becomes apparent. The worked examples illustrate key ideas and demonstrate important types of calculations, and the problems at the end of chapters are designed to reinforce important concepts and show the broad range of applications. Most can be solved using digitized data from open access databases and a spreadsheet. Answers are provided for the numerical problems.



A particular theme of the book is the calculation of the equilibrium composition of systems, both reactive and non-reactive, and this includes the principles of Gibbs energy minimization. The overall approach leads to the intelligent use of thermodynamic software packages but, while these are discussed and their use demonstrated, they are not the focus of the book, the aim being to provide the necessary foundations. Another unique aspect is the inclusion of three applications chapters: heat and energy aspects of processing; the thermodynamics of metal production and recycling; and applications of electrochemistry.

This book is aimed primarily at students of chemistry, chemical engineering, applied science, materials science, and metallurgy, though it will be also useful for students undertaking courses in geology and environmental science.

A solutions manual is available for instructors.
Preface xiii
A note to students xv
Author xvii
Units xix
Nomenclature xxi
Constants xxiii
Chapter 1 An overview of thermodynamics
1(4)
Scope
1(1)
Learning objectives
1(1)
1.1 What is thermodynamics?
1(1)
1.2 A brief history
2(1)
1.3 The laws of thermodynamics
3(2)
Chapter 2 Fundamental concepts
5(20)
Scope
5(1)
Learning objectives
5(1)
2.1 Introduction
5(1)
2.2 Substances and the states of matter
5(3)
2.2.1 Amount of substance
7(1)
2.3 Systems
8(6)
2.3.1 Composition of systems
10(3)
2.3.2 Macroscopic and microscopic properties
13(1)
2.3.3 The concept of equilibrium
13(1)
2.4 Processes
14(2)
2.5 State functions and path functions
16(3)
Summary
17(1)
2.5.1 The standard state
18(1)
2.6 Energy, work, heat and temperature
19(3)
2.6.1 Energy and work
19(1)
2.6.2 Heat
20(1)
2.6.3 Temperature
20(2)
Problems
22(3)
Chapter 3 Gases
25(10)
Scope
25(1)
Learning objectives
25(1)
3.1 Introduction
25(1)
3.2 Gas pressure
25(1)
3.3 Ideal gases
26(3)
3.3.1 Avogadro's law and Avogadro's constant
26(1)
3.3.2 The combined gas law
27(1)
3.3.3 The ideal gas law
27(1)
3.3.4 Gas mixtures
28(1)
3.4 Real gases
29(4)
3.4.1 The p--V--T relationship
29(2)
3.4.2 Compressibility
31(1)
3.4.3 Equations of state for real gases
32(1)
Problems
33(2)
Chapter 4 The first law
35(24)
Scope
35(1)
Learning objectives
35(1)
4.1 Introduction
35(1)
4.2 The first law
35(5)
4.2.1 Internal energy
36(1)
4.2.2 Mathematical statement of the first law
37(3)
4.3 Enthalpy
40(1)
4.3.1 The nature of enthalpy
41(1)
4.4 The enthalpy of mixing
41(1)
4.5 The enthalpy of phase changes
42(1)
4.6 Heat capacity
43(2)
4.7 The enthalpy of substances
45(4)
4.7.1 Variation of enthalpy with temperature
46(1)
4.7.2 Enthalpy increments
47(2)
4.8 The enthalpy of formation
49(2)
4.9 The enthalpy of reaction
51(3)
4.10 Experimental determination of heat capacity and enthalpy
54(1)
Problems
55(4)
Chapter 5 Sources of thermodynamic data for substances
59(8)
Scope
59(1)
Learning objectives
59(1)
5.1 Introduction
59(1)
5.2 Compilations of thermodynamic data
59(4)
5.2.1 The reference state
60(1)
5.2.2 The NIST-JANAF, NBS and US Geological Survey tables
60(3)
5.2.3 The FREED software program
63(1)
5.2.4 Barin's thermochemical tables
63(1)
5.3 Thermochemical software programs
63(3)
Problems
66(1)
Chapter 6 Some applications of the first law
67(14)
Scope
67(1)
Learning objectives
67(1)
6.1 Introduction
67(1)
6.2 Heating and cooling of substances
68(2)
6.3 Energy balances
70(5)
6.4 Adiabatic temperature of reaction
75(2)
6.5 Heat utilisation in furnaces
77(1)
Problems
78(3)
Chapter 7 The second and third laws
81(22)
Scope
81(1)
Learning objectives
81(1)
7.1 Introduction
81(1)
7.2 Entropy and the second law
82(5)
7.2.1 The nature of entropy
82(2)
Summary
84(1)
7.2.2 Broad implications of the first and second laws
84(1)
7.2.3 Alternative statements of the second law
85(2)
7.3 The entropy of mixing
87(3)
7.3.1 The mixing of ideal gases
87(2)
7.3.2 The general equation for mixing
89(1)
7.4 The entropy of phase changes
90(2)
7.5 The third law and the entropy of substances
92(3)
7.6 The entropy of formation and entropy of reaction
95(3)
7.7 Entropy as a criterion of spontaneity
98(1)
7.8 Experimental determination of entropy
98(1)
Problems
98(5)
Chapter 8 Gibbs and Helmholtz energies
103(20)
Scope
103(1)
Learning objectives
103(1)
8.1 Introduction
103(1)
8.2 Combined statement of the first and second laws
104(1)
8.3 Helmholtz and Gibbs energies
105(3)
Summary
106(1)
8.3.1 The criteria for spontaneity
106(1)
8.3.2 The Gibbs-Helmholtz equation
107(1)
8.4 The Gibbs energy of phase changes
108(1)
8.5 The Gibbs energy of mixing
108(1)
8.6 The Gibbs energy of substances
109(2)
8.7 The Gibbs energy of formation
111(2)
8.8 The Gibbs energy of reaction
113(4)
8.9 The use of Gibbs energy to study reactions
117(3)
8.9.1 The importance of kinetics
119(1)
Summary
120(1)
8.10 Experimental determination of Gibbs energy
120(1)
Problems
120(3)
Chapter 9 Solutions
123(34)
Learning objectives
123(1)
9.1 Introduction
123(1)
9.2 Types of solutions
124(2)
9.2.1 Aqueous solutions
124(1)
9.2.2 Organic solutions
124(1)
9.2.3 Molten solutions
124(1)
9.2.4 Solid solutions
125(1)
9.3 Integral and partial quantities
126(6)
9.3.1 Relative partial and integral quantities
128(1)
9.3.2 Calculating partial quantities from integral quantities
129(2)
9.3.3 The Gibbs--Duhem equation
131(1)
9.4 Gas mixtures
132(6)
9.4.1 Ideal gas mixtures
132(4)
9.4.2 Non-ideal gas mixtures
136(2)
9.5 Liquid and solid solutions
138(10)
9.5.1 The concept of activity
139(2)
9.5.2 Pure substance standard state
141(1)
9.5.3 The infinitely dilute standard state
142(3)
9.5.4 Conversion between standard states
145(2)
9.5.5 The Gibbs--Duhem equation
147(1)
9.6 Properties of solutions
148(5)
9.6.1 Ideal solutions
149(2)
9.6.2 Non-ideal solutions
151(1)
9.6.3 Excess molar quantities
152(1)
9.7 Experimental measurement of activities
153(1)
9.8 Sources of activity data
153(1)
Problems
154(3)
Chapter 10 Reactive systems -- single reactions
157(22)
Scope
157(1)
Learning objectives
157(1)
10.1 Introduction
157(1)
10.2 The feasibility of chemical reactions
158(2)
10.3 The equilibrium constant
160(6)
10.4 Choice of standard state
166(2)
Summary
168(1)
10.5 The effect of temperature, pressure and concentration on equilibrium
168(2)
10.5.1 The effect of temperature
169(1)
10.5.2 The effect of pressure
169(1)
10.5.3 The effect of composition
169(1)
10.6 The equilibrium composition of a system
170(4)
10.6.1 Single reactions
170(1)
Single phase reactions
171(1)
Heterogeneous reactions
172(2)
10.6.2 Multiple reactions within a system
174(1)
Problems
174(5)
Chapter 11 Gibbs energy applications to metal production
179(16)
Scope
179(1)
Learning objectives
179(1)
11.1 Introduction
179(1)
11.2 Stability of oxides
180(2)
11.3 Reduction reactions
182(9)
11.3.1 Reduction using carbon
183(1)
11.3.2 Reduction with carbon monoxide and hydrogen
184(6)
11.3.3 Reduction using another metal
190(1)
11.4 Oxidation reactions
191(1)
11.5 Metal production strategy
192(2)
Problems
194(1)
Chapter 12 Electrolyte solutions
195(26)
Scope
195(1)
Learning objectives
195(1)
12.1 Introduction
195(1)
12.2 Aqueous solutions
195(2)
12.3 Enthalpy, Gibbs energy and entropy of ions in aqueous solutions
197(5)
12.3.1 Sources of thermodynamic data for aqueous solutions
200(2)
12.4 Activities in electrolyte solutions
202(7)
12.4.1 The unit activity coefficient approximation
203(2)
12.4.2 Mean ionic activity
205(1)
12.4.3 Activity of the electrolyte
206(2)
12.4.4 Multiple electrolytes in solution
208(1)
12.5 The activity of ions
209(5)
12.6 Partial dissociation
214(1)
12.6.1 Degree of dissociation
215(1)
12.7 The pH scale
215(3)
Problems
218(3)
Chapter 13 Phase equilibria: non-reactive systems
221(30)
Scope
221(1)
Learning objectives
221(1)
13.1 Introduction
221(1)
13.2 Equilibrium in multi-phase systems
222(1)
13.3 The phase rule
222(2)
13.4 One-component systems
224(8)
13.4.1 An example of a p--T diagram: carbon
225(1)
13.4.2 Stability of phases -- The Clapyron and Clausius--Clapyron equations
226(2)
The solid--liquid boundary: melting point
228(1)
The liquid--gas boundary: vapour pressure and boiling point
229(2)
The solid--gas boundary: sublimation temperature
231(1)
13.4.3 The effect of external pressure on vapour pressure
231(1)
13.5 Two-component systems
232(9)
13.5.1 Solid--liquid, solid--solid and liquid--liquid systems
233(1)
13.5.2 Interpreting phase diagrams
234(4)
13.5.3 Liquid--vapour systems
238(1)
Miscible liquids
238(3)
Immiscible liquids
241(1)
13.6 Thermodynamic basis of phase diagrams
241(4)
13.7 Determination of phase diagrams
245(2)
13.8 Partitioning of components between phases
247(1)
Problems
248(2)
Further Reading
250(1)
Chapter 14 Phase equilibria: reactive systems
251(16)
Scope
251(1)
Learning objectives
251(1)
14.1 Introduction
251(1)
14.2 The phase rule for reactive systems
251(6)
14.3 Phase stability diagrams
257(1)
14.4 The distribution of elements between phases
258(6)
14.4.1 Solvent extraction
260(2)
14.4.2 Distribution of elements in gas--slag--metal systems
262(2)
Problems
264(3)
Chapter 15 Complex equilibria
267(12)
Scope
267(1)
Learning objectives
267(1)
15.1 Introduction
267(1)
15.2 The stoichiometric approach
267(3)
15.3 Gibbs energy minimisation
270(4)
15.4 Commercial software to perform Gibbs energy minimisation
274(3)
Problems
277(1)
Further Reading
278(1)
Chapter 16 Electrochemistry
279(26)
Scope
279(1)
Learning objectives
279(1)
16.1 Introduction
279(1)
16.2 Definitions of Ampere, Coulomb and Volt
279(1)
16.3 Electrochemical reactions
280(2)
16.3.1 An example of an electrochemical reaction
281(1)
16.4 Conductors and conduction
282(1)
16.5 Electrochemical cells
283(17)
16.5.1 Contact potential
285(1)
16.5.2 Half-cell and cell reactions
285(1)
16.5.3 Gibbs energy of cell reactions
286(1)
16.5.4 Electrode potentials
287(3)
16.5.5 Types of electrochemical cells
290(1)
Electrolytic cells
290(2)
Galvanic cells
292(5)
16.5.6 Kinetic effects
297(1)
16.5.7 Total cell potential and Ohmic heating
298(1)
16.5.8 The laws of electrolysis
299(1)
16.6 Phase stability diagrams
300(1)
16.7 The use of galvanic cells to measure thermodynamic properties
301(1)
Problems
302(3)
Chapter 17 Some applications of electrochemistry
305(8)
Scope
305(1)
Learning objectives
305(1)
17.1 Electrolysis
305(4)
17.1.1 Electrowinning of metals
305(2)
17.1.2 Manufacture of chlorine
307(1)
17.1.3 Electrorefining
307(1)
17.1.4 Electroplating
308(1)
17.1.5 Anodising
308(1)
17.1.6 Energy required for electrolytic processes
308(1)
17.2 Cementation
309(1)
17.3 Corrosion
310(1)
17.4 Batteries
310(1)
17.5 Fuel cells
311(2)
Answers to problems 313(4)
Index 317
W. John Rankin has BSc and PhD degrees from the University of Queensland, Australia. He worked initially for MINTEK, then lectured in extractive metallurgy and chemical engineering at the University of Stellenbosh (both in South Africa), the Royal Melbourne Institute of Technology (Australia), and the University of Waterloo (Canada). During the 1990s, he was Professorial Research Fellow and Director of the G.K. Williams Cooperative Research Centre for Extractive Metallurgy at the University of Melbourne. Later, he accepted a position in CSIRO (Australia's national science agency) and held the role of Chief Scientist of the Division of Process Science and Engineering. His research interests are in the fields of thermodynamics, pyrometallurgy, and the implications of sustainability for the minerals industry. He has published over 130 research papers, authored the book Minerals, Metals and Sustainability: Meeting Future Material Needs (CRC Press), and edited the third edition of the Australasian Mining and Metallurgical Operating Practices (published by the AusIMM). He is co-editor of the journal Mineral Processing and Extractive Metallurgy, Adjunct Professor (Swinburne University of Technology, Melbourne), and Honorary Fellow (CSIRO).
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