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.
1. An overview of thermodynamics
What is thermodynamics?
A brief history
The laws of thermodynamics
2. Fundamental concepts
Substances and the states of matter; amount of substance
Systems; composition; macroscopic and microscopic properties; concept of equilibrium
Processes
State functions and path functions; the standard state
Energy, work, heat and temperature
Problems
3. Gases
Introduction
Gas pressure
Ideal gases; Avogadro’s law and Avogadro’s constant; combined gas law; ideal gas law; gas mixtures
Real gases; the p−V−T relationship; compressibility; equations of state for real gases
Problems
4. The first law
The first law; internal energy; mathematical statement of the first law
Enthalpy; the nature of enthalpy; enthalpy of mixing; enthalpy of phase changes
Heat capacity
The enthalpy of substances; variation with temperature; enthalpy increments
Enthalpy of formation
Enthalpy of reaction
Experimental determination of heat capacity and enthalpy
Problems
5. Sources of thermodynamic data for substances
Compilations; the reference state; the NIST−JANAF, NBS and US Geological Survey tables; the FREED software program; Barin’s thermochemical tables
Thermochemical software programs
Problems
6. Some applications of the first law
Heating and cooling of substances
Energy balances
Adiabatic temperature of reaction
Heat utilisation in furnaces
Problems
7. The second and third laws
Entropy and the second law; the nature of entropy; broad implications of the first and second laws; alternative statements of the second law
The entropy of mixing; mixing of ideal gases; the general equation for mixing
The entropy of phase changes
The third law and the entropy of substances
Entropy of formation and entropy of reaction
Entropy as a criterion of sponteneity
Experimental determination of entropy
Problems
8. Gibbs and Helmholtz energy
Combined statement of the 1st and 2nd laws
Helmholtz and Gibbs energy; the criteria for spontaneity; the Gibbs−Helmholtz equation
Gibbs energy of phase changes
Gibbs energy of mixing
Gibbs energy of substances
Gibbs energy of formation
Gibbs energy of reaction
The use of Gibbs energy to study reactions; the importance of kinetics
Experimental determination of Gibbs energy
Problems
9. Solutions
Types of solutions – aqueous, organic, molten and solid solutions
Integral and partial quantities; calculating partial quantities from integral quantities; The Gibbs−Duhem equation
Gas mixtures − ideal and non−ideal gas mixtures
Liquid and solid solutions; the concept of activity; pure substance standard state; infinitely dilute standard state; conversion between standard states; the Gibbs-Duhem equation
Properties of solutions; ideal and non−ideal solutions; excess molar quantities
Experimental measurement of activities
Sources of activity data
Problems
10. Reactive systems – Single reactions
The feasibility of chemical reactions
The equilibrium constant; choice of standard state
The effect of temperature, pressure and concentration on equilibrium
The equilibrium composition of a system; single reactions; multiple reactions within a system
Problems
11. Gibbs energy applications to metal production
Stability of oxides
Reduction reactions; reduction using carbon; reduction with carbon monoxide and hydrogen; reduction using another metal
Oxidation reactions
Metal production strategy
Problems
12. Electrolyte solutions
Aqueous solutions
Enthalpy, Gibbs energy and entropy of ions in solution; sources of thermodynamic data
Activities in electrolyte solutions; the unit activity coefficient approximation; mean ionic activity; activity of the electrolyte; multiple electrolytes in solution
The activity of ions
Partial dissociation; degree of dissociation
The pH scale
Problems
13. Phase equilibria: non−reactive systems
Equilibrium in multi−phase systems; the phase rule
One component systems; an example of a diagram (carbon)
Stability of phases; the Clapyron and Clausius−Clapyron equations; the effect of external pressure on vapor pressure
Two−component systems; solid−liquid, solid−solid and liquid−liquid systems Interpreting phase diagrams
Liquid−vapor systems
Thermodynamic basis of phase diagrams
Determination of phase diagrams
Partitioning of components between phases
Further reading
Problems
14. Phase equilibria: reactive systems
The phase rule for reactive systems
Phase stability diagrams
The distribution of elements between phases; Examples: solvent extraction and distribution of elements in gas - slag - metal systems
Problems
15. Complex equilibria
The stoichiometric approach
Gibbs energy minimization
Commercial software to perform Gibbs energy minimization
Further reading
Problems
16. Electrochemistry
Definitions of Ampere, Coulomb and Volt
Electrochemical reactions; example of an electrochemical reaction
Conductors and conduction
Electrochemical cells; contact potential; half−cell and cell reactions; Gibbs energy of cell reactions; electrode potentials; types of electrochemical cells; kinetic effects; total cell potential and Ohmic heating; the laws of electrolysis
Phase stability diagrams
The use of galvanic cells to measure thermodynamic properties
Problems
17. Some applications of electrochemistry
Electrolysis − electrowinning of metals; manufacture of chlorine; electrorefining; electroplating; anodizing
Energy required for electrolytic processes
Cementation
Corrosion
Batteries
Fuel cells
Answers to problems
Biography
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).
