Chemical Thermodynamics Theory and Applications

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

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).