热力学 : 电极反应的真实热效应是多少？

Chapter 1 On Thermoelectrochemistry1．1 Theory and Application of Thermoelectrochemistry1．2 Some Basic Matters on the Heat Effects at Electrode-Electrolyte Interfaces1．3 Thermoelectrochemistry and Its Application to Metallurgical Research1．4 The Electrochemical Peltier Heat of the Standard Hydrogen Electrode Reaction1．5 Response to“Comment on‘The Electrochemical Peltier Heat of the Standard Hydrogen Electrode Reaction’by Zheng Fang et al”1．6 Basic Equations for Thermo—electrochemistry and the Entropy Change of the Standard Hydrogen Electrode Reaction1．7 The Peltier Heat and the Standard Electrode Potential of Ferro—ferricyanide Couple at 298.15 K Determined by Electrochemical—calorimetry1．8 Determination of the Entropy Changes for Electrode Reaction and Dilute Enthalpy of Some Ions by Thermoelectrochemical Technology RererencesChapter 2 On Solution Chemistry2．1 A New Model for Predicting Thermodynamic Properties of Ternary Metallic Solution from Binary Components2．2 A Metallic Solution Model with Adjustable Parameter for Describing Ternary Thermodynamic Properties from Its Binary Constituents2．3 A Model Describing the Osmotic Coefficients and the Activities of Water for Electrolyte Solutions2．4 The Mean Activity Coefficients of LaCl3 in Dilute Aqueous Solution at 298.15 K2．5 A Simplified Regular Solution Model for Solubility of Nonmetal（2） in Metal（1）-Metal（3）Alloy Systems2．6 Modeling of Thermodynamic Properties of Muhicomponent Electrolyte Solutions2．7 A Simplified Subregular Solution Model Describing the Activites of MgCl2 in Both KCl-MgCl2-LiCl and CaCl2-MgCl2-NaCl Molten Salt Systems2．8 A Model for the Activity Coefficients of Water in Aqueous Solution of HCl-MCln（M=Ni，Cu，Na，and Fe）with Constant Concentration Ratio XHCl／XMcln2．9 A Prediction of the Excess Partial Molar Free Energies of MgCl2 in the KCl-MgCl2-LiCl Molten Salt System Containing MgCl2 below 0.5 from Thermodynamic Properties of Binary Systems ReferencesChapter 3 On Phase Boundaries of Multicomponent System3．1 Complete Integration of Gibbs—Duhem Equation along Phase Boundaries in Multicomponent System3．2 Activities on Phase Boundaries in Multicomponent Systems-A Recursion Formula for Calculation of Activities3．3 An Analogue Margules Equation on Phase Boundaries in Multicomponent Systems RefrencesChapter 4 On Oxygen Potentials of Buffer Gases4．1 Oxygen Potentials and Oxygen-potential Diagrams for Buffer Gas System at Normal Pressure4．2 Effect of Oxygen Contents on Oxygen Potentials of H2O-H2 and H2O-H2-Inerts Gas Mixtures4．3 Oxygen Potentials of C02，H20（g）and C02一CO Gas Mixtures—with Extension of Application of Ellingham Diagram ReferencesChapter 5 On Thermodynamic Properties of Substances5．1 A Study on Thermodynamic Properties in the System M002-Mo by Gas Equilibration Method5．2 Equilibria of the System M003-M002-H20-H2 and Phase Diagram for the System Mo-O between 400 and 700℃5．3 Equilibrium between Non-stoichiometric M002 and Mo with Application of Sieverts’Law Constant to Smiltens’Integration5．4 A New Molybdenum Oxide Phase5．5 Recovery of Gallium from Coal Fly Ash Reflerenees

The volume named Thermodynamics-How much are the real heats of electrode reaction？ is an anthology on a scholarly topic，which embodies the outcome of the author‘s original research over the years and shows his some fresh ideas in the area of physicochemistry in process metallurgy． The author’s academic work has been mainly focusing on the heats of electrode reaction．In the research into this project，the author has discovered that the heat release and heat absorption of an electrode process could not really be predicted according to the current knowledge of the thermodynamics or electrochemistry，although this type of heats can truthfully be measured by experiments and a fairly accurate forecast of the released or absorbed heats for a cell reaction can also be given．Certainly，the settlement of this problem has to do with the entropy change of an electrode reaction．Therefore，the issue becomes very basic．For example，whether is it always appropriate in all cases to stipulate the entropy change for the standard hydrogen electrode reaction to be zero at any temperature？ What is the exact expression of the first and second laws of thermodynamics when they are used to an electrode reaction？ Inorder to predict and experimentally measure the real heats of electrode reaction，the author proposed the concept of the absolute scale first on which the entropy change for standard hydrogen electrode reaction at room temperature has been given．Besides，the content is also complete with the studies of“solution chemistry”．“phase boundaries of muhicomponent system”．“oxygen potential of buffer gases”and“thermodynamicproperties of substances”． Among them，there are the discussions on the thermodynamic models of aqueous solution of electrolyte and molten salt system，the relationship between the probability-distribution function of water molecules near the solute ion and the osmotic coefficients of electrolyte solution，the complete computation and analytic expression for partial molar properties of components along the phase boundaries，the new representation for the chemical potentials of oxygen，which is different from the classical one，and can be applied to construction of the diagram of oxygen potential against temperature，etc． The author has attempted to systematize the papers in different points．This will be indispensable to researchers in the field to grasp these contents more deeply and to understand the contribution in treatment and development of some basic issues．Of course，those conclusions in the collected papers might not be utterly strict and cautious．Some of them still need more deeply academic researches and further experiments to be improved．For example，whether it is appropriate and reasonable to specify both all the entropy change and electrode potential of a reversible electrode reaction to be zero when the temperature in Kelvin approaches zero． The volume as a valuable reference reading could be useful for student study and postgraduate study of the related specialist area，especially for those interested in mastering the experimental and theoretical aspects of physicochemistry in process metallurgy．The publishing of the book is also expected to be able to enlighten them to know that there might be still something that hampers further development of the discipline，even for the relatively mature discipline and some knowledge that has been more widely accepted． At the time when the book is published．the author would like to thank the National Natural Science Foundation of China for financial support．It is the support that has created a great surrounding，where the author is able to meditate on the some academic issues in the related projects．The author also wishes to express his appreeiation to the State Education Committee of P．R．China and the University of Manitoba 0f Canada for the researches during the study abroad，and to the research collaborators who give the valuable help． Professor Xinmin CHEN was my doctoral advisor．He was a well—known scientist of physicochemistry in process metallurgy and the member of the Chinese Academy of Sciences．This year is just the centennial of his birth．To him I dedicate this volume in token of affection and gratitude．