It is the purpose of this book to present a concise and sufficiently detailed de scription of the present state and possibilities of calculating chemical equilibria of gas mixtures. It is based on a book by one of the authors, published in Czech by the Publishing House Academia in Prague. The rapid development of the topic during the two years since publication of the Czech edition has made it necessary to revise practically all the sections in order to bring them up to the present level of know ledge. One reason for writing this book was the practical requirement of contemporary industry, where a rational utilization of equilibrium composition calculations may provide valuable information concerning processes under study in all stages of their implementation. A second reason was the need of a text-book for studying this part of chemical thermodynamics in the scope as taught at the Institute of Chemical Technology, Prague. These two basic motives determine the overall structure of the book, as well as the proportions and arrangement of the chapters. The book includes fundamental thermodynamic concepts as well as the mathematical apparatus needed to solve the problems involved, care being taken that the discussion should always l! ! ad to a practical procedure of performing equilibrium calculations in gas-phase systems of any degree of complexity whatever. Knowledge of chemical thermodynamics on the level of a fundamental university course is assumed.
Inhaltsverzeichnis
List of contents. - 1 Introduction. - 2 Stoichiometry of Chemical Reactions. - 2. 1 Definition of a chemical reaction. - 2. 2 Determination of the number of linearly independent reactions. - 2. 3 Calculation of the matrix of stoichiometric coefficients. - 2. 4 Expression of the mass balance. - 3 Chemical Equilibrium of a System. - 3. 1 General considerations. - 3. 2 The equilibrium constant and ? G° of a reaction. - 3. 3 Selection of the standard state. - 3. 4 Dependence of the equilibrium constant on variables of state. - 3. 5 Dependence of the equilibrium constant on the absolute magnitude of the stoichiometric coefficients. - 3. 6 Properties of the free enthalpy of a system. - 3. 7 Procedure of calculating a chemical equilibrium. - 4 Chemical Equilibrium of Simple Systems in the Ideal Gas State. - 4. 1 Reaction coordinate. - 4. 2 Calculation of simple equilibria. - 4. 3 Dependence of the degree of conversion on individual reaction conditions. - 4. 4 Dependence of the equilibrium composition on individual reaction variables in the case of more complicated systems. - 5 Chemical Equilibrium of Complex System in the Ideal Gas State. - 5. 1 Introduction. - 5. 2 Single-purpose procedures. - 5. 3 General methods requiring stoichiometric analysis of the system. - 5. 4 General methods which do not require stoichiometric analysis of the system. - 5. 5 Evaluation. - 5. 6 Description of selected methods. - 5. 7 Calculation of the enthalpy balance of complicated systems. - 6 Chemical Equilibria in Real Gas Systems. - 6. 1 Fundamentals thermodynamic notions. - 6. 2 Determination of equilibrium composition. - 6. 3 Determination of the fugacity coefficients of constituents in the system. - 6. 4 Determination of the constants of equations of state of pure constituents. - 7 Practical Calculation Procedure. - 7. 1 Source of thermochemicaldata. - 7. 2 Strategy of calculation. - 7. 3 Processing the calculated results. - 7. 4 Example. - Appendix 1 Solution of one non-linear equation. - Appendix 2 Solution of a set of non-linear equations. - Appendix 3 Proof of the inequality. - Appendix 4 Proof of the asymptotic relationship. - Appendix 5 Maximum yield of a reaction. - Appendix 6 Proof of the existence and unambiguous nature of the solution to the problem of chemical equilibrium in ideal gas systems. - Appendix 7 Values of the most frequently encountered compounds in the range of 298. 15 to 1200 K, and values of in cal mole and cal mole resp. . - Appendix 9 Critical data of selected organic substances. - Appendix 10 Values of constants of the Beattie-Bridgman equation. - Appendix 11 Values of constants of the Benedict-Webb-Rubin equation. - References.
