Chemical and Engineering Thermodynamics, 3rd Edition

by Stanley I. Sandler (Univ. of Delaware)

• ISBN13: 9780471182108
• ISBN10: 0471182109
• Edition: 3rd
• Format: Hardcover
• Copyright: 1998-08-01
• Publisher: Wiley

Summary

A More Accessible Approach to Thermodynamics In this third edition, you'll find a modern approach to applied thermodynamics. The material is presented in sufficient detail to provide a solid understanding of the principles of thermodynamics and its classical applications. Also included are the applications of chemical engineering thermodynamics to issues such as the distribution of chemicals in the environment, safety, polymers, and solid-state-processing. To make thermodynamics more accessible, several helpful features are included. Important concepts are emphasized in marginal notes throughout each chapter. Illustrations have also been added to demonstrate the use of these concepts and to provide a better understanding of the material. Boxes are used to highlight equations so that students can easily identify the end results of analyses. You can also visit the text's web site to download additional problem sets, computer programs to solve thermodynamic and phase behavior problems, and Mathcad(r) worksheets used for problem solving.

Author Biography

About the author STANLEY I. SANDLER is the H. B. du Pont Professor of Chemical Engineering at the University of Delaware as well as professor of chemistry and biochemistry. He is also the founding director of its Center for Molecular and Engineering Thermodynamics. In addition to this book, Sandler is the author of 235 research papers and a monograph, and is the editor of a book on thermodynamic modeling and five conference proceedings. He earned the B.Ch.E. degree in 1962 from the City College of New York , and the Ph.D. in chemical engineering from the University of Minnesota in 1966.

Table of Contents

NOTATION	xv
CHAPTER 1 INTRODUCTION	1	(21)
1.1 The Central Problems of Thermodynamics	1	(2)
1.2 A System of Units	3	(2)
1.3 The Equilibrium State	5	(2)
1.4 Pressure, Temperature, and Equilibrium	7	(5)
1.5 Heat, Work, and the Conservation of Energy	12	(3)
1.6 Specification of the Equilibrium State; Intensive and Extensive Variables; Equations of State	15	(3)
1.7 A Summary of Important Experimental Observations	18	(2)
1.8 A Comment on the Development of Thermodynamics	20	(1)
Problems	20	(2)
CHAPTER 2 CONSERVATION OF MASS AND ENERGY	22	(67)
2.1 A General Balance Equation and Conserved Quantities	23	(4)
2.2 Conservation of Mass	27	(3)
2.3 Conservation of Energy	30	(13)
2.4 The Thermodynamic Properties of Matter	43	(8)
2.5 Applications of the Mass and Energy Balances	51	(24)
2.6 Conservation of Momentum	75	(1)
2.7 The Microscopic Equations of Change for Thermodynamics and Fluid Mechanics (Optional)	76	(6)
Problems	82	(7)
CHAPTER 3 ENTROPY: AN ADDITIONAL BALANCE EQUATION	89	(86)
3.1 Entropy: A New Concept	90	(7)
3.2 The Entropy Balance and Reversibility	97	(6)
3.3 Heat, Work, Engines, and Entropy	103	(9)
3.4 Entropy Changes of Matter	112	(3)
3.5 Applications of the Entropy Balance	115	(13)
3.6 Liquefaction	128	(4)
3.7 Power Generation and Refrigeration Cycles	132	(22)
3.8 The Thermodynamics of Mechanical Explosions	154	(9)
3.9 The Microscopic Entropy Balance (Optional)	163	(2)
Problems	165	(10)
CHAPTER 4 THE THERMODYNAMIC PROPERTIES OF REAL SUBSTANCES	175	(85)
4.1 Some Mathematical Preliminaries	175	(4)
4.2 The Evaluation of Thermodynamic Partial Derivatives	179	(15)
4.3 The Ideal Gas and Absolute-Temperature Scales	194	(1)
4.4 The Evaluation of Changes in the Thermodynamic Properties of Real Substances Accompanying a Change of State	195	(24)
4.5 An Example Involving the Change of State of a Real Gas	219	(6)
4.6 The Principle of Corresponding States	225	(13)
4.7 Generalized Equations of State	238	(4)
4.8 The Third Law of Thermodynamics	242	(1)
4.9 More About Thermodynamic Partial Derivatives (Optional)	243	(6)
Appendix A4.1 A Program for Thermodynamic Properties Calculations Using the Peng-Robinson Cubic Equation of State, PR1	249	(2)
Problems	251	(9)
CHAPTER 5 EQUILIBRIUM AND STABILITY IN ONE-COMPONENT SYSTEMS	260	(64)
5.1 The Criteria for Equilibrium	260	(5)
5.2 Stability of Thermodynamic Systems	265	(7)
5.3 Phase Equilibria: Application of the Equilibrium and Stability Criteria to the Equation of State	272	(7)
5.4 The Molar Gibbs Free Energy and Fugacity of a Pure Component	279	(16)
5.5 The Calculation of Pure Fluid-Phase Equilibrium: The Computation of Vapor Pressure from an Equation of State	295	(8)
5.6 The Specification of the Equilibrium Thermodynamic State of a System of Several Phases: The Gibbs Phase Rule for a One-Component System	303	(4)
5.7 Thermodynamic Properties of Phase Transitions	307	(6)
Problems	313	(11)
CHAPTER 6 THE THERMODYNAMICS OF MULTICOMPONENT MIXTURES	324	(64)
6.1 The Thermodynamic Description of Mixtures	324	(9)
6.2 The Partial Molar Gibbs Free Energy and the Generalized Gibbs-Duhem Equation	333	(4)
6.3 A Notation for Chemical Reactions	337	(3)
6.4 The Equations of Change for a Multicomponent System	340	(9)
6.5 The Heat of Reaction and a Convention for the Thermodynamic Properties of Reacting Mixtures	349	(5)
6.6 The Experimental Determination of the Partial Molar Volume and Enthalpy	354	(10)
6.7 Criteria for Phase Equilibrium in Multicomponent Systems	364	(4)
6.8 The Criteria for Chemical Equilibrium, and Combined Chemical and Phase Equilibrium	368	(5)
6.9 The Specification of the Equilibrium Thermodynamic State of a Multicomponent, Multiphase System; the Gibbs Phase Rule	373	(4)
6.10 Some Concluding Remarks	377	(1)
Problems	377	(11)
CHAPTER 7 THE ESTIMATION OF THE GIBBS FREE ENERGY AND FUGACITY OF A COMPONENT IN A MIXTURE	388	(90)
7.1 The Ideal Gas Mixture	388	(4)
7.2 The Partial Molar Gibbs Free Energy and Fugacity	392	(4)
7.3 The Ideal Mixture and Excess Mixture Properties	396	(10)
7.4 The Fugacity of Species in Gaseous, Liquid, and Solid Mixtures	406	(8)
7.5 Several Correlative Liquid Mixture (Activity Coefficient) Models	414	(14)
7.6 Two Predictive Activity Coefficient Models	428	(9)
7.7 A Corresponding States Principle for Mixtures; The Pseudocritical Constant Method	437	(7)
7.8 The Fugacity of Species in Nonsimple Mixtures	444	(7)
7.9 Some Comments on Reference and Standard States	451	(1)
7.10 A Combined Equation-of-State-Excess Gibbs Free Energy Models	452	(3)
7.11 Electrolyte Solutions	455	(6)
7.12 Concluding Remarks	461	(3)
Appendix A7.1 A Statistical Mechanical Interpretation of the Entropy of Mixing in an Ideal Mixture	464	(3)
Appendix A7.2 A Program for Multicomponent Vapor-Liquid Equilibrium Calculations Using the Peng-Robinson Cubic Equation of State, VLMU	467	(1)
Appendix A7.3 Multicomponent Excess Gibbs Free Energy (Activity Coefficient) Models	468	(2)
Appendix A7.4 A Program for the Prediction of Activity Coefficients and Low Pressure Vapor-Liquid Equilibrium Using the UNIFAC Model, UNIFAC.	470	(1)
Problems	471	(7)
CHAPTER 8 PHASE EQUILIBRIUM IN MIXTURES	152	(478)
8.1 Vapor-Liquid Equilibria Using Activity Coefficient Models	478	(40)
Problems for Section 8.1	511	(7)
8.2 Vapor-Liquid Equilibria Using Equations of State	518	(18)
Problems for Section 8.2	534	(2)
8.3 The Solubility of a Gas in a Liquid	536	(14)
Problems for Section 8.3	547	(3)
8.4 The Solubility of a Liquid in a Liquid and Vapor-Liquid-Liquid Equilibrium	550	(25)
Problems for Section 8.4	571	(4)
8.5 The Solubility of a Solid in a Liquid, Gas, or Supercritical Fluid	575	(11)
Problems for Section 8.5	585	(1)
8.6 The Partitioning of a Solute Among Two Coexisting Liquid Phases; The Distribution Coefficient	586	(12)
Problems for Section 8.6	597	(1)
8.7 Freezing-Point Depression of a Solvent Due to the Presence of a Solute; the Freezing Point of Liquid Mixtures	598	(5)
Problems for Section 8.7	602	(1)
8.8 Osmotic Equilibrium and Osmotic Pressure	603	(5)
Problems for Section 8.8	606	(2)
8.9 The Phase Behavior Modeling of Chemicals in the Environment	608	(6)
Problems for Section 8.9	613	(1)
8.10 The Phase Behavior of Solid Mixtures	614	(9)
Problems for Section 8.10	622	(1)
8.11 Concluding Remarks	623	(7)
Additional Phase Equilibrium Problems	624	(6)
CHAPTER 9 CHEMICAL EQUILIBRIUM AND THE BALANCE EQUATIONS FOR CHEMICALLY REACTING SYSTEMS	630	(114)
9.1 Chemical Equilibrium in a Single-Phase System	630	(33)
9.2 Heterogeneous Chemical Reactions	663	(13)
9.3 Chemical Equilibrium When Several Reactions Occur in a Single Phase	676	(7)
9.4 Combined Chemical and Phase Equilibrium	683	(8)
9.5 The Balance Equations for a Tank-Type Chemical Reactor	691	(8)
9.6 The Balance Equations for a Tubular Reactor	699	(3)
9.7 Overall Reactor Balance Equations and the Adiabatic Reaction Temperature	702	(9)
9.8 The Thermodynamics of Chemical Explosions	711	(6)
9.9 Introduction to Electrochemical Processes	717	(10)
9.10 Coupled Chemical Reactions	727	(3)
Appendix A9.1 A Program for the Calculation of Chemical Equilibrium Constants As a Function of Temperature, CHEMEQ	730	(1)
Problems	731	(13)
APPENDIXES	744	(19)
Appendix I Conversion Factors for SI Units	744	(1)
Appendix II The Molar Heat Capacities of Gases in the Ideal Gas (Zero Pressure) State	745	(3)
Appendix III The Thermodynamic Properties of Water and Steam	748	(10)
Appendix IV Enthalpies and Free Energies of Formation	758	(3)
Appendix V Heats of Combustion	761	(2)
INDEX	763