Introduction to Chemical Engineering Kinetics and Reactor Design

CHARLES G. HILL, JR., SC.D, is Professor Emeritus at the University of Wisconsin–Madison with over 200 peer-reviewed publications to his credit. In addition to his academic work, he has served as a consultant to government agencies and private corporations. Dr. Hill’s research has been highly interdisciplinary, including experience as a Fulbright Senior Scholar collaborating on studies of enzymatic reactions at the Institute for Catalysis and Petrochemistry (Spain).THATCHER W. ROOT, PHD, is Professor of Chemical Engineering at the University of Wisconsin–Madison. Dr. Root was awarded an NSF Presidential Young Investigator Award and recently received the Benjamin Smith Reynolds Award for Excellence in Teaching Engineers.

• Preface ixPreface to the First Edition xi1. Stoichiometric Coefficients and Reaction Progress Variables 11.0 Introduction 11.1 Basic Stoichiometric Concepts 2Literature Citation 32. Thermodynamics of Chemical Reactions 42.0 Introduction 42.1 Chemical Potentials and Standard States 42.2 Energy Effects Associated with Chemical Reactions 52.3 Sources of Thermochemical Data 72.4 The Equilibrium Constant and its Relation to ΔG0 72.5 Effects of Temperature and Pressure Changes on the Equilibrium Constant 82.6 Determination of Equilibrium Compositions 92.7 Effects of Reaction Conditions on Equilibrium Yields 112.8 Heterogeneous Reactions 122.9 Equilibrium Treatment of Simultaneous Reactions 122.10 Supplementary Reading References 15Literature Citations 15Problems 153. Basic Concepts in Chemical Kinetics: Determination of the Reaction Rate Expression 223.0 Introduction 223.1 Mathematical Characterization of Simple Reaction Systems 253.2 Experimental Aspects of Kinetic Studies 293.3 Techniques for the Interpretation of Kinetic Data 34Literature Citations 53Problems 544. Basic Concepts in Chemical Kinetics: Molecular Interpretations of Kinetic Phenomena 724.0 Introduction 724.1 Reaction Mechanisms 734.2 Chain Reactions 834.3 Molecular Theories of Chemical Kinetics 93Literature Citations 103Problems 1045. Chemical Systems Involving Multiple Reactions 1175.0 Introduction 1175.1 Reversible Reactions 1175.2 Parallel or Competitive Reactions 1255.3 Series or Consecutive Reactions: Irreversible Series Reactions 1335.4 Complex Reactions 137Literature Citations 142Problems 1426. Elements of Heterogeneous Catalysis 1526.0 Introduction 1526.1 Adsorption Phenomena 1536.2 Adsorption Isotherms 1566.3 Reaction Rate Expressions for Heterogeneous Catalytic Reactions 1606.4 Physical Characterization of Heterogeneous Catalysts 1706.5 Catalyst Preparation, Fabrication, and Activation 1746.6 Poisoning and Deactivation of Catalysts 177Literature Citations 178Problems 1797. Liquid Phase Reactions 1897.0 Introduction 1897.1 Electrostatic Effects in Liquid Solution 1917.2 Pressure Effects on Reactions in Liquid Solution 1927.3 Homogeneous Catalysis in Liquid Solution 1937.4 Correlation Methods for Kinetic Data: Linear Free Energy Relations 202Literature Citations 207Problems 2078. Basic Concepts in Reactor Design and Ideal Reactor Models 2168.0 Introduction 2168.1 Design Analysis for Batch Reactors 2258.2 Design of Tubular Reactors 2288.3 Continuous Flow Stirred-Tank Reactors 2348.4 Reactor Networks Composed of Combinations of Ideal Continuous Flow Stirred-Tank Reactors and Plug Flow Reactors 2548.5 Summary of Fundamental Design Relations: Comparison of Isothermal Stirred-Tank and Plug Flow Reactors 2568.6 Semibatch or Semiflow Reactors 256Literature Citations 259Problems 2599. Selectivity and Optimization Considerations in the Design of Isothermal Reactors 2739.0 Introduction 2739.1 Competitive (Parallel) Reactions 2749.2 Consecutive (Series) Reactions: A →k1→ B →k2→ C →k3→ D 2789.3 Competitive Consecutive Reactions 2839.4 Reactor Design for Autocatalytic Reactions 290Literature Citations 294Problems 29410. Temperature and Energy Effects in Chemical Reactors 30510.0 Introduction 30510.1 The Energy Balance as Applied to Chemical Reactors 30510.2 The Ideal Well-Stirred Batch Reactor 30710.3 The Ideal Continuous Flow Stirred-Tank Reactor 31110.4 Temperature and Energy Considerations in Tubular Reactors 31410.5 Autothermal Operation of Reactors 31710.6 Stable Operating Conditions in Stirred Tank Reactors 32010.7 Selection of Optimum Reactor Temperature Profiles: Thermodynamic and Selectivity Considerations 324Literature Citations 327Problems 32811. Deviations from Ideal Flow Conditions 33711.0 Introduction 33711.1 Residence Time Distribution Functions, F(t) and dF(t) 33711.2 Conversion Levels in Nonideal Flow Reactors 35211.3 General Comments and Rules of Thumb 358Literature Citations 359Problems 35912. Reactor Design for Heterogeneous Catalytic Reactions 37112.0 Introduction 37112.1 Commercially Significant Types of Heterogeneous Catalytic Reactors 37112.2 Mass Transport Processes within Porous Catalysts 37612.3 Diffusion and Reaction in Porous Catalysts 38012.4 Mass Transfer Between the Bulk Fluid and External Surfaces of Solid Catalysts 40612.5 Heat Transfer Between the Bulk Fluid and External Surfaces of Solid Catalysts 41312.6 Global Reaction Rates 41612.7 Design of Fixed Bed Reactors 41812.8 Design of Fluidized Bed Catalytic Reactors 437Literature Citations 439Problems 44113. Basic and Applied Aspects of Biochemical Transformations and Bioreactors 45113.0 Introduction 45113.1 Growth Cycles of Microorganisms: Batch Operation of Bioreactors 45213.2 Principles and Special Considerations for Bioreactor Design 47213.3 Commercial Scale Applications of Bioreactors in Chemical and Environmental Engineering 495Literature Citations 516Problems 517Appendix A. Fugacity Coefficient Chart 527Appendix B. Nomenclature 528Appendix C. Supplementary References 535Author Index 537Subject Index 545