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CHEMICAL PROCESS PRINCIPLES ADVISORY BOARD For Books in Chemical Engineering T. H. CHILTON, Chem. E. Engineering Department, Experimental Station, E. I. du Pont de Nemours and Company T. B. DREW, SM. Professor of Chemical Engineering, Columbia University O. A. HouGEN, Ph.D. Professor of Chemical Engineering, University of Wisconsin D. B. :g^YEs; A.D. Vice President, Heyden Chemical Corporatioti i K. M. WATSON, Ph.D. Professor of Chemical Engineering, University of Wisconsin HAROLD C. WEBER, D.SC. Professor of Chemical Engineering, Massachusetts Institute of Technology CHEMICAL PROCESS PRINCIPLES A COMBINED VOLUME CONSISTING OF Part One • MATERIAL AND ENERGY BALANCES Part Two • THERMODYNAMICS Part Three • KINETICS AND CATALYSIS OLAF A. HOUGEN AND KENNETH M. WATSON PROFESSORS OP CHEMICAL ENGINEERINC UNIVERSITY OF WISCONSIN NEV YORK JOHN WILEY & SONS, INC. CHAPMAN AND HALL, LIMITED LONDON e M }o&i'^ PART I COPYRIGHT, 1943 BY OLAF A. HODGEN AND KENNETH M. WATSON PART II COPYBIGHT, 1947 BY OLAF A. HOTJGEN AND KENNETH M. WATSON PART III COPTBIGHT, 1947 BY OLAF A. HonoEN AND KENNETH M. WATSON All Rights Reserved Thin hook or any 'part thereof must not he reproduced in any form without the written permission- of the publisher. PRINTED If* THE UNITED STATES OF AMERICA PREFACE " In the following pages certain industrially important principles of chem istry and physics have been selected for detailed study. The significance of each principle is intensively developed and its applicability and limitations scrutinized." Thus reads the preface to the first edition of Industrial Chemical Calculations, the precursor of this book. The present book continues to give intensive quantitative training in the practical applications of the principles of physical chemistry to the solution of complicated industrial problems and in methods of predicting missing physicochemical data from generalized principles. In addition, through recent developments in thermodynamics and kinetics, these principles have been integrated into procedures for process design and analysis with the objective of arriving at optimum economic results from a minimum of pilot-plant or test data. The title Chemical Process Principles has been selected to emphasize the importance of this approach to process design and operation. The design of a chemical process involves three types of problems, which although closely interrelated depend on quite different technical principles. The first group of problems is encountered in the preparation of the material and energy balances of the process and the establishment of the duties to be performed by the various items of equipment. The second type of problem is the determination of the process specifications of the equipment necessary to perform these duties. Under the third classification are the problems of equipment and materials selection, mechanical design, and the integration of the various units into a coordinated plot plan. These three types may be designated as process, unit-operation, and plant- . design problems, respectively. In the design of a plant these problems cannot be segregated and each treated individually without consideration of the others. However, in spite of this interdependence in application the three types may advantageously be segregated for study and development because of the different principles involved. Process problems are primarily chemical and physicochemical in nature; unit-operation problems are for the most part physical; the plant-design problems are to a large extent mechanical. In this book only process problems of a chemical and physicochemical nature are treated, and it has been attempted to avoid overlapping into the fields of unit operations and plant design. The first part deals primarily with the applications of general physical chemistry, thermophysics, thermo chemistry, and the first law of thermodynamics. Generalized procedures for estimating vapor pressures, critical constants, and heats of vaporization have been elaborated. New methods are presented for dealing with equilib rium problems in extraction, adsorption, dissolution, and crystallization. The construction and use of enthalpy-concentration charts have been extended to complex systems. The treatment of material balances has been elaborated to include the effects of recycling, by-passing, changes of inventory, and accumulation of inerts. vi PREFACE In the second part the fundamental principles of thermodynamics are pre sented with particular attention to generalized methods. The applications of these principles to problems in the compression and expansion of fluids, power generation, and refrigeration are discussed. However, it is not at tempted to treat the mechanical or equipment problems of such operations. Considerable attention is devoted to the thermodynamics of solutions with particular emphasis on generalized methods for dealing with deviations from ideal behavior. These principles are applied to the calculation of equilib rium compositions in both physical and chemical processes. Because of the general absence of complete data for the solution of process problems a chapter is devoted to the new methods of estimating thermody namic properties by statistical calculations. This treatment is restricted to simple methods of practical value. All these principles are combined in the solution of the ultimate problem of the kinetics of industrial reactions. Quantitative treatment of these problems is difficult, and designs generally have been based on extensive pilot-plant operations carried out by a trial-and-error procedure on succes sively larger scales. However, recent developments of the theory of absolute reaction rates have led to a thermodynamic approach to kinetic problems which is of considerable value in clarifying the subject and reducing it to the point of practical applicability. These principles are developed and their apphcation discussed for homogeneous, heterogeneous, and catalytic systems. Particular attention is given to the interpretation of pilot-plant data. Eco nomic considerations are emphasized and problems are included in estabhshing optimum conditions of operation. In covering so broad a range of subjects, widely varying comprehensibility is encountered. It has been attempted to arrange the material in the order of progressive difficulty. Where the book is used for college instruction in chemical engineering the material of the first part is suitable for second- and third-year undergraduate work. A portion of the second part is suitable for third- or fourth-year undergraduate work; the remainder is of graduate level. To assist in using the book for undergraduate courses in thermody namics and kinetics those sections of Part II which are recommended for such survey courses are marked. This material has been selected and arranged to give continuity in a preliminary treatment which can serve as a foundation for advanced studies, either by the individual or in courses of graduate level. The authors wish to acknowledge gratefully the assistance of Professor R. A. Ragatz in the revision of Chapters I and VI, and the suggestions of Pro fessors Joseph Hirschfelder, R. J. Altpeter, K. A. Kobe, and Dr. Paul Bender. OLAF A. HOUQEN KENNETH M. WATSON MADISON, WISCONSIN August, 194s CONTENTS Page PREFACE . v TABLE OF SYMBOLS ix PART I MATERIAL AND ENERGY BALANCES Chapter I STOICHIOMETRIC PRINCIPLES 1 II BEHAVIOR OF IDEAL GASES 27 III VAPOR PRESSURES 53 IV/ HUMIDITY AND SATURATION 89 V SOLUBILITY AND SORPTION Ill Vr/ MATERIAL BALANCES 167 YJy THERMOPHYSICS 201 viy/ THERMOCHEMISTRY 249 IXy FUELS AND COMBUSTION 323 • X CHEMICAL, METALLURGICAL, AND PETROLEUM PROC ESSES 383 PART II THERMODYNAMICS XI THERMODYNAMIC PRINCIPLES . . . . . . . . ' 437 XII THERMODYNAMIC PROPERTIES OF FLUIDS . . .. 479 XIII EXPANSION AND COMPRESSION OF FLUIDS . . .. 538 XIV THERMODYNAMICS OF SOLUTIONS 595 XV PHYSICAL EQUILIBRIUM 644 XVI CHEMICAL EQUILIBRIUM 691 XVII THERMODYNAMIC PROPERTIES FROM MOLECULAR STRUC TURE 756 vii viii CONTENTS PART III KINETICS AND CATALYSIS Chapter Page XVIII HOMOGENEOUS REACTIONS 805 XIX CATALYTIC REACTIONS 902 XX MASS AND HEAT TRANSFER IN CATALYTIC BEDS . . 973 XXI CATALYTIC REACTOR DESIGN . 1007 XII UNCATALYZED HETEROGENEOUS REACTIONS . . . 1049 APPENDIX jcvii AUTHOR INDEX xxiii SUBJECT INDEX xxvii TABLE OF SYMBOLS A area A atomic weight A component A A total work function a activity external surface per unit mass Om ttp external surface per particle ttv external surface per unit volume B component B B constant of Calingaert-Davis equation B thickness of effective^ film C component C C concentration per unit volume c degrees centigrade c number of components c over-all rate constant c. heat capacity at constant pressure c. heat capacity at constant volume c. Sutherland constant c concentration of adsorbed molecules per unit mass of catalyst c specific heat c velocity of light molal heat capacity at constant pressure Cp molal heat capacity at constant volume Cv d surface concentration of adsorbed molecules per unit catalyst area D diameter diffusivity of A and B DAB Dp effective particle diameter equal to diameter of sphere having the same external surface area as particle D', effective diameter equal to diameter of sphere having , same area per unit volume as particle d differential operator E energy in general E energy of activation, Arrhenius equation E^ effectiveness factor of catalysis