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Second Edition, , CHEMICAL ENGINEERING, KINETICS, , JM. Smith, , Professor of Chemical Engineering, University of California at Davis, , SMITH, J.M., , ‘CHEMICAL: ENGINEERING, KINETICS, , ncisco St. Louis, 2, , Siyah

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This book was set in Monophoto Times Roman by Holmes Typography, Inc., and printed, on permanent paper and bound by The Maple Press Company. The designer was Janet, Bollow'; the illustrations were done by John Foster. The editors were B. J. Clark and, Stuart A. Kenter. Charles A. Goehring supervised production., , 129434, , TP 149 SS8 1970, , 4, Chemical engineering Kinet, , 0021, , 0115063, , METU LIBRARY, , , , CHEMICAL ENGINEERING KINETICS, Second Edition ., , Copyright © 1970 by McGraw-Hill, Inc: All rights reserved. No part of this publicati:, may be reproduced, stored in a retrieval system, or transmitted, in any form or by 4:, means, electronic, mechanical, photocopying, recording, or otherwise, without ti:, prior written permission of the publisher. =, , , , , , Printed in the United States of America. ey, , Library of Congress catalog card number: 74-99204 ., 567890 MAMM 798765432 " 4, , 58693 :

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rar HALLO, , , , ‘PREFACE, , “he first edition of Chemical Engineering Kinetics appeared when the, rational design of chemical reactors, as opposed to empirical scaleup, was, an emerging field. Since then, progress in kinetics, catalysis, and particularly, in engineering aspects of design, has been so great that this second edition is, a completely rewritten version. In view of present-day knowledge, the, treatment in the first edition is inadequate with respect to kinetics of multiple‘eaction systems, mixing in nonideal reactors, thermal effects, and global, cates of heterogeneous reactions. Special attention has been devoted to these, subjects in the second edition. What hasn't changed is the book’s objective:, the clear presentation and illustration of design procedures which are based, upon scientific principles., , Successful design of chemical reactors requires understanding of, chemical kinetics as weli as such physical processes as mass and energy, transport. Hence, the intrinsic rate of chemical reactions is accorded a good, maeasure of attention: in a general way in the second chapter and then with, specific reference to catalysis in the eighth and ninth. A brief review of, chemical thermodynamics is included in Chap. 1, but earlier study of the, fundamentals of this subject would be beneficial. Introductory and theoretical, , vii

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vin PREFACE, , , , material is given in Chap. 2, only in a manner that does not make prior study, of kinetics mandatory., , The concepts of reactor design are presented in Chap. 3 from the, viewpoint of the effect of reactor geometry and operating conditions on the, form of mass and energy conservation equations. The assumptions associated, with the extremes of plug-flow and stirred-tank behavior are emphasized., A brief introduction to deviations from these ideal forms is included in this, chapter and is followed with a more detailed examination of the effects of, mixing on conversion in Chap. 6. In Chaps. 4 and 5 design procedures are, examined for ideal forms of homogeneous reactors, with emphasis upon., multiple-reaction systems. The latter chapter is concerned with nonisothermal behavior., , Chapter 7 is an introduction to heterogeneous systems. The concept of, a global rate of reaction is interjected so as to relate the design of heterogeneous reactors to the previously studied concepts of homogeneous reactor, , . design. A secondary objective here is to examine, in a preliminary way, the, method of combining of chemical and physical processes so as to obtain a, global rate of reaction., , Chap. 8 begins with a discussion of catalysis, particularly on solid, surfaces, and this leads directly into adsorption and the physical properties, of porous solids. The latter is treated in reasonable detail because of the, importance of solid-catalyzed reactions and because of its significance with, respect to intrapellet transport theory (considered in Chap. 13). With this, background, the formulation of intrinsic rate equations at a catalyst site is, taken up in Chap. 9., , The objective of Chaps. 10 and 11 is to combine intrinsic rate equations, with intrapellet and fluid-to-peilet transport rates in order to obtain global, rate equations useful for design. It is at this point that models of porous, catalyst pellets and effectiveness factors are introduced. Slurry reactors offer, an excellent example of the interrelation between chemical and physical, processes, and such systems are used to illustrate the formulation of global, rates of reaction., , The book has been written from the viewpoint that the design of a, chemical reactor requires, first, a laboratory study to establish the intrinsic, tate of reaction, and subsequently a combination of the rate expression, with a model of the commercial-scale reactor to predict performance. In, Chap. 12 types of laboratory reactors are analyzed, with special attention, given to how data can be reduced so as to obtain global and intrinsic rate, equations. Then the modeling problem is examined. Here it is assumed that a, global rate equation is available, and the objective is to use it, and a model,, to predict the performance of a large-scale unit. Several reactors are considered, but major attention is devoted to the fixed-bed type. Finally, in the

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PREFACE is, , last chapter gas-solid, noncatalytic reactions are analyzed, both from a, singlé pellet (global rate) viewpoint, and in terms of reactor design. These, systems offer examples of interaction of chemical and physical processes, under fransient conditions., , ” No effort has been made to include all types of kinetics or of reactors., Rather, the attempt has been to present, as clearly and simply as possible,, all the aspects of process design for a few common types of reactors. The, material should be readily understandable by students in the fourth undergraduate year. The whole book can be comfortably covered in two semesters,, and perhaps in two quarters., , The suggestions and criticisms of numerous students and colleagues, have been vajuable in this revision, and all are sincerely acknowledged. The, several stimulating discussions with Professor J. J. Carberry about teaching, chemical reaction engineering were most helpful. To Mrs. Barbara Dierks, and Mrs. Loretta Charles for their conscientious and interested efforts in, typing the manuscript, I express my thanks. Finally, the book is dedicated, to my wife, Essie, and to my students whose enthusiasm and research, accomplishments have been a continuing inspiration., , ILM. Smith