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AN INTRODUCTION TO CHEMICAL ENGINEERING KINETICS & REACTOR DESIGN CHARLES G. HILL, JR. The University of Wisconsin JOHN WILEY & SONS New York Chichester Brisbane Toronto Singapore To my family: Parents, Wife, and Daughters Copyright © 1977, by John Wiley & Sons, Inc. All rights reserved. Published simultaneously in Canada. Reproduction or translation of any part of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful. Requests for permission or further information should be addressed to the Permissions Department, John Wiley & Sons, Inc. Library of Congress Cataloging in Publication Data: Hill, Charles G 1937An introduction to chemical engineering kinetics and reactor design. Bibliography: p. Includes indexes. 1. Chemical reaction, Rate of. 2. Chemical reactors—Design and construction. I. Title. QD502.H54 660.2'83 77-8280 ISBN 0-471-39609-5 Printed in the United States of America 20 19 18 Board of Advisors, Engineering A. H-S, Ang University of Illinois Civil Engineering—Systems and Probability Donald S. Berry Northwestern University Transportation Engineering James Gere Stanford University Civil Engineering and Applied Mechanics J. Stuart Hunter Princeton University Engineering Statistics T. William Lambe R. V. Whitman Massachusetts Institute of Technology Civil Engineering—Soil Mechanics Perry L. McCarty Stanford University Environmental Engineering Don T. Phillips Texas A & M Industrial Engineering Dale Rudd University of Wisconsin Chemical Engineering Robert F. Steidel, Jr, University of California—Berkeley Mechanical Engineering R. N. White Cornell University Civil Engineering—Structures Preface One feature that distinguishes the education of the chemical engineer from that of other engineers is an exposure to the basic concepts of chemical reaction kinetics and chemical reactor design. This textbook provides a judicious introductory level overview of these subjects. Emphasis is placed on the aspects of chemical kinetics and material and energy balances that form the foundation for the practice of reactor design. The text is designed as a teaching instrument. It can be used to introduce the novice to chemical kinetics and reactor design and to guide him until he understands the fundamentals well enough to read both articles in the literature and more advanced texts with understanding. Because the chemical engineer who practices reactor design must have more than a nodding acquaintance with the chemical aspects of reaction kinetics, a significant portion of this textbook is devoted to this subject. The modern chemical process industry, which has played a significant role in the development of our technology-based society, has evolved because the engineer has been able to commercialize the laboratory discoveries of the scientist. To carry out the necessary scale-up procedures safely and economically, the reactor designer must have a sound knowledge of the chemistry involved. Modern introductory courses in physical chemistry usually do not provide the breadth or the in-depth treatment of reaction kinetics that is required by the chemical engineer who is faced with a reactor design problem. More advanced courses in kinetics that are taught by physical chemists naturally reflect the research interests of the individuals involved; they do not stress the transmittal of that information which is most useful to individuals engaged in the practice of reactor design. Seldom is significant attention paid to the subject of heterogeneous catalysis and to the key role that catalytic processes play in the industrial world. Chapters 3 to