‘Second Edition CHEMICAL ENGINEERING KINETICS JM. Smi Professor of Ch University of Califor SMITH, J.M. CHEMICAL ENGINEERING KINETICS co St. Louis Siyah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 4, Kenter. Charles A. Goekring supervised production 129434 TPL $64 1970 . | aaa wi ‘0020115063 CHEMICAL ENGINEERING KINETICS, Second Ealtion Copyright © 1970 by McGraw-Hill, In: All ights reserved. No part ofthis publica may be reproduced, stored in a retrieval system, or transmitted, in any form or by means, electronic, mechanical, photocopying, recording, or otherwise, without prior written permission of the publisher. i Printed in the United States of America, : Library of Congress catalog card number: 74-9920 567890 MAMM 798765432 » 53693ww. Melt PREFACE = “he first edition of Chemical Engineering Kinetics appeared when the rational design of chemical reactors, as opposed to empirical scaleup, was aan emerging field, Since then, progress in kinetics, catalysis, and particularly in engineering aspects of design, has been so great that this second edition is 1 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 rates 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 well as such physical processes as mass and eneray transport. Hence, the intrinsic rate of chemical reactions is accorded a good rheasure of attention: in a general way in the second chapter and then with spebific 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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-fiow and stirred-tank behavior are emphasized A brief introduction to deviations from these ideal forms is included in this chapter and js 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 noniso- thermal behavior. Chapter 7s an introduction to heterogeneous systems. The concept of 2 global rate of reaction is interjected so as to relate the design of heteroge- neous 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. 11). 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 isto combine intrinsic rate equations with intrapellet and fluid-to-pellet 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 rate 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 dati 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 con- sidered, but major attention is devoted to the fixed-bed type. Finally, in thelast chapter gas-solid, noncatalytic reactions are analyzed, both from a sing pellet (global rate) viewpoint, and in terms of reactor design. These systems offer examples of interaction of chemical and physical processes under transient conditions No effort has boen 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 under- graduate 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 valuable 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 @ continuing inspiration. JM. SmithNOTATION (Ah Ca ope ae concentration of component 4, moles/volume feequency factor in Arrhenius equation area activity or pore radius external surface per unit mass molal concentration, moles/volume initial or feed concentration, moles/volume concentration in bulk-gas stream, moles/volume concentration of component adsorbed on a catalyst surface, moles/mass molal heat capacity at constant pressure, energy/(moles) (temperature) concentration at catalyst surface, moles/volume specific heat at constant pressure, energy/(mass) (temperature) combined diffusivity, (length)*/time bulk diffusivity, (length)*/time Knndsen diffusivity, (length)?/timeeffective diffusivity in a porous catalyst, length)*/time diameter of pellet activation energy/mole feed rate, mass or moles/time free-energy change for @ reaction, energy/mole fugacity, atm fluid mass velocity, mass/(area) (time) enthalpy, energy/mass AH enthalpy change for @ reaction, energy/mole b heat-transfer coefficient, energy/{time) (area) (temperature) JO) residence-time distribution function K equilibrium constant for a reaction adsorption equilibrium constant k specific reaction-rate constant K reverse-reaction-rate constant ky Boltzmann’s constant, 1.3805 x 107!° erg/°K effective thermal conductivity, energy/(time) (length) (temperature) ky rmass-transfer coefficient (particle to fluid) k overall rate constant ic length M molecular weight (17), mass/mole m N N’ Se p ROB USS number of moles 7 molal rate, molesjtime > partial pressure, atmospheres B total pressure, atmospheres Q volumetric flow rate, volume/time Q heat-transfer rate, energy/time q heat flux, energy/(area) (time) r radius, radial coordinate r reaction rate, moles/(volume) (time) r average rate of reaction, moles/(volume) (time) i global reaction rate, moles/(mass catalyst) (time) global reaction rate, moles/(volume of reactor) (time) ‘gas constant, energy/{(temperature) (mole) or (pressure) (volume)/(temperature) (mole)pope Bes oe NSH EEE NRE tae ep rt aos selectivity overall selectivity entropy, energy/(mole) (temperature) entropy change for a reaction, energy/{mole) (temperature) pore surface area (of catalyst) per unit mass temperature, absolute time overall heat-transfer coefficient, energy/(time) (length?) (temperature) superficial velocity, length/time pore volume (of catalyst), volume/mass reactor volume specific volume, per unit mass molecular weight (M), mass/mole weight fraction conversion, yield, or distance mole fraction axial distance ratio of global rate to rate evaluated at bulk-fluid conditions void fraction solids fraction effectiveness factor residence time mean residence time viscosity, mass/length) (time) density, massjvolume density of catalyst pellet, mass/volume Thiele-type modulus for a porous catalyst density of bed of catalyst pellets, mass/volumeCONTENTS Preface Notation INTRODUCTION 1-1 Interpretation of Rate Data, Scale-up, and Design 1-2 Principles of Chemical-reactor Design 1-3. Chemical Kinetics 1-4 Kinetics and Thermodynamics 15. Thermodynamics of Chemical Reactions 16 Classification of Reactors KINETICS OF HOMOGENEOUS REACTIONS, 24 Rate of Reaction -2 Concepts of Kinetics 2:3 The Arrhenius LawRate Theories 44 2-4 Collision Theory 4 25 Activated-complex (Transition-state) Theory 47 2-6 Unimolecular Reactions 50 Analysis of Rate Equations 32 27 Integrated Rate Equations for Irreversible Reactions 52 28 Reversible Reactions 60 29 The Total-pressure Method of Studying Kinetics B Analysis of Complex Rate Equations 15 2.10 First-order Complex Reactions 16 211 Chain Reactions 2 212 Rate Constants and Equilibrium 86 2.13 Precision of Kinetic Measurements 87 3. DESIGN FUNDAMENTALS 7 5-1 Reactor Design and Laboratory Rate Data 7 3-2 Mass and Energy Balances 100 3-3 The Ideal Stirred-tank Reactor »/ ; 105 3-4 The Ideal Tubular-flow (Plug-flow) Reactor ” 110 3-5 Deviations from Ideal Reactors: Mixing Concepts Ls 3-6 Space Velocity and Space Time in Tubular-flow Reactors “117 3-7 Temperature Effects 121 3-8 Mechanical Features 12 4 HOMOGENEOUS REACTOR DESIGN: ISOTHERMAL CONDITIONS 130 Ideal Batch Reactors “ 130 41 Simplified Design Equation for Constant Volume 131 42 Design Procedure 132 Ideal Tubular-Flow (Plug-Flow) Reactors 137 43 Interpretation of Data from Laboratory Tubular-Flow Reactors 137 44 Design Procedure 156 Ideal Stirred-Tank (Flow) Reactors “ 166 45 Singlestirred-tank Reactors _ 166‘cones 446 Stirred-tank Reactors in Series 47 Comparison of Stirred-tank and Tubular-flow Reactors 48 Non-steady-flow (Semibaich) Reactors 5 TEMPERATURE EFFECTS IN HOMOGENEOUS. REACTORS 5-1 Ideal Batch Reactors 5-2 Ideal Tubular flow Reactors 5-3 Ideal Stirred-tank Reactors (Flow) 5-4 Stable Operating Conditions in Stirred-tank Reactors 5-5 Semibatch Reactors 6 DEVIATIONS FROM IDEAL REACTOR PERFORMANCE, Mixing Concepts and Models The Residence-time Distribution Function Residence-time Distributions from Response Measurements 6-4 Residence-time Distributions for Reactors with Known Mixing States 6-5 Interpretation of Response Data by the Dispersion Model 6-6 Interpretation of Response Data by the Series-of stirred-tanks Model 6-7 Conversion in Nonideal Reactors 6-8 Conversion According to the Segregated-flow Model 6-9 Conversion According to the Dispersion Model 6-10 Conversion According to the Series-of-strred-tanks Model a 6. 6 7 HETEROGENEOUS REACTORS 7-1 Global Rates of Reaction 7-2 Types of Heterogeneous Reactions 8 HETEROGENEOUS CATALYSIS General Characteristics 8-1 The Nature of Catalytic Reactions 8-2 The Mechanism of Catalytic Reactions nm 175 184 203, 206 212 27 230 236 243 246 248 251 254 258, 261 263 266 268 273 274 279 282 283 283 28510 Adsorption on Solid Surfaces 8:3 Surface Chemistry and Adsorption 8-4 The Langmuir Treatment of Adsorption Physical Properties of Catalysts 8-5 Determination of Surface Area 86 Void Volume and Solid Density 8-7 Pore-volume Distribution Classification and Preparation of Caralysts &8 Classification of Catalysis &-9 Catalyst Preparation 8-10 Promoters and Inhibitors $11 Poisons (Catalyst Life) KINETICS OF FLUID-SOLID CATALYTIC REACTIONS Chemisorption Rates and Equilibriam 9-1 Rates of Chemisorption © 9-2 Adsorption Isotherms Rates of Fluid-solid Catalytic Reactions 9-3 Rates of Adsorption and Desorption 94 Rate Equations in Terms of Concentrations in the Fluid Phase at the Catalyst Surface 9-5 Qualitative Analysis of Rate Equations 946 Quantitative Interpretation of Kinetic Data EXTERNAL TRANSPORT PROCESSES IN HETEROGENEOUS REACTIONS Fixed-bed Reactors 10-1 The Effect of Physical Processes on Observed Rates of Reaction 10-2 Mass- and Heat-transfer Correlations 10-3 Calculation of External Concentration Differences 10-4 Calculation of External Temperature Differences 10-5 Effect of External Resistances on Selectivity Fluidized-bed Reactors 10-6 Mass-and Heat-transfer Correlations 287 287 291 294 296 302 306 318. 318, 320 322 323 329 329 329 332 335 336 339 343. 347 397 358 360 362 368, 370 379 380 381u 12 Sturry Reactors 10-7 Mass-transfer Correlations 10-8 The Effect of Mass Transfer on Observed Rates REACTION AND DIFFUSION WITHIN POROUS CATALYSTS: INTERNAL TRANSPORT PROCESSES Intrapellet Mass Transfer 1-1 Gaseous Diffusion in Single Cylindrical Pores 11-2 Diffusion in Porous Catalysts 113 Surface Diffusion Intrapellet Heat Transfer 11-4 Concept of Effective Thermal Conductivity ILS Effective-thermal-conductivity Data Mass Transfer with Reaction 11-6 Effectiveness Factors 11-7 The Significance of Intrapellet Diffusion. Evaluation of the Effectiveness Factor 11-8 Experimental and Calculated Effectiveness Factors 11-9 The Effect of Intrapellet Mass Transfer on Observed Rate ‘Mass and Heat Transfer with Reaction 11-10 Nonisothermal Effectiveness Factors I-11 Experimental Nonisothermal Effectiveness Factors Effect of Internal Resistances on Selectivity and Poisoning IL-I2 Selectivities for Porous Catalysts 11-13 Rates for Poisoned Porous Catalysts THE GLOBAL RATE AND LABORATORY REACTORS 12-1 Interpretation of Laboratory Kinetic Data 12-2 Homogeneous Laboratory Reactors 12-3 Heterogeneous Laboratory Reactors 12-4 Calculation of the Global Rate 12-5 The Structure of Reactor Design 383 387 390 399 aul 419 423 423 424 427 a8 434 439 4 445 409 452 453 451 466 468, 416 499 481 48513. DESIGN OF HETEROGENEOUS CATALYTIC REACTORS 493 Fixed-bed Reactors 494 13-1 Construction and Operation 494 13-2 Outline of the Design Problem 499 13-3 Isothermal Operation 500 13-4 Adiabatic Operation 506 13-5 Heat Transfer in Fixed-bed Reactors 509 13-6 The One-dimensional Model 522 13-7 The Two-dimensional Model 536 138 Dynamic Behavior 347 Fluidized-bed Reactors 349 13-9 Heat Transfer and Mixing in Fluidized-bed Reactors 550 13-10 Design Procedures 553 Sturry Reactors 5s7 Optimization 561 14 FLUID-SOLID NONCATALYTIC REACTIONS sm 14-1 Design Concepts sm 142 Reaction Models 5B 14-3 Global Rate Equations (Shrinking-core Model) 516 14-4 Conversion vs Time for Single Particles (Constant Fluid Concentration) 580 Reactor Design 585 145 Uniform Composition in the Fluid Phase 585 1446 Variable Composition in the Fluid Phase 589 Index 597CHEMICAL ENGINEERING KINETICS Second Edition1 INTRODUCTION ‘The design and operation of equipment for carrying out chemical reactions require analysis of both physical and chemical processes. The principles governing energy and mass transfer are often as important as those which govern chemical kinetics. This combination of physical and chemical operations is also a distinguishing feature of chemical engineering; the design of chemical reactors is an activity unique to the chemical engineer. In designing a reactor the following factors must be considered the type and size needed, provisions for exchange of energy (usually as, heat), with the surroundings, and operating conditions (temperature, pressure, composition, low rates). We identify this problem as the process design of the reactor. A cost analysis to determine the most profitable design introduces further questions about construction materials, corrosion, utility requirements, and maintenance. In order to maximize profits, the instrumentation and a control policy (ranging from manual to closed-loop computer control) for optimum operation must be determined. Optimum design will also depend indirectly on estimates of such market conditions as the price-volume relationships for reactants and products. While these factors are important in overall design and operation of reactors, they willcuurten |_nemopucriox not be discussed in this book. Our use of the term design will be restricted to process design. ‘The rate of transforming one chemical species into another cannot be predicted with accuracy. It is a specific quantity which must be obtained from experimental measurements. Measuring the rate of chemical reactions is the art and science of chemical kinetics (to be discussed in Sec. 1-3). Chemical kinetics is not concerned with physical processes, but only with the rate of transformation of atoms and molecules from one structural form to another. In contrast, the rates of physical processes such as heat and mass transfer can in many types of reactors be estimated reliably from the flow and geometrical arrangements. Hence it is desirable to consider the design of types of reactors, rather than approach each chemical system as a separate entity. Because of the specific nature of chemical processes, this generalization is not as successful as it would be, say, for designing heat exchangers. However, some conclusions are possible for reactors, because the kinetics of chemical reactions of a given type, such as homo- geneous gas phase or gas-solid catalytic, have similarities ‘Our chief objective is to determine how to answer process-design questions for various types of chemical reactions and reactors. 11 Interpretation of Rate Data, Scale-up, and Design The chemical engineer depends on data from the chemist’s laboratory, the pilot plant, or a large-scale reactor to help him in his design work From this information he needs to extract, among other things, the rates of the chemical reactions involved, i.., the chemical kinetics of the system. Todo thishe must separate the effects of physical processes from the observed data, leaving rate information for the chemical-transformation step alone. He can then reintroduce the influence of the physical steps for the particular reactor type and operating conditions chosen for the commercial plant. The interrelationship of the physical and chemical steps must be considered twice: once in obtaining rate-of-reaction expressions from the available laboratory or pilot-plant data, and again in using these rate-of-reaction equations to design the commercial-scale reactor. The fist step, interpreta- tion of the available data, is as important as the second and entails generally the same type of analysis. Hence the interpretation of laboratory data will sometimes be discussed in parallel with the reactor-design problem in the chapters that follow. Interpreting laboratory-reactor data is not necessarily as difficult and does not always entail the same steps (in reverse order) as reactor design. Because there are fewer restraints (economic ones, for example), there is more flexibility in choosing a laboratory reactor. Itis common practice to design a laboratory reactor to minimize the signifSECTION I-]_OVTERPRETATION OF RATEDATA 3 icance of physical processes (see Chap. 12). This eliminates the need for accurate separation of physical and chemical effects and produces more accurate results forthe rates of the chemical steps. For instance, a laboratory reactor may be operated at near-isothermal conditions, eliminating heat- transfer considerations, while such operation would be uneconomical in a ‘commercial-scale system. It is important to consider the relationship between reactor scale-up (projection of laboratory or pilot-plant data to the commercial reactor) and reactor design. In principle, if the rates of the chemical reactions are known, any type of reactor may be designed by introducing the appropriate physical processes associated with that type of equipment. Scale-up is an abbreviated version of this design process. The physical resistances are not separated from the measured laboratory data but are instead projected directly to a large unit which presumably has the same intertelationship of chemical and physical processes. If the dimensions and ‘operating conditions for the large-scale reactor can be determined to ensure that the interrelationships of chemical and physical processes are the same as in the laboratory unit, then the laboratory results may be used directly to prodict the behavior of the large-scale reactor. In a scale-up process no attempt is made to determine the rate of the chemical steps, that is, to evaluate the chemical kinetics of the process. However, when scale-up is applicable, it provides a rapid means of obtaining approximate reactor sizes, and also indicates the important parameters in the interrelationship between physical and chemical processes (see Sec. 12-5). ‘Scale-up will have a much better chance for success if the laboratory and commercial operations are carried out in the same type of system. Suppose that laboratory data for the thermal cracking of hydrocarbons are obtained in continuous tube through which the reaction mixture flows. Ifa tubular-flow reactor of this type is also proposed for the com= mercial plant, it may be possible to scale-up the pilot-plant operation in such a way that the temperature and concentration gradients within the tube will be the same in both systems. Then performance of the large-scale reactor—for example, conversion of reactants to various products—can be predicted directly from the laboratory results. However, ifthe laboratory results were obtained from a batch reactor, # tank or vessel into which the reactants are initially charged (see Sec. 1-6), itis difficult to project them directly to a large-scale tubular reactor. In this case it would be necessary to analyze the laboratory data to obtain the rate equation for the chemical reactions and then use these results to design the commercial reactor. Our emphasis will be on this two-step process of determining the rates of reaction from laboratory data and then using these rates for design. ‘The foregoing comments do not imply that pilot-plant data from asmall-scale replica of a proposed commercial unit are of no value. Such information provides an important evaluation of both the laboratory rate data and the procedures used to reintroduce the physical processes in the pilot reactor and, presumably, in the final equipment. Our discussion thus far of the interrelationship of chemical and physical processes in a reactor has been general. Let us look further into the problem by considering a very simple reaction system, the conversion of ortho hydrogen to the para form.' Owing to thermodynamic restrictions (Gee Sec. 1-5), this reaction must be carried out at a low temperature in order to obtain a large conversion to para hydrogen. At low temperatures it is necessary to use a catalyst to obtain a rapid rate of reaction. The pre- ferred type of reactor is a continuous steady-state system in which hydrogen flows through a tube packed with pellets of the solid catalyst. Consider the interpretation of rate measurements made with a laboratory version of this type of reactor. The observed data would consist of measurements of hydrogen compositions in the inlet and exit streams of the reactor. Probable variables would be the flow rate of hydrogen through the reactor, the mole fraction of para hydrogen in the feed to the reactor, and the temperature. The heat of reaction is negligible, so that the whole reactor system can easily be operated at isothermal conditions, The first problem in designing a reactor for the production of para hydrogen is to obtain from the observed measurements a quantitative expression for the rate of reaction on the surface of the catalyst. Specif- ically, we must separate from the observed data the diffusional resistances between the point at which the composition is measured—the exit of the reactor—and the point at which the chemical transformation occurs—the gas-Solid interface at the catalyst surface. There are three diffusional effects that may cause a difference between the conversion measured in the exit of the reactor and that predicted from the rate at the catalyst interface. ‘The first arises from the mixing characteristics of the fluid as it flows around the particles in the fixed bed. There may be some bypassing or short cir- cuiting, so that part of the flowstream does not come into contact with the catalyst; also, there may be diffusion or back-mixing of fluid as it flows through the bed. As a result, the observed amount of para hydrogen in the exit gas may be less than expected. The second factor is the tendency of the fluid to adhere to the catalyst pellet, so that the pellet is surrounded by a more or less stagnant layer of fluid which resists mass transfer. Thus a con- centration gradient of para hydrogen must be established between the outer surface of the pellet and the bulk gas before the para hydrogen will "This reactor-esin problem has some practical significance because of the supeior storage «properties of liquid hydrogen when iis in the para form. Noriaki Wakao and J. M. Smith AICHE J, 8,478 (1962),move on into the gas stream. This reduces the amount of para hydrogen available to the bulk-gas phase. A third factor is that most of the active surface of the catalyst is in the pores within the pellet. The reactant must, reach this interior pore surface by diffusing into the pellet, and the product, must diffuse out. This process is impeded by intraparticle resistance, causing. another reduction in the para-hydrogen content of the gas stream. Thus to determine the rate of reaction on the surface of the catalyst (the chemical kinetics of the process) it is necessary to evaluate the concentration changes, for each of these diffusional effects, ultimately arriving at the concentration of para hydrogen in the interior pore surface of the catalyst pellet. The interior concentration can then be used to establish a rate-of-reaction equation. ‘The second problem is use of the rate equation to design a commercial reactor. The individual diffusional resistances are now reintroduced so that, we may determine the actual composition of para hydrogen in the exit stream from the reactor. Once the equation for the surface rate is known, it is possible, in principle, to predict the exit conversion for any type of re- actor, any size catalyst pellet, any conditions of gas flow around the pellet, and any condition of mixing of fiuid around the particles in the fixed bed. If the same problem were approached from a scale-up standpoint, the procedure would be to attempt to choose the operating conditions and reactor size forthe large-scale reactor such that the diffusional resistances, were the same as in the laboratory equipment. 12 Principles of Chemical-reactor Design Now that we have discussed briefly the problems in chemical-teactor design, let us explore the concepts necessary to solve these problems." First, we must know something about the formulation of equations for the rate of ‘chemical transformation from one species to another. This is the subject of chemical kinetics. While we cannot predict the rate of a chemical reac- tion, chemical kineticists have developed a number of valuable generaliza- tions for formulating rate equations. It is necessary to understand these generalizations before proceeding with the design problem. Also, the rate equation must account for the thermodynamic limitations on the chemical reaction. For example, the ortho-para hydrogen conversion is a reaction in ‘which the maximum conversion is less than 100%. An understanding of the equilibrium conversion as a function of operating conditions is necessary before a satisfactory rate equation can be formed. Thermodynamics also "RAs [Und Eng. Chem, 56,22 (1968)] and J, M. Smith (Chem. Eng. Progr 64 78 (1968)] have show how physical nd chemical sciences play role inthe design, analysis, nd contol of reactor,6 ccuartex |_isrmopucTion ‘comes into play in evaluating energy transfer in the reactor. Hence @ primary requisite is a knowledge of chemical thermodynamics (Sec. 1-5). ‘Along with kinetics, the engineering concepts required to evaluate the conversion in the product from a reactor are of two types: the principles, of conservation of mass and energy and rate equations for the physical processes. The conservation of mass and the rate of mass transfer determine the composition as a function of position in a continuous reactor and as a function of time in a batch reactor. Similarly, the conservation of energy and the rate of energy transfer determine the temperature as a function of position or time. The application of these principles is discussed in sub- sequent chapters, starting with Chap. 3 where mathematical formulations are considered for various types of reactors, 1-3 Chemical Kinetics Chemical kinetics is the study of the rate and mechanism by which one chemical species is converted to another. The rate is the mass, in moles, of a product produced or reactant consumed per unit time. The mechanism is the sedjence of individual chemical events whose overall result produce the observed reaction. Basolo and Pearson! have described the term” “Smechanism’” as follows: ‘By mechanism is meant all the individual collisional or elementary processes jinvalving molecules (atoms, radicals ‘and ions iochuded) that take place Siul- tateouslyor consecutively in’ producing the observed overall fate. It is also tinderitood that the mechanism of a reaction should give a detailed stereo- chemical picture of each step 28 i occurs. This implies 2 knowledge of the soiled activated complex or tanstion slate, not only in tems of the con- stituent molecules but also in terms ofthe geometry, suchas interatomic distances and angles. In most instances the postulated mechanism isa theory devised to explain the end esults observed by experiments. Like other theories, mechanisms are subject to change over the years as new data is uncovered or as new concepts regarding chemical intereactions are developed. Itis not necessary to know the mechanism of a reaction in order to design a reactor. What is necessary is a satisfactory rate equation. A know!- edge of the mechanism is of great value, however, in extending the rate data beyond the original experiments and in generalizing or systematizing the kinetics of reactions. Determining the mechanism of a reaction is a very difficult task and may require the work of many investigators over a period of many years. Reaction mechanisms are refiably known for only a 1, Rasolo and R. G. Peareon, “Mechenisms of Inonganie Resetions,” Inc, New York, 1958, fohn Wiley & Sons,SECON 1-3 _cHenaca few systems. However, postulated theories for mechanisms are available for a wide variety of reactions, ranging from simple, gas-phase homogeneous systems to complicated polymerization reactions involving initiation, propagation, and termination steps. Since reactor design necessitates a reliable rate equation, this aspect of chemical kinetics is presented in detail in Chap. 2. Successful procedures for predicting rates of reactions will not be developed until reaction mechan- isms are better understood. Tt is important for those involved in reactor design to be aware of developments in this area so that they may take advantage of new principles of chemical kinetics as they are developed. ‘A brief discussion of theories of reaction and mechanisms is included in Chap. 2 The rate of a chemical reaction can vary from a value approaching infinity to essentially zero. In ionic reactions, such as those that occur on photographic film, or in high-temperature combustion reactions, the rate is extremely fast. The rate of combination of hydrogen and oxygen in the absence of a catalyst at room temperature is immeasurably slow. Most industrially important reactions occur at rates between these extremes, and it is in these eases that the designer must apply data on kinetics to termine finite sizes of reaction equipment. It is particularly important to know how the rate changes with operating parameters, the most important of which are temperature, pressure, and composition of reaction mixture. ‘The science of kinetics is young. The first quantitative measurements of reaction rates were made in the middle of the nineteenth century by Wilhelmy,' Berthejot and St. Gilles,’ and Harcourt and Esson.? The first attempt to develop a theory explaining the manner in which molecules of a substance react was that of Arrhenius’ in 1889. He postulated that the reactants had both inert and active molecules and that only the active ones possessed sulffcient energy to take part in the reaction. Since these early developments there have been a great many experimental studies of reaction, rates for a wide variety of reactions, but few noteworthy advances in theory were made until the work of Byring and Polanyi,® beginning in 1920. Using only such fundamental information as the configurations, dimensions, and interatomic forces of the reacting molecules, they postulated an activated- complex theory for predicting the rate of reaction. Lack of exact knowledge of the interatomic forces, and hence of energy-position relations, for any but the most simple molecules has prevented the activated-complex theory L, Wilhelmy, Pops. Ann, Bt, 413; 499 (1850) 2M, Berthelot and LP. St. Giles, Ann. Chim. Phys, 63 (3,385 (1862). 2A: V. Harcourt and W. Esso, Proc. Roy. Soe (London), 14, 470 (1865). 3, Arthenius, Z. Physik Chem, 4, 226 (189). *H. Eyring and M. Polanyi, Z. Physik Chem. 8, 12,279 (1931)8 carrer |_nitmooucrion eee etecouee from being useful for predicting reaction-rate data accurately enough for engineering work. While these theoretical developments have been of great value in the search for an understanding of how and why a chemical reaction takes place, the quantitative evaluation of the rate remains an experimental problem. ‘The large amount of experimental data on rates of chemical reaction have established reliable empiriéal forms for the mathematical expression of the effects of such variables as temperature and composition on the rate These results are interpreted for various types of reactions in Chap. 2. 1-4 Kinetics and Thermodynamics From the principles of thermodynamics and certain thermodynamic data the maximum extent to which a chemical reaction can proceed may be calculated, For example, at 1 atm pressure and a temperature of 680°C, starting with 1 mole of sulfur dioxide and 1 mole of oxygen, 50% of the sulfur dioxide can be converted to sulfur trioxide. Such thermodynamic calculations result in maximum values for the conversion of a chemical reaction, since they are correct only for equilibrium conditions, conditions such that there is no further tendency for change with respect to time It follows that the net rate of a chemical reaction must be zero at this equilib- rium point. Thus a plot of reaction rate [for example, in units of g moles product/(Sec) (unit volume reaction mixture)] vs time would always approach zero as the time approached infinity. Such a situation is depicted in curve A of Fig, 1-1, where the rate approaches zero asymptotically. Of course, for some cases equilibrium may be reached more rapidly, so that the rate becomes almost zero at a finite time, as illustrated by curve B. Similarly, the conversion (fraction of reactant transformed or con- verted) calculated from thermodynamic data would be the end point on ‘2 curve of conversion vs time such as that shown in Fig. 1-2. Again, curve 1A represents the case where the time required to reach equilibrium con- ditions is great, while in case B the equilibrium conversion is approached rmore rapidly and is attained essentially at a finite time. Curves 4 and B could apply to the same reaction; the difference between them reflects the fact that in case B the rate has bees increased, for example, by use of a catalyst. The rate of the reaction is initially increased over that for the ‘uncatalyzed reaction, but the equilibrium conversion as shown in Fig. 1-2 is the same for both cases. ‘The time available for carrying out a chemical reaction commercially is limited if the process is to be economically feasible. Hence the practical range of the curves in Figs. 1-1 and 1-2 is at the lower time values. However, the equilibrium conversion is important as a standard for evaluating the actual performance of the reaction equipment. Suppose a kinetics experi-secrion 1-4 _ KINETICS AND THERMODYRAMICS ° Rate of regetion 4 | Equilibrium ‘Time Fig. PI Rate of reaction vs tie ment is carried out with a time corresponding to the dashed vertical line shown in Fig. 1-2, At this point the conversion for the noncatalytic reaction js about 25% (curve 4). A comparison with the equilibrium value of 50% indicates that the noncatalytic rate is rather low and that a search for a catalyst is advisable. Curve B, giving a conversion of 45%, shows the benefit of using a catalyst and also indicates that additional effort to find a more Fig. 1-2. Conversion vs time Equilibrium Conversion, % Seale change:10 curren 1_nemooucTion effective catalyst is unwarranted. Without prior knowledge of the equilib- rium conversion, erroneous conclusions might well be drawn from the kinetic studies yielding curves A and B. For example, it might be reasoned that the catalyst giving curve Bis only moderately effective, and considerable time might be spent in attempting to discover a catalyst which would give a conversion of 70 or 80% Thermodynamic calculations are particularly valuable for such comparison of kinetic and equilibrium results. However, the actual design of reactors usually depends on the location of the curves shown in Figs. I-I and 1-2 and must therefore be determined by kinetic studies Prediction of the equilibrium conversion requires knowledge of the free-energy change for the reactions involved. Although the body of thermodynamic data is growing, it is still not possible to estimate the equilibrium conversion accurately for all reactions. The calculations and data available for gascous systems are most reliable. The application of thermodynamics for such calculations is illustrated very briefly in the following section. More detailed treatment of the thermodynamics of chemical-reaction equilibrium is given in thermodynamics textbooks." The rate of energy transfer is important in determining the temperature distribution in reactors. Also, beats of reaction are significant in connection with equilibrium calculations. The following section deals with data and methods concerning heats of reaction, followed by a discussion of equilib- rium conversion. 15 Thermodynamics of Chemical Reactions Heat of Reaction ‘The heat of reaction is defined as the energy absorbed by the system when the products after reaction are restored to the same tempera- ture as the reactants. The pressure must also be specified for a complete definition of the thermodynamic states of the products and reactants. If the same pressure is chosen for both, the heat of reaction is equal to the enthalpy change; this is the customary definition of the heat of reaction. The heat of any reaction can be calculated by combining heats of formation or heats of combustion of the products and reactants. Thus the basic information necessary for calculating heats of reaction are heats of formation and 'B, F, Dodge, “Chemical Engineering Thermodynamics," McGraw-Hill Book Company, New York, 1944; J. G. Kirkwood and Irwin Oppenheim, “Chemica! Thermodynamics,” McGraw-Hill Book Company, New York, 1961; G. N. Lewis and M. Randall, “Thermo- dynamics,” 24 ed, rev. by K. S. Pitzer and Leo Brewer, McGraw-Hill Book Company, [New York, 1961; J, M. Smith end H. C. Van Ness, “Introduction to Chemical Engineering “Thermodynamics” McGraw-Hill Book Company, Now York, 1959; H. C. Van Ness, “Classical Thermodynamics of Non-lectrolyte Solutions,” The Macmillan Company, In., New York, 1964sicmk 1-5 _TERNODYWAMICS OF CHEMICAL REACTIONS u Table 1-1 Standard heat of formation and combustion fr reaction products H,0(0 and COL4) a1 25°C, in calories per gram moe Substance ‘Normal paraffins Methane Ethane Propane neButane ‘Pentane n-Hexane Increment per C atom above Ce ‘Normal monoolefins (I-alkenes) Etbylene Propylene 1Botene Pentene -Hexene Increment per C atom above Cy, Miscellaneous organic compounds Acetaldehyde ‘Acetic acid Acetylene Benzene Benzene 1,3-Butadiene Cyloherane Cyclobexane Ethanol Ethanol Ethylbenzene Ethylene elyeot Ethylene oxide Methanol Methanol Methyeyelohexane Methylyclohexane Soyrene Toluene Toluene Miscellaneous inorganic compounds ‘Ammonia CCaleium carbide Calcium carbonate Calcium edoride Caleium chloride Calefur hydroxide Calcium oxide Formula cH Cay Cote Cities CH Cte oH, CH Cae CoHie CB cH CHO, State AHiaow ~ 17889 =20236 24820 30.150 35000 39960 4925 186 4379 “30 =5.000 33960 43925 -39,10 = 116/400 sa94 19820 10 26330 29430 37340 35.240 66,356 7129 ~ 108/580 = 12190 = 48,100 =57036 36990 45450 35220 11950 2810 =11,040 = 13/000 788,450 190,000, 023.150 235,800, =151;900 abies 212,800 372,820 30,600 es7.640 845,160 1,002,570, 157440 31.230 491.990 649,450 06.850 964.260 157,440 310,600 79,080 ‘70.930 607,450 984.790 936,880 1,101,120 1,059,590 091,130, 1060900 943,380 934,3002 ‘cuarrex |_pergooucTion Table 1-1 (Continued) Substance Formula sute AHjay Bane Sere carbon c Graphite 94052 Carbon dioxide co; | ~94052 ‘Carton monoxide co. 2 25416 67,656 Hydrochloric acd Re. 2-206 Hydrogen Hy 9 8317 Hydrogen slide Hs etc) Iron oxide FeO. 5 64,300 Iron oxide FeO, s 267/000 Iron oxide Fe,05 2 196,500 Iron suide FS, = 782520 Lithium ebloside ict = ~97700 Lithium ebloride Licl- H,0 r ~110310 Tithium chloride LiCl 2.0 s -247,100 Lithium eboride LiCl 34,0 = 313,500 Nitec acid HNO, 1 =4la04 Nitrogen oxides NO @ 21,600 NO, a Bot NO a 19,490 N04 a 2,309 Sodium carbonate NaC, F ~220,300 Sodium earbonate Na,C0,-10H,0 s—=975,600 Sodium chloride Nel 98282 Sodium hydroxide NaOH, =z ~ 101390 Sulfur dioxide 80, 2 -70960 Sulfur trioxide 805 2 94450 Sulfor tioxide 805 it =108,800 Sulfuric acid H,SO, 1 =193810 Water 0 a 51,98 Water 10 1 68317 “ounce: Most values have been selected from the publication of F. D. Rossini etal, Selected Values of Physi and Thermodynamic Properties of Hydcocerbons and Related Compounds, Mme Petrol, Test. Res, Proj. 44, Carnegie Institute of Technology, Pitsburgh, 1953; FD. ‘Rowing cal, Seested Values of Chemical Thermodynamic Properties, Natl. Bur. Sds. Cir 500, 1952. combustion. Extensive tables of these data have been accumulated,’ and a few values are summarized in Table 1-1 ‘Selected Values of Chemical Thermodynamic Properties, Natl, Bur. Sds. Cre. 00, 1952: Selected Values of Physical and Thermodynamic Properties of Hydrocarbons and Related Gorapounds, dm. Pewol. Inst. Ret. Proj 4, Carnegie litte of Technology, Pitsburg, 1953.