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, flow 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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. Its 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 physicel 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 asa 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 1-1 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-stale 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, ic, the chemical kinetics of the system. ‘Todo this he 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 physica 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, aad again in using these rate-of-reaction ‘equations to design the commercial-cale reactor. The first step, interpreta- tion of the available data is as important as the second and eniails 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 dificult and does not always ental the same steps (in reverse order) as reactor design. Because there are fewer restraints (economic ones, for example), thete is more flexibility in choosing a laboratory reactor. ‘Icis common practice to design a laboratory reactor to minimize the significance of physical processes (see Chap. 12). This eliminates the need for accurate separation of physical and chemical effects and produces more accurate results for the rates ofthe chemical steps. For instance, a laboratory reactor may be operated at near-isothermal conditions, eliminating heat- trarisfer considerations, while such operation would be uneconomical in a commercial-scale system I 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 fare 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 ditectly to a large unit which presumably has the same interrelationship of chemical and physical processes. Ifthe 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 predict 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 @ 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. If a tubular-low reactor of this type is also proposed for the com- ‘mercial plant, it may be possible to scale-up the pilot-plant operation i 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 producis—can bbe predicted directly from the laboratory results. However, ifthe laboratory results were obtained from a batch reactor, a tank or vessel into which the reactants are initially charged (see Sec. 1-6), it is 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 @small-scale replica of a proposed commercial unit are of no value. Such information provides an important evaluation of both the laborajory 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 (see Sec. 1-5), this reaction must be cartied out at a low temperature in order to obtain a large conversion to para hydrogen. At low temperatures itis necessary to use a catalyst to obtain a rapid rate of reaction. The pre- ferred type of reactor isa 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 laydrogen compositions inthe 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 beat 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 hhydrogen is to obtain from the obsecved measurements @ quantitative expression for the rate of reaction on the surface of the catalyst. Speci ically, we must separate from the observed data the diffusional resistances between the point at which the composition is measured—the exit of the teactor—and the point at which the chemical transformation occurs—the sas-solid interface at the catalyst surface. There are three difusional 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 xing characteristics ofthe fuid as it flows around the particles in the fixed bed. There may be some bypassing or short ci citing, so that part of the fowstream does not come into contact withthe 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 isthe tendency of the fluid to adhere to the catalyst pellet, so that the pellet is surrounded by a more of less stagnant layer of fuid which resists mass transfer. Thus a con- ceniration gradient of para hydrogen must be established between the outer surface of the pellet and the Bulk gas before the para hydrogen wil "This ectondsgnpoblon has some practi siitnace bea ofthe pero seraye «prope fli! yogen when i i the ur Tor, Noval Wakao and. Seth CAE S, 8, 8 (1952)2erION 1-2_PRINGILES OF CHEWCAL REACTOR DESON 5 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 surfact 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 nother 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 ofthe 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 fluid 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 for the large-scale reactor such thatthe diffusional resistances were the same as in the laboratory equipment. 1-2 Principles of Chemical-reactor Design Now that we have discussed brelly the problems in chemical-reactor design, let us explore the concepts necessary to solve these problems." First, we ‘must knows something about the formulation of equations for the rate of chemical transformation ftom 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 forthe thermodynamic imitations 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 cquilibrium conversion as a function of operating conditions is necessary before a satisfactory rate equation can be formed. Thermodynamics also SR. Alia [ind Eng. Cher, 56,22 0968 a3 M Sait (Chm Brg Por, 64, T1965} have shown how psa snd chemi eenes play arlene Ss, aa, and onl treater.‘comes into play in evaluating energy transfer inthe reactor. Hence a primary requisite is a knowledge of chemical thermodynamics (See. 1-3). ‘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 @ function of time in a batch reactor. Similarly, the conservation of enerzy 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 Kineties ‘Chemical kinetics is the study of the rate and mechanism by which one chemical species is converted to ancther. The rate is the mass, in moles, fof a product produced or reactant consumed pér unit time. The mechanism ig the sequence of individual chemmical events whose overall result produce the observed reaction. Basolo and Pearson! have described | “nechanism’™s follows: By mechanism is mesat all the individual collisional or elementary processes, involving molecules (atoms, radials and ions fachuded) that take place simul tancovsly or consecutively in producing the observed overall ate. It is also ‘underitood that the méchanism of a reaction should give a detailed stereo- chemical picture of each step as it occurs. This implies a knowledge of the so-called activated complex or transition slate, not only in terms of the con- stituent molecules but aso in terms ofthe geometry, suchas interatomic distances ‘and angles. In mos instances the postulated mechanism i a theory devised to ‘explain the end results observed by experiments. Like other theories, mechanisms ‘are subjert to change over the years as new data is uncovered or as new concepts regarding chemieslinterreactions are developed. It is 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 aver a period of many years. Reaction mechanisms are reliably known for only a 4, Basolo and R. G. Pearson, "Mechanisms of tnorganie Reations” John Wiley & Sons, Ine, New York, 1958,few systems. However, postulated theories for mechanisms are available fora 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 {or predicting rates of reactions will nt be developed until reaction mechan- isms are better understood. It is important for those involved in reactor Gesign 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 aceur 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 @ catalyst at room temperature is immeasurably slow. Most industrially important reactions occur at rates between these extremes, and it is in these cases that the designer must apply data on kinetics to ddotermine finite sizs 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,' Berthelot and St. Gilles? and Harcourt and Eston.? 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 sufficient 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 Eyring 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.Witheiny, Pogg. am, 81,413; 499 (1850, 2M, Berthelot and L. Pt. Giles, Aim. Chin. Phys, 6 3), 385 (1852. S40 Harcourt and W. Eason, Proc. Roy. Soe. (London), 14,40 (1969). *S. Acthenius,Z. Poet Chane 4 26 (188), PHL Eyring and M. Polanyi, Z. Poet Ohm, B, 12,279 (1931).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 experimentat problem, ‘The large amount of experimental data on rates of chemical reaction have established reliable empirical 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 Kineties and Thermodynamics From the principles of thermodynamics and certain thermodynamic data the maximum extent to which a chemical reaction ean proceed may be calculated. For example, at 1 atm pressure and a temperature of 680°C, Starting with 1 mole of sulfur dioxide and '/ mole of oxygen, 50% of the sulfur dioxide can be converted to sulfur troxide. Such thermodynamic Galeulations result in maximum values for the conversion of a chemical reaction, since they are correct only for equilibrium conditions, conditions Such that there is uo further tendency for change with respect to time. Itfollows thatthe net rate of a chemical reaction must be zero a this equlib- rum point. Thus a plot of reaction rate [for example, in units of g moles product(scc) (unit volume reaction mixture)] vs time would always approsch Zero as the time approached infinity. Such a situation is depicted in curve A of Fig. 1-1, where the rate approaches 2ero 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 2. Simalarly, the conversion (Fraction of reactant transformed ar 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 4 represents the case where the time required to reach equilibsium con- Givions is great, while incase B the equilibrium conversion is approached nore rapidly and is atained 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 Geel increased, for example, by use of a catalyst. The rate of the reaction is initially increased over that for the Luncatalyzed reaction, but the equilibrium conversion as shown in Fig. 1-2 isthe same for both case. ‘The time available for carrying out a chemical reaction commescally is limited if the process is to be economically feasible, Hence the practical range ofthe curves in Figs. I-1 and 1-2 isa the lover time values. However, the equilibrium conversion is important as a standard for evaluating the actual performance of the reaction equipment. Suppose a Kinetics experi-seen vows ao rumwopmusaes 9 Rate ofeation Sexe change “ |= etn Time—~ Fig) Rote of reaction rs te meat is carried out with a time corresponding to the dashed vertical line shown in Fig. 1-2. Atthis point the conversion for the noncatalytic reaction is 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 @ catalyst is advisable. Curve B, giving a conversion of 45%, shows the banefit fof using a catalyst and also indicates that additional effort to find a more Fig.12 Conversion wine a quilibiun, z é Sle chan’ Time >effective catalyst is unwarranted. Without prior knowledge of the equilib- rium conversion, erroneous conclusions might well be drawa from the kinetic studies yielding curves 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%. Thetmodynamic calculations are particularly ‘valuable for such comparison of kinetic and equilibrium results. However, the actual design of reactars usually depends on the location of the curves shown in Figs. 1-1 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 gaseous systems are most reliable. The application of thermodynamics for such calculations is illustrated very brielly 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- 1-5 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. Ifthe ‘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 necessaiy for calculating heats of reaction are heats of formation and 'B. F, Dodge, “Chemical Engineering Thermodynamics," McGraw-Hill Book Company, [New York, 1944; JG. Kickwood and Irwin Oppenheim, “Chemical Thermodynamics,” MeGraw-Hill Book Compaoy, New York, 1961; ©. N. Lewis end M. Randal, “Thermo yoamics” 24 08, ror by K. S. Biter and Leo Brewer, McGraw-Hill Book Compny, "York, 1961; J. M. Smith and H.C. Van Ness, “Iauoduetion to Chemical Engineering Thermodyamica,” McGran-thill Rook Company, New York, 195% H. C. Van Nes, “Classical Thermodyaamies of Non-seczoste Solution,” The Macmillan Company, Toc. New York, 1964SécTON IL-5 tMaRNOO ANICS OF CHEACAL REACTIONS 4 Tobe 1 Standard hee of formation and combaton for reaction products M,OXD and COs) 129°C, in oleres pr gram mote Substance Formula State AM ap BN Nowmal pacais| Methane cH 3 = Inge 212800 Ethane Gaile 9 =10236 37200 Propane Gite 3 7482 53n.600 eBatane Coie 5 301s) 7640 Pentane coi 338000 45160, iene ca 2 3390 1002570 Increment per Catom above Cy, 9 naps "1sta80 ‘Normal monooleas (alkenes) Edhyene on . ssi230 Propylene om 9 ‘1300 1Batese cm 2 o5a30 1 Pentene Cie ° 6380 THterene Coie ° 94260 Increment per Catom shove Cy 2 sro Micllaneousexeanie compounds ‘Acetalehye CHO. 2 ‘Acetic aeid CyHLOs t ‘Acetylene ca * 310,60 Benzene Ee 8 78,30 Denzene ct 7 ‘0980 Butadiene can ‘ 50 Ghetobexane Cathe 2 984,750 Gyelonoxane coi i 6380 Ethanol HO ° Ethanol Gao i Ethylbeazeae Cie @ 70 1.10120 Elen pyc! CHO, 108300 Ethylene oxide Ho ° — 12190 Methanol cio 3 4800 Methanol co b sno Methyeylohesane CHa 2 =36950 1.059550, Metiytyctoherane Ce 1 Za530 081,130, Speene ci 535220 1010300 Tolvene ci 5 11950 943.580 ‘Tolvene im : 23m 934500 Miscellaneous inorganic compounds ‘Ammonia Na, ° Calum exebide ac, : (Caleta carbonate exc, : lsum chloride ac, : Cate chloride Gah, 6H4,0 5 Cale hydride xO), 5 Calsiam ovide G0 52 caurren |_nernooucrio mr scone Table 11 (Contiued) Substance Formila State Munn 4g carbon c Geaphite os (Carbon dosige co, 3 Hos ‘Carton monoxide co 3 8K 67636 Hiyérochloi acid Bet a 2208 yerogen By ° 317 Hydrogen sli Hs o ~aals ron oxide FeO 2 64300 ton onde FeO, 267,000 Iron oxide Fe0, f=136.500 Iroo slide Fe: za iho ehtride ict 2 n31 700 Lithium chloride ict 1,0 2 =170310 Tithiom ehloide Lici-2#,0 52287100 Thiam chloride Lil 38,0 F =3b500 Ntsc sca HNO, 1 Saneoe Nitroge exis NO 3 tks No, 5 S81 NO e 19.490 NO. ‘ 2308 Sodiom carbonate NaC, ¢ =770300 Sodium carbonate Ns,CO,-10H0 + ~975,600 Sodium chloride Nach Ba pa232 Sodium hyaeoxide Na0H + Sof diode 50; : Sole wloxide 0, a Sulfur wioxide 50; i Sulfuric #30, 1 Water 0 ‘ Water #0 : ee ounce: Most values have been select from the publications of FD. Rossin ta, Seaett Foe at Puyseal and Toermodyoamic Propet of Hydcocarbons and Relsed Compounds, seesscrot nce, Rez, Po} 4, Carnegie loaitue of Technology, Patsbure, 1953; FD. ‘Robin ta Slerted Valucs of Chesiea! Termodynanic Properties, Nat. Bur. St. Cs ‘00,1952. ‘combustion. Extensive tables of these data have been accumulated,! and & few values are summarized in Table 1-1 ‘seected Valots of Chemical Thermodynamic Properties, Natl, Par. Sts, Cie. 50, 1952; Suinted Valu of Physical and Thermodyaanic Propeciss of Hydrocarbons and Related ee an ain Pel Int Res. Pro 44, Camegie Toit of Technology, Pitsburg, 953SECTON I-S_TiERNeo NAC oF CHMNOEAL REACTIONS In the absence of experimental data, there are procedures available for predicting heats of reaction. These are all based on predictions of the effects of differences in the chemical structure of the reactants and products. One of the most useful procedures from an engineering standpoint is thet, proposed by Andersen etal, and described in detail by Hougea and Watson? ‘This method is applicable to compounds involving carbon, hydrogen, ‘oxygen; nitrogen, and the baloyens, ~~~ ~~ ‘The variation of heat of reaction with temperature depends on the difference in molal heat eapacites ofthe products and reactants. The fol- lowing equation relates A7/ at any temperature T tothe known value at the tase temperature Ty Ally = AF, + face ar ay Here AC, is the dflerence in mola heat capacities, LOC Dart = DOMC peer aay mean heat capacities C, are known for the reactants and products over the temperature range J, to T, it is not necessary to integrate Eq, (I-1). Under these conditions the relationship of AM, and AH, is AG, Atly = Mir + ENE pJyna © — 13) ~ LTD (P ~ Te) as ‘When reactants and products enter and leave a reactor at different tempera- tures, it is usually simpler to bypass calculating AM, and evaluate the desired energy quantity directly. This is ilustrated in Example 1-1, ‘The cfiect of pressure on the heat of reaction for gaseous systems depends on the deviation of the components from ideal-gas behavior. Ifthe reactants and products behave as ideal gases, there is no effect. Even for rather nonideal systems the effect of pressure is generally small. Details of the methods of calculating the effects of temperature and pressure are discussed in standard thermodynamics textbooks. 1. W, Andersen, G. H. Bejer, and K. M. Watson, Nall, Petrol Nowe, Teh. See. 36 (R476), Sly 5, 1948; RL. Evel nd ng. Chem. 32, 78 (190); FD. Resin, Ind Eng Chem 29, 142 (1937; Mott Souders, Jr, C. S. Mathews, ad C. 0. Hurd, Ind. Eng. Chem 1037, 1088 (1945); RC. Re and T,X, Sherwood "The Propertss of Gass and Liquid 2d ed, chap. 5, McGraw-Hill Book Company, New York, 1966 20. Hougen nd K. 4 Walon, “Chemieal Pres Princip,” 2d ef, vl. I, Joa Wiley # Sons, Inc, New York, 1991s urn 1_nrsooucri we tari tern ‘The application of heat-of-reaction information for calculating energy- transfer rates in reactors is illustrated in the following example © example 141 Ethylene oxide is produced by direct ordation with ar using a bed of atalyst particles (iver on a suitable easier). Suppose thatthe stream enters the ow eactor at 200°C and contains $ mole % ethylene and 95% air If the exit temperature ‘docs not exzeed 260°C. jt is posible to convert 50% ofthe ethylene to the oxide, although 440% is also completly bumed 0 carbon dioxide, How much heat must be removed {rom the reaction, per mole of ethylene fed, inorder not to exceed te limiting tempera ture? The average molal heat capacity of ethylene may be taken as 18 Btu/ib mle) (CR) between 25 and 200°C and as 19 Bro moleJCR) between 25 and 260°C. Similar Salts for elene oxide are 20 and 21 Brad moleX°R). The pressure is essentially atmospheris. Soluion Since heat effects at constant pressure are equal to enthalpy changes, the ‘aetual process may be replaced by ove that utlizs the available heatof-eaction ddata at 25°C (Table Il), The steps in this process are 1. Cool the reactants and sir from 200 to 25°C. 2. Carry out the reactions at 25°C 5. Heat the products and the ar from 25 to 260°C, “The sum of the enthalpy changes for each step willbe the total heat absorbed by the reaction sytem. rep} With basis of 1 mole of ethylene, there wil be °%41) ~ 19 moles of at fed ie rector. The mean heat capacity of tr from 25°C to 200°C is 7.0, Hence All, = 1(18(-477 = 392) + 19(1.0K+77 ~ 392) = —5,700 ~ 41,900 = = 4,600 Bed moe ser 2 Theonly heat fect is to the vo reasons Gas + 40, + HOF) CH, + 30, = 200, + 24010) Using the heat-f formation data in Table 11, for the fist reaction we obtain Ally, = ~12190 ~ 12,496 —0 = -24686caljg mole or ~44,500 Brajb mole and for the second ‘AFly, = 2(-51,798) + 294052) — 12,496 — 0 16,196 cag mole or ~569,000 Brae mole ‘Since, per mole of ethylene, there will be 0.5 mole reacting to form ethylene oxide and ‘04 mole to be completly burned, Alig, = 05(~44,500) + 0-4(—369,000) 250,000 Btu/tb moleSenin IS THERNOD AMIS OF CHEMICAL RENCTONS 1s _sror3_The products will consist ofthe following quantities: 1 mole Carbon dioxide Nitcogen = 19(0.79) = 150 moles , = 7.0) Oxygen = 190021) = '4(0.8) = 304, = 26:oles(C, ‘The values shown for C, ace mean values between 25 and 260°C: AH, = [01(9) + 0.521) + 0818.25) + 0.89.4) + 1547.0) ++ 2.6(1.25)} 500 = 7) 725) 50(500 ~ 77) = 63,500 Buufle mole “Then the net heat absorbed willbe (2 = ~47,600 ~ 250,000 + 63,500 ‘= ~234,000 Brofb mole ethylene Hionce the heat that must be removed is 234,000 Btu/lb mole of ethylene fed to the Chemical Equilibriam When a reaction occurs at equilibrium, the temper ture and pressure in the system remain constant and the change in free energy is zero, These restraints can be used to develop the following reation- ship between the standard free energy change AF* and the equilibrium constant K: AP = -R,TInk (4) ‘The standard free-energy change AF” is the difference between the free energies ofthe products and reactants when each is in a chosen standard state. These standard states are chosen so as to make evaluation of the fie energy as simple as possible. For example, for gases the standard state is normally that corresponding to unit fugacity at the temperature of the reaction. Ifthe gas is ideal, this standard state reduces to 1 atm pressure ‘The equilibrium constant X is defined in terms of the equilieriom activities a, of the reactants and products. For a general reaction ah 4 5B 00+ aD rey the equilibrium constant is ~ K a9 ‘The activities refer to equilibrium conditions in the reaction mixture and16 geren 1_nermmoucrion ren nemcovriot are defined as the ratio of the fugacity in the equilibrium mixture to that in the standard state; that is, f f For gaseous reactions with a standard state of unit fugacity the ex pression for the equilibrium constant becomes ay a8) If, in addition, the gases follow the ideal-gas law, the fugacity is equal to the pressure, and Eq. (1-8) reduces to Ke as) Here p (partial pressure) is the total pressure p, times the mole fraction of the component in the mixture; for example, PAPA (419) In many situations the assumption of ideal gases is not justified, and itis necessary to evaluate fugacities. This isthe case for such reactions as the ammonia synthesis, where the operating pressure may be as high as 1,500 atm. The fugacity in Eq. (I-8) is that of the component in the equilibrium mixture. However, the fugacity of only the pure component is usually known. To relate the two we must know something about how the fugacity depends on the composition. Normally this information is not available, so that it is necessary to make assumptions about the behavior ‘Of the reaction mixture, The simplest and most common assumption is that the mixture behaves as an ideal solution, Then the fugacity at equilib- rium, fis related to the fugacity of the pure component, J", at the same pressure and temperature by ALM aay ‘Substituting this expression in Eq. (I-8) leads to equations for the equilibrium ‘constant in terms of pure-component fugacities and the composition of the equilibrium mixture, (FOU 5 rte” K= a2) a)Scio IS THERODYNANIC OF CHEMICAL REACTIONS a In gaseous reactions the quantity K, is frequently used. This is defined as — Weed VDP! _ ps eranteen ° upvGae® ~ MP! oo From Eq, (19) it is clear that K'= K, foram idesl-gn reseton mistue. For sonideal systems Eq, (I-14) may still be employed to calculate from measured equilibrium compositions (A). However, then Kis notequal ta K determined from thermodynamic dat, for example, from Eq, (13) Equation (I-12) permits the evaluation of the composition to Ke in tems ofthe equilitium constant. This is @necesary step toned eval ating the equlbriam conversion ftom fre-energy data The steps inthe proses area follows 1. Evaluate AP, 2 Determine the equilibrium constant K, using Ea. (1-4) 3. Obtain K, from Eq, (I-12) 4. Calculate'the conversion from K,, ‘The first and second steps require thermodynamic data. A brief tabulation of standard free-energy changes AF” at 25° is given in Table 1-2. More extensive data have been assembled.' Also, estimation procedures have been developed for use when the data are unavailable.” Usually itis necessary to calculate the effect of temperature on AF* in ‘order to obtain an equilibrium constant at reaction conditions. The yan’t Hoff equation expresses this relationship in differential form, dink) aH? Re as) where AEP is the standard-state enthalpy change for the reaction. Equation (-15) has important implications in reactor design for reversible reactions. Tt shows that K will decrease with an increase in temperature for an exo- ‘thermic reaction. Hence provisions must be made for removing the heat of reaction to avoid a thermodynamic limitation (decrease in K) to the potential conversion in exothermic systems. The oxidation of sulfur dioxide is a practical illustration. For endothermic reversible reactions energy must be added to maintain the temperature if a decrease in Kis to be avoided Dehydrogenation of hydrocarbons, such as butanes and butenes, is an ‘example ofa situation in which the addition of energy is important. f AZ? ‘Selected Values of Chemical Thermodynamic Properties, Nau. Bur. Sid. Cir. $00 195; Sekcted Value of Pysieal and Thermodynamic Properties of Hydrocazbons aod Related Garou, dm. Pol It Re. Pro 4, Came Insite of Tena, Push 2R. ©. Reid and T. K. Sherwood, “The Propertis of Gates and Liquids," 24 e, chap. 5, McGraw-Hill Book Company, New York, 96wor ninco Table 12 Standard fee energies of formation at 29°C Substance Formula sate oF Normal parafioe ‘Methane cH. 5 Ethane Gat ° Propane Gi ° m-Batane Cie e Peetane He a Herane 2 eepane Ome ° mOetane Cie. ° Tperement ger C atom above Cy ° [Normal monoolefs (alkenes) Ethylene cot . Propylene cil. 3 IeBetene cy . ‘ePentene Gite é CHexene ca ° Increment per C tom above Cy 6 Miscellaneous organic compounds ‘ectldehyde cxtt.o * ‘Aes acd CHAO, 1 ‘acayieae cH ’ Benzene cone 3 ‘Benzene coe t 13-Batadene cot a Gytobesane cis a Getohesane ihe : Ethanol CHO 4 Ethanol CHO : Etisibnzene ithe . Ethylene glyco! CH.0, i Ethylene oxide cyH.0 ° Methane! co. o Methsnol cH0 t Metiyieycohexane Gla ‘ Metiyiseobeae CH 1 Soyene cH ’ Toluene ca 2 ‘Tolueae oH 1 Miseslaneow inorganic compounds ‘Ammonia NH 2 ‘Ammonia NH, 29 (Caleta carbide aac, 7 Caleim carbonate Co, 2seonoy |-5_TWoD US OF cHDACAL REACTIONS Substance Formule sate Fix Miseansovs iormani compounds (Continued) (elem chionde cect, 2 Caleiom chloride ec, Calm bydeonie cxo8), : Caleom ydeoxide ~~-COH)s ag Caicom enize Go 7 Carton deride <0, a Ccarvon monoxide co o Hyeroclone aid Hel : Hydrogen sale HS 3 Iron oxide FAO, : Tren oxide Feo, 2 ion safe Fey 5 ite aci HNO, 1 Nite ace HNO, a Nitrogen oxides No ? No; e No a 0. ’ Sodiam carbonate Ni,C0, : Sodium eblovide Nac 2 Sodiven eb Nac = Sodium hydroxise Nz0H : Sodium hydroxide 308 rT Sulfur dioxige 80, ’ Sulu triode $0 2 ‘Sulfuric aid H80, a Water 0 . Weer #0 i ‘ores: The standard fee energy of formation AF i he change in free energy when the ne compound formed from is elements with etch svbtane ints tandard tte 298°K (05°C) Standard sats are: 1. Gaze (9, the pare ge at unt fugacity and 25°C 2 Liguids (ad solids (), te pure substance at asmospbare pressure and 25°C 2: Soltes in equeous solution (ag) the BypothetclI-molal solution of the sole in water at aosphere pressure and 2°C The wits of A are clones per gram mole ofthe ited substance ounce: Select manly rom F-D. Resi et, Selected Values Propetesofydocarbons aod Relted Compounds, Ame. Petals Re. Pro. 4, Carnegie lnstitete of Techs, Prusburgh, 1953, and lose af supplements (by permisson); FD. Rossini etal, in D.D. Wagman (ed), Seleeted Vales of Chemical Thermodynamic Property, Nat Bur Sede Ce 50,185, end loose eat suppierent20 urn |_ra90ucTIN is approximately indepeadeat of temperature, the integrated form of Ea ape Key ale ge (f 3) 0-16) If AH? is not constant, but can be expressed by Eq. (I-1), the integrated form is AH, , 4a Ab, Ac MMe Ming 2 T+ +c - ee ar aay where AH, C, and Aa, Ab, and Ac are constants and da, Ab, and Ac arise from the expression AC, = Aa + Ab T + AcT? (48) Kean be determined feom Eqs. (1-17) and (1-18) fora gaseous reaction at any temperature, provided the constants C and AF7g can be evaluated. Experimental data for K at two temperatures is sufficient for this evaluation. Alternately, AH, can be found from the knoivm heat of reaction at one temperature with Eq, (I-1). In this case only one experimental value of the equilibrium constant is needed in order to determine the constant C. Of course, in both methods it is necessary to have heat-capacity data for reactants and products in order to evaluate the coefficients Aa, Ad, and Ac. ‘Application of the foregoing concepts in evaluating the equilibrium conversion from free-energy data is illustrated by the following examples. mK, ‘Example 1-2 The following equilibrium data have been reported for the vapor: ‘phase hydration of ethylene to ethanol:! at MS*C X= 68 x 10™* and at 320°C K= 19 x 10". From these data develop geoeral expressions for the equilibrium constant as a function of temperature. Solution From the two valves of K the constants Afig and C in Eq, (1-17) may be “determined. Frst the values of Aa, Ab, and dc must be obtained from hest-capacity data, For the reaction CxHA(g) + 1,066) > C2H,OH@) ‘these are A= GOH ~ GH, — #0 ‘Aa = 6990. 2.830 ~ 7.256 = ~3.096 ‘bb = 0.039761 ~ 01028601 — 0.002298 ~ 0.008843 Ae = (11926 + 8.726 — 0.283) x 10°F = ~3.483 x 10-6 HEM, Stanley eta, Soe. Chem nd, 58, 205 (1838); RH. Biss and B. F, Dod, fad Exp Chem. 28,19 (957.‘Substituting these values in Eg (+17), we have, at 145*C, ones yin <10r) = 2% soi + 28 ay 3483 x 107% ZH ie? + CR, bly . - Be cay — Ryle 68x10") 3.096 in 48 “+ Ban44a¢418) ~ (S80 x 10-4418)? = 11.59. (A) and a3 alle - ee chy = — Ayia (1.9 = 107%) — 3.08610 585 ++ .00442(598) — (0.580 x 10-4597 = 491) Equations (A) and (B) may be solved simultaneously for AN and C.The results Ally = ~9460 cal c= ~556 ‘Then the general expression for X asa funetion of temperature i 3.086 5 7 5 00082 OSE IO yg R 4760 ink =A ~ 1558 7 + oor ~ 029 x 10-¢T? — 5.56 Example 1-3 stimate the maximum conversion of ethylene to aleahol by vapor- ‘hase hydration at 250°C and SO0 sia. Use the equiiium data of Example 1-2 and assume an inital steam-etylene ratio of 5 Solution The equiliriim constant at 250°C can be evaluated from the equation for K Aeveloped in Example 1-2: 760 In = AED — 1.558 in 523 + 0.00222(523) — 0.29 x 10-*(8254) 513 kaso x10? Tis necessary to assume that the gas mixture isan ideal solution. Then Eq, (1-12) is applicable, and “2 aarren |_porsoouerin “The fugacites of the pure components can be determined from generalized correlations! nd are evaluated atthe temperature and pressure of the equilibrium mixture 0.84 forethanol = 0.98 for ethylene = 091 forwater Substituting these data in Bq. (A), we eve 5098081) 500 jew 8 Os 147 021 @ 1 the initial steamn- 107 at atm pressure and 300°C, what are the numerical values ofthe flowing quantities at this temperature? (@) Katp,= Lata ©) Katy, = atm (@) Kyatp, = 50atm () a 10 2nd 30 atm total pressure (©) Kat 10, and 50 atm total presure 1.8, Newton and Dodge! and von Wettbere and Dodge? measured the composition of equilibrium mixtures of CO, Hy, and CH,OH in the methanol synthesis, ‘Compute the vale of and AF at 309°C from the following data taken from their work: f= sore. P= 170 atm. ‘The equilibrium gas analysis, in mole % is Hydrogen = 60.9 Carbon monoxide = 13.5 Methanol = 21.3 4, Am Chem Soe, 56, 1287 (193). nd Bg. Cher, 2, 1060 (193),0 ‘exon 1_nergopvctIon Iners = 43 Total = 1000 1-9. Tae complete rerults referred to in Prob. 1-8 are as follows: a mais 375 365-330 310 ~3.20 ~3.00 —250 Les 188 19T a) 92 205 205, 208 298 —260 270 300-230-230 ~215 ~235 From this information determine the best relationship between K and T in the form 1 Inka Ant Ink=Apee 1-10. The determination of K in Prob, 1-8 was based on direct measurement of caulibrium compositions, Use the calorimetric data below and the third law {aprepazea lot of log K vs IP forthe methanol synthesis. Inchudea temperature ‘age of 258 0 800°K. Compare the graph withthe result obtained in Prob. 19. "The entropy of CO gas at 298,16°K in the ideal-gas state at 1 atm is 47.30 callg mole)(R). A similar value for hydrogen is 3121, The heat of vaporization for methanol at 298.16°K is 8943.7 eal/g mole, and the vapor pressure at 298 16°K is 0.1632 atin, Heat of formation of CH,OH in the ieat-gas sate at 1 aim i 48,490 callg mole, Low-temperature specificbeat and hest-f- transition data for methanol areas follows: 1K igo 2155 4 272s MMB M4087 c.call jie 15219572292 298A e227 (emoie°) 493 4807 5602-95) 6329 69S TROT amo 5404 6425 GRAS 722 BOO 8382S sist 9532 $929, nak 97z2 tLe 211797 poor 9295 9692 93 1023 gs a8 uig79 (2144 12507 17938 37 1476 15029 15398 heat 1 1K 1228 es FG 1W648 16628 160.75 181.09 18510 18806 19617 21034 9 16 168601667 16771698 1697 2S8t 25631 ass awsIs 29201 va) 1770 183018709 "Methanol crystals undergo a phase transition at 157.4°K for which AH 134.3 cal/g mole. The melting point is 175.22°K, and the heat of fision i 7570 calls. mole. Specife-heat dats at temperatures above 298 16*K are as folove 2716 = 0400500 oD 70000 CCH OK. caMemol KC) 108 1081275163 n c 25100 200300 aon 500 (CO.caMl@NC) 078902500253 0288 0264 02 ONE Coen IO saz 3MS 347347 34h)2 KINETICS OF HOMOGENEOUS REACTIONS Kinetics is concerned with the rates of chemical reactions and the factors Which influence these rates. The first kinétic measurements were made before 1820, but interpretation in terms of quantitative laws began with the studies oon the inversion of sucrose by Wilhelmy,! the esterification of ethanol with facetic acid by Bethelot and St. Gilles,? and the reaction between oxalic acid ‘and potassium permanganate by Hazcourt and Esson.? These investigations established the relations between rate and concentration of reactants. The important contribution of Arrenius* for the effect of temperature was also ‘made in the nineteenth century. ‘in this chapter the definitions and concepts used in kinetics are pre sented, followed by a brief description of theories for reaction velocity L, Wisin, Bogs. Arn, 81 413, 499 (1850) 2Nf Berthelot and LP SCs, An. Phys, 63, 385 (185). 2A. V. Hazeourt and W. Esion, Proc. Roy. See. (London), 14 470 (1865); Ph. Tron, 156,193 (186), Phil Tran, 157, 117 (850, 45, Arbenin, Z Phy Chom, 4, 26 (185). 2section 2 Rare oF azACTION o ‘Then the use of rate equations for studying the kinetics of reactions is illustrated for simple systems and some complex ones. Only homogeneous reactions, devoid of any physical resistances, are considered here. The kinetics of heterogeneous reactions is taken up in Chaps. 8 aud 9. 2 Rate of Reaction . - ‘Therateof reactions formallydefined asthe changin molesofacomponent ~ vith fespect To He, per unt volume of reaction mixture. This quantity is _ {eave i the Component isa reactant and posilive ifthe ‘component is a ‘plodiet Wis important that there be but one definition of rate, regaidles “GF the type of reactor—flow or batéh, tank or tube. Thus the rate must bea Jocal.or point. value that, it must refer toa differential volume of react ‘ixture. With tis restriction the rate becomes a unique property for & sven Bystem. I the rate is to be the’same throughout the volume of tank reactor, ‘the concentrations and temperature must_be_unil e {rom_point 10 poin_in.the reaction volume, In_heterogen reactions, particularly those with solid phases, it may be convenient 10 base the rate on a unit mass or surfaée rather than volume, will always ‘Gra point in the reaction resion. For the concentrations and tem- the mathemati expression Toethe rater 1 aN Va ~ Sohune x tae! / ey svbere i the volume of the reaction mixture and Ns the mmnter of mols /ofaproduct species IFW eters to moleofrecant, thet aMlhioseenans * a minus sign is commonly used in front of the derivative so that the rate is always postive. Fora tubular reactor witha steady fow of stevia in od out the laependent nn the tube, of reactor olan dod tie composition and rate elange wit tis vancie-tetcad of "To formulate the poi rte a diferente semen of tescor vole, inustb chosen IFW is teil tea ow ef componsstints he vere Clement thera wil be [a 2) | wv {These two equations will be used throughout the book to describe the rate of reaction quantitatively ‘The couse of areaction is normally measured. bythe change in on ‘engin of & eatiant or product, PANG in gene eehen CHAPTER 2 KINETICS OF HOMOGENEOUS REACTION volume changes may also occur (for example, because of a change in total moles). Then concentration changes arise from a change in volume as well ts from reaction. The influence of volume change can be examined by writing N = C¥. Thus Eg, (2-1) becomes +e es vai If the volume, or density, of the reaction mixture is constant, Ea. 2-3) reduces to the common form ac Ms a ae 4) Care must be exercised in deciding when Eq. (2-4) is applicable. In a flow reactor, used for a gaseous reaction with a change in moles, itis aot correct (Gee Examples 4-3 and 4-4). However, itis correct for all gas-phase reactions jn a tank-lype reactor, since the gascous reaction mixture fils the entire ‘vessel, so that the volume is constant. For many liquid-phase systems density changes during the reaction are small, and Bq. (2-4) is valid for all types of reactors. The use of Eqs. (2-1) to (2-4) will become clear as we consider various kinds of reactions and reactors. If the stoichiometric coefficients for two reactants are different, the rate expressed in terms of one reactant will not be the same as the rate expressed in terms of the other. Suppose the reaction aA + bB+cC + dD ‘occurs at constant volume] so that Eq. (2-4) is applicable. The concentration changes for the four reactants and products are related as follows 1 aay _ tafe) 1 A} _ 1 Ad) ’ ee a ow 1 where [4] is the concentration of reactant A, etc. For example, if the reaction is uessc a) a) _ at DP a —4AY AL, aD dt a aschon 22. concerts oF xnenice 3s For reactions with nonequal stoichiomettic coefficients, Ea. (2-4) shows that arate which ithe same for all components can be defined as* 1 dc, ade her the stoichiometi cofcient ais negative for reactant ‘and positive for producti, and C; is the concentration : r 4) "(923 Concepts of Kinetics The early workers in kinetics found that simple relations existed between rates of reaction and concentrations of reactants. Thus Berthelot and St Gilles discovered that the rate of esterification was proportional to the first power of the concentration of ethanol and to the first power of the concentration of acetic acid. The rate is sud to be frst order with respect to each reacignt. In general terms, suppose that the rate of the reaction ad + DB 0C 4 aD ray be written © Fm KARRI ¥ @s) Then ais the'order of the reaction with respect to A, and f isthe order with respect to B. In subsequent sections kinetics will be discussed with respect to a batch tank reactor, usually at constant density, so that Eq, (2-4) is applicable. Measured in terms of reactant A, this limitation means that Eq, (2-5) may be written 6 ‘The order of the reaction is determined by comparison of experimental Gata with Eg, 2-6) oF ntegrated forms off, a desribed in Sy 2719210 ‘As such order is an empiial quantity, and 2 anf do not anys have integer vals ‘Theres no necessary connection between oder andthe stoichiometric coefiients inthe eaction equation; that i, isnot required that a = « and f = bin eacion (2-5). For example, tie woiciomry of the ammonia. Sythe reaction is 2N + 3H 2NH, "Mis comept of niet ses edo deo eau of the emt extn ks the sme vee of compere welt oor te Tos sete eet of con dee! ich Boar Pcp. Prete in, Engerod Cet eh Pe Behl and LP St ile me Pgs 85,182)Couarren 2 KINENCS OF oNOGENEOLS REACTIONS but for many catalysts the rate equation that best fits experimental data is first order in N, and zero order in hydrogen. "As kinetic studies of many kinds of reactions have accumulated, it hhas become increasingly clear that formation of the final products from the, igi ly ¢ "simple steps. The- fe te explnato ‘The rat ‘and the Fate of the overall reaction’ will rest of these steps. The mechanism of a 1 that deseribe how the final products ace Tore fm th If the mechanistn is knows, i is usually possible to-evaluate a rate oquation _such as (2-6) and, hence, the order ofthe reaction. In contrast, itis generally ‘ot possible to infer a mechanism from the rate equation alone ‘These points are wel illustrated by the gaseous photochlorination of propane, CH, + Ch > CHCl + HCL [At certain concentrations stoichiometry and order do not agree, for the fats is found! to be second-order in chlorine and independent of propane Concentration (ero order) according tothe rate equation aay) " AC — pfca} en However, the actual mechanism of the reaction probably entails many Steps comprising an initiation reaction in which light is absorbed, propaga dion stepe involving the free radicals C,H, and Cl and termination steps in which the radicals ae eliminated "A fortultous example in which ordec and stoichiometry are identical isthe decomposition of NOs, N,O; > 2NO, + $02 ee as found that while the rate is fist order ia NO, the mechanism probably consists of theee steps: 1. Ny0s=2NO, + NOs 2. NO; + NO,+NO + 0, + NO, 3, NO + NO, + 2NO; Ifthe second step is second order and very slow with respect to the othess, 1A. B, Cassano and J. M, Smith, AICAE J 12, 11241966), ARAL Ogg, Irv. Chem, Phys 15,337, 613 (0940),secre 2-2 CONCEETS oF eINeics the rate of the overall process will be proportional to the product of INO, and NOs concentrations. Furthermore, equilibrium will be quickly attained in the fist step, s0 that [NO;][ NOs] will be equal to K;[N0.], where K; is the equilibrium constant for the first step. These postulates tnd the three-step mechanism thus explain the first-order rate equation, [Note tha it would be incorrect toassumeasingle step forthe overall reaction ona basis of the observed first-order dependeney on the rate ~The individual steps; which together describe the overall action, auc called elementary processes. Theories about kinetics (Aisussed in Secs 24 to 2-6) refer to these elementary processes. Order and stoichiometric numbers are usually identical for elementary processes, but not alas. ‘The moleclarty of an elementary step is the number of reactant molecules that take part in the reaction. This is usually equal to the total order, ‘exceptions exist for unimolecular reactions. For example, unimolecular fractions (molecularity = 1) are not necessarily frst order; in fact, gaseous reactions which involve one molecule always become second order at low pressures (se See. 2-6) ‘Upto this point we have considered the influence only f concentration con the ate, The specific rare other variables, The most important ofthese is temperature, but thers may f signilicant. For example, a reaction may be primarily homogeneous but ‘ith the nature and extent of the surface. A reaction may be homogeneous | Dualso require a catalyst. An example is the reaction forthe iaversion of sugar, witere the acd acts asa catalyst. In these instances k may depend on the concentration and nature ofthe catalytic substance. However, | the catalyst concentration in Faq. (2-5), 80 that k is independent of all con- centrations. | ‘The dependency of k on temperature for an elementary process fol ‘the Archenius equat the frequency (or preexponential) factor-and E is the ombining Eqs. 2-8) and (26) yields 4) RT Lap By Se ary) 9) This provides a description of the rate in terms ofthe measurable variables, SQucentration and temperature. It is rigorously limited to an elementary ‘rocéss because the Archenius equation is 0 restricted, However, the expo- ieivial effect Gt” temperature often accurately represents experimental% AFTER 2 KINETICS OF HOMOGENEOUS REACTIONS rate-data-for-an overall reaction, even though the activation energy is rot clearly defined and may be a combination of £ values for several of elementary steps 23 The Arrhenius Law [Acrhenius developed sis concepts about the variation of rate with tem- -Priaure trough thermodynamic arguments," For aeation whose rats ae fapid enough to achieve a dynamic equilibrium the vant Hoff equation ‘states that ~ ink) _ aH SRO RE 5 eo If the reaction may be written A+BeC the equilibrium constant is (J x= 1d 4 (aital | Sinc¥ this is an elementary proces, the rates of the forward and reverse reactions may be formulated [by Bq, (2-6)] with order and stoichiometric numbers identical Forward rate = ks[ AJL) Reverse rate = K{C] ‘At equilibrium the to rates are equal. This fact, plus Eq, (2-11), yields k,L4]{8) = KIC] @2) eu [q)_ ke _ ' taal = % oe Using this cesult in Eq. (2-10) gives dink) aa) At a RE ew Arches, Z Phyik Chem, 4 226 (889). Ta simply the easoning the complies introduced by the dierences beeen ative, upon which io Eq, (2-10) is Based, and concentrations, which express A ia Eq, (211), are Ignore fhe form of Eq, 0213) fran overall ection it considered in Sec. 212,sxcrow 2-3 WE amen LAW “ y ‘The right-hand side of Eq. (2-14) may be divided into two enthalpy changes, AH, and AH,, such that AH = SH, ~ AH, as) ‘Then Eq. (2-14) may be split into two equations, one for the forward reaction and another for the reverse reaction, which will have a difference in agree- rent with (2-15). Bw, e9 nk a ed a eam Integrating either equation and setting the integration constant equal to Jn A gives a result of the form of the Arrhenius equation, Eq. (28): Kem Aen aitor @18) ‘An alternate derivation is based on the concept of an intermediate ate, often called a sransition or activated siate, which is a postulate of the tramsition-state theory (Sec. 2-5). Suppose that product C'of the reaction A+ BSC | is formed only by decomposition ofan activated form of reactants 4 and B, || which wil be designated (48)*. Then the reaction occurs by two elementary | steps, DL 4+ Bea 52 Bac |__ the fst step is comparatively rapid in both forward and reverse directions, | (aay wil be in equilibrium with A and B so that its concentration is | sven by (aay) = KLA1(8) @19) “where K* is the equilibrium constant for the formation of (48)*. The rate of reaction (rate of formation of C) is then given by the rate of the first- ‘order decomposition step. With Eq. (2-19), this may be expressed as = flan) = kx LA) 020 I we integrate the vant Hoft equilibrium equation for dink?) AH* 21)