2 KINETICS OF HOMOGENEOUS REACTIONS Kinetics is concerned with the rates of chemical reactions and the factors, Which influence these rates. The first kinetic measurements were made before 1820, but interpretation in terms of quantitative laws began with the studies on the inversion of suerose by Wilhelmy,' the esterification of ethanol with, acetic acid by Bethelot and St. Gilles,” and the reaction between oxalic acid ‘and potassium permanganate by Harcourt and Esson.* These investigations established the relations between rate and concentration of reactants. The important contribution of Arrhenius* 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. Wihelmy, Pogg. Amn, 1,413,499 (185. 2M, Bertelot apd LP, St, Giles, Amn Phys, 63, 385 (186) DALY. Harcourt and W. Esson, Proc. Roy. Soe. (London), 4, 470 (1865); Phi. Tron, 156,193 (1866); Phil. Trans, 157,117 (1860, 48, Artheius, Z, Phyl Chem. 4,226 (1889. 3\ secmaw 2-1_ RATE OF REACroN 3 Then the use of rate equations for studying the kinetics of reactions is illustrated for simple systems and some complex ones. Only homogencous reactions, devoid of any physical resistances, are considered here. The kinetics of heterogeneous reactions is taken up in Chaps. 8 and 9. 21 Rate of Reaction : . The rate of reaction is formally defined as the changin moles.ofa.component with respect fo ime, per unit volume of reaction mixture. This quantity is _ aegative if the component is a reactait arid positive if the component is a “Product. It is important that there be but one definition of rate, regardless ‘FEE type of reactor—flow or batch, tank or tube. Thus the rate must be a local, or point, value: thats, it must refer to a differential yolume of reaction ‘inture, With this reatition the rate becomes a unigue property fora biven solid phases, it may be base the rate on a unit masy oF sUrfuée rather Tian VoTume, but it Fefer TO a point in the reaction region. "For the baéch tank reactor, perature, the independent variable ine, forthe rete ions 1 an moles [aie solemebaticg! en) and the mathematial expression ‘where V is the volume of the reaction mixture and Nis the number of moles ofa product species. If N'refers to moles of reactant, so that dN/dt is negative, * a:minus sign is commonly used in front of the derivative so that the rate is always positive, For a tubular reactor with a steady flow of méterial in and ‘Out, the independent variable is position in the tube, or reactor volume, and the composition and rate change with this variable instead of time. ‘To formulate the point rate a differential element of reactor volume, dV, ‘must be chosen. IFW" is the molal rate of flow of acomponent into the volume element, the rate will be | an’ wv These two equations will be used throughout the book to describe the rate of reaction quantitatively. ‘The course.of a.reaction is normally measured by the change in con- centration of a reactant or product. Parlicilarly in gaseous reactions, (2-2)Pa 2__rnverics OF HOMOGENEOUS REACTIONS ‘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 as from reaction. The influence of volume change can be examined by writing N = CV. Thus Eq, (2-1) becomes 1 (cv) aeaeaee (23) If the volume, or density, of the reaction mixture is constant, Eq. (2-3) reduces to the common form : then | de = @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 not correct, (Gee Examples 4-3 and 4-4). However, it is correct for all gas-phase reactions in a tank-type reactor, since the gaseous 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 Eq, (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 ad + 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 11 ate) 1 i) _ 1 AD a. dt dt dt a x en) where [4] is the concentration of reactant 4, etc. For example, if the reaction is 2A +B C orsecon 2.2 CONCERTS OF KINETICS 35 For reactions with nonequal stoichiometric coefficients, Eq. (2-4’) shows that a rate which is the seme for all components can be defined as! 1 dc, bagi de where the stoichiometric coeflicient a is negative for reactant i and positive for product j, and Cis the concentration. 4") Concepts of Kineties ‘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 said to be first order with respect to cach reactant. In general terms, suppose that the rate of the reaction aA + bB-+cC+dD may be written AYE * @5) ‘Then wis the'order of the reaction with respect to A, and f is the order with respect to B. In subsequent sections kinetics will be discussed with respect io 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 han KLAR BY (2-6) The order of the reaction is determined by comparison of experimental data with Eq, (2-6) or integrated forms of it, as described in Secs. -7 to 2-10. As such; order is an empirical quantity, and « anid fi do not always have integer values There is no necessary connection between order and the stoichiometric, coefficients in the réaction equation; that is, itis not require god f= Bin reaction 2-9), For example the stoichiometry of Synthesis reaction is ye 2N, + 3H, + 2NHy "This concept ofa unique rate has beea uted to develop measute ofthe amount of reaction hich is the same regardless of the component used to follow the course ofthe eeaction This so-called extent of reaction is described in Michel Boudar, “Kinetics of Chemical Processes,” p. 10, Prentice-Hall, Ine, Englewood Clif, NJ, 1968 °M, Berthelot and L. P. St Gilles, Ame. Phys, 63,385 (1862,6 cartes 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 has become increasingly clear that formation of the final p Prous rom the lies the explanation fc Eee rates se oF the Gverall action wil: be determined: primarily Slowest of these steps. The mechanism 20 that describe how the final products are Forined from the o If the mechanism is knows, it is usvally possible to-evaluate a rate equation “such as (2-6) and, hence, the order of the reaction. In contrast, itis generally not possible to infer a mechanism from the rate equation alone. These points are well illustrated by the gaseous photochlorination of propane, CH, + Ch > CHCl + HCL ‘At certain concentrations stoichiometry and order do not agree, for the rate is found! to be second-order in chlorine and independent of propane concentration (zero order) according to the rate equation a Hd _ gop en However, the actual mechanism of the reaction probably entails many steps comprising an initiation reaction in which light is absorbed, prope tion steps involving the free radicals C,H, and Cl, and termination steps in which the radicals are eliminated. ’A fortuitous example in which order and stoichiometry are identical is the decomposition of NOs, N,O; > 2NO, + $02 ‘Ogg? has found that while the rate is first order in NOs, the mechanism probably consists of three steps 1, N,O,=2NO; + NO; 2. NO, + NO, + NO +0, + NO, 3. NO + NOs -*2NO; If the second step is second order and very slow with respect to the others, 'A.B. Cassano and J. M. Smith, AICKE J. 12,1124 (1966) PRA, Ogg, Jr, J. Cham. Py, 15,33, 615 (1987)concerts oF xnemncs ” 0 the rate of the overall process will be proportional to the product of NO, and NO, concentrations. Furthermore, equilibrium will be quickly attained in the first step, so that [NO,][NO,] will be equal to K,[N1Os], where K, is the equilibrium constant for the first step. These postulates and the three-step mechanism thus explain the first-order rate equation. Note that it would be incorrect to assume a single step for the overall reaction a basis of the observed first-order dependency on the rate ~The inclividual-steps, Which” together describe the overall reaction, are called elementary processes. Theories about kinetics (discussed in Secs. 2-4 to 2-6) refer to these elementary processes. Order and stoichiometric numbers are usually identical for elementary processes, but not always. ‘The molecularity of an elementary step is the number of reactant molecules that take part in the reaction. This is usually equal to the total order, but exceptions exist for unimolecular reactions. For example, unimolecular reactions (molecularity = 1) are not necessarily first order; in fact, gaseous reactions which involve one molecule always become second order at Jow pressures (See Sec. 2-6) Up to this point we have considered the influence only of concentration on the rate. The specific rate a other variables. The most important of these is temperature, but others may “ ‘8 significant. For example, a reaction may be primarily homogeneous but ‘With the nature and extent of the surface. A reaction may be homogeneous ‘il also require @ catalyst. An example is the reaction for the inversion of sugar, where the acid acts as a catalyst. In these instances k may depend | on the concentration and nature of’ the catalytic substance. However, ‘gp when the concentration effect of the catalyst is known, itis better to includé | ‘the catalyst concentration in Eq. (2-5), $0 that k is independent of all con- centrations. ‘The dependency.of k on temperature for an elementary process follows the Arrhenius equation (see Sec. 2-3), (2-8) | | Where A is the frequency (or preexponential) factor.and E is the activation | “gastey. Combining Eqs. (2-8) and (2-6) yields | | | ' (2-9) “This provides scription ofthe rt in es ofthe meamable acl, ‘Soncentration and temperatuce. It is rigorously limited to an elementary Process because the Arrhenius equation isso restricted. However, the expo- | ential effect “oF temperature often accurately represents experimental E8 CHAPTER 2 KINETICS OF rate-data-for-an overall reaction, even though the activation energy is not clearly defined and may be a combination. of £ values for several of te elementary steps. 2:3 The Arrhenius Law snius developed his. concepts about the variation of rate with tem- ‘are through thermodynamic arguments." Fora reaction whose rates are Tapid enough to achieve a dynamic equilibrium the van't Hoff equation states that “ dak) _ Ai freee 1 RP en) ir he eneion maybe writen Aepec the equim constant is i J (2-11) WA) / Sincé this ig an elementary process, the rates of the forward and reverse reactions may be formulated (by Eq. (2-6)] with order and stoichiometric numbers identical: Forward rate = k,[4](B] Reverse rate = K:[C] At equilibrium the two rates are equal. This fact, plus Eq. (2-11), yields k,{A)(8) = UC @1 ea - Talla ~ =e Using this result in Bg. 2-10) gives dink) dak) AH aah = Rae oe 48, Armhenius, Z. Physle Chem. 4, 226 (1889). To simplify the reasoning the complexities introduced by the diferences between activites, ‘upon wich in Bq, (210) is based, and concentrations, which express K in Eq, (2-11), are ignored. The form of Ea. (2-13) for an overall reaction is considered in Sec. 2-12‘The right-hand side of Eq. (2-14) may be divided into two enthalpy changes, AH, and AH, such that AH = Ai ~ AH, (15) ‘Then Eq, (2-14) may be split into two equations, one forthe forward reaction and another for the reverse reaction, which will have a difference in agree- ment with (2-15) Qin kz) _ Att, - 016) a(n ki) _ AH, rae 19 Integrating either equation and setting the integration constant equal to In A gives @ result of the form of the Arrhenius equation, Eq. (2-8) Kem Aen MRT (218) ‘An alternate derivation is based on the concept of an intermediate state, often called a transition or activated state, which is a postulate of the transition-state theory (Sec. 2-5). Suppose that product C of the reaction A+BSC is formed only by decomposition of an activated form of reactants A and B, ‘which will be designated (4)*. Then the reaction occurs by two elementary steps, L A+ BR (AB) 2 (By +c If the first step is comparatively rapid in both forward and reverse directions, (48)* will be in equilibrium with A and B so that its concentration is given by [aay] = K*LA]LB) 19) Where K* is the equilibrium constant for the formation of (4)*. 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 = e[(AB)*] = K*[ ANB] (2-20) If we integrate the van't Hoff equilibrium equation for K*, nx) _ ane a RP 21)0 CcuAPTER 2_ KINETICS OF #0 wwe obtain Kea fe eT en) where J is the constant of integration. Combining Eqs. (2-20) and (2-22) gives r= kt Les? CATR] (2.23) ‘Comparison with Eq. (2-6) shows that k= Ae erin 224) where A = kt, Equation (2-24) is also of the form of the Arthenius equation. ‘Since AH™* is the energy required to form the activated state (4B)* from A and B, e~*""%T js the Boltzmann expression for the fraction of molecules having an energy AH* in excess of the average energy. This gives some meaning to the activation energy £ in the Arrhenius equation. The diagram in Fig. 2-1 shows that this value is the energy barrier that must be overcome to form (4B)*, and ultimately product C. ‘The value of Eq, (2-8) rests substantially on the accuracy with which it represents experimental rate-lemperature data (see Example 2-1). When ‘measured rates do not agree with the theory it is usually found that the reaction is not an elementary step or that physical resistances are affecting the measurements. In other words, Eq. (2-8) correlates remarkably well the rate measurements for single reactions free of diffusion and thermal resistances, The Arrhenius equation provides no basis for discerning the value of E. However, Fig. 2-1 indicates that the activation energy must be ‘greater than the heat of the overall reaction, AH, for an endothermic case In view of the success of the Arthenius equation, there have been many attempts to develop theoretical interpretations for the frequency Fig. 21 Energy level of iil, activated, and fnal states tivated state AB Energy level amar % Ave eneay J (hetivation energy) ~S__of Prod! Aye. eneray / Ml = Heat of reaction (ovenainSECTION 23_THE ARRHUS LAW . factor A and the activation energy E. The collision theory (see Sec. 2-4), in-which the frequency factor is treated as a collision rate, was inspired by the kinetic theory of gases. Subsequently the more sophisticated activated- complex theory was developed to take advantage of the more detailed description of collisions made possible with statistical thermodynamics and quantum chemistry. the rate of hydrogenation of ethylene, using a copper-magnesium oxide catalyst, over restricted pressure and composition ranges. Their data may be interpreted with a first-order rate expression ofthe form (Ep Ps co) where ris the rate of reaction, in g motes/(cm*\see), and py, isthe pertial pressure of tydcogen in atmospheres. With this rate equation (k,), willbe reported in g moles} (cm’\ecyatm). The resuls for (,), at various temperatures are given in Table 2 (6) What ithe activation energy from rate equation (A)? () What would it bei the rate equation were expressed in tems of the concentration of hydrogen rather than the para pressure? Solution (a) Inthe last column of Table 2-1 the reciprocal ofthe absolute temperature isshown foreach run, Figure2-2isa plot of (k), vs I/ Ton semilogarithmic coordinates. Ttis apparent thatthe date describe a straight line, except for runs 8, 20,21, and 22. thas been suggested that water vapor may have caused the low rates in these case.* ‘The line shown in the figure was located by iting the data points by the least-mean- squares technique. This requires writing Eq, (2-8) in logarithmic form, Ey indy, mina Fee This isa linear relation between In (k,),and 1/T with a slope of ~E,/R,. I(T) repre- sents one of m data points, the values of A and E,/R, which destibe the least-mean square fit are ®) g, » Deoaroam-(E un) nk = Ppeeeencreaegeiceeieeeest © % a nd on (Sam) ina = LBKE ITY ~ FUT UTI) a nLaTy — ut Carrying out the summations indicated forall the data points, with the data in Table 2-1 for k, and T,, we find £, eo 60 E, = 6A6OR,~ 12800 callg mole *Raymond Wynkoop and R. H. Wilhelm, Chem. Eng. Prog 46,300 (1950),2 CHAPTER 2 _RINETICS OF HOMOGENEOUS REACTIONS Table 2-1 Data fr hydrogenation of ethplene (ey «10%, Run —_gmoles/eeeKaumyem") 1 270 2 283 3 148 4 on 5 0.86 6 2a 1 240 5 126 9 on 10 070 n 2.40 2 ba B 0.69 “ 08 15 3.03 16 3.06 7 131 6 137 9 070 20 014s a 0.59 2 0.260 B os 4 0x3 25 0283 6 0.286 n 02m 28 oss 2 xz 0 0326 3 0312 2 o3ia 3 0307 source: Raymond Wynkoop and R. H. Wilhelm, Chem. Eng. Progr. 46, 300 (4950), n n 3 533 533 16 16 16 529 529 18 a7 339 537 5 5 eo 60 585 392 383 a 402 402 02 402 29 02 02 02 99 399 38 236 235 285 307 3.07 235 298 306 3.06 283 283 197 291 3.05 320 321 310 39 319 319 31s 320 3s 319 319 319 319 3:9 [A quicker but les accurate method isto draw, visually, a straight line through the data plotted asin (ky), v8 1/T, measure its slope, and multiply by R, to obtain the activation energy. (8) For gaseous reactions the rate equation can be expressed in terms of con- centrations or pressures, Equation (A) isthe pressure form for this example, In terms of conceatrations, the rate is (kde [a]Secroh 2.3. THE ARRMEMIUS LAW s oo fof Wynkoop and Wilhel «| ‘tO 3 hn Eng Pg 6 2000850] moles Tentecyatm) ea), 104, Water vapor in reactants I 1 Pee 1000 yt eee Fig.2-2. Plot of Archenis eqution for hydrogenation of ehylene Expressing (Kye in the Arrhenius form and then differentiating gives (ede = Ace tte? snd alin kde] _ _ Fe aay R = © ‘This may be related to Ea. (A) by noting that for an ideal-gas mixture the concentration of Hy is © “8“4 CHAPTER 2 KINETICS OF HOMOGENEOUS REACTIONS Comparison of Eqs. (A) and (F) gives the relationship between the two rate constants, bide = (i), RT © Differetiating the logarithmic form of Ea, (G) and using Eqs. (B) and (B), we obtain ain kd _ afta te], dln 2) aun ~~ ayn * aan) fee % Mee B+ RT « “Thus the activation energy, in principle, depends on whether the rate equation isexpressed in terms of concentrations or partial pressures. Also, the difference between Ez and E, depends on the temperature. Ia practice this difference is not significant. In this exemple, at a temperature of TPC, Fc ~ By = 2850°K) = 700 cal/g mole ‘This difference of 6% is too small to be discerned from rate measurements of the usual precision. Hence it generally makes litle difference whether £ is evaluated from # rate equation expressed in terms of pressures or in terms of concentrations. RATE THEORIES 2-4 Collision Theory ‘The Arrhenius concept as pictured in Fig, 2-1 requires that the molecules of reactants have an energy E above their normal, or average, energy. There is a possibility that some molecules will possess this excess because of the wide range over which the energy is distributed and the large number of ‘molecules that make up the system. According to classical kinetic theory, ‘some gaseous molecules will possess much larger amounts of translational energy than others because of variations in their molecular velocities. It is logical to suppose that collisions between these reactant molecules ‘would provide the activation energy necessary for the reaction to occur. ‘By assuming that the molecules behave as hard spheres, it is possible to develop simple expressions for the rate. This approach, originally advanced by Lewis! and Polanyi," has become known as the collision theory ‘The theory has a number of weaknesses and has been extended and supplemented by later developments. However, it offers 2 simple picture SWVC. MeC. Lewis, J, Chem. Soe. (London), 113, 47 (1918) 2M, Polanyi, Z. Elirocker, 26, 48 (1920.sores 2-4 _coLLisoN THEORY of the mechanism of reactions. According to the collision theory, the number of molecules of product formed per unit time per unit volume—ice., the rate—is equal to the number of collisions multiplied by a factor f- This factor takes into account the fact that only a fraction ofthe collisions involve ‘molecules that possess the excess energy (activation energy) necessary for reaction. For a gascous reaction, such as A + B-+C + D, this may be stated mathematically as, r= . 225) were zis the number of collisions between molecules A and B in | em? of reaction mixture per second. From kinetic theory (with the assumption that molecules are hard spheres), the number of collisions is given by ‘ ) 025 ‘where the concentration is in molecules (not moles) per cubic centimeter, and £= [Altes (‘e,7 4g = effective diameter of A plus B upon collision ‘M = molecular weight R, = gas constant = kyNo, the product of Boltzmann's constant and Avogadro's number, ergs/(°K)(g mole) Then the rate equation (2-25) may-be written FACE (sen, Mee) e2n The cate may sso be expressed in terms ofthe specie rte constant, = KALB] 2-28) Using the Arrhenius equation (2-8) for k, we may write this as r= Ae" [AIL] 229 Combining Eas. 2-27) and (228) gives the following esl forthe fequeney ctor EIR 2 M, + Mg\* esr Mc) The fraction of the molecules that possess the required excess energy for reaction should not depend on the number of collisions but on the magnitude of the energy itself. If a Maxwellian distribution is assumed, the fraction of the total molecules having an energy at least equal to E46 zl CCUAPTER 2 KINETICS OF HOMOGENEOUS #EACTIONS can be shown to be e~##7, Hence f may be taken as e~***7, and then the frequency factor is given by M, + My\* MM Finally, substitution of this value of frequency factor A in Eq. (2-8) gives the collision-theory expression for the specific reaction rate, A=ot (sear 2-40) My + Ms % k vin (8084 fe HRT cm’ /(molecule)(sec) 31) ‘The first part of the equation represents the number of collisions per unit time per unit volume (when [4] = [B] = 1), and e~#/*7 represents the fraction of the collisions that involve molecules with the necessary activation energy. Example 22 Use the collision theory to estimate the specific reaction rate for the decomposition of hydrogen iodide, 2HT ~> 1, + H,- Assume that the colision dismeter «@ is 354 (3.5 x 10° em), and employ the activation energy of 44,000 cal/g mole Getermined experimentally by Bodenstein." Also evaluate the frequency factor. Solution According to the collision theory, the specific reaction rate is given by Eq. (2531) ia units of em?/(molecule) (se0). For the reaction 2H1 -» Hy + Ts My = My = Muy = 128 ‘The other numerical quantities requied are Ry = kyr = (138 % 10° *96.02 107) = 8.30 x 107 ergs(*KXE mole) or 1.98 calf(g mole) (°K) 35 x 10-Fem E = 44,000 cal/g mole Tam 4 31 Substituting these values in Bg. (231) yields = BAEK k : 655 09 [aco x wy se (Zp essen 1.70 x 10-!e-37 —m?/(molecule)(ses) ‘To convert this result to the usual units of liters/(g mole)(sec) it should be mult MM, Bodenstein, Z. Physik Chem, 100,68 (1922)ACTIVATED-COMPLEX (TRANSITION STATE) THEORY a stcnon plied by Avogedro’s number, 602 x 10° moleculeymole, and divided by 1,000 ean fier: SOE IO TO x 107 34 000 = 1.02 x 10! & 374 4 $7 x 10°° liter moleyse) ) [As we shall see in Example 2-6, the data is found “to be 20 x 10°" iter/(g mole}sec). complex molecules the experimental rates are usually much less than the theory predicts. Comparison of the form of Eq. (A) and the Arrhenius expression shows that the frequency factor is A= 10 x 10" liters(g mote)sec) 25 Activated-complex (Transition-state) Theory ‘The collision theory has been found to give results in good agreement with experimental data for a number of bimolecular gas reactions. The decomposition of hydrogen iodide considered in Example 2-2 is an illus. tration. The theory has also been satisfactory for several reactions in solution involving simple ions. However, for many other reactions: the predicted rates are much too large. Predicted frequency factors lie in the rather narrow range of 10° to 10'*, while measured values may be several orders of magnitude less. The deviation appears to increase with the com- plexity of the reactant molecules. (Moreover, unimolecular decompositions jt dificult to rationalize by the collision theory.) As a means of correcting {for this disagreement it has been customary to introduce a probability, | or steric, factor (having a value less than unity) in Eq. (231), To retain | the hard-sphere concept we must then explain why all the collisions supplying the necessary energy do not result in eaction.? Beginning in about 1930 the principles of quantum mechanics were applied to this problem by Eyring, Polanyi, and their coworkers, and the result is known as the activared-complex theory.” In this theory reaction is Stil presumed to occur asa result of collisions between reacting molecules, but what happens aftr collision is examined in more detail. This examination is based on the concept that molecules possess vibrational and rotational, 45 well as translational, energy levels, {Fe more detailed and complete description ofthe collision theory and its limitations see Neck Moshon-Hughes, “Kinetics of Reactions in Solution,” Oxford Universy Prose, New York, 1946 StmVel Glastone, K. J. Laidler, and Henry Eyring, “The Theory of Rate Process," McGraw-Hill Book Company, New York, 1941 i4 CHAPTER 2 _ KINETICS OF HOMOGENEOUS REACTIONS ‘The essential postulate is that an activated complex (or transition state) is formed from the reactant, and that this subsequently decomposes to the products. The activated complex is assumed to be in thermodynamic ‘equilibrium with the reactants. Then the rate-controlling step is the decom- position of the activated complex. The concept of an equilibrium activation, step followed by slow decomposition is equivalent to assuming a time lag between activation and decomposition into the reaction products. It is the answer proposed by the theory to the question of why all collisions are not effective in producing a reaction. ‘These ideas may be illustrated by a simple reaction between 4 and B to form a product C. If the activated complex is designated by (4B)*, the overall process can be written as A+ B= (ABYC Since equilibrium is assumed for the first step, the concentration of (4B)* js that determined by the equilibrium constant. Then the rate of the overall reaction is equal to the product of the frequency of decomposition of the complex and its equilibrium concentration, ot 1 = v[(4B)*] _ molecules/(sec)(em") 2-32) ‘where vis in units per second and the concentration [(4B)*] is in molecules per cubic centimeter. If the equilibrium constant for the formation of ABis K*, then in terms of activity a, Sa Yasl(AB)*] aay (PAL AD(eLB)) ‘where yi the activity coefficient. The concentration of the activated complex can be substituted in Eq, (2-32) to give (233) tale eeLAyEB] eo “The equilibrium constant is related to the standard free-energy change for the formation of the activated complex. From Eq. (1-4), this relationship is, Kee erin Se It can be shown! that the decomposition frequency is, kT h ‘samuel Glasstone, K. J. Laider, and Henry Eyring, “The Theory of Rate Processes,” McGraw-Hill Book Company, New York, 1941 (236)section 25 _ACTIVATED-COMPLES (FRANSITION-STATE) THEORY where ky = Boltzmann's constant, 1.380 x 10” '*erg/"K, and A = Planck's constant, 6.624 x 1077? exgs(sec). Substituting Eqs. (2-35) and (2-36) in Eq. (2-34) gives, 2 the specific react (2-38) ‘The latter form follows from the thermodynamic relation AF = AH — TAS. Comparison of Eq. (2-38) with the Arrhenius equation shows that (2:39) E=AH* (2-40) ‘These two relations are the predictions of the activated-complex theory for the frequency factor and the energy of activation. The collision theory (Eq. (2-31)] does not offer a method for caleu- lating the activation energy. The activated-complex theory suggests that is the enthalpy change for formation of the activated complex from the reactants (Eq. (2-40)]. To predict this enthalpy we must know exactly what the activated complex is; ie., we must know its structure, Even then the prediction of enthalpy from molecular-structure data by statistical mechanics is an uncertain operation for any but the simplest molecule. Eckert and Boudart! have illustrated the calculation procedures with the hydrogen iodide decomposition reaction. If an activation energy is available from experimental measurements, the theory need be used only for estima- ting the frequency factor from Eq, (2-39). Again the structure of the activated complex is necessary, this time to calculate the entropy of activation, AS* Uncertainties about the structure of the activated complex and the assumptions involved in computing its thermodynamic properties seriously limit the practical value of the theory. However, it does provide qualitative interpretation of how molecules react and a reassuring foundation for the empirical rate expressions inferred from experimental data. The effect of temperature on the frequency factor is extremely difficult to evaluate from rate measurements, This is because the strong exponential function in the Archenius equation effectively masks the temperature dependency of A. 'C.A. Eckert and M, Boudar, Chem. Brg. Sei, 18,144 (1963)50 COAPTER 2 KINETICS OF HOMOORLEDUS REACTIONS Equation (2-39) suggests that A is proportional to T, the collision theory indicates a T% dependency (Eq. (2-30)], and the Arrhenius relationship (Eq. @-8)] implies that A is unaffected by temperature. It is normally impossible to measure rates of reaction with sufficient sensitivity to evaluate these differences. In Eq. (2-32) it is supposed that the rate is proportional to the con- centration of the activated complex. Similarly, in the collision theory, Eq. (2-25), itis tacitly assumed that the concentration determines the collision frequency and the rate. However, if the results of thermodynamics were followed, the rate might be assumed proportional to activity. Ifthe activity replaced concentration in Eq. (2-32), the activity coefficient of the activated complex would not be needed in Eq. (2-34). The final expression for the rate constant would then be EAP yg Am IESE ean k instead of Eq. (2-38), Since the activity coefficient is a function of pressure, K-values predicted from the two equations would vary differently with pressure, Eckert and Boudart analyzed rate data for the decomposition of HI in this way. Their results were more compatible with Eq. (2-38), suggesting that the rate is proportional to the concentration of the activated complex. In this text the rate equation will be written in terms of concentrations. 2-6 Unimolecular Reactions ‘The activated-complex theory provides a plausible explanation of the first order rate of unimolecular gaseous reactions. In such a reaction the reacting molecules gain the energy of activation by collision with other molecules ‘This might be thought of as a second-order process, since the number of collisions is proportional to the square of the concentration. However, Lindemann’ showed in 1922 that activation by collision could result in first-order rates, If A* is an activated molecule of reactant, the equilibrium between A and 4* and reaction to products B can be represented as A+ABA EA (2-42) ASB (2-43) If the pressure (¢.g,, concentration) in the reaction mixture is high enough, °F, A. Lindemann, Trans, Faraday Soc, V7, $98 (1922)| > secnio 26 UIMOLECULAR REACTIONS 3 the mumber of collisions between A and A* will be so large that equilibrium exists between A and A*, according to Eq, (2-42) Ithe equilibrium constant, is A, the concentration of 4° is given by ey) ae (2-44) (= 6 ae The rate of formation of products is determined by the second reaction, the decomposition of activated molecules. No collisions are needed for reaction, 50 the rate is first order in A*, that is, r= k[A*] (2-45) Substituting [4*] from Eq. (2-44), the rate is seen to be first order in A, r=bK [4] (2-46) At low pressures the collision rate is low and equilibrium is not attained between A and 4*, so that Eq. (2-43) should be written AtAM AEA 47) If the A* has a short lifetime, its concentration will be low with respect to that of A or products. Then [4*] will rapidly reach a constant, low value after which d[A*]/dt = 0,1 Summing the rates of formation and destruction of A* by reactions (2-47) and (2-43) yields tar] 0 =k [AP — k[4*] ly (2-48) ‘Substituting this result into Eq. (2-45) gives a second-order rate : Fak UP 2-49) ‘This changeover from first-order to second-order kinetics at low pressures has been observed experimentally for a number of unimolecular reactions. “This statement is teed the ations stat hypothesis —a concept widely wed or cectins | involving species of a transitory nature such a fie radicals and toms See See, I fora discussion of its use in photochemical kinetics. It is equally applicable her to the high-pressure ‘se and also leads to Eq. (246), but by 2 mare complicated route52 CHAPTER 2_ KINETICS OF HOMOGENEOUS REACTIONS ANALYSIS OF RATE EQUATIONS / ‘The most common experimental procedure for establishing rate equations is to measure the composition of the reaction mixture at various stages during the course of reaction." In a batch system this means analysis at ‘various times after the reaction begins.? Then the data are compared with various types of rate equations to find the one giving the best agreement. ‘The comparison can be made in two ways 1. The integration method, comparison of predicted and observed com- positions. For this approachitis nocesary to integrate the rate expression [for example, Eq, (2-6)] to give concentration as a function of time 2. The differential method, comparison of predicted and observed rates, “The latter are obtained by differentiating the experimental data,/ In this chapter we are concerned only with the rate equation for the ghemical step (no physical resistances). Also, it will be supposed that “te temperature is constant, both during the course of the’ reaction and in all parts of the reactor volume. These ideal conditions are often met in the stirred-tank reactor (see-SeC. 1-6). Data are invariably obtained with this objective, because it is extremely hazardous to try to establish a rate equation from nonisothermal data or data obtained in inadequately mixed systems. Under these restrictions the integration and ‘differential methods can be used with Eqs. (2-1).and (2-5) or, ifthe density is constant, with Eq. (2-6). Even with these restrictions, evaluating a rate equation from data may be an involved problem. Reactions may be simple or complex, or reversible or irreversible, or the density may change even at constant temperature/(for example, if there is a change in number of moles in a ‘gaseous reaction). These several types of reactions are analyzed in Secs 2-7 to 2-11 under the categories of simple and complex systems, 2-7 Integrated Rate Equations for Irreversible Reactions If all the reactants and products can be explained by a single reaction, the reaction system is simple. Within this category the reaction may be of any order and may be reversible or irreversible. "Many other methods are weed for studying kinetics, particularly for fast reactions. For a desertion of various methods see F. J. W. Roughton and B. Chance, in S. L.Fress and A, ‘Weisberger (eds), "Rates and Mechanisms of Reactions,” chap. 10, Interscience Publishers, New York, 1953, 2a continuous teactors the course ofthe reaction i measured a diferent flow rates, or reactor ‘volumes. The analysis is different from that for batch reactors and involves Eq. (2-2). Analysis fof such systems i dizcussed in Chaps. 4 snd 8SECTION 27_INTEGRATED RATE EQUATIONS FOR IRREVERSIBLE REACTIONS 3 Zero Order Zero order, meaning that the rate is independent of the con- centration, may occur in two situations: when the tate is intrinsically independent of concentration and when the species is in such abundant supply that its concentration is nearly constant during reaction, In the latter case the dependency of the rate on concentration cannot be detected, and apparent zero order prevails. Thus in the oxidation of NO o NO, in the presence of a large excess of O,, the rate is zero order in O, For @ zér6-Order reaction at c 5) becomes: 44) #4. 5, 2-50) Integrating from an initial condition of [4] = [4]Jp yields [4] = [Jo — kot @s1) This result shows that the distinguishing feature of a zero-order reaction is that the concentration of reactant decreases linearly with time. It is difficult to cite a homogeneous reaction that is intrinsically zero order, although many reactions have apparent zero-order characteristics when the concentration of the species is large. However, in some heterogeneous reactions where the solid phase acts as a catalyst the rate is zero order. ‘An example is the decomposition of NH on platinum and tungsten surfaces." Equation (2-51) ean be used with measurements of concentration vs time to determine if a reaction is zero order and to evaluate k. If two reac- tants, 4 and B, are involved, experiments can be carried out with A in large excess, so that the rate equation is independent of [4]. Then the concentration of B can be varied and its order determined. In this way the concentration of one reactant can be rendered ineffective in order to study the effect of another. Tt may be’ simpler to measure the time when-a certain fraction of reactant has disappeared than to obtain concentration-vs-time data. Com- ‘mon practice is to obtain the time required for one-half of the reactant to disappear. Defining this half-life as z,,, we have from Eq. (2-51) ‘AlAlo = [A]o ~ koty, or ne S Half-life data can be used with Bq. (2-52) to evaluate ky as an alternate to Eq. (2-51). 'C.N, Hinshelwood and R. E. Burk, J. Chem. Soe, 127, 1051, 1114 (1925).se CARTER 2 KINETICS OF HOMOGENEOUS REACTIONS First Order Equation (2-6) for a first-order rate is AA et) @53) If the initial condition is [4] = [4], integration yields A wt skit 054) A plotof In [AYLA]p vs t should be a straight line of slope equal to —K, ‘The half-life is given by In (2-55) or tap (2-56) Equations (2-54) and (2-56) show that the half-life and fraction of reactant remaining are independent of initial concentration fora first-order reaction. "Among the numerous examples of homogeneous first-order reactions are the rearrangement of cyclopropane to propylene,’ certain cis-trans- isomerizations, and the inversion of sucrose. ‘Second Order Two types of second-order reactions are of interest rel A+A>P 4) 2 : ~44 - ity e57) qyrell A+B>P a4] a > BLA) (2-58) For type I reactions integration of Eq. (2-57) yields ket (2-59) In terms of the halflife, this becomes, oo “ello Note that for a zero-order reaction ty, is directly proportional to [4]o; for (2-60) 'T. 8. Chambers and G. B. Kistiokowsky, J. rm. Chem. Soc, 56, 399 (1934),SECTION 2-7 INTEGRATED RATE EQUATIONS FOR IRREVERSIBLE REACTIONS 38 a first-order reaction it is independent of [4], and for a second-order reaction inversely proportional to [4]. Two well-known examples of type I reactions are the decomposition of HI in the gas phase and dimeriza- tion of cyclopentadiene in either gas or liquid phase. When order and stoichiometry of type II reactions do not agree, the analysisis somewhat different. Suppose the stoichiometry may be represented = a seers wat bBaP : - and the rate expression is Eq. (2-58). Initially [4] = [4], and [2] = [Bos let [X] be the amount of 4 that has reacted, expressed as a concentration. ‘Then at any time [4] = [4]o ~ [XT (2-61) i=c)- 209 eon a4} _ ax] ae ae (2-63) ‘Substituting Eqs. (2-61) to (2-63) in (2-58) gives. tN - A -.c-0(t-200) een Integration from t= O gives the concentration of.X or 4 and Bt anytime: [lo~ EY] _ LA) _ Aad ~ of) 4, Ale "TB, — Gia] =" [a] eae Tele (2-65) 1 In terms of A, ty, corresponds to [AI/[A]o = ¥4, and Eq, (2-65) can be solved to yield "a alas” Baa HCAs Ifinitial concentrations ae stoichiometri, then (ho = > LA. and Eq. (2-64) becomes 18 ba =e bap 067)36 CHAPTER 2 RINETICS OF HOMOGENEOUS REACTIONS “This is the same as Eq. (2-57), with Ks multiplied by b/a. Numerous reactions of type II have been observed: for example, HI formation from gaseous Hy ‘and 1,,! dimerization of cyclopentadiene in benzene solution, and certain ‘esterification reactions in aqueous solution, Concentration-time data can easily be analyzed to test second-order kinetics. For type I (or type II with stoichiometric proportions of A and B initially), Eq. (2-59) indicates that the data should give a straight line if LA] is plotted against t. For type TI, Eq. (2-65) shows that a plot of log [AJ/(B] ws # should be linear. In this case the slope (6[A]o ~ aL Bodko/a will be positive or negative, depending on the stoichiometric coefficients and b and the initial concentrations. In the following example first- and second-order rate equations are used to interpret data for an isothermal, constant-density, liquid system. Example2-3 The liquid-phase reaction between trimethylamine and n-propyl bromide vas studied by Winkler and Hinshelwood? by immersing sealed glass tubes containing, the reactants in a constant-temperature bath. The results at 1394°C are shown in ‘Table 2-2. Initial solutions of trimethylamine and n-propyl bromide in benzene, ‘0.2-molal, ate snixed, sealed in lass tubes, and placed in the coastant-temperature bath ‘After various time iatervals the tubes are removed and cooled to stop the reaction, fand the contents are analyzed. The analysis depends on the fact that the product, a ‘quaternary ammonium salt is completely ionized, Hence the concentration of bromide ions ean be estimated by titration. Tabie 22 Run min Conversion, 1 3 2 2 4 231 3 2 367 4 Bo 552 From this information determine the first-order and second-order specific rates, se, and k, assuming that the reaction is irreversible over the conversion range covered by the data, Use both the integration and the dferential method, and compare the results, Which rate equation best fits the experimental data? Solution “The reaction may be written N(CH,)y + CHJCH,CH,Br ~ (CH,),(CH,CH,CH)N” + Br «Mt Bodenstein, Z: Physle Chem, 13,56 (184); Z. Physik Chem, 22, 1 (18975 Z. Posie Cher, 29, 295 (1899). SCA, Winkler and C. N. Hinshelwood, J. Chem. Soe, 1147 (1955)secrion 2.7. INTEGRATED RATE EQUATIONS FOR IRREVERSIBLE REACTIONS 7 ‘Since the concentrations of reactants and products are small and the temperature is constant, the density may be assumed constant without serious error. Then the rate equations (2-53) and (2-58) are applicable for the fist- and second-order possibilities, IFT denotes trimethylamine and P n-propyl bromide, the rate expressions are ar) 4 kr “ re 8 ® INTEGRATION METHOD. For the first-order case, the integrated form of Eq. (A) is Eg, (2-54); thats, © band [T]p = [P]p = 0.1 moll In the second-order ease it is noted that Hence [7] ~ [F], and Eq (8) reduces fo a type Lseeon-andcragiion, a{7] 2 ~— a 7 BLT o ‘The lutions Ea (2-8), which may bested fork to give tat s-r(ia- mm) 2 ‘The conversion x is the fraction of the reactant that has been consumed, In this, problem yo UTe=1 (le (7l=()0-% ® ‘The caleulation of ke and le, will be illustrated for the fist run. From Eq, (F), (7) = E71. - 0.112 = 0.100.888) ‘Substituttg ia Eq. (C), we find Lyle tg ga 7 Cry ~ Tay Does = 14 * 10 ‘The, using Eq. (E) forthe second-order possibility, we obtain aya oun socoe (ea) aommn orm = 1.63 x 10 liters/(g mole}sec) Table 2-3 shows the results obtained in a similar way for the four runs. The values show a definite trend with time, and therefore the first-order mechanism does not8 caurten 2. KINETICS OF HOMOGENEOUS REACTIONS Table 23 Specific reaction rates for trimethylamine and mpropyl bromide reaction ky x10, Ua. Run sec Iteryig moles) gmolefiter 1 780 Ls 63 pou 2 2.080 146 70 0.0257 3 3.540 130 Kea 0.0367 4 7200 ue im 0.0582 stay satisfactorily explain the kinetic data, The k, values not only are more nearly identical, but the variations show no definite trend. DIFFERENTIAL METHOD The moles of bromide ions B produced are equal to the tri- ‘methylamine reacted. Hence ()=(7)-7 and from Eq. (P) (4) = (he - [To Gd ~ 9 = *[7o “Thus [2B] can be calculated from the conversion data, A plot of [2] vs time of reaction is chown in Fig. 23. The slope ofthis curve at any point is equal tothe rate of reaction, eal oe: a dt Slopes determined from the curve are given in Table 2-4 Fig. 2-3. Concentration vs time for reaction between (CH,)3N ond CH,CH, CH Br 0.06 005) J | 008 08 02] Br~ cone, g mol oot ooo 2000 3000 40005000 6000 70008000 Time, se.SECTION 27 INTEGRATED RATE FQUATIONS FOR IRREVERSIBLE REACTIONS 59 Table 2-4 Concentration, g moeflter ee rye, wo om sgmole/iteryeee) 00 0.10 1.58 « 1078 001 0.09 138 10-8 00 0.08 tis 1077 003007 0.79 x 10°3 00 006 064 x 1079 0050s 04s x 10"? If the reaction is first order, the rate is given by Ba-(A), which may be written loge = log ky + log [7] @ Similarly, i the reaction i second order, rom Bq, (D) we have loge = log ks + log [7] = log ky + 2log (7) « For the first-order ease log plotted against log [7'] should yield a straight line with @ slope of 1.0. For the second-order case the result should be a straight lige of slope of 2.0, in accordance with Eq, (H). A plot of the data in Table 2-4is shown in Fig. 2-4 ‘While there is some scattering, the points do suggest straight line ofa slope epproxi- mately equal to 2.0. For comparison purposes lines with slopes of both 20 and 1.0 have been included om the plot. The equation of the solid line (slope 2.0) is logr = ~2.16 + 200g [7] Fig. 24 Rate vs concentration of trimethylamine 54) “ cA 32 B Ww loge -si 50 ~49 48 100 110 120 130 tog [7]o Couyren 2_RaVerict OF HOMOGENEOUS REACTION By comparison with Eq. (H), log k, = -2.76 ky 73 x 107? literfg motes) ‘This value agrees well with the average result 167 x 10°? obtained by the integration method Both methods show that the second-order mechanism is preferable. However, the failure of the first-order assumption is perhaps more clearly shown by the differential method than the integration approach. The data in Fig 24 do not approach a slope Of 1.0 at all closely, bu the k, values in Table 23 are ofthe same magnitude, difering fiom en average value by not more than 17%. This is because the integration process tends to mask small variations. ‘Third-order reactions are uncommon. Fractional orders exist when the reaction represents a sequence of several elementary steps. Procedures for establishing the order and rate constants for these cases are similar to those given above. Experimental data that suggest fractional-order rate equations should be examined carefully for effects of physical resistances. Sometimes these effects, rather than a sequence of elementary processes, can be responsible for the fractional order. An example is the study of the hydrochlorination of lauryl alcohol with zinc chloride as a homogeneous catalyst:! CH,(CH,);9 CH,OH() + HCI(g) + CHy(CH,)19 CHCl, + H,0() ‘The reaction was carried out by dissolving gaseous HCI in a stirred vessel containing the alcohol. The resulting concentration-time data could be correlated with a rate equation half-order in alcohol concentration. How- ever, the rate constant was found to vary with the gas (HC) flow rate into the reactor, suggesting that the observed rate was influenced by the resistance to diffusion of dissolved HCI in the liquid phase. A method of analysis which took into account the diffusion resistance indicated that the chemical step was probably first order in dissolved HCI and zero order with respect to lauryl alcohol. 2-8 Reversible Reactions For an elementary process the ratio? of the forward- and reverse-rate constants is equal to the equilibrium constant, Eq. (2-13). Hence the net rate of reaction can be expressed in terms of one and the equilibrium constant. Then the integrated form of this rate expression can be used with UL A. Kingsley and H. Bliss nd. Eng. Chem. 44, 2479 (1952) 2See See, 2-2 fora discussion of this ratio for nonelemeatary reactions.SECTION 2-8 _REVERSILE REACTIONS a concentration-time data to evaluate k, just as for irreversible reactions, However, the evaluation procedure is more complex. First Order If k, and ki, are the forward- and reverse-rate constants for the elementary process ASB then — ae aA] ae [4] - KB] 2-68) ‘The concentration of B can be expressed in terms of [4] by a simple mass balance. At constant density, and since the number of moles is constant, the concentration of Bis its initial concentration [8]y plus the concentration of A that has reacted; that is, [2] = [Bo + (Alo ~ [4D (2-69) Combining this esl with Eq. 2-68 gives ~~, + ot - Kile + Ca @7) At equilibrium the forward and reverse reaction rates are equal, and Eq. (2-68) becomes killa = Kile ey gh ; [ge ae — here Kis the equilibrium constant. Eliminating from Ea, (2-70) by using Be @.7) yields 1 $b + ema} en Now, applying Eq. (2-69) at equilibrium conditions to find [2] and substituting this result in Eq. (2-71), we have [lo + [Jo = [leg (5 [Alg(K + 1) = [Blo + [4] 73)