DETERMINATION OF MECHANISM OF CATALYZED GASEOUS REACTIONS K. H. YANG and O. A. HOUGEN University of Wisconsin, Madison, Wisconsin N the industrial applications of kin- ties a knowledge of the mechanisms ff chemical reactions is helpful in es tablishing the optimum conditions of operation relative to such variables as pressure, temperature, feed composition, space velocity, extent of conversion, and recycling ‘This paper is written as a guide in the planning of experimental programs in applied kinetics and as an aid to the selection of the mechanisms of catalytic reactions. It has been observed that tnuch time is lost in failing to pursue fan orderly experimental program, and in failing to. recognize the important variables, Often it is discovered after years of experimental effort thatthe in portant variables were not investigated. In a previous paper by Hougen and Watson (2) various mechanisms which may be encountered in gaseous reactions when catalyzed by solid surfaces were Aeveloped with appropriate mathemati= cal equations for expressing rates Tn a large measure the concepts of chemical kinetics used in this paper afso stem from the work of Eyring and Tn any given chemical process sev- eral reactions may be proceeding con- secutively or simultaneously but for each reaction it may be assumed that only one or two chemical steps are rate- controlling. From the standpoint of theoretical kinetics this assumption is not acceptable, but it usually serves as a satisfactory basis for practical pur- poses. ‘Where a gaseous reaction is catalyzed by flowing the gas through a bed of solid catalyst pellets, the physical steps involved are the transfer of the compo- ent gases up to the catalyst surface, diffusion of reactants into the interior of the pellet, diffusion of products back to the exterior surface, and transfer of the products from the exterior surface to the main stream. These physical steps are usually present. To simplify tion of experimental data it is desirable to minimize the resis- tance offered by each of these physival steps and thus to cleal only with the chemical aspects of the reaction ‘The chemical steps involve activated adsorption of reactants with or without dissociation, surface reactions on active sites, and activated desorption of prod ucts. ‘The uncatalyzed reaction also takes placé in the main gas. stream simultaneously with the surface reac: tion, This last should be of negligible importance where an eifective catalyst |s used, In addition to the alive possibilities, fouling and changes in the activity of the catalyst may take plac. Tt is evident that an experimental study of all these possible effects simul aicously is prohibitive hecxuse of com plesity. It is desirable, therefore, that experimental procedires he arranged t0 permit separate determination or sep rate elimination of these different ¢ fects, Resistances to the transfer of mass and heat can he minimized by operating at sufliciently high mass ve- locities to make the partial pressure and temperature gradients across the gas film negligible. ‘The retarding effect of diffusion of reactants and of products in the interior of the catalyst pellet can be minimized by using pellets of small size, The effect of fouling can be climinated by extrapolating rate data t0 the beginning time of catalyst service and the effect of clanging activity ean be eliminated by continued use of the catalyst until a stable steady state has been attained, ‘The means of minimizing the various physical steps and the effects of fouling and deactivation will be analyzed sepa- rately. Minimizing Resistances Due to Transfer of Mass ond Heat. The gen- eral rate of a catalytic reaction in a fiow system based upon unit mass of catalyst is given by the relation, rd = Faery a) CHEMICAL ENGINEERING PROGRESS where r= moles of reactant A converted per (unit time) (nit macs fof catalyst) F = flow rate of feed, moles per tanit time WW = mass of catalyst noles of reactant A converted per mole of feed Values of the reaction rate r should be correlated against the conditions of composition -and temperature whiclt prevail at the surface of the catalyst where the catalytic reaction actually takes place, From equations for mass ‘and heat transfer the film gradients for partial pressures of each component gas and for temperature can be evalu ted. However, this correction is trot Diesome, dificult, and uncertain. 10 experimental work it is desirable, if possible, to render these gradients in Significant by flowing the gos at high mass velocities. If the rate of a cata Tytie reaction is plotted against mass velocity the rate increases progressively from a value at zero mass velocity to an asymptotic value at high velocities as Shown in Figure 1. It is desirable t0 operate at sulficiently high velocities 30 that film gradients become negligible The value of v at zero mass velocity is the reaction rate obtained in a_nonfiow system. Ie is evident from Figure 1 that reaction rates calculated from equal residence times in nonflow and flow sy tems are not the same. In general cata- lytic reaction rates obtained in nonflow systems are not applicable directly flow systems. Indeed it is doubtful reaction rate data taken in nonflow sys tems of gases catalyzed by solid sur- faces and without agitation in the re- actor are of any value in reactor design Decause of nonsteady state conditions and the uncertainty of concentration gradients due to natural convection within t ‘The general equa for is given as Ded. jon for mass trans- ‘March, 1950P= hoya @ where AP Pana Experimental data on mass transfer are related to ky by the relationship: inn (BABEL) 09 Experimental data on values of jy were ‘obtained for mass transfer in a granular bed by Gazason, Thodos, Wilke, and Hougen (1, 6) and related to a modified M26 tess than 620, «= 244 and * = 081; and for values of YE greater than 620, a= 125 “and mea, By 2 Combination of Equations (2), (3), and (4) there results: ara 3 Me Jn igure 2 values of apy /pa ate plot= tat against values of 4 senction rate humier "for lifferent. values of VenG/m where (aetate)( ot) Patem N@Dany In Figure 3 values of ap4/Ps over the limited range 0 to O41 are. similae plated. Figure 4 is a cross plot of Fig tre 3 where X is plotted agatasé valu of \/’e,G/u for values of ap4/py equal to 0.1 and below. If the required ex- perimental accuracy in reaction rated need not be greater than JD% then the film gradient can be neslested if ‘pa/Pa is O1 oF less; for an accuracy of Ue the film gradient can be neglected Ff Apa/Pa is O01 0F less, and so forth ‘The flim gradients become wegligible where surface reactions proceed slowly und alo at high partial pressuzes of the reactants, For example, from Figure 4 the following conditions prevail: _—— y G Fig. 1. Effect of Mass Velocity Upon ‘Reaction Rates. ‘Thu, if an accuracy of 10% is tolerated where the rate number X' is 5. the modi- fied Reynolds mmber should not be less than 450, whereas if 1% aceuracy is re- quired the modified Reyaokls number should not be less than 25,00 for the same rate number. ‘The rate of mass transfer becomes entirely rate-controlling where iy, = 0 and &p4/Pa = 1.0, This limiting condi tion is approached with an ideal eatalyst where surface reactions are instantan- cous. Under these conditions the reas (APa/Ps range 0 to 1.0) Vol. 45, No. 3 oa CHEMICAL ENGINEERING PROGRESS we (eat ays vig. 3.22 vere 5 Causes sange 0 t0 10) Page 147°\5 zeae goad 60-209 ~400 600 1000 2000, ‘me vine Fig. 4X versus at Various Values of \P./Ps. Fig. 5, Limiting Values at X versus oar + a os 008 ova ocr] oaff oo ° +t SST EN vee AP sergus fat Various Values of 6. Fig. 6. AT versus 1° at Various Values of 2" Fig. 7. YESS Page 148 CHEMICAL ENGINEERING PROGRESS Morch, 1950n° Fig. 8 foverue @ at Various Values of 84/Ps for = Specific Sytem tion rate is controlled entirely by the Tate at which the reactants canbe ‘brougitt up to the surface and the prod- ucts returned, Equilibrium prevails at the interface. This limiting rate is shown by the relationships of Figure 5. ‘Thus from Figure 5 mass transfer be- comes entirely controlling and the rate hnumber X cannot exceed the values given for the following modified Rey- olds number For example, when the modified Rey- nolds number is 100 the rate number X cannot exceed 23, which condition cor- respoirls to the behavior of an ideal catalyst. The general equation for heat trans- fer is given as gag at = —AHr (6) at th Experimental data on heat transfer are related t0 tg by the relationship, a Experimental data _on jy were ob- tained for heat transfer in a granular bed (1, 6) and related as follows Vol. 46, No. 3 aha" zoo teae 2008 4050 6000 IA000 20500 hs aka ae da aB5a *T50 4000 H5GE #800 versus G for a Specific System. Fig. 9. Limiting » © Cylindrical pellets 16 X J6 ino where for values of \/%jG/a less than D = 24 it Bp=V/TS D = 00127 fe G0. ef 22, n= OSI for values of ——_g, = wy? = 0.000507 sat ViaG/ greater than 620, af = 1.35, 300 micropoises = 0.0726 N20 Sty a combination of Equa Th,/(hir.) (fe) fons (6), (7). and. (8) the result is a A(R Ge) ° p> Patt NE), In Figure 6 values of al/T are plotted against X° for various values of Vas6/n where xr = (BLS 6 sq fe. ‘quilt NE 50 Ib. ut Film temperature gradients can be a= 2 192 my ft neglected if they do not exceed a few 692 sal degrees Centigrade, Ifthe required ac- curacy in reaction rates need not be greater than 10% then the fin temper ture gradient can usualy be negleted {fare less than 10° C. These values require veritcation for specie systems. ( total pressure 0,00 Btuib. mole 4 converted Tt should be recognized that the temper- (+ ), = 150 ature coefficient for reactions catalyzed \Zam by rae a much en tan for (Se), = gan noncatalytic ones because of the offse- CE )! ting effects of desorption on the cata- Inte reactions 070 Bitw./(Ib.)(* R) 620; G = 2,000 tb./(hr.) A Hypothetical System. For a hypo- thetical system the following conditions (sq.t.) CHEMICAL ENGINEERING PROGRESS Page 149Fig. 10 (7.—T) Versus r at Various Values of Nya te Then Bea ar Me XAG where at values of V/a,G/u < 620: = 215; » = 051 at values of ¥/ 656 /u > 620 e470: 0 = 041 For this system values of aps/p4 are plotted against r/N, for the’ various parameters of G (Fig. 7) for values of ‘Ab4/P4 ranging from 0 to O.1 and values ‘of 7/Nq are plotted against G for various. parameters of Apa/Pa in Figure & From Figure 7 the following valuec are obtained from this special system an oo i 35.000 ‘Thus if an error of 10% is tolerated the film gradient for mass wansfer cau be neglected for a reaction rate r/N'4 ‘equal {0 § when the mass velocity G is 11,000 Ib,/(hr.) (sq.ft.) or greater. If the reaction at the catalyst surface is instantaneous then the ratio of Apa/b4 becomes equal to 1,0 and the rate depends pon mass transfer alone Poge 150 For this specific system this ease is plotted in Figure 9 and values of Af are plotted against 7 tor various parameters of G in Figure 10. For this special system mass transfer becomes entirely controlling and the re- action rate r/N., cannot exceed the fol- lowing values for the given mass veloci- ties (Fig. 9) In order to keep the filmy temperature drop below 10° C. for this specific sy tem at a reaction rate of r= 1.0, the mass. velocity G should be 1600 or greater (Fig. 10). It should be noted that the relation ships given in Figures 2-10 are based tupon experimental work for water va por-air mixtures at relatively low te peratures and extrapolated through gen ferally accepted relationships of the transport properties of gases. Extensive ‘experimental work i this field should be ‘encouraged to give greater certainty. Effect of Size of Catalyst Pellet. The relationship. between the effectiveness factor of a catalyst and its modulus are expressed by the relationship of Equa tion (10) first developed by Thiele (4) for a first-order gaseous reaction neg lecting the effects of activated adsorp: CHEMICAL ENGINEERING PROGRESS tion and varintions in the porosity a permeability within = single pelle. = oweomm=2) 00) ‘The modulus ‘m may be related to pellet size, porosity, and temperature by the following (2): an DY, = diameter of sphere having the ‘ame stirface area per unit Volume as the particle. For a elinder of height D equal to diameter, -p-—% Pp PF, ~ interior void Fraction of the pellet ip = density of pellets, mass per wit volume By using two pellets of identical com position, porosity, and temperature hnt OF different sizes the ratio of moduli is m Ds mg Ds aay Iy establishing reaction rates. for tw runs at neatly identical conditions: of fgas temperature and composition at the Surface of the catalyst with these two pellets the following: ratio prevails ay From Equations (10), (12), and (13) ‘aims cote anny 1 = ba (ig oth my —1) as) From Equations (14), mg ean be calew lated and ry, By. and Ey from Equa jons (10), (12), and (13). “The effectiveness factor approach unity as the particle size is reduced. For ‘establishing Fate mechanisms it is desir able to operate with small catalyst pel Tets in order to minimize the effects of diffusional gradients inside the pelle land to attain effectiveness actors. ap. proaching nity. This procedure alse minimizes the uncertainties due to time fag in attaining the steady state amd te the assumptions made in deriving the relationship of Eto. m. Cylinders 4 X46 in, seem to be the smallest size ‘which ean he economically pelleted ai tused ina stationary’ bed and at the same time permit high mass velocities with out excessive pressure drops and losse Effect of Fouling. Where fouling o: A catalyst occurs it is desirable to ex trapolate rates to zero time of servic: and to make all correlations on the fres) “This introduces an uncertaints catalyst ‘March, 195alue to the Tack of stexdy conditions in Muarting a rin, Where these difficulties become insurmountable it is necessary to find a temperature range where foul- ing is negligible. Effect of Changing etivity of Cata- Iyst. The activity of a catalyst changes due to deactivation caused by employ ment uf eaceasive temperatures and by poisoning. Where the feed consists of Sifferent streams for the separate re factants the poisoning component in each Stream can be removed often by passing cach stream separately throngh a special bed of the same eatalyst heiore the re action takes place. This proves effective if the poison is present in stall traces. CC. Watson and Stevens (3) have shown in an synpublished thesis that Steady-state conditions carmot be at- tained until the catalyst attains chem- jeal equilibrium with the gas stream this is in addition to the attainment of physical equilibrium in temperature and concentration gradients through the catalyst. The effect of changing activity can be eliminated by continuous use of the catalyst sntil complete equilibriom is attained both chemical and physical Vihis may introduce @ serious time lag where composition and temperature of the gas stream are changed Trom run (© run. It may prove impossible with some reactions to eliminate both fouling and Tack of equilibrium, of Rate-Controlling Chemical Step. When effects of eat and mass transfer, diffusion, fouling fand deactivation have been minimize od for, selection Determination Jinated, oF acco ff the rate-determiining chemical step is in order. Complex chemical processes may be considered as consisting chiefly fof a combination of separate bimilect Jar and unimoleewlar reactions and for complex reactions the rate equations ray not be related to the over-all stoieh- fometric relations. For gaseous reac tions catalyzed by solid surfaces each separate molecular change usually con: Sits of one or two rate-controlling: chemical steps stich as chemisorption with or without association of one or Doth reactants; surface reaction between adsorbed! reactants and products, and impact of a nonadsorbed component with one that is adsorbed. Mathematical expressions for rate ‘equations can be derived from the prin- ciples given (2). In general these rates may be expressed by a combination of three terms, the kinetics term, the poten: tial term, and the adsorption term, ar ranged thus, m) term) (potential (adsorption term)* y= Line as) Vol. 46, No. 3 These terms are ammarived berewile for the fallowing four types of reac- () 4k: Uy (Ul) 4+ BER: (IV) Ad BaRES Leaks: and and for the following rate-controlling: techamismns Rate-Controlling Mechanisms Reaction between molecularly: ad- sored reactants ard. products with- fout dissociation of any component ‘upon adsorption a, Adsorption of 1 controlling 1b. Adsorption of B controlling ©, Desorption of A controlling {4 Surface reaction controlling B, Reaction between atomically _ad- sorbed , where RR, and S are molecularly adsorbed. Upon disso- ciation is adsorbed on adjacent sites fe. Adsorption of controlling (with dissociation) , Adsorption of B controlling 2 Desorption of K controlling (or s) h, Surface reaction controlling C. Reactant B is not adsorbed, 4. R, and 5 are molecularly adsorbed i. Adsorption of A controlling j. Desorption of R controlling Kk. Surface reaction controlling D, Reactant B is not acdsorhed. Ais atomically adsorbed, Rand S. are inoteeuarly adsorbed. Upon disso ciation is. adsorbed on adjacent sites |. Adsorption of controlling tm. Desorption of & controlling tn Surface reaction controlling TABLE 1. DRIVING FE. Reactant of is not adsorbed, 1, sand S sare mule] adsorbed vu. Impact of J controlling p. Desorption of & controlling (or Ss) 4g. Adsorption of B controlling P, Cncatalyzed Reaction 1. Homogeneous gas reaction As the field of applied Kinetics dle velops it may be found that examples of Some of these mechsinisms as rate-con: trolling steps will not he discovered. For example, the assumption of adsorption ea rate-controlling step over the entire composition range for a bimolecular re- aetion is untenable, Rate of adsorption of 4 reaches # maximum for the pure fas, but obviowsly there is no reaction Ih the absence of B and the adsorption fof 4 will stop when the catalyst bes comes saturated with A. Under these Circumstances the rate of adsorption di mninishes to zero without any reaction. From-this it follows that two chemical steps become rate-controlling. Driving Potential Term, The driving potential in any rate equation fulfills the eanditions af hecoming 2¢r0 at con ditions of equilibrium where the eqt librium constant is related to the ap- propriate activity ratio for the over-all reaction. For example, for the reaction AFBAR4S the driving potential is zero where yen = wane in accordance with the definition of the fenuilibrium constant for the over-all reaction. These driving potentials -are summarized in Table 1 for the four reactions and various mechanisms. ‘kine Kinetic Term, ‘The designation POTENTIAL TERMS Reaction Axas | eee Adsorption of & con~ trolling Adsorption of B cons | 0 troliing Desorption of R con- trotiing Surface resection com ‘trolling Tapact of A control- Hing (A not. adeorbea) Homogeneous reaction ‘cont roiling| eee CHEMICAL ENGINEERING PROGRESSTABLE 2, KINETIC TERMS. Waleiply each of the torwe below by EL except for the homogeneous reaction. y Bl mt Adsorption of A controiling ke Adsorption of B controlling ‘ Desorption of R controlling gk Adsorption of A controlLing with dissociation 3 iq Iapact of A controlting ake onogeneous reaction controlling x Surtace Reaction Controlling AZER| Aas] asta | ABST RS Uithout dissocsation Kak, | ky # Ky | Rae Kak |e © Kato With dissoctation ofA ge Ky | ky 8 Kg | kyele-deyha yal 2KaKg B not adsorbed we | kee ke [ke ha [ke he B not adsorbed, Adis kya K,| kz 8 Ky | ky eX, kes K, a Agi Ry a] eK | hee Ra [Kore Fa tie term," includes all factors whieh appear in the numerator of the reaction rate equation other than the driving potential stich as L, the total number of active sites; the effectiveness factor E; appropriate kinetic constants for ad- sorption controlling, ky and 5 for de sorption controlling, ky and ky; for surface reactions controlling £y; and for the homogeneous reaction controlling, k. The factor + represents the number ‘of adjacent active sites. Values of L and ‘will usually not be known and will be included in a characteristic constant for a specific catalyst. Over-all equili- Drium and adsorption equilibrium cor stants of the reactants 4 and B may also ‘appear in the kinetic term. Factors in the kinetic term are tabulated in Table 2 Adsorption Term. Where all rea tants, products, and inerts are adsorbed ‘under equilibrium conditions and witl- out dissociation the adsorption term is (14 Kyou + Kate + Katy + Kaas + Korl® Under other conditions the replacements shown in Table 3 should be made. The exponent n of the adsorption term is equal to 1 where the reaction in volves only one site, equal to 2 when reaction involves two adjacent sites, and is equal to 3 when the reaction in~ volves three adjacent sites. The ex- ponents take the values shown in Table 4. Formulation of Rate Equations. From these relations the rate equation for any of the above reactions and rat controlling mechanisms can be readily formulated. For example, RAS is Where the reaction 4 4+B Poge 152 surface-controlling with equilibria adsorption of all components, the driving potential term is 49 — (from Table 1) kinetic term is LskK Ky (Crom Table 2) adsorption term is (14 Kao + Kytn + Knit Katy +k the exponent is 2 (Table 4) and the rate equation becomes J+ Berk Where the resetion pro- ‘ceeds with adsorption of -f controlling (16) and with dissociation of the driving potential term is (e - i) (irom Table 1) the adsorption term is salem Lab (004 222) Te Raat Kite t Rute + Koos + Kies Initial Rates, Initiad rates. forthe pure reactants present in stoichiometrie proportions and in the absence of prod- lucts and inerts can now be readily eal culated in terms of total pressure, ‘Thus, for Equation (17), since atm and Equation (18) reduces to = ie ny ‘The remainder of this paper will be devoted to an initial selection of the Imnost plausible mechaniem from a virus inspection of the shape of rate curves when data are properly oblained to per init such plots. ‘The actial evaluation of the appropriate covistants should then be made by statistical methods of ‘fitting data to the selected equation. From the Shape of rate curves when plotted against such variables as pressure, feed ‘composition, temperature and conver- sion, the most plausible mechanism of @ simple reaction can be estimaved. Es- amples given herewith are for the four molecular types of gaseous reactions cited assuming only one rate-controlling chemical step. Where several reactions fre involved and where more than one chemical step is rate-controlling in each, the analysis becomes complicated. Com? plexities, however, ean he minimized by extrapolating rates to conditions of zero a7) Feciprocal space velocity at which condi- tion the complicating effects of several reactions have not begun, By systematic and separate variations in pressure and feed composition, the ‘mechanism can be fairly well established by visual inspection of the rate curve. When more than one chemical step is rate-controlling the number of constants in the rate equations becomes so numer- [rs Ve 4 Kote + Kyte + Kay | (Aram Table 3) K the exponent is 2 (Table 4) and the rate equation becomes Lhe(aa— afte y/ he Rox CHEMICAL ENGINEERING PROGRESS iy) tee __~ as) 4 Kya + Kite + Kes | ‘March, 1950ous and the accuracy af evalation of tick so uncertain that some empirical short eat aay’ prove expedient. The fect of extent of conversion is dificult to generalize and the effect of temper- ature is of minor value in establishing snechanism, Effect of Pressure, Pressure is by far the most Inportant variable in de termining the mechanism) of a ascous reaction catalyzed by a solid. Unless Caperiments are set ap to operate with pressure as a controlled variable over a Wide range it may not be possible 10 Sstabish with certainty the. probable techanism, Variations in total pressure 4s well ay partial pressures are este tial Partial presses can be diversitied by varying feed composition, but in {dition Hh total pressure mst be var- ied independently. For convenience the fects of total presstre will be ils: trated by observing variations inthe initial reaction rate with the use of {resh feed with no praduet present. Un- der these conditions the reverse reaction is neghgibte In Table 5 effects of pressure upon initial reaction rates are sen to fall imo Mine types of surven Tn Type 1 the initial rate, r5 independent of pressure, This type ine tleates that ‘desorption of product from the catalyst 1s the rate-controlling step when the reverse reaction iS neg Tigible. “This sitaation occurs when all the active sites are saturated with re spect to all components except product Tand ander itil conditions when no products have accunsulated inthe main gas stream, ‘The sae sitmiGion ie fountered for finite values of the equilic briam constant K where a second prod. act Sis formed and adsorbed under tclibrium conditions, As the Feaction proceeds with accumulation of product Hin the gas stream the renction rate is tw longer constant but progressively di= thinks. "The value of 7 at zero pres Sure is a hypothetical initial rate of de- Sorption. Since there is no spply of reactants at zero pressure, there is no Feaction and desorption reaches zero Reaction rates of Type Tare encoun. tere sen catalysts are poisoned Tm Type TI the initial rate increases Tinearly with total pressure, ry — ae. This situation applies wien the adsorp tion of reactant (or B) is rate-con- tolling where the other reactant 1 (or 4) is not adsorbed or not present as in inimolecular reaction. ‘This type as0 Holds for the wncatalyzed unimolecular reactions de Tn Type lil the initial reaction rate can be expressed by the relations ‘TABLE 3. REPLACEMENTS IN THE GENERAL ADSORPTION TERMS, (i+ Bao = Kyeg © Meee © Hots ey)” Reaction asta Aste | MB otK nore adsorption of A is Pate controlling replace Kaen by rate contfoiling Feplace tgs OF mere desorption of K is ute controlling Peplace Rasa by fimere assorption of 4 se ‘rate conureliing with Giscocsation of k Peplace faa, BY Kpaas rae i cy Were equitibriua adsorption of lie and similarly for other component lof A replace Kya, by kes place with olssoctation Tees [Pen fire imere & is not adsorved replace Kya, OY | Jang similarly for other components which are not adsorbed. lo ° | In this type the rate increases with pressure ‘maximum asymptotic value. This type is encountered where adsorption of either 4 or B is control- ling in a bimolecular reaction 4 + Bes also where surface reaction is rate-con” trolling ina unimolecular reaction A= with or without dissociation; and where desorption of 2 is controlling for Finite values of the equilibrium constant Kin a forward bimolecular reaction 14+ Beak. In Type IV eS hie Fae sction rate starts off linearly with caches maximum vale and the 6 total pressure to a constant asymptotic value, This type is characteristic of A=ER4S where the surface reaction is Tate-controlling and is also encotn- tered in the reaction A+Ba2R+S where adsorption of A is controlling and proceeds with dissociation on dual In Type V, This the rate increases progressively with pressure, staeting of linearly and ap proaches a value proportional to the Square root of pressure, This type ap= plies to the reaction 4+ Bes where Adsorption of B is rate-contrelling and 4 is adsorbed with dissociation, In Type V Tree = Te Vat ee the rate starts off as the square of the pressure and approaches a rate propor- tional to the first power of pressure TABLE 4, EXPONENTS OF ADSORPTION T2RMS impact of A without dissociation A+B => Res ne? Sy hk | Axe Res] eB OR] ABT RS. acti Py? ye 3 wae a | a | a 2 teinot adsorbed) 2 | 2 2 2 CHENICAL ENGINEERING PROGRESS Foge 159TABLE 5. INITIAL REACTION RATES OF SIMPLE GASEOUS REACTIONS. Eflecte of Total Pressure. Pre 1 \dsorption of one reactant A (6! PE fie x - q 2 % ara 4 ‘az an ae Bf on on Us bien Adsorption of A controlling Controlling Adsofpein of A controlling with # Sf 8] controdling where other re= tua 3 Desorption of Ove Product [actant b (or A) is not adsorbed Adsorption of Bveantrolling | ggrereatg ar not present ee elena Raacuiol IT TOIT TE) ipcataiysed eaction (AcE) A, * Surface reactfon controlling e| @)] €@ & (aa) S$) EE] | meme] cel 2 product ate) a] 8 |inennst a] ascEPStPiag PR Peete - P P ele Reaction] 1 Tit [in| tv Tea ~ i ala i Mechani al b 3 Desorption of One Product t] ty ipe aot Controlling (K*0o) ala neal it1) ‘Equilibrium adsorption fors)| a (3) j 2 fecal aa | 2) wehania} yc H 3} § $ 3) 3 3 2) 2 a ° aE TPE irre v1 an an on am TH on eer TH bi Tae ’ entrar 9 % is + 7 Adsorption of B controlling with dissociation of 4 (eats Surface reaction controlling (B not adsorbed) (ReB => a} Impact of A controlliny TRenoe adsorbedl (ArB SB) Surface reaction contratLing Uh dissosdated, not a sorbed) (AB so ) Gissociation (A+B +z Rr Reactiod I Tir fim Ta Mechaniso ¢ . © | reastieay yar x fechan ise TT ‘This type is manifest when the sur- lyst surface by chemisorption on a face reaction is controlling for the re action A+B 22 where B is not ad. ASBE where the surface reaction is rate-con- trolling with 4 dissociated upon adsor sorbed; and for reaction tion and with B not adsorbed. holds for the reaction Page 154 AtBER where A is not adsorbed and the con- trolling step is the impact of pon reactant B which is held on the eit single sit. Type VIL TebVetatae Te also is a common type where the reaction starts out as the square of the pressure nd then falls off in slope to a zero value reaching a rate of constant asrmptotic CHEMICAL ENGINEERING PROGRESS Jseacvion [1 [11] uit] tv] ee chanisa * T ° 2 ata [i value, This case is typified by four cases, (1) by the reaction A+B == where the surface resction is controlling and which proceeds without atomic dis Socintion; (2) for-s surface reaction controlling without adsorption of B: (3) in the reaction 44+ B2R4S where impact of A is controlling or (4) where desorption of product R is con- trolling for the reaction A+ B=2R and for finite values of K. ‘March, 1950aE W axe (tore serra ) y pire vin TABLE 5. (Continued) Effecte of Total Pressure 7a MOF orate rere 1x Asan Surface reaction controlling (no eissociation|(ArB =] surface reaction controlting Surface reaction controlling with dissociation of AlA+Be= | Uncatalyzed reaction control~ fing (h'* Baz) {B not adsorbed) Keaction [a _[al [ani [iv | Reaction: ma a Impact. of A control lin chant sa chan sm e pact of Ag e iechant: ha |Mechani 5 pesorptTon of one produet_con- trolling (4:8 ez R)(K SO) | aig ar Wy ‘Wechan: ° pons, I tt EFFECTS OF TOTAL PRESSURE In Type VIL, is no B present there is no over-all re- In Type 1V, ee action, the catalyst soon becomes satur- ala al-Ne ne ated with 4, and adsorption stop. This rag = STE or TG ye bbe ten? the rate initially increases az the square { pressure, the slope then falls off to ver at a maximum rate and becomes negative with further increase in pres- sire. This type applies where surface reaction is rate controlling with disso- ciation of A in the reaction t+ = “Type IX, re = aa, represents the be- havior of the uneatalyzed bimolocular reaction A+ B= where the rate in creases progressively with the square of pressure Effect of Feed Composition pon Initial Rates. ‘The effect of feed compo sition ina ‘bimolecular reaction upon the rate of disappearance of the limiting, reactant 4 falls into six types of rate curves, as shown in Table 6, assuming ‘only one rate-controlling step. Tn Type I, rao = aN, the rate in- creases Tinearly with the mole Fraction ‘Of A. This type holds where adsorption fof 4 is the controlling step when B is, hot adsorbed, ‘The extrapolation of the Straight Tine to Ng = 10 means that the adsorption rate for 4 is fastest when there is no F present. However. if there Vol. 46, No. 3 Situation indicates that when the mole fraction of approaches unity the rate ‘of reaction must be less than the instan= taneous rate of adsorption and hence some other mechanism must also be controlling such as the surface reaction or the impact of F upon the adsorbed is difficulty can be eliminated by ap- plying adsorption as rate-controlling Step only to the limiting reactant, In Type Ty rae = @(1— Ng), the rate of adsorption of B is controlling where 4 is not adsorbed. Extrapolation to N, =U gives 2 maximum value cor- responding 40 the rate of adsorption of Fin the absence of A. Under this cir tcumstance there is no over-all reaction, ‘The same anomaloys. situation is en. countered as in Type 1 In Type TH, aN aN thie rate curve increases more than Tine ‘early with the mole fraction of land is represented hy the adsorption of A con- ‘rolling with or without dissociation where # attains equilibrium adsorption ‘The same situation at V4 = 1.0 is em countered as in Type I CHEMICAL ENGINEERING PROGRESS the situation corresponds to the ausorp. fhon of Bas controlling with ot without issoeiation, when 4 is. at cquilibrigm adsorption, In Type I, re = @, the rate is inde pendent of ‘feed composition, This fneans that the desorption of product controlling when K is infinite for the reaction f+ Be2R. In the extreme ranges of gas composition in the ab fence of either reactant no product ean be formed and henee the rate represents desorption and not Feaction. At low eon. centrations of either 4 or B desorption Of R no longer remains the only rate controlling step. Tin Type VE the reaction rate is zero in the absence of either -1 or B and at- tains a maximum value near the middle cof the composition range. For catalytic ‘reaetions this situation holds (1) for all, cases where the surface reaction is con- trolling; (2) where desorption is con- {rolling and K is finite for the reaction A+B R; and (3) where impact of fan unabsorbed reactant is controlling. This situation also applies (4) to the homogeneous bimolecular gas reaction. ‘The following specific equations apply Poge 155to Type VI aml are not shown in Table eee 80) he eg wk and Te aXe) env ay Ny jl Ne Ha begeet vf Batons of Comeersion Un Canalstie Reaction Rates. "Vor vtalish the nee satin af a catalyse reaction by a stuuly of the etivet ni conversion upon reaction rates is tow extensive fur de- tailed examination in this paper. Curves shown in Tables 5 and 6 for the effects fof total pressire and feed composition sare for zero percentage conversion. To Show the effects of conversion each of these extrves would be replicel by a amily of curves, one for cael percens faye. Each curve would he of a shoe sigilar to the parent curve at zero conversion yt woul lea. progressively with increase in pe fentage conversion anid reach w zero rate carve at equilibrin, In general where aulsorption is cootrolling, swe rate curve plotted! against conversion at constant TABLE 6. INITIAL, REACTION RATES OF BIMOLECULAR GASEOUS REACTIONS. (Effect of feed composition upon ini I reaction rates) Desorption of 8 controling (K 2) decnanler &y ay 3¢ Be rescaptlna of eadtcoladng Ea fe | Pah es) re a 40 a11-M) 4, "4 ° Ta >——3 4 worption of A emtrating (Bat | Aésrplon of 8 controling (A nt sarees sore set. fethrin ren mn oo 4 — — sorption of b gona (ith oe] AsoptionofBearteing (eth or “Hidout esnefstion 0) SoBe abe fiae of)" een stein Bar? Seo wot for ot BEL) tora man estayted cecattyed 5 Wa a > A 4 despantem ef gy Je te snp surface reaction conten areing’ (0 Tarbes) vopestalytze reacthin” Tectar Page 156 CHEMICAL ENGINEERING PROGRESS ess 11). Far reversible reactions the relative effects are obsereed hut the fall: ing off i rate is more marked. Effect of Temperature, The effet temperature of nine importanre it the selection oF reaction mechanisuis 0 catalytic reactions, contrary $9 pop notions, bat iulipensale 5 estas ing the entropies and enthalpies a for Imation oF the activated complex and of the adsorption compounds of the ata vyeaceants andl prod Iyst with the saries sects, ‘This anosialos situation i en cuumitereel even lire the reverse re action is neghigibie, Where adsorption for desorption ate rate-contolling. steps int irreversible cataletic reactious. the tate is aevelerated) sith increase in ten perature whether the over-all eaction is fexothecwie or endothermic (Fig. 12). The same is 171¢ jor the wneatalyzed inveversible pexetion. However, where the surface yeaction is rate-controlling the rate ineceases with temperature to {a vaxinnne teal ben decreases. as shown by ‘Tschernitz. Bornstein, Beck frann and Hoge 3). ‘This reversal of rate is due to the unfavorable effect fof tempernmny xe removing the reae~ tants {fom the surtace whiell more than offsets the favorable effect of temper ‘ature upon the reaction velocity con stam, Summary In this paper a survey is giver of the general procedures ia plaming avil cor- relating, experimental daa on gaseous reactions catalyzed by sols, Methods are given for eliminating, minimizing, br evalnating the temperatere and con centration grotients i xss Gls and in catalyst pellets, .\ samimarized proved fare is eiven for sting up the rate equations for many postulated mechan isms of four simple wolecular reactions AR: Ae 8: ALBA ani AYBER4S. The selection of re- Action inechanism irom the eifects of ‘eee! composition, aml extent presen conversion and temperatre is. given especially with reference 10 the visual appearaice of rate curves. Miter the rechanism of a reaction has been estab- Fished the various constants in the ap. propriate rate equations can be obtained froin the experimental data by graphical fin statistical ethos. ‘These methods fare not presented ip this paper, but are given in (5) Tt is recognized that there are short comings to the equations presented in this paper, that chemical reactions are riot a8 simple as these imply, that several steps may be rate-controlling, that the adsorption equililiriam constants may be March, 1950Fig. a Reaction Rates. presvare-dependent as well as tempers ature-depenlent. The present approach represents an attempt to compromise between methods which are so involved im theory as to be beyond the experi- ‘ences ancl training of those entrusted to process design, and methods which are so empirical as to be unsafe for extra~ polation beyond the range of experimen- tation. Acknowledgment Credit is herewith given the Wiscon sin Alumni Research Foundation for the support of this project Notation A= component A 2 = activity iy, @; = activities of components A,B, R, S, 1, respec tively a, = surface area per single catalyst pellet wuriace area of pellets per unit mass constant constant component B Specific heat constant diameter mean diffusivity of com- ponent 4 in a gas mix- ture D, = effective particle diam cter equal to diameter of a sphere having the same surface area as the particle lective particle diam- eter equal to diameter of a sphere having the same volume as par E PF = deed rate, moles pet unit time nm u Vol. 46, No. 3 Fig, 1b, Fig. 11, Effect of Extent Conversion Upon Catalytic G = mass velocity AH = heat of reaction hig = heat transfer coellicient of gas film 1 = inert gas factor for mass transfer factor tor heat transter K = over-all equilibrium con- stant adsorption equilibrium constants for _cqmpo: nents 4, B, R, S, I, respectively = thermal conductivity ig = mass transfer coefficient of gas film 1k = reaction velocity constant for the homogeneous reaction hy = reaction velocity constant ‘where adsorption of is controlling by = reaction velocity constant ‘where adsorption of B is controlling reaction velocity constant where desorption of R is controlling reaction velocity constant where surface reaction 5 controlling mean molecular weight modus mole fraction nent A constant partial pressure pressure factor Pas bos Pre . Ps: Pr= partial pressures of com: ponents A, B, R, S, 1, respectively. rate of heat tranamission le of reaction, moles per amit mass Of cata lyst r= initial rate of reaction, moles per init mass of catalyst R= component F S = component 5 compo CHEMICAL ENGINEERING PROGRESS Fig 123 Fig. 12. Effect of Temperature Upon Catalytic Reaction Rates. 12b, 1 = temperature, absolute £ = temperature 1 = mass of catalyst a= (zeta n fay east w= (Sere), fractional conversion of component A per mole of feed Greek Lerrens 6, @', a” = constants viscosity = total pressure p= density nn = density of bed fy = density of particle Senseners = components 4,8, R, Sf, respectively = gas film seas film interface particle volume Literature Cited 1. Gamsen, BW, Thados, Gand Hougen, 0, Al, Trou. dm. Inst Chem Engrs, 39, 1/1083) 2, Hougen, Oo Ay and Watson, K, M., nds Bug. Chem, 35, 508 (1943), Stevens, William F, tod. Watson, C, Ce "Gpputlished thes, Unie of Wis bw). 4 Thiele, E,W. Ind. Eng. Chem, 31, Sto (1938). 5, ‘Techernitz, JL, Borate, S. Beck: mana, R, B, and Hongen, O. Trans, dm, inst, Chem. Engrs; 42, aes (isto) 6 Wilke, CR, and Hougen, O. A. ‘Trang, dm, Inst, Chom. Engre, i, 445 (88). Page 157TaBLa 148 Coeficientes de las ecvaciones cinéticas reducidas Adsorcién de A Reaccién superficial Desorcién de B | Adsorcién de A Rad+ apa boat cpp Reaccién superficial R=d+apq+bpatcpy Desorcién de B | om 1 Ky 1 1 R=d+ap,+bpalpo)+epy | pp ‘an,K ‘nKKy Desorcién de D Pa Ky I 1 R=d+ap,+bpo+ctpalps) | vps | Key,K ‘niK fapKKs | Kap, KKe__ (kinetics term) (potential term) (adsorption term)* TABLE 1. DRIVING POTENTIAL TERMS Reaction acew | AroRes | ap ook | aes a Adsorption of A con- [an -"f | a, - “BES trolling Adsorption of B con- | 0 trolling Desorption of R con- |a, = 8 trolling | * K- a Surface reaction com |a,~ = ‘trolling | * Impact of A control- | 0 ing (A not. adsorbed) aR Homogeneous reaction |a, - aa controlling] & TABLE 2, KINETIC TERMS. Multiply each of the terms below by EL except for the homogeneous ‘reaction. Adsorption of A controlling ky Adsorption of B controlling kg Desorption of R controlling kgk Adsorption of A controlling with dissociation — § ky Impact of A controlling Kgkp Homogeneous reaction controlling k Surface Reaction Controlling AgeR A ZeRS| ABER | ACB RS Without dissociation kg K, ky 8 Ky | kgs Kyky | ky & Kakp With dissociation ofA kgs Ky | ky 8 Kg | kya (8-lKyky kgs (S-DK akg) B not adsorbed ky Ky | ky 8 Ky | ky Ky kg Ky B not adsorbed, A dis ks Ky} ky 8K, | ky eK, [ky 8 Ky sociatedTABLE 3. REPLACEMENTS IN THE GENERAL ADSORPTION TERMS. A f + Kay + Kpag * Kpag + Ksas + ay] Reaction Age R | ASR RS | AB TMR] ABT RS} Where adsorption of A is Tate controlling k Kaa Sets replace Kya, by ~ on a5 ad Where Gesorption of B is Tate controlling 0 ° Kan Kpapas replace Kya, by Ray Kay Where desorption of R is rate controlling kgey | Kk, A |] ayaa | Hm B8B replace Kpap by | ag a Where adsorption of A is r : Fate controlling with o was | Kya nana dissociation of A fee 7 “ie Hoa replace Kya, by B Where equilibrium adsorption of A takes place with aissociation of A replace Kay by fers Yen Pe ifr and similarly for other components adsorbed with dissociation. Where A is not adsorbed replace Kya, by ° 0 ° and similarly for other components which are not adsorbed. TABLE 4. EXPONENTS OF ADSORPTION TERMS Adsorption of A controlling without dissociation asl Desorption of & controlling asl Adsorption of A controlling with dissociation ae2 Impact of A without dissociation A+ BOR nel Impact of A without dissociation AB? RS. ne2 n+0 Homogeneous reaction Surface Reaction Controlling AST R | AST RS| AB TOR AB Res No dissociation of A T z Dissociation of A 2 8 5 Dissociation of A (B not adsorbed) 2 2 2 No dissociation of A (B not adsorbed) 1 2 i 2