11 HETEROGENEOUS CATALYSIS 11.1 11.2 11.3 11.4 115 Introduction The Steps in a Heterogeneous Catalytic Reactions Diffusion Adsorption Adsorption Isotherms The Brunauer-Emmett-Teller Equation Surface Reaction etic Factors Porous Nature of the Solid -11.10.. The Catalyst“t rogencous Catay, I pete roups on the bagi, Reactions which Proceed ; Of in N il : saw t general £1 a 8 if m £ isc aes involved free radical: a 5 OF Is as in f terme Catalysed FF actions 3m he ecules, ions OF” mechanis™s a reps if ving © ing in an interfacial layer between two g% ge! a oct — 7 Rea 0 ot called petcrogencously catalysed Teaction These 3 ave some characteristics of both ies ay, fo P cactants in different Phase h ing iron as catalyst, the Prelim, acess for the SYM iz. the xidation of ammonia to nitric oxi nay oe nufacture O HNO3, ee damsidation of SO, to SO, ales ea few representative examples. The ref ical industry employs a variety of catalysts: aly * (conversior high molecular weight hydrocarbons to fg, : i ina catalyst for ‘catalytic reforming’ (cones rbons and hydrogen), etc., to cite a few ita hydrogenation employs nickel cals m 0c! ito a i of cycloalkanes 10" d vegetable oils by A n takes place at the interface. The varin, The Kardening ofthe animal an : Itiphasic reactions, the reactiol rations in Table 10.1. Among the heterogeneously catahy: lid catalyst and reactants in the Vapour combinations of phases ar¢ given i reactions, a Very large number involves a solie ¢ 1 liquid phase. Such reactions will be considered in some detail. 11.2 THE STEPS INA HETEROGENEOUS CATALYTIC REACTION hases form p oO" involve © third gro4 : it reactions ., nia employ? groups: «ly importal wap industrially IPT, sis of ammo ones), In all heterogencous reactions, there are interfaces and the reaction takes place att Because the different species come into contact only at the interface, toot: | I kinetic data for these reactions, it is important to know the concentrationd lace where the reaction is taking place. In catalytic reacties yst, in order that the reaction may take place, the folloit| interface. meaningfu the reactants at the pl involving a solid catal requirements must be satisfied: (1) The reactants must migrate from the bulk to the surface of the catalyst (di @ ae reactants must interact with the surface (adsorption), (3) me must get transformed on the surface into products (surface 1 hemselves from the surface (desorption) and ® The products must dissociate (5) The products must move away from the surface (diffusion). ffs |— | Heterogeneous Catalysis 591 be considered like a relay race and the overall rate of the reaction Te five stePs by the slowest step. Any one of these steps can be slow and the ety determined rate expressions will then be reflections of these slow steps. imental therefore to identify the step responsible for the rate expression before his pat ng any interpretation.eS Heterogeneous Catalysis. 591 sidered like a relay race and the overall rate ofthe reaction stepscan bem slowest step. Any one of these steps can be slow and the Meine eg rate expressions wll then be reflections af these slow coms ae ealy defor to iden the step responsible fr the rate expresion before 05 08 soy iterpretation. ission depends on concentration. So if the diffusion of the reactants to itesnalyat is the rate determining step, the reaction will have a first order .f300 ote entration, whatever be the real order of the reaction. If the diffusion ca from the surface is rate determining, the apparent order will be be Pr jucts. . 1 nati ibe products tfusion being very low, a few kJ mol » the determination of the * bea erat the reaction will give an indication as to whether the diffusion sisto the surface ofthe solid or the diffusion ofthe products away from the lid is rate controlling, of oe 332), one can prevent these steps from being ate controling ete reaction system. Even in flow reactors employing solid catalysts this has oes 4 ? been ieved by using fluidised beds. As the rate of stirring is increased the rate of the raion wil reach a limiting value (Fig. 11.1). If the rate of stirring is maintained at Rate of reaction Rate of stirring ——= ‘The variation of rate of a heterogeneous reaction ith intensity of stirring of the system.ios of chemical Transformations 52 Kinetics ond Mechan! ; | onding tothe val jue at wl ich the rate coal not be the rate determining step, Me valu greater than the a it attains its Himiting et jffusion as @ Fale controlling step js tlng in a fied bod ge recalls a8 5g po emg an a ac oreacantsan vm oe cata Min nl eduction in particle sie does ny * a is il further re ot sizeof the catalyst svar unl Fe sen ome of aa any sie eal 12) Pte (@ Particle size — Teas of ete Fig, 11.2 Dependence of rate ofa heterogeneous reaction ot (a) particle size and (b) volume of catalyst. than that corresponding to the one giving the limiting rate is used, difason wil» rt deterting Siar on can nd ou the maximum volume of calls pat shal an ewe witout fain bing rate conling by the rate for diferent volumes of catalyst keeping the flow rate constant. Te, increas with increasing volume to reach limiting value [Fig 11.20), Fo, ofthe gen partic ft wil not be rate controling forall us the one corresponding to the limiting rate, if if lysed by solid, atleast one of the rt sulicient fr reaction to take place wo jthere is an accumulation of the sphase becomes ess thant2 SEESEEEOS CMAYSIS — S93, 5, (Eq. 1.1) at constant pressure and temperature, } : ; AH , + ccessarily negative. Adsorption must therehate toe eer Ption He so ianereore ¢ be an exothermic ne cal and Chenteat Adworption At PO on pre can be broadly classified into two grou, 7 a jis Physical adsorption is usually the eanieaieee ses ee wo cular forces like those operating in the condensation of a vapour to a Tiguid 6 ; et arise from the interaction of permanent dipoles, ii i a r at m les, induced di wee i ce For this reason, physical adsorption is also known as van pear elon. Mm eption involves very strong forces between the solid surface Segoe ement of clectrons and formation’ of strong bonds. One oft in oe oe bond formation is the coordinative unsaturation of the atoms on th jes a ell, The surface atoms have lesser nomber of neighbours than the bulk stl Chemisorption can, for all practical purposes, be considered as a chemical snes Cj is restricted to the surface of the adsorbent. Chemisorption is therefore rato alayes on the surface only one molecule thick. 1 rat al clasifications, there arc situations where itis difficult to distinguish between " ‘ical adsorption and chemisorption. There are several critcria that can be used to ch between the two. Some of them arc listed below: ‘Inthe case of physical adsorption, the heat of adsorption is of the same magnitude asthe beat of | liquefaction of the adsorbate, It is rarely more than twice this value. The tahes are of the order of 8 to 24 ki mol", though occasionally, one comes across a reported value of 80 kJ mol"? In the case of chemisorption, the heats of adsorption are ofthe same order of magnitude as the heats of bond formation, For example, the heats {adsorption of oxygen on some metals are of the order of 400 kJ mol", Generally, the tat of chemisorption is not less than 100 kJ mol", Some values of the heats of chemisorption of different gases on metals are presented in Table 11.1 Tuble 11.1 Some representative values of heats of chemisorption in kJ mort Gas Ha O2 Na Nib CO Element \ c 209 999 326 ie Ti a a = 640 Re ae - 188 192 aN 121 410 155 a Beeb, x 343 293 585 3972. The heats of adsorption vary with the coverage of the Surface marked for chemisorption. The variation in heat of adsorption With cover this ‘othe lateral interaction ofthe adsorbed molecules as the surface bee 8 cnt® also due to the heterogeneity of the surface. The surface atoms are environments and so their bonding capabilities will diffe, This jr tain! heterogeneity ofthe surface. This heterogeneity will have a greater effert Meds tion than on physical adsorption. The lateral interactions are repuji ts contribute to a decrease in heat of adsorption as coverage increases Thiru be common to both physical adsorption and chemisorption, The effec np ¥en! Willalso be a decrease in heat of adsorption with coverage because the eng surface atoms will be the ones that willbe the first to adsorb and they yap ns evolution of the highest amount of heat. ay 3. When physical adsorption takes place, the volumes of gases adsorbed ay to the physical properties of the gases like boiling point or critical temperaa® volumes of different gases adsorbed on 1 g of active charcoal at 288 ite K along wig © boiling points and critical temperatures of the gases arc given in Table 117-8 7 Table 112 Physical adsorption of gases on 1 g of active charcoal at 283 Volume Boiling point Giigy Gas adsorbed of substance temperatu om? K of ubsany Hydrogen H, 5 20 3 Nitrogen N, 8 6 1% Oxygen 0; 8 ” 15 Carbon monoxide = CO 9 8B B Methane CH, 16 112 1 Carbon dioxide 0, 48 195 sat Acetylene GH, 49 189 w Nitrous oxide N,0 54 185, 310 Hydrogen chloride HCI n 190 au Hydrogen sulphide HS 9 21 3B Ammonia NH, 181 240 405 Chlorine cl, 235 239 a Methyl chloride CH,Cl mn 249 a Sulphur dioxide oe 380 263 a Phosgene COCI, 440 265 = 4, Since physical Bo i rption is not dependent on the chemical bonding forts#™ surface ofthe, occurs with any gas on any solid, provided the condi ‘are suitable, Physical adsorption being similar| toace “a tlow temperatures. On the other hand, chemisorptio® igh temperature, ; es ibe removed from the surface by lowering HF sorption has taken place. The Ftc higher temperatures and some!‘eterogeneous Catalysis 595 rate conditions, physical adsorption can le: , C eorithe surface while in the penis to the formation of p jayers #4 ‘med. On the chemisorbed monolayer, i chemisorpti ayer #8 fort ‘misorption, only a further physical adsorp- c. ve place. takes place to an appreci Si ake Pee option ee ppreciable ext 1 adsorPlion on conditions. Ip, isthe saturation vapour means atc ne [Togsteion i580" ‘significant. However, this is not true when the solid fe Moke 1 i i solid is hight ‘a e porcs. Chemisorption takes ighly £0 9 pas very fine DO Li es place at much lower pressures and ys atures. ef ih eption does not require any activation and so takes place rapid physic, on tH ‘other hand, being practically a chemical process, requires ae peor takes place slowly. There are exceptions, however, in both the cases, and Mon the nature of i sure, are ° © Factivation for the desorption of physically adsorbed gas i Be ofafewkd mol"!. On the other hand, a pea ess. The energy of activation is generally greater than 100 ky mol! than the heat of adsorption. , -d surface, physical adsorption of gases is unlikely to play any ye since the gaseous molecules are not subjected to any force different from inpotan ve in liquefaction. During chemisorption, the gas molccules are subjected ipse operative nd originating from the surface and hence the reactivity of the be altered. Hence, to express the rate of the surface reaction, crisis the concentration of chemisorbed molecules. This concentration fin terms of the number of molecules or moles, per unit area of the surface of the solid available to the reactants. gs ter 5" ply grea 5 lysis on a soli d ed molecule can us ADSORPTION ISOTHERMS For adsorption to take place, molecules must collide with the surface. If the molecule hounds on collision, there will be no adsorption. Some molecules will rebound on alliion and some molecules will stay on the surface for a certain time before leaving thesurface that is adsorbing. The ratio of the number of molecules staying on the surface ‘nailison to the number of molecules striking the surface per unit time is called the sikng coeficient represented by t. When the gas is allowed to equilibrate with the aufice,at any given time, there willbe a fixed number of molecules per unit surface area beease the rate at which molecules strike the surface will become equal to the rate at vi itch molecules leave the surface. I Se Rate of Adsorption mi assumed that the surface of the solid is unifort ee na could form only a single layer one ‘molecule thick even t = Vaale adsorption. 'e (NV) at which gas molecules co! Of gases as m and that the adsorbed hough the adsorption lide with a flat surface is given by the kinetic (11a)506 Kinetics and Mechanisms of Chemical Transformations where N;is the number of molecules per m? and is the average velog| Ey pressure P in Newton m?, the mass of the molecule m in kg and kpiny ds "Sy face of the solid is ehh ‘ of collision of molecules with the sur F. io = ———9 molecules m=? 5~1 Rate of collision @am katy? sv since = (8kp7/1m)/2, Langmuir considered the rate of adsorption on ws (ty i ilable, and the rate of collisio: be proportional to the bare surface availabl » 1S On the gt Gis the Fraction of the surface that is already covered, the rate of adsorption ey Sh by ”* Geant? = k,P(1- 8) where ' 5 ky Gane 1 being the proportionality constant ty ‘The rate vgat which molecules leave from the adsorbed layer willbe proportional surface already covered. vg & 0 = ky Itis assumed that the molecule has not undergone any drastic change on beings and desorption is a first order process. The net rate of adsorption vg(aet) = Y= kyPCL = 8) — kop . ‘The ratio of the number of molecules adsorbed N to the maximum number of moked that can be adsorbed Ninay is 8. 9 = N/Nmrax 0 v,(net) = k,P(1 — N/Nanax) — kg(N/Ninax) At constant pressure v,(net) = k{(Niax — N) — kiN w and kj =kg/Nmax @ e_sBeNCOUS Catalysis 597 Neq Oi a (119) jon for a reversible process first order in cit it xpress! in cither direction (Sec. 4.1, 4.1.2), wl a the surface of a sample of silica g Whe cl was equili . oy A Meo? Nm~2at 0°C, 5 per cont ofthesurace vara ith oben at este requires 10! molecules per m2, estimate the h ate Ifthe formation i a layer alf time for the adsorption, fl ss Neg § 52 = Vics he rom £4 (11-7), Nox 100° 20° (Ky +g) yaks= fa : chP/Nowe rom Eq. (11.6) 1 P 1a . No= Qn a: 73 molecules m™? en (112) Pt Ho od 1° Qamkgl? dependence= S98 Kinetics and Mechanisms of Chemical Transformations Tt 1, exp(—AH/RT) T, is of the order of 10-1? to 10-4 s, Lindemann has suggested the value of Most of the common adsorbents. Since AH is negative at a given temperatur, ey larger, the greater the exothermicity of the adsorption. Prob. 11.2. The heat of adsorption of argon is -16 kJ mot! at 27¢, Will appreciable adsorption of argon on a solid surface at 10-2 N m-27 rey Solution tao = 1-H (5% 16x ‘m 831 x 300 = 6.128 x 107s Pry Nj, the number of molecules on the surface = 2, (2m kgT)? Pressure in Nm? =10? 40 x 1073 ‘min kg molecule" =—— Smoke 6.02 x 10 kg in J molecule"! deg"! = 1.36 x 10733 nm 107? x 6.128 x 107? x (6,02 x 10°3)¥72 WW 6.128 x 107 (6.02 x 107 (2.x 3.14 x 40 x 1073 x 1.36 x 10723 x 300)? = 148 x 10 molecules m=? No. of molecules per m? of gas, N, = PE RT 07 x 6.02 x 1073 831 x 300 415 x 10!8 molecules m~3 The number of molecules N, normally present on 1 m? of surface will be (the mun molecules present in 1 m3)23, N,m™? = (N,m~3)¥3 = (2.415 x ea = 18 x 10! molecules m~ Since N; is smaller than N,, there is no adsorption of argon undcr these conitos® ion Isotherm at e surface reaction, we Reed to know the total surfarerst isHeterogeneous Catalysis 599 KP Kg t kp a Ee aor © 1+ Ky /kg)P T+ bP (41.11) (11.12) ation (11.11) is known as the Langmuir adsorption isotherm. It will be noticed, isthe equilibrium constant for the adsorption-desorption Process and is known as t gsorption coefficient. Sincek,/ky = b, one can writeb = 6/P(1 ~ 6). Itwille nen es unis ofb will be (pressure)"! and that 6 = 1/P when 6 = 05. The adsorption aoe being exothermic, b will decrease with increase in temperature. If AH is the apap of adsorption, using the van’t Hof equation b =D, exp (—AH/RT) b=kJky (11.13) Here b, is the adsorption coefficient when the temperature is infinite. ‘Acomparison with Eq, (11.10) shows that /t, = b/b,, Iftwo different molecules A and B are being adsorbed on the same sites, the same procedure can be used to obtain @, and 6p, If P, and Py, are the partial pressures of A and Bat adsorption equilibrium KX Pa (1-8 — Op) = ky Oy A)X Py(1 - 8, — 5) = kj Oy ekg Py 9 ahiPA kfkg Py 8 KP, (1-9, —sataPB%ay _ a (Iq kykjP, ) 748 = kPa AS AL Mat haPy + (kkaPa/ kd) © Ay oa LN GASP. + ETE DPs = _baPy Lope BaPp 2 (1.14)0 Kinetics and Mechanisms of Chemical Transformations For agascous stem consisting of gases, the surface coverage by thy y baPa 80 = Ta bP; + baPa + by Pa “TH EDP bP Ifthe molecule undergoes dissociation into two fragments on adsorpigg {hy fore needs two sites to be adsorbed, fora single gas A, the equation at os ‘ kPa 8 = kPA and so yone gee Ae OK? PK? : ‘ K Inthis case, the adsorption is a chemisorption. One of the weaknesses of the Langmuir model is the assumption that the sy, homogeneous and that there is no lateral interaction among the adsorbed m, q Several approaches have been made taking into consideration the heterogeaiy surface and the change in AH with coverage. It suffices for our purpose tat tees of the surface covered by an adsorbate can be determined. 1153 Application of Transition State Theory to Adsorption One can apply the transition state theory to the adsorption process and are x adsorption isotherm, Let N, be the number of molecules in Vm ofthe gasphez the area ofthe surface be S m?. Concentration in gas phase c, = N,/V molecules m? Ny x tes mr? = 5 sites my : : N Concentration of activated adsorbed species c, = —* molecules mi According to the transition state theory (ref. Sec. 6.6.3) Concentration of adsorption sites c, oe nee fs NEN, OV = 95g, 8 Foal tol) vr th terme he picn ction 10 te pron Q > 48779, (Ey hal) sites of the i kind isHeterogen, = cote BE On COME Cotabsis egy Yat) = EHO OG. PE, er js homogencous, the rate of adsorption is ce so ae kT O, Ve = es Gig CP (— a sh 0, 3p (—E,, ,/kpT) tion process, if N, and N™ are the number of desorPt ort erated molecules ready to desrb, then molecules of adsorbed al nt * . Kj=%x Sui s “NG 2 Q* 7 =. exp (—E, g/kg) "2 aytetbe same for adsorption and desorption, vi kT Q* Cag, OP (Fo,a/koN) Ya se atvated complex and the adsorbed species are immobile, Q*/0, wil be ap- jmately unity. ey adsorption equilibrium, ke OF kT g* Ee E,, /kpT) = 6, 2— 2 exp (-. fsb 0,0, °° ¢ ‘o,a/Kpl) = Ca 2 exp (Eq, g/kg?) Gq Oi ae E/k a8 0 xP ‘o/kpT) steing equal to (Eg — Eo, 2) is the heat of adsorption at OK. {,may be taken as unity and Q, represented by (2m kgTy? 5 a ag (Og= aX ae X = KX 4 ) . me ‘san be represented as q Since there is no translational contribution. p28. Ph? Ia yl) = DP To ee PE o/s 9 Gemy? (kgT)? Me 65 bP 1+ bp (ui)42DWOUDW OW 84909-doigels alg szpowowsau, = Lb aing u2S0yin Zu qing wna ty dung d sayonsases 6 2734 2Bnog PO27 NOON aqny iskininp 2y2snq s09 au) UOW WV Is| a i Ne seasarement a, Merrion Meroe, Cateye | ett S Fhe various gas nS tied in os | Eee Ee ontained ee ea Peston in Pers ache 5 te a ne fixed mark on the oe sM ements pe RR, ee Theat repre. | oP ysy andl This is dome bee OmeLer 4, Tat the volume (PME Mithin | pe measured, This i one by frst evacuating nctding hare Peas ne (# solume offas Vata known pressure p fray hs sp the - and then j wer cock $12 and measuring the pressure of pre MEME Ging ne tO opeok is FORE ee OF the Bas in gee iO this gn we the mercury level in the right limb is at the fj inthis space oq Pa ting tee nd the pressure measured on the ATK. Let the yop nometer | eis uniform and constant "ere p, Mebe temper the S Ure Of the i py = Py can be calculated. 280 e adsorption study is to be mad the solid is ‘when an a e, the solid AS introduced j eine system evacuated. Thesopeok Syn and eA State | opie required gases and stopcock $, closed, The system ig en Rt filled with | & bulb is filled with another gas. Whe sane uated apa A n the required © again and jeviolesystem is evacuated again and stopcock Syeneed Re he filled inthe bubs, | i Ie required | wn into the gas burctte G through stopcock $5, A ‘equited gavgaces dv is transferred to the catalyst tube and siopeoct lume ofthe gas at Esoplrated with the solid, the pressure is ead onthe mez et: Alter the pas isbe equilibrium pressure, ter. This pressure p, The expected pressure if no adsorption had taken place is PV/y = Po Since the served pressure p, is less. thanp,, some gas has been adsorbed, The volume of gas that soildgive a pressure p, is PV/p, = v, which isless than. The difference (v4) equal to, isthe volume of gas adsorbed. One can introduce different volumes of gas from the gas burette and hence have | reat equilibrium pressures for adsorption. The ratio of the volume ¥y to the ‘ninum volume of gas that can be adsorbed v,, is equal to@ atthe equilibrium pressure 4vtich is measured. From Eq. (11.11), it is scen that as P increases, 8 approaches 1 ‘dwothe limiting volume v,, can be determined by linearising Eq. (11.11). (11.17) ives the { . iprocal of the intercept gives Versus 1/P is a straight line and the reciproca’ 0 orion be %s/Vq can be plotted versus P to give the Langmuir adsorption tsp sui rm a monolaye is trement of Surface Area Using Langmult nite ering that the entre ® be maximum volume of gas adsorbed to fo the surface area of the solid, consid604 Kinetics and Mechanisms of Chemical Transformations covered by the gas, by multiplying the ni cross-section of the molecules. in the plot according to aa intercept in the p eg + (1, of eee the value of b, the ee the value of Bh, surface wil be completely covered. When the voltne: 0! £0) 1 Onbtalis pays rve is obtained as represented 9 PIB. 28% TD plot in the js the pressure, a cul 10?x + Paseals Ney 15 ae 18 of molecules j, umber inv, by the vevolume of gas adsorbed at NTPfem? ° ° 10 20 30 40 50 Pressure /10° Pascals. © ——m Fig.114 A typical Langmuir adsorption isotherm and its representation in the lineatl form is also given in the same figure. In Fig, 11.5, are given the Langmuir ads? isotherms for different values of b. The pressure is plotted on a logarithmic convenience, :1.5.6 Types of Adsorption Isotherms When the adsorption isotherms of various gascs or vapours on different solids » compared, it is found that they can be broadly classified into five groups based ont shapes of the isotherms. Th e five different types of isotherms are schematically 7 sented in Fig. "11.7. The variety of sha pes arises because in physical adsorption, adsorption need not be confined to a monolayer. The van der Waals forces responsi for this type of adsorption are effective even over the adsorbed layers. ‘The first isotherm mark ed 1 is of the form of the Langmuir isotherm already sidered in Sec. 11.5.2. Isotherms of type II have been exp! Jained as due to the formult of multimolecular layers of adsorbed gas on the surface. The heat of adsorption 4h when the first layer is formed is different from the heat of adsorption in the subst layers AH; which is considered to be equal to the heat of liquefaction. The shapes® jsotherms depend on whether AH, is greater than or less than AH, A arise due to the condensation of vapour ia the oflAmount adsorbed TeSsure —_? 9 Pp F817 Types of physical adsorption, ots filing them at pressure considey ably less than the Saturatic sift ope and 1V isotherms shat AH For besten BE Hy < AHL. . Table 11.3 Types of adsorption isotherms ineot Nature of isotherm Relation between Examples iether AMi and AH, jt Monolayer = N) at 78 K and 0, at | 90K on charcoal 1 Malayer AH,> AH, Nyonslicagelandiron Catalysts at 78 K. Multilayer AH, < AH, Bry on silica gel at 352 K AH, Benzene on ferric abe A, oxide at 323K Water vapour on char- coal at 373K : ACEREMMETTTELLER EQUATION stale fetlaver adsorption takes place, the Langmuir ited the surface area of a solid, Even though Langm!oS multilayer adsorption, he had not worked out an equation. Brunauer, derived an expression for multilayer adsorption which can be en’. calculating surface areas. This equation is known as the BET equation Let the fractions of the surface covered by a unimolecular, bimolecg; etc. layers be 0}, 63, 03, .. .; respectively (Fig. 11.8). The total number Se, o adsorbed per cm? is given by 1 layer Sth ta einige, 3rd layer 2nd layer Ist layer 608 Kinetics and Mechanisms of Chemical Transformations ett Dien 2 OO rr). QO BSS. Fig. 11.8 Multilayer adsorption. Ny = NO, + 2.NiO2 + 3.N1O3 + ...1N,8; where N; is the number of molecules covering 1 cm? of the surface with a monday Np=N, = 18, i=1 (u This will be constant at equilibrium. The bare surface 0, is also a constant at equi 6@,=1- [22 #82 183.722 Bi] (th If N, molecules strike the surface in unit time and all of them are adsorbed, the 1 adsorption is Ny. One can consider that the rate at which molecules leave thesut will be determined by the vibrational frequency v of the absorbed molecule ina dirt perpendicular to the surface. The rate of desorption from the first layer will be»; At equilibrium, Udon x N09 = ¥N 9, td The constancy of 6, at equilibrium is determined by the number of ne adsorb € Surface @, and the number of molecules leaving from ti wo together are responsible for the formatio ‘of moleculés evaporating from the first layer and th co yn of the ee wwHeterogeneous Catalysis 609 ¥2N\O2 = NO, jve layers 3 i 000 NO(i — 1) = ¥iN,9; sg assumption is made that sii ne ¥% that the heats of adsorption are the same in layer 2 and above. 1/v can be selectors whichis the average time that a molecule remains on the surface, vet NO:= NPG 1 si, NiO, = N95 N02 = TNA isreasonable to consider tT) = T3 = ...7;, since the second layer and onwards are all cxadensed layers. Going back to Eq. (11.18) N; =m! r 16, =u Si Bo, i=l (11.22) ee ee 7%610 Kinetics and Mechanisms of Chemical Transformations rien Oy +4, ot oF, 4h he 6 (Ite 27) 7! Replacing 14/1, by Ca constant and substituting for , from Eq. (11.23) ing, i" we have (hy Therefore 7 NC ee Me a-7 | CMY *a=na-71+&) (uy pe ere A N, a-nd-7+%) (uy It is not possible to determine y experimentally, Since the formation of the sos! ‘and subsequent adsorbed layers have been considered to be equivalent to condensii, this takes place as the pressure Ptends to the saturation pressure P,. ‘When the press of the adsorbate is equal to Poy Ny/N, will tend to infinity. N,/N, = @ when P= Py In Eq, (11.25) Ny/N; will tend to «as y tends to 1. So P/P, which tends 01? P—» P, can be substituted for y. Equation (11.24) then becomes ad N,C(P/P,) ue o- (PPI — (P/P.) + C(P/Po) ne Ny, C(P/P,) t- ao = @/P)E-O) w wtHeterogeneous Cotalysis 611 gas or vapour adsorbed and V,,is the volume of a d gas that will form jo mingthis equation oye TO 5 14+ (C-1)P/P, | VW, -P) = cv, “aig Ga cv, m Po (11.29) roposed is valid, a plot of P/V(P, ~ P) versus P/P, will be a straight line, ae00He Pind the intercept, both V,, and C can be caleulated, at OP eof gas that should be adsorbed to form a monolayer. An examination pisthevo dsorption isotherm (Fig. 11.7) shows that the ihe PE uy, i to become constant over a certain range of é wihich the slope tends to be constant could corre: is point is called point B. It may not be always erm. Hence the linear plot of the iat eV, Knowing the area of cross-section of the adsorb: Var oe ec canbecalculated. ‘Cisequal t7,/t) and this can be written using Eq, (11.10) as T_T) exp(—AH,/RT) Ty exp( ART) slope of the isotherm Pressure. The point on ‘spond to the monolayer convenient to determine BET equation is used to ate molecules, the surface C= = exp ( (AH, ~AH,)/RT) (11.30) Wend, << AMC will be very large and so, small compared tor, Sincey inchudes ‘prvilbe very small compared to C. So Eq. (11.26) can be written as (1131) Ststuing for N, from Eq, (11.2) P es 1 rmkgNy OP (132) ting for C/ from Eq, (11.32) in Eq, (1131) | BaP fgg. tit andSec. 1154) p Vq 1+ bP “the Langmuir equation. k, = 1, b= Gand from Eq. (13) he = Gan 'd612 Kinetics and Mechanisms of Chemical Tr ‘vansformations po 1 ole keg(20 m kT)? N, (20 m kgT) 2 t= Ngy/kg and 7 = kig/Ny (us, For the determination of the surface area, the adsorbate usually chosen is nitrog: gas and the isothermis determined at the boiling point of nitrogen. The saturation vapw pressure P, will therefore be the atmospheric pressure.Telus ofthe area do not differ very much. Saou a mage ong ee Anujor weakness of the BET approach is the assumption of a uniform surface as in rage approach, Further, b in the Langmuir equation and Cin the BET equation cen 0 be constants, Because of their dependence on AH, they cannot be "Vdange s the Surface coverage increases, the lateral interaction increases and AH With coverage,O14 Kinetics and Mechanisms of Chemical Transformations 11.7 SURFACE REACTION To study the reaction on the surface, one must know the concentration of react the surface. While itis relatively easy to determine concentrationsin the bulk, ite it to make such a determination at the solid surface. The Langmuir adsorption ison Provides a means of relating the concentration of the reactants at the interface i erm actual pressure of the reactants in the gas phase. When a catalytic reaction takes 9 ona surface, the assumptions used in the derivation of the Langmuir adsorption igo, may be considered to be still valid. Then the rate of the reaction will be propo; tong the fraction of the surface covered and so can be connected to the gas pressures p adsorption from solutions, if the Langmuir isotherm is applicable, one uses concen, tion in place of pressure. If the reaction is followed by measurement of chang; pressure, the rate is dP/dt and if a change in concentration is followed it will be dela, They are related as follows. n = pRT =cRT Therefore dP/dt = RT(de/dt) or dn/dt = (V/RT)dP/dt assuming V to be constant, If there is a single reacting gas A, the fraction of the surface covered 8 is given by baPa “1+ baPs (11.11) If the reaction takes place among n adjacent adsorbed molecules, the rate of formation of product M is _ aM] _ v= A = ion (139 Whenn = 1 'b P _ Ara va k= ky ( + a, (1135) If ba is large of Pa is large or bP, is large compared to 1 4 ky (1138) and we have a zero order reaction. It just means that as soon as a molecule of A reads on the surface and desorbs, a fresh molecule of A takes its place. The surface of Se catalyst is saturated with A and the reaction takes place as though the. rate is independ of the pressure of the reactant. This is because the rate of the reaction is determin covered and this is maintained constant. v ‘ a He v= kbAPA (3) A 1e0 p real order of the reaction can be obtained on ee ‘BaP, >>1, all reactions will appear to be 2°" (139)Heterogeneous Catalysis 615 baPa>> I vek ih : , (11.36) The fraction of the surface covered by A when there i oe is a mixture of gases A, B, C all competin} baPa 1+ baP, + bpPp t bcPc (11.15) pepending on the relative values of Wn bpPp and bePe the denominator can get nodified. I bcPc = DpPp >> baPa = On = aS baPa A bpPp t bcPc (11.39) d C, the coverage of the surface by A is considerably Dueto the strong adsorption of B an he rate of the reaction of A. reduced and there is a decrease in t tuned decamnosition of hydrogen iodide obeys the rateThe rate will be 250 torr s™* at a hydrogen 1uwuy prenesw ve ay wor, 11.7.1 Order of the Reaction If we consider the initial rates for a reaction involving a single reactant A, the baPa_)" i= kn TH baPA tiy kn Vn 1 E “barat tty By finding out what value of n will give a linear plot of (1/v)!" versus VP sity be possible to determine the order of the reaction n. However, because k, andb,y, constants whose values are not known are present in the equation, it is found that vi experimental error, a straight line can be obtained for more than one vale (Fig. 11.10). So this is not an unambiguous method for determining the order ds reaction. This is further discussed in Sec. 11.8.1(b). Ray This can be written in the form 11.7.2 Rate Constants of Surface Reactions Ordinarily, the progress of areaction is monitored by ‘measuring the pressure/con= tion of the reactant in the gas phase at various times. The data can be analysed? procedures described in Chapter 2. | } Prob. 11.6 The conversion of acetic acid to acetone over thoria catalyst was se at 573 K in a static reactor. For an initial pressure of 54,25 x 10° Pa, the pressure with time was as given below. min” s 0°15 20s 5 a 10-3AP/Pa 433, 8.20.-11.0 13.46 14.86 17.20 1853 mo ° ¢ ion and the rate constant. COCH, + H,0 + CO2 e crease ¢ formed. So, the in i nt that has reacted.Heterogeneous Catalysis 617 S 6 ° o o 02 i iF Oz = wo ples rgt110 Relation between initial rate of dehydrogenation of 2-propanol on zine chromium ferrite and pressure at 678 K. Theorder is obviously not zero, since the rate changes with ime. The data inthe form sired o determine the rate constant and order are tabulated below for First second adthird order (ref. Eqs. (2.7), (2.16), (2.42). f 10 ae rd t ween a4 loge) WX GIS Ga ee 1.6589 219 481 i 15781 oa ‘a ae 1.5085 3.10 9.62 2133 face ae es BS 1.3897 408 we 12.85 12978 504 258 pais 1.2353 582 3M 3 toe aot 6196 8.24 at the data ita firs order expression ig. 11.11. Itwll be obsorved that lope of the straight line is — 0.0148 min”. : ihans sformati ®18 Kinetics and Mechanisms of Chemical Transler” 100 or oi 75 50 Fig. 11.11 (Prob.11.6). The rate constant obtained thus will be dependent on the surface area of the ca that is available for the reaction. Therefore, unless this is kept constant, one will ob, different values for k from experiment to experiment. Let us designate the rate cons determined thus ask,, to distinguish it from the rate constant k,, which takes into acw the surface area of the catalyst. The rate per unit volume of gas phase in terms of ky is vy = kycy molecules ms The rate per unit surface area in terms of k, is v, = k,c, molecules m~ If the total surface area is A m? and the total volume of the gas phase V m}, since total amount of reactant transforming is the same whichever way the rate is expres PV. kp sh Kee = kee = kya where N, is the number of sites per m?. Substituting for @ from Eq, (11.11). iy - DP ST + OP woHeterogeneous Catalysis 619 using the BET procedure (Sec. 11.10) ang ured Whats i Nis calculated assuming oe sy planes exposed. There will no doubt be some uncertainty regardis ne oars "8 tof Ne dL Vv + vp io ig” RAN IGTS * hanige oe plotted versus P and from the slope and the intercept, k, and oo VI Lape ition State Theory and the Rates of Surface Reactions 3 nes reaction can De considered to be taking place through the activation of the ered reactant. ws adsorbed reactant §==—= activated state —_, product eo acentration of adsorbed species (number per cm?) is Cy, the rate of this reaction written as (Sec. 6.6.4) abe) as kT Q vec STmoR exp(-E,/RT) stere 0% is the partition function for the activated state of the adsorbed molecule and ¢, tbe partion function for the adsorbed molecule. They can ordinarily be considered M tobe equal, so that the rate becomes kpT vc, emp(-E,/RT) trb, 11.7 The activation energy for the desorption of carbon monoxide from phtizum is given as 133.9 kJ mol! at 873 K. The number of adsorbed species per cm? 's10°, Calculate. E, (i.c.) AH® and the rate of desorption at 873 K. Solution . Beas ots = kp? N#03/Q, = 1, k= —— exp (-E,/RT) and so ESE4+RT [Sec. 6.6.7(a)] kgT OF back = 1, exp (-E,/RT) = ot Se eap(-Ey/RT 7 : rttion function of the adsorbed species can be taken tobe uty. 339x103 — g31 x 873= ALY Sy MEE ¢, 1114 Types of Processes Leading to Reaction ‘lin catalysed reaction tekes place among more than on¢ molecule, formation can occur either through an interaction aaa adsorbed en moleculesinteracting from the gas phase with some adsorbed ile Cea 624 Kinetics ana Mechanisms of Chemical Transformations A ction between molecules. When the transformation results’ from reaction by Only ag ™molccules, the mechanism is gencrally called a Landmuir-Hinshetwoog mecha (LH). oy aM =k OM, Ancxample of a reaction proceeding by the LH mechanism is the esterification gf, acid on thoria, ; ThO. ry. CH,COOH + CHjOH 2+ CH;COOCH, + 1,0 When reaction is between a reactant adsorbed on the surface and another from the £48 phase or from a weakly adsorbed layer, the mechanism is called the Ridcary mechanism or the van der Waals chemisorbed interaction (VCI). An cxample of g reaction is the hydrogenation of ethylene on nickel, Beck has suggested that cthylee from the gas phase reacts with chemisorbed hydrogen atoms on the surface. Onthenigt surface, cthylenc is dissociatively adsorbed to form acetylene and hydrogen. The Surface is predominantly covered by acetylene. When the chemisorption of the reactants or the desorption of the Products is ray determining, one has a type of mechanism known as the Temkin-Pyzhev’ mechanism, oy the industrial iron catalyst for ammonia synthesis, adsor] Plion of nitrogen is rate deter. mining for synthesis and for the decomposition of ammonia desorption of nit vn rogen is rate determining, Wthe reactants are A and B, for the LH mechanism, the rate will he Vek baPy yn TH daPA + bpPy] [T+ BAP, + PyPy (119) bP abuPa (1+ baPy + by Py)? and for the VCI mechanism {Para x Pn or k, (— 2nPn x Py Tae 2 |B a THDAPA + byPy 2 (aay =k a PAPy + bpPa ies with temperature in the same way as ky The ture is given by the Archenius equation (Eq, 52)! activation, E,. Considering the rat fen the true order of the reaction ea temperat ergy of tions whi one can determinc-an eni te of the surfact reaction at low concentrat ' yy n be determined, ¥ = k(bPyn = k'pr tally obtained under: ly c these conditions isthe pol ge edsorption coefficient raived to an approp™ (3)Heterogeneous Catalysis 625 hs (11.12) o7 ke exp(-AH/RT) (11.13) 2 a ogo 8? (“EY RM oH (—AH/RT) a 2 kyo OP (-E,/RT) (11.44) erimentally determined cnergy of activation E, is therefore equal to the ov “adsorption being an exothermic process, E, will always be less than the true Bt + activation for the surface reaction by AH, if the experiments are performed ee for the true order ofthe reaction to be manifested. ae ndionditions are such that the reaction follows zero order, the rate is vmks (11.36) ese conditions, E, and E, are equal. The true energy of activation of the so, under th 8 surface reaction is therefore obtained only under conditions when the reaction follows mero order kinetics. This corresponds to conditions when the reactant concentration is sufficient to saturate the surface. : Depending on the reactant concentration, the order of the reaction can vary from the true value to zero. Unless the concentrations are such that the surface is covered to the same extent at different temperatures a linear Arrhenius plot will not result. Even if a straight line is obtained, E, ¥ E, unless the conditions correspond to saturation of the suface by the reactants. To ensure that the true energy of activation is obtained, the tales are measured under zero order conditions at all temperatures. If the true surface rae constant can be calculated, there will not be any difficulty in obtaining the true snergy of activation E,. The safe procedure is to determine the lowest concentration/pressure P [Fig. 11.12 ‘that is required at the highest temperature to change the order to zero. If now the ‘action is carried out at all the lower temperatures at this pressure, the reaction can be considered to manifest zero order at these temperatures also. So the rates measured Inder these conditions can be’ used to determine E,. If the rate data for any lower "iis sed it will be noticed that the Arshenius plots not linear [Fig 11.12(6)}. _ ihereisa product (M) that is very strongly adsorbed, the rate expression will be wm (baa eet v= "S174 bP, + byPm (11.45) M>(1 +.b Px), the rate will be fe bP, Us |B Pa (11.46) activation E, in this case will be (11.47)nisms of Chemical Transformations Kinetics and Mecha’ oe ] Sut 328°C sk | | i 60 @ 60x30? Pa no 0 28x10? Po B 17x10? Pe © 125107 Pe 1 175 | at ass 165 3 18s 19) 1 ah a) initial rate versus pressure at different temperitim ¢ corresponding Arrhenius plot. Fig. 11.12 Schematic plots of: and b) th is not a surface reaction, but the rate of advo f adsorption with coverage and the changes#? When the rate determining step circumstances, lead to avy? or desorption, the variation of heat o} extent of coverage with temperature can, in some energy of activation for the reaction. varies with coverage, it can mean either that th of varying activity on the surface, the more active ones getting covered first of a more and more lateral interaction among adsorbed molecules as the surface increases or both. A site on which adsorption takes place with a high beat of i talllead to astrongly bound adsorbed state which will require a high energy of3" igh value of AH means a high E, and so when the cP : ated by for reaction. Thus a high g ed, the large E, is compens ere aE i apparent If the heat of adsorption AH leaving E, pt tee 118 KINETIC FACTORS he adsorption of the reactants as well as a soly, The manner and intensity of r hes vel enti as the medium are very important in determining the reactivity on the cata adsorption is reflected in the adsorption coefficient whichis a measure of th, é di h Udy: of the reactant between the bulk and the interface, between the homogeneous the adsorbed phase. We shall consider its influence on the activity and select be catalyst. 11.8.1 Simple Reactions (a) Reactions involving a single molecule: The rate of a first order reaction on acas i surface that is completely covered is vok, baPa + 25,P; fu because b,P, + £b,P; >> 1. This expression indicates that it is not sufficient tolx ahigh value for the rate constant but also suitable values for the adsorption coeffcee The adsorption coefficient of the reactant b , must be large compared to the adsorp: coefficients of the other constituents present in the system. Thus ifb, << Z bali product of the reaction is among the species contributing to the high value of 3,5 velocity of the reaction will fall more rapidly than the decrease in concentration¥# suggest. If the two terms are equal, the order will approximate to 1 and if b, >> the order will approach zero (Fig. 11.15). Consider the behaviour of two catalysts, one with a rate constant k and the . which is less than k. If A is the reactant and M the product, let b be equal toby ual catalyst with higher rate constant k and let b, be very much larger than by, fo" a catalyst. The variation of the concentration of A with time for reaction carriod baPa the two catalysts is y represented in Fig. 11.16. It will be obseredt th lieu tne a moderate rate and realises 1 ti the catalyst with higher rate cone at ce’ of both the rate constant and the A ogi a chemisorption and therefore the ost i ims.A kinetic investigation is the ™ ' : wet BE ehydrogenation of 2-propandl Or iI within 30% conversio®Meteropencons Catalysis om Relative velocity 1 Moletraction of reactant Fe-tldS Relative rates of a simp le unimolecular ren different ratios of adsorptio 0 of molefraction for Coefficients, iction as a functio duilled off as the rea ea Ath reaction is given by bac = ACA, aki i + val Where since we are dealing with a soluti cis used instead of Pressure, "Fg. 15 jg Constructed for various the experimental data for this action can be Plotted on this figure and from the curve to which the data corresponds Wy determined, Alternately, Eq, (11.50) can be transformed to a linear form M = Ca)o- Cy i a (11.50) ion concentration, values of b «Dy, v Np ibe 5 dis culated. (ibe pou Yersus 1/¢,. From the straight lin, b /byy canbe cal initial hols can be Teacted in the presence of a ee ae pared. From the adsorption coefficients obtained raeten imibeiene be "lle adsorption Coefficients for the different alcohols.632 Kinetics and Mechanisms of Chemical Transformations 1a Py ' ye JAPA. #! eccuse b> oy, = aap BO Pressur Time ——— Fig. 11.16 Change of concentration with time fo reaction with two catalysts different rate constants and different ratios of adsorption coefficiente Proviig represented by C. Then since ,/bcandb ¢/b¢for the two alcohols A and are know, 5 x/b, can be calculated, Table 11.5 Relative adsorption coefficients of some alcohols ____ 400°C) Alcohol (A) Ba/b2-propanot oll mi Teg cat) alk pbaey 2-propanol 1 65 1 2-butanol 0.25 38 os 2-pentanol 0.16 27 0.065 2-hexanol 0.16 1.0 0.025 4-methyl-pentanol-2 0.16 23 0.06 *Relative reactivity From the results in Table 11.5, one can foresee that the hydrogenation of ketonesi! reaction approaching zero order, because coefficients of adsorption of ketones ¥* much larger than that of the alcohols, . (b) Reactions involving two molecules: If two reactant molecules A and B et “on a catalyst to form product M, the Feaction can take place through a Langmuit! LA deal-Eley (RE) mechanism (Sec. 11.7.4).i Heterogeneous Catalysis 633 baPabpPa ——T Pp tbe. + bP (Ly v2*2 (+ baPa + OpPp + byPyy)? ) (1251) PAPI kbePoP, ep tike Thad " TFEP FoF Try RD A ae 11.52) Spratt eer (1152) Pa Wicd 7 Py +++ (RE) “5 tO apaeate & PPREATB ass) ze tional to the product of the Pressures of each of the reactants. So, eis tbo Fe ctions, the reaction is second order, first order in each reactant, ween >> (@pPp + bvPx)» be. A is the only species that is strongly ad- a when Keb xP ab sith ya tPatabehe uy (1+ BaP)’ iss) kbpPaPp kabpPaPa Y= GHBPA) OFEsPa) ee (11.56) suaP,isvery small s0 that b ,P,, may be neglected compared to 1, the rates given 5 v=kb,PabpPp (LH) (ais7) vekbaPaPp ot kpbpPpP, (RE) (11.58) ‘Terrates are the same as given by Eqs. (11.53) and (11.54). When bP, is sufficiently ‘ep, 1is negligible compared to b 4P, and the rates become bpPp | vek, BaPa (LH) or ix) bpPa ee) aoe Pacis) shows inhibition by the reactant A identifying a LH mechanism while na ‘eveals that the rate is independent of P,. ‘tulace that is completely covered, the rates will be (11.61) (RE) (11.62)oN 4 Kinetics and Mechanisms of Chemical Transformations Relative velocity ° i Maletraction of A Fig 11.17 Variation of relative velocity with molefraction for different values of ag " bx PaboPo ——_baPaboPa __ (os Pa + bp Pp + bx Poms) the rate equation » = where b, Py = bp Pp Taking the LH mechanism, let us consider a reaction carried out under ccaitz uch that bP, = DpPg. The rate will now be oe Pa (2baPq + bvPo)* | dow one can construct a series of curves relating velocity of reaction and tee raction of A for different values of b4/by4. Such a set of curves are given ia Fi! t will be observed that to obtain higher rates, b ,/b,q should be large. Further aust be equal to bpPg. This means that if the reactants are taken in stoicior mounts, their adsorption coefficients also must be equal to give a high rate of ni ‘he stoichiometry in these reactions is to be looked at in terms of the produ coefficient and the concentration taken as a unit. dsog? monoxide is 50 times more strongly adsorbed than bye rates one must use hydrogen and carbon monor ay t that is very little active for a stoichiometric mixture the composition of the reaction mixture. Po A A witHeterog ‘eropeneous Catalysis 635 01 Molefraction of A Boo y= 08 (2); 05(3); 14);208); 1081; 90017), Fig. 11.18. sted that it is not often easy to distinguish between the LH and RE mechanisms, ‘eeznse one may be able to fit the experimental data to the group of curves correspond- *gto either the LH or the RE mechanism, depending on the combination of the rate cesant and ratio of adsorption coefficients. neh «veo she hurdrogenation of pyridine onMb, 11.13 The following results were obtaincd for the dehydration of methanol over shmina under conditions where the catalyst surface is completely covered at a tempera- tue of 20°C, The extent of reaction is 1.5%. Male fraction of methanol in feed 1 0% = 0.94 0.89 0.865 Mol fraction of water in feed 0 0.04 = 0.% O11 0.135 Alnethyl ether formed in 5 min 440 323 254 189 160 Cdculate the ratio of adsorption coefficients bi o/bc,on = byy/byy. What conclu- fins ‘anbe drawn about the order and the mechanism? ‘ution lt the react, ‘action is yn} ~~ s unimolecular on the surface{Utho reaction is bimolecular and the mechaninnn iy ay 2 Drang weky 2 TMM yay, Ww \ p a her Lt aw Py” Ey Daag A the mechanism is RE, rn fi ww Vo, bwtw Vat ky by XM 1 byway Mt owe vk” ky byatng Depending on the mechanism, we may use cquations (a), (b) or (c). The dust linear plots are given below. a v VW dye @M/¥) aw ™ Hy v id 44 0.0227 0.1508 0.0227 0 1 0 323 0.0310 0.1761.———(0,0297 0.04 09% aK 254 0.0394 = 0.1985 0.0370 0.06 094 ae 189 0.0529 0.23 0.0471 0.11 089 160 0.0625 0.25 0.0541 0.135 0.865 a The data satisfy all the three equations (Fig, 11.20). Therefore, itis nots! decide between the orders and the mechanisms, Equation (a) Intercept = 0.023 Slope = 0.246 = —Slope_ 0.653 _ Intercept ~ 0.151 43Heterogeneous Catalysis 639 ys Slope 0653 = Slope =0.213 ® equation (a) © equation (4) 3 equation (c) Fig. 11.20 (Prob. 11.3), b pw = Slove_ 0213 _ byq Intercept ~ 0.023 This difficulty in distinguishin, cases where. ‘an havi 'g among mechanisms can be overcome as follows in we c A+B—s Mand A + A © two competitive parallel reactions like : — > N. If reactions are carried out with different mole facions of A and B, the results obtained should fit on one or other of the curves that etheoretically Constructed (Fig, 11.18), «consider the ketonisation of Propionic acid, By taking some alcobol along with aie ean have the form: ation of ester too, These reactions take place on thoria at GHCOOH + GHsCOOH—+ GH,COC,H, + CO, + H,0 HCOOH + cH,oH—- C,H,COOCH, + H,0 Telati aig i Tates of forma of ester are plotted versus the mole fraction of reactants a © data for the ¢ By ditt sterification of acetic acid and benzoicacid are also, Lae] io veto, fretting the rate equation with respect to mole fraction an £70 itwill be seen thatthe maximum rate occurs when byca = Fain UH mechanism and when b ack = bach in the case of the RE mechanism. C1 Of the maximum, one can calculate two values for the ratio of cients of A, the acid and B, the alcohol.Be. | 642 Kinetics and Mechanisms of Chemical Transformations Teactions that are not autocatalysed. This becomes absolutely ne, beterogencously catalysed reaction where the products are strongly adeoy, Sy 1182 Complex Reactions ; One can consider under this head equilibrium reactions or ractions whey, the reverse reaction is not negligible compared to the rate of the forwang te consecutive reactions and parallel reactions ; teas (a) Equilibrium reactions: ‘The role of the catalyst in such a reaction i the of the approach to equilibrium. Consideration of simple reactions has s hau, coefficient of adsorption is favourable for a forward reaction, it will be as meat the reverse reaction. kybaXan kerbulT-Xq) DpXa + By (1%) Moletraction of A versus molefraction for equilibrium reactions d different values otf. ilHeterogeneous Catalysis 643 Kb aPa a kay bP baPa + bygPyy (11.63) yy. cpeium ¥y = YI" _ cea Ay DaPa = ky bP (11.64) ion translates the relationship that thermodynamics imposes on the kinetic THs tics of the system. With respect to k,, k_y will be small or large, depending si ficients of adsorption b, and by In Fig, 11.23 are presented the net velocities - tion uaimolecular in either direction with an equilibrium constant equal to 5 by bas different values. vient ge observed that the catalyst remains good for both forward and reverse rons,in the one case duc to a good value for the rate constant and in the other case, reads favourable value for the adsorption coefficient, dor tke case other than the one considered, the resulting equations are more difficult touse practically. For the reaction A == M+tN JitvewsatPaPa | buPubnPr 1tbgPa + byPy + byPx] "711 + byPa + byPy + byPy)? ifthe LH mechanism is considered. The equilibrium constant in this case is Kyba(1 + baPy + byPy + byPy) PrP Kae AA ENN! MEN k_2byby - Pa ‘ich isnot independent of the pressures (concentrations). It is possible to clear this nonaly by making certain other assumptions which are not being discussed since they >not contribute to the facilitation of the kinetic analysis. ©) Consecutive reactions: Let us consider a consecutive reaction where all the actions are of the same order. cathe coe baPa . a 7% APA + ByPuy + BNP ‘face ofthe catalyst is completely covered 1 buPy , byPat bP + byPy = AiaP a)" — kimPy)" AP a + byPy + ByPr)®G44 Kinetics and Mechanisms of Chemical Transformations K{byP a)" 7 au ay, 4 HOwPwl | tak (PM a! dt Ay(baPa) Py This expression shows that the ratio of the concentration of the inte (4, reactant is determined by the ratio of reactivities K. ned Equation (11.65) can be integrated to pve Pye qo (Pa +n Pf) a ( i uated by applying the condition that att = Q, Py i The integration constant is eval Py=O. BH “Py = eg Pa Pw) (u ‘The experimental results can now be treated in the manner discussed in Sec, 42, ‘ec. 4.2.4 is the inverse of the ratio K used iy should be noted that the ratio K used in S One can construct a set of curves as in Fig. 11.28 (ref. Fig, 4.11) and by ploizg experimental points oa such a figure, estimate the value of K. The experimental fox the hydrogenation of phenol on Raney nickel are plotted in Fig. 11.24. ‘The reactivity K determines the maximum concentration of the intermediate in) reaction mixture. If the initial pressure of A is taken as unity, the maximum is ca, terised by the following conditions. nate Pa at maximum = KO-9 (w (J Pp at maximum = KV (u Equations (11.68) and (11.69) enable the ‘construction of a figure similar to Fig 4 relating the concentration of M to the ‘composition of the system for different vats K (c)Paralletreactions: Fora reaction where one reactant givestwo different prods ‘and the catalyst surface is completely covered ( ki APA)" ers are the same for both the reactions. dP _ ky (bal? dP kgOA) ERE nd a straight line should result. qwHeterogeneous Catalysis 645 Temp. 140°C Raney Nickel catalyst <=+ Calculated curve for K24 a ® Fig. 11.24 Plots of [M] versus [A] for different values of Whe orders are different, the resulting expression is not Teadily amenable to {xerinental application, When the orders are different, a solvent wll help the enhan- nent of one of the reactions, the one with the lower order provided the solvent will ‘asta dilution in the adsorbed phase. "two different reactants react on the same Catalyst surface as in the case of the ‘hydrogenation of two alcohols on nickel, assuming a first order for the reaction AM By f (11.72) rit IMY/Ca + aN) as a function ofthe mole fraction ofA ith respect to The et for various values of Kis represented in Fig, 1.25. ; Feta wtence in reactivity of substances taking part in parallel reactions on i day a Can be used to purify mores a compounds Among neue beng Ms, 2-ropenl wl dhydogenat ater han eral. Be There clone wil ydogenate ae han ter Ketones on a ing gt": ftom a mixture of ketones, 2xpropanol will be formed Eee i siilain Process, the hydrogenation of a mixture of ketones com i " i jin a higher pagal © 8 certain ent of reaction the prod wen 5 Ol. Thi ¥ ill give a mir “1 Ielonee Thisproduct, ifdehydrogenated, ill ge be al F this product is now hydrogenated, the prod Ki“= 652 Kinetics and Mechanisms of Chemical Transformations rate of hydrogenation increases because there is a greater surface cove [Sec. 11.8.1(b)}. TAECby j 11.8.4 Some Mechanisms and Corresponding Rate Expressions It is possible that when two molecules of the same or different Teactants the reaction, there are a number of possible ways in which the reaction n° Bi, Some of these are as follows. Might, (1) Both get adsorbed and reaction is between two chemisorbed Speci (2) One is chemisorbed and the other interacts from the gas phase cs adsorbed layer. O aby (3) Both react from physically adsorbed layers. (4) The reactants are adsorbed on different kinds of sites and so are », competitively. Ot ay (5) One reactant displaces the other reactant from the surface and so the is competitive but still reacts only from the gas phase. Asay ‘The combinations of mechanisms thus become numerous. The mode of itself can be different involving coordinate bonds or dissociation and single sites on the catalyst. The sites themselves may have a gradation in activity net ability to adsorb may be selective. In addition to this, itis necessary to consider the ofthe catalyst which may make it accessible to certain reactants and notto certs ‘The combination of these aspects can give rise to a variety of kinetics. Onedy particular combination and the corresponding kinetic expression dependingoais ft agrees with the experimental data. The difficulty in arriving at mecha heterogeneous catalytic reactions arises in the first place from the fact tht different mechanisms can lead to rate expressions of the same form and sonot per experimental distinction. Another cause is the inherent problems involved indi catalytic reactions. Due to the limitations in the reproducibility of the catalystsax instability, the experimental data are not as good and accurate as those obtiz homogeneous reactions. Tin the case of a bimolecular reaction, the following possibilities can be const 1. Only one type of site is involved: Reactant A is adsorbed and the reactant Bree the gas phase and reacts from there (RE mechanism). The catalyst site may bere byS.. “(a) A+S === “AS adsorption step (®) AS+B === MS+N reaction (©) MS «0 === -M+S © desorption @ a Pz Gi)Heterogeneous cao cosider NS tobe tbe species f — Catalysis 653 y te =— NSM trace reaction f xS =— Ns irecbon ; is rate determining on per beracesresin we iniens onvth cae oe 2 eae () apt et Wl ay Hy wb P as of Pp, rate expression (ii) holds, at constant P, eee °a and be inde- Fe serena be rite atom ead ey wa a en kabsPaPa ka Pp Pp 1/v will vary linearly with /P,. © ved that ifthe surface is completely covered expression nehich can be verified like (i). Diane " and A reacts from the gas phase without getting adsorbed and 1. reacts i etian bencaageet lL i= srooastast Inmaybe per =kPe IfBis ee coe type of site is invo! sobscripts- 2: is adsorbed ond reacts with two molecules of A from the gas Phase (RE mechanism). The following two possibilities arise. QB + See SBS adsorption @ B+2A == mM.+ nN +S reaction If (0) is rate determining v=kPg @) If@ is rate determining = baPp vo (is Ph ®) Expression (jv) is similar to (i) and can be verified in the same mat, the rate being | With expression (v), at constant Pp, the rate will ‘Bacar with Pp and independent of P ‘ay lncarly with P&, and at constant Pay the reciprocal of v wil vary linearly with the [Paprocal of Pp Ifthe surface is completely covered with B, expression (s) will become roby, hA and B are adsorbed on similar sites ond reaction is between the adsorbed species BS adsorption AS adsorption MS + NS reaction M +S desorption desorption N +Sos 654 Kinetics and Mechanisms of Chemical Transformations When (h) is rate controlling, we obtain the following rate equation, Cgg that the surface has only specics A adsorbed since, as soon as B is adsorb tty of the reactions take place rapidly. The surface He for Bis theyeeitlig me Which is equal to 1/(1 + baa): Therefore, Pn P If (i) is rate controlling Pa as, vek, fren Fs Hl (vii) If (j) is rate controlling baPabuPs a vak,{—S AEB _ viii) (1+ baPa + bpPa) When (k) or (1) are rate controlling v = constant (ix) Expression (vi) is verified by observing whether at constant P., the rateislieary Px and also whether at constant Pp, the reciprocal of the rate is linear with Pai there is enough B to completely cover the surface v will vary lincarly with the inveng P,.A similar verification with interchange of reactants can be made for expresin( If expression (viii) is applicable, at constant Pa, (Py/v)/? constant Pp, (P,/v)¥/2 will be linear with P,. will be linear with Pas 4, Both A and B are adsorbed on similar sites but the reaction is between one cis reactant and the other from the gas phase (RE mechanism). (m) A+S == AS adsorption (n) B+S =— BS adsorption (o:) AS+B == MS +N reaction (p) MS == Mts desorption If adsorption of A (m) is rate determining, the rate expression will be _ 1 YE RPAX TEP, FOP) 3 label eacts rapidly with B from thc gas phase, the surface avait 7,9, — ) but 1 — Ay. So &)Heterogeneous Catalysis 655 baPaPp 12TH APA + bP 9) is rate determining ip) y = constant (xii) sider A to be reacting from the gas phase with adso A sim ne could ons will be obtained with A and B interchanged eed A similar ot rate wation (x) is similar to equation (vi) and so can be verified in the same manner. Rate ‘can be written in the form . ion squat Pp 1 bpPp +B 3. vw kt kybyPx ky baPa teanstant Pp, Pa/v will vary linearly with Py and at constant P,, Pp/v will vary xearly with Pp. Both A and B are adsorbed but on dissimilar sites and react in the adsorbed phase. @ B.+s BS adsorption () A +S" = AS’ adsorption () BS +s’ === MS’ +NS reaction Ms’ — M +S’ desorption Ns == N +S desorption 4(@)is rate controlling v=kaPp (xiit) ndif() is rate controlling v=k,Py (xiv) Oisrate Controlling Beene, (as }f se.) ne ij 1+b,Pa] [1+ bpPy o' (0) is rate determining, - Y= constant (xvi) it ‘on (xv) can be verified by a linear plot of Py/v versus Pp at constan linear plot of P,/v versus P, at constant Pp.Y anisms of Chemical Transformations 686 Kineties and Mechanism te prevails for me than one step, 5. In steady sta ates ad of sees ee ice from the gas phase with Adsorbed 4 Suppose A is adsorbed a 7 of the reaction is = iO Ph covered by adsorbed A. The rate f the surface covered by a ate of where @, is the fraction of the st oe | of A is given by of A is given what bak Ifa steady state is established ‘3 Km OP zm kL a 94) PA On(kmPR + KyPA) = KyPA | KP wa =e— Keg PB + A : KPA pa les deg! elt asi " LkyPR + k,PA |B Rate expression (xvii) can be verified by keeping P. of 1/v versus 1/P5, will be linear, Similarly, when Pp is kept constant and P, varied, Th the one that can be obtained by assuming a completely covered surface with both Ae! B adsorbed on similar sites but the Products being formed only by the interaction oft) of them from the gas phase and the other in the adsorbed phase, Rate expression(t! the surface is completely covered, is A Constant and varying Pp, Api a plot of 1/v versus 1/, PA should be Tine) is rate expression is substantially similar! ky byPaPy aA ASB DaPa t+ bpPy ‘Sting to note that in spite of imilar rate e: 6. It is ne Itis interest the same or gi 7 ! «operat f different reaction mechanisms being oP, « pressions may in Table 11, Y result. The rate equations are grouped!" therefor os x¢ {0 perform several supplementary ex" on scheme, le