___CHAPTER 5 Hotorogensous Catalysis. ___ 17% ky Ch + * Sa" be CO + Ch* A> COCI* K coc" * Cock + + Assuming only Cls* and COCI,* are present on the surface, the following rate expression is derived: Fitting the data to the above equation results in the following rate model: 1.642[CO][Cla} ( mol ) P= T¥ 1244[Cl,] + 581[COCh] \gearh, ‘where concentrations ere actually partial pressures expressed in atm. Even though all the kinetic parameters are positive and fit the data set reasonably well, this solution is not guaranteed to represent the actual kinetic sequence. Reaction kinetics ean be consistent with @ mechanism but they cannor prove it. Numerous other models need to be constructed and tested against one an- other (as illustrated previously in this section) in order to gain confidence in the kinetic model, Rate constants and equilibrium constants should be checked for thermody- namic consistency if at all possible. For example, the heat of adsorption MHes derived from the temperature dependence of Kags should be negative since adsorption reactions are almost always exothermic. Likewise, the entropy change ASqas for nondissociative adsorption must be negative since every gas phase molecule loses translational entropy upon adsorption. In fact, |ASyu.l Nz + O* 8 CO + * = cor (4) CO* + 0* —+ CO, + 2* N,O + CO => Nz + CO} (a) Assume that the surface coverage of oxygen atoms is very small to derive a rate expression of the following form: K Pro where the K's are collections of appropriate constants. Do not assume a rate-determining step. (b) The rate expression in part (a) can be rearranged into a linear form with respect to the reactants. Use linear regression with the data in the following table to evaluate the kinetic parameters Ky, Ko, and Ks, Rates of NO + CO reaction at $43 K 304 16 0.00503 30.4 152 0.00906 30.4 304 0.0184 30.4 45.6 0.0227 30.4 16 0.0361 16 304 0.0386 15.2 304 0.0239 45.6 30.4 0.0117 16 30.4 0.0077 Source: J. H. Holles, M.A. Switzer, and R. J, Davis, J, Cara, 190 (2000) 247 (©) Use nonlinear regression with the data in part (b) to obtain the kinetic parameters. How do the answers compare? (d) Which species, NO or CO, is present on the surface in greater amount?CHAPTER 5__Heleoganeous Catalysis ue 12. ‘The reaction of carbon monoxide with steam to produce carbon dioxide and dihydrogen is called the water gas shift (WGS) reaction and is an important process in the production of dihydrogen, ammonia, and other bulk chemicals. ‘The overall reaction is shown below: CO + H,O = CO, +H iron-based solids that operate in the temperature range of 360 to 530°C catalyze the WGS reaction. (a) One possible sequence is of the Rideal-Eley type that involves oxidation and reduction of the catalyst surface. This can be represented by the following steps: H,O + * => H, + 0+ CO + O* == CO, ++* Derive a rate expression. (b) Another possible sequence for the WGS reaction is of the Langmuir- Hinshelwood type that involves reaction of adsorbed surface species. For the following steps: CO + * cor a HO + 3* == 2H* + OF Q) CO* + O* @AP CO, + 2* a 2H* @2 Hy + 2* 4) derive the rate expression. (Notice that step 2 is an overall equilibrated reaction.) Do not assume that one species is the most abundant reaction intermediate, For the hydrogenation of propionaldehyde (CHsCH:CHO) to propanol (CHsCH,CH,OH) over a supported nickel catalyst, assume that the rate- limiting step is the reversible chemisorption of propionaldehyde and that dihydrogen adsorbs dissociatively on the nickel surface. (@) Provide a reasonable sequence of reaction steps that is consistent with the overall reaction. (b) Derive a rate expression for the rate of consumption of propionaldehyde, At this point, do not assume a single mari (©) Under what conditions would the rate expression reduce to the expe- rimentally observed function (where prop corresponds to propionaldehyde, and P represents partial pressure): KP, ep Pie13. CHAPTER 5S. Heterogeneous Catalysis” ___483, Some of the oxides of vanadium and molybdenum catalyze the selective oxidation of hydrocarbons to produce valuable chemtical intermediates. In a reaction path proposed by Mars and van Krevelen (see Section 10.5), the hydrocarbon first reduces the surface of the metal oxide catalyst by reaction with lattice oxygen atoms. The resulting surface vacancies are subsequently re-oxidized by gaseous Q2. The elementary steps of this process are shown, below. Electrons are added to the sequence to illustrate the redox nature of this, reaction. RH, + 207% —+ RO +H,0 + 20 (+ 4e7) hydrocarbon lattice product surlace oxygen vacancy O, + 20 (+ de“) —> 2077 RH, + 0; ==> RO + H,0 Derive a rate expression consistent with the above sequence, For this problem, assume that the vacancies do not migrate on the surface. Thus, 20™? and 20] can be considered as 4 single occupied and a single unoccupied surface site, respectively. Show that the expression can be transformed into the following, form: 1 1 1 r RiRm] * RIO) where the K’s are collections of appropriate constants,Exercise 1: part a) The full BET equation is as follows: Pp 1 (¢ 1\P Vi(P,~P) eV, er, JP, Y After dividing both the numerator and denominator of the left hand side of equation (1) by Po, Pp (2) Vly) vs Pf, for sample 1, the following can be concluded (only the By plotting P Vall) P, following data points were used in these calculations 0.05 $03): The regressed slope of the resulting line = SF = 0.035 gem? a The regressed y-intercept of the resuiting line = x =9.15x10° gem? R? value of the fitted line = 0.99 Therefore ¢ = 386.4 and V,= 28.3 cm’ g The one-point BET equation is as follows: P (iP pf 3 TPP) (I, JP, ° where we assume that &>>1 Choose one point to calculate Vm. Choose P/P,= 0.3,At P/Po= 03, Vou, = 39.1 em? gi Therefore Vy= V(1-P/P,) = (39.1em’ g'"\(0.7) = 27.4 cm? gt Note that assuming ¢>=1 was.a good assumption, as seen from the calculations done using the full BET equation Now we need to calculate the surface area, 5, for each solution, ‘The surface area is related fo the number of molecules adsorbed in a monolayer, N, in the following way a) where & is the cross-sectional area of the adsorbing gas (dinitrogen in this case). VN, ¥ is the volume of gas at STP (1 atm and 273 K) per mol, 22409 cm’ mot" N= # molecules adsorbed per monolayer where No is Avagadro’s number and For dinitrogen, ct = 0.162 nm’. For the full BET equation (0.162 ) mol U0%om 22400em’mol™ molecules, 28.3em?g(6.,02x10" Similarly for the one-point BET equation, = 119m’ ‘These values are essentially the same (3% difference), part b) Repeat the same analysis as in part a) except on Sample 2 Full BET equation: c=24 Vn = 0.689 emg 52Note that this sample has a smaller BET constant than sample I (c is not much greater than | here). For the one-point equation: Von = V(I-P/Po) = (0.89cm° (10.3) = 0.623 emg" ‘The surface areas for the full BET equation and the one-point equation are 3,00 m? g" and 2.7 m? g'', respectively Due to the small BET constant, the two methods do not give the same answer (10% difference). Exer Note that: # moles H chemisorbed irreversibly (strong sites) moles H chemisorbed in Run |- # moles H chemisorbed in Run 2 Fist, plot H/PI vs P for each run; find the y-intercepts | “2 \ (Pils) cd = 0.93- 0.34 =0.59 H H/Prinreversibly adsorbed= 5) Dispersior " t\ pot Pel ‘The average particle size is estimated using the following relationship, assuming that the particles are spherical: Particle diameter (am)=1/dispersion In this case the particle diameter is 1,69 nm. Exercise 3: The reaction investigated by A. Peloso is CH)CHOH + CH;CHO + Ha o (Ep (Ad) (DH) 53The proposed mechanism is: KP —(PusPow)/K,] @) DK, + Ka Pal To formulate a mechanism the following clues can be gained from inspection of the proposed expression: 1) Pow is raised to the 1" power, so the adsorption and desorption of DH is equilibrated (itis not dissociative adsorption) 2) The denominator is raised to the 2” power, so surface sites are involved in the RDS. The following mechanism is proposed: 1 ee ee 2 pee adt+ DHF 3 MER Ad * DH* & DHx* The following analysis is used to derive the expression in equation (2), AED = LANL = LOL 6) (Ent) alt] TDHYel From the RDS, = HLEtIe A [Ad eILDHAL ® [lo The site balance is [+], = [+] + LEM] + [Ade] + [DH] 6) Afier substituting equation (3) into equation (5) 384Uh Le Ky llth Ky LA] + Kyu (DH) ©) After substituting equation (6) into equation (4), with the assistance of equation (3), the proposed rate expression can be derived. Note that the constants are all lumped into k and K. In addition, the assumption that Kou DH]<, J [DO}” (FR UP]+ KU + KE[DO}") 03) The rate expression in equation (2) is obtained by grouping all of the constants, Exercise 6: The overall reaction that is being studied here is the following: CO + Ch ~ COCh a The proposed rate expression for this reaction is the following: KeoFes, fewer, « ® The exponent in the denominator suggests that there are two adsorbed species in the RDS. The tack of a KsFep term in the denominator suggests that CO does not adsorb strongly on the surface The following mechanism is suggested to explain the fanctional form of the rate expression given in equation (2) $7Cote @ CO* +c @) coe + Che FE COCK ++ COCh* € COCh ++ The rate of the RDS is ACOs] (4) (le ‘The following equilibrium relationships are valid since the surface reaction step is the RDS: (Ch) ong x, = LCOCh4 and Ky = 5s (ChIP 2° [COCL IE ° The site balance for this system is [*], =i} + (CO*] +[Cl,*]+[COCI,*] (6) After substituting equation (5) into equation (6), [l. B= eae OC) mM 1+ K,[CO]+ K,[Cl,]+K,[COCK] Substituting equation (7) into equation (4), AK [CO]+], KsiCh] (8) (TK, [CO}+ KCI, ]+ K[COC Again, in order to arrive at the rate equation in equation (2) we must asseme that KICO}<<1 58reise 7: proposed reaction rate has the form: pe ARP (FKP, + KP Y fa large quantity of inerts readily adsorb on the catalyst surface, K;P/ is large compared to KyP, and KyPs and 1. The reaction rate is as follows: KK P, ——_ KP 2 (4K ,P, + KP, +K,PP @ scan be simplified to KK Py KP GB) ‘The reaction order with respect to A is | with a large quantity of inerts that adsorb on the catalyst surface. Exercise 8: ‘The following reaction is studied over a zirconium oxide-silica gel catalyst: CaHy + HCI = CHCl @ Step }: Assume a plausible reaction mechanism. Colt + * BE OH HCL + * Qe HCI* CoH + HCI PE HCI + * (5) CoHSCI QP CHSCL + * CH, + * @ cH 5.9The equilibrium relationships are as follows: ICH] (HCI) | [CH] (CA, Ji)? CACHE)” [CH Me + o and K, = 1CHsCl4] (CHC) ‘The rate of reaction is that of the RDS: AIC HA (Coll Clie] — = o The site balance is U], =(°0 4 (C,H, ¢] + UCI] +(C, HCl] + (CH) 6) After substituting equation (6) into the site balance: bes a eT © 1 K,[C,H,]+ K,[HCl] + K,[CH + K,[C,H,Ch, The rate expression in terms of only the reactants and products is: AKC HA LACIK, ~ kK [CH CN), 0) (14 KIC, H, | + KyLHCl] + K,(CH,}* KC) HCL From the overall equation, equation (4), K ay After substituting equation (11) into equation (10) and rearranging, + op IH cn, : Hicargteren © MJ "TER IG H+ KCI KC H,Cl+ KICH 5.10where & is a grouping of constants. Use nonlinear regression to fit the data to this form. Each program that is used to solve for the best ft parameters will give a slightly different answer depending on initial values, We obtained the following parameters: k= 3.86 K)=25.4 K:=32.95 = 1.98 = 32.19 The following graph shows that how these parameters represent the data. 2.00028 . I 2900027 | = ocones 3 3 ° = 0.00023, ’ , wooo: |g 00019 — . ‘100019 0.00021 0.00029 0.00088 0.00027 e.ontz8 Observed Rate | Now assume a different mechanism, namely that of Rideal-Etey. The mechanism is as follows: Citi * QE OM Coit + HCL PE Cobscl® GE CaCI + * “HSCI* ay CH, + * CH The rate is then the rate of the RDS, SalKC HA HCI)-k, (CHCl) (13) The other three steps are assumed to be quasi-equilibrated, and the equilibrium expressions are the following: KIC He = KACHCII=(C,4Cl+] (a) K,[CH Ib] =1CH 4] ‘The site balance is the following: [+], =[)+(C, He] +1C, HCP] +1CH,§) ds) fier substituting equations (14) and (15) into equation (13), the rate is given by the following expression - ater ntrcy LOY | EK IGA KICA.Cl+ K[CH,) (16) However, after fising this expression to the data, negative numbers are found for some of the constants. Since this is unreasonable, the Rideal-Eley mechanism does not fit the data. Exercise 9: part a) ‘The proposed mechanism is as follows: Nyt eR Noe “ No*+ 3H, INH + © 2) The rate of reaction is therefore, P= kLN, Me] kN] 8) ‘The equilibrium expression is: S12ANHPE] Tarte ® ‘The site balance for this reaction mechanism is fm, =P +041 © Afier substituting equation (4) into the site balance, l= at wn 6 “HTK Substituting equations (5) and (6) into equation (3) results in the tate expression for the reversible formation of ammonia with associative adsorption of dinitrogen ga) part b) Its not possible to distinguish equation 5.3.7 from the rate expression in part a) from experimental data, Equation 5.3.7 is (8) (9) 5.13(WHT From part a) if we ALN IE], r= (WH? ~ALEL, (10) [HP K, Since equation (10) and equation (9) are identical it is probably not possible to distinguish between the two rate expressions experimentally unless an extreme! range of accurate data is used Exercise 10: ‘The proposed mechanism is: 04+ BEMO¥ N20+ —® N3+ O# a CO*+* cow CO*+ 0# —® CO,+2* The adsorption of N2O and CO on the surface is equilibrated. Where the overall reaction is N20 + CO = Ny + CO) Q) part a) ‘The site balance for this mechanism is, (1, =f] +14,041+ C04] + (04) 6) However, ifthe surface coverage of oxygen is assumed to be very small, the site balance is reduced to [+], = [+] + [N04] + [C08] a) ‘The equilibrium relationships are as follows 5.4WW,0) _ (com feiew,o} (coy © After substituting equation (5) into the site balance and rearranging, +, fl - © “T+ KIN,O]+ RICO] The rate of reaction is either the rate of N2O reaction on the surface or the rate of CO2 formation, 1 = kLN,O4] = k,[CO#|[O*] ay Aer substituting the site batance and the equilibrium relationships into equation (7), the rate expression is then determined. The rate expression is as follows: ER LLNO} TEKIN,Ol+K(CO} © Iw addition, et Kile. = &, pat) First, linearize the rate expression in equation (8) from part a) ae wo 1 Pro 3 Plot 22. vs Py., at constant Pro to get slope = ‘ and the intercept = > rN Pag ‘ > yy Plot “"2-ys Peoat constant Py,. to get slope => and the intercept The results of the regression analysis are shown below SasLinear Regression (Hoiding Pco Constant) 2500 ao 1800 | year+ 14806 Re09 1000 | 500 0 ° 20 40 80 80 Pano Linear Regression (Holding Pwo Constant) | 5000 | 400 | 30004 E 2000 | S20 y= 45.304 4604 1000 Ra19 a - 0 ~» “0 60 0 There are now four equations to solve with three unknowns. Therefore, there are four differem ways to solve the set of overdetermined equations. The average of the 4 cases was laken here K)= 0,007 s torr"! K2= 0.069 torr! K;=0.320 torr! part c) The results of the non-linear regression using the rate expression in part a) and the data in part b) yielded the following results, Ky 0,004 s torr! K2= 0,025 orf! 5.16Ks= 0.168 tore! The answers in parts b) and c) will be different because two different methods were used, ‘The answers in this case are within a factor of 3 of each other. part d) Since Ky is large compared to Ky and Kz where 1,04) V0] {com} (coll) and K. and K; from the regression analysis was equal to the equilibrium constant Ki, The coverage of CO on the surface must be larger than the coverage of N30 on the surface. Exercise LI: The proposed mechanism is the following Hy0 + #4 Hy + Ow a) CO+ O40 +COp+# Since we cannot assume that either step is the RDS, the steady state approximation is used KHON] ~ kL A, O*] = K[CONLO#]~k.1CO, J] Q) Use equation (2) to solve for [0+] ALON ka1COs]] 6) (0) EICOV KEEL The site balance for this system is the following: (+), =P) +109 (4) Afr substituting equation (3) into the site balance and rearranging, 5.17(6) Next, substitute equations (5) and (3) into equation (2). AOI (kslCO}+ kL kU I], Ce 401+ & s1COsD) [CO]+ k(H,}+ &[H;0}+ &1CO,] part b) ‘The Langmuir-Hinshelwood type mechanism for the WGS reeetion is COs * Coe H;0 + 34 €% He + O# COr+ 0+ QE CO, +2" 2H €% th +2 a) The rate of the RDS is, p HICOMIO {COT @ fr. fl, The adsorption of CO on the surface, the desorption of H, from the surface and the dissociation of water are all assumed to be equilibrated. Therefore the following relationships are used. {CO}, [He P[0+] » Ky 5 ~ + GB) weoyey’ “ PH0) ‘The site balance for this mechanism is: [+], =[41+ [CO + (0+) +409 @ After substituting the equilibrium expressions into the site balance and rearranging 5.18tH, KROL, (4) Ke 1+ K [CO]+ () Substituting equation (5) and the equilibrium expressions into equation (2) results in the following rate expression: KR, Keks[COMH, OM}, (CON (Hs) © wwf +K[CO}+ A va} Exercise 12: The overall reaction is the following CHsCH:CHO + Hp= CHsCH:CH:OH part a) A reasonable sequence of reaction steps for this reaction is the following: CH:CH;CHO + « 9% CH:CH;CHO+ Hy + 24@QP 2He CHSCHCHO* + Ht @% CHYCHICH;0% + + a) CHICHCH,O+ H&P CHCHCHOH# + + CHCUCH:OH® 2 + * CHSCH-CH;OH part b} The rate of consumption of CHsCH:CHO is (since the adsorption of CHsCH CHO is the RDS) {CH CH,CHO) Z =&(CH,CH,CHO][*]-k(CH;CH,CHO*] (2) 5.19Since the adsorption of CH:CH,CHO is the RDS, all other steps are quasi-equilibrated, Therefore, the following equilibrium relationships are used. (Hey x, = CH CHCH ONL x, (AeL * (CH,CH,CHO*)[H*)]” GB) (CHCH,CH,OH*\(¢] [Hs[CH,CH,CH,O%| and K, ~PICHLCH,CH,OM) °° (CH,CH,CH,OH#) ‘The site balance for this mechanism is the following: [+], =[4]+ [CH,CH,CHO*] + [H*] +]CH,CH,CH 0") +|CH,CH,CH,OHS) (4) After substituting the equilibrium expressions into the site balance and then plugging the resull into the rate expression in equation (2), the rate of consumption of CH:CHCHO is the following: k,{CH,CH,CHO} POM gang 9 KKK) 7 4k [CH,CH,CH, OH) KK KK[H,) (CH,CH,CH,OH]| KKK? = AlCH,CH CHOY a part) A Py, (orfHa)) is lange and Poy cy,cyjn (Ot (CHSCH:CHOH)) is small, the reaction rate reduces to Ke AS\CH CH CHOY Ky LH, KP, ‘Therefore, in order to reduce to r= "2", H must be large and that of CH;CH;CH:0H a must be small 5.20Exercise 13: Use the steady state approximation since we cannot assume that one step is the RDS. Therefore, Ay[RA, 207] = k,[O,][2* tel Oo Solving for the concentration of vacaney pairs yields, e120") ( k,{O;) ‘The site balance for this system is fr. = (2071+ (2 toed 8) ‘After substituting the expression for the concentration of vacaney pairs into the site balance and solving for the concentration of O°, o) Lastly, substitute equation (4) into the cate expression in equation (1). ARH, 6) K,[RH,) 14 SUES “10,1 After simplification, the rate expression in equation (5) becomes ' \ 1 CORUNA MRC RCAl where K/= kif*]oand Ke 5.21Fundamentals of Chemical Reaction Engineering Mark E. Dayis California Institute of Technology Robert J. Davis University of Virginia is Burr Ridge. IL Dubuque, 1A Madison, Wi Bogota Caracas KualaLumpur Li Milan Montreal New Delhi Santiago Seoul Singapore Sydney Taipei lew York San Francisco St on London Madrid Mexico City TorontoMcGraw-Hill Higher Education A Division of The MeGrave Hill Companies FUNDAMENTALS OF CHEMICAL REACTION ENGINEERING Published by McGraw Hil, business unit of The McGraw-Hill Companies, ge, 1221 Avenue Of the ‘Americas, New York, NY 10020. Copyright © 2003 by The MeGraw-lll Companies, Inc.All rights reserved, [No past ofthis publication may be reproduced or distibute in any form or by any means, oF stored in a ‘database or retrieval system, without the prior writen consent of The McGraw-Hill Companies, tne, including, but not Limited to, in any network or her electronic storage or ansmission, or broadcast fr distance fearing Some ancillaries, including electronic and print components, may not be avilable to customers outside the United States. ‘This book is printed on acid-free pape Inwereational 1234567890 DOCIOC 98765432 Domestic 1 234567&89ODOCDOCO9RT 65432 ISBN 0-07-245007-X ISBN 0-07-119260-3 (ISE) Publisher: Elicaberh A. Jones Sponsoring editor: Suzanne Jeans Developmental editor: Maja Lorkovie ‘Markeliog manager: Sarah Marian Project manager: Jane Moh Production supervisor: Sherry L. Kane Senior media project managet: Tammy Juran Coordinator of freelance design: Rick D. 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