Chee3005, assignment 5 Due time: 12:30 pm 21 Oct 2013 Problem set H 8.2, Fogler P11-5 (a) and (b), question please see tute week 11 Problem set H8.4, H8.8 Fogler 12-3 (a) -(g), question attached Fogler P12-6 (a) and (b), question attached82 84 88 Suppose an enzyme catalyzed reaction has the following mechanism A+E@AE (a) A+ AE © AE Q) AXE > P+ QB) in which A is substrate, P is product, E is the enzyme and AB, AoE are enzyme- substrate complexes. The third reaction is rate controlling and is irreversible and of first order. Derive an overall rate expression for the formation of P in terms of the concentration of A and total concentration of enzyme The following rates were observed for a first order irreversible reaction carried out on a spherical catalyst: for dp= 0.6cm; ross = 0.09 mol/gcat-hr for dy = 0.3cm; raps = 0.162 mol/gcat.hr Significant diffusional limitations were observed in both cases. Determine the true rate of reaction. Is diffusional resistance still important with d, = 0.lem? ‘The first order reaction A —> B is conducted in a laboratory fixed bed reactor. The reactor is isothermal, and the following data are provided for the gas-phase reaction, the catalyst particles and reactor: Peclet no. = 5 Reactor length 750m Reactor diameter 7 linch Bed porosity 0.35 Rate Law = kCy, moles/em?.cat-sec Inlet flow rate = 0.5em’/see k 10° cm/sec Surface area = 60mg Pellet density = 1.5 g/cm? Pellet diameter = 3mm (spheres) D, of A in pellet = 10%cm*/see Estimate the conversion of A in the react transfer resistanceQuestion 8.2 A,E—*->P +E rate controlling step “We want tp = f(Ca, Cua) “K. K. Ca PO Cn Clue kCa KC yCye 1, = KK CiCe but Cy = Ce + Cap + Cae Cy = Cp + Ky Cle + KC Car Cy = Cp + Ky Cale + K aK aCiCy —_Su_ “Cp = ; T#K,C,+ Kak Ch =K,K,C}| ———*"__ 14 KyC,+KKyCyQuestion 8.4 Actual Rate 3 Actual Rate __ 3-4 eotnyg)—1 Rare at surface condition = g@ ON) -D KC us Eyp,S Mast PSs Ey _ 0.09 _ 9 556 rasa RCycEyp,S, Ey 0.162 = 0.556 ----(1) & Sinceg = R, = 28, From equation (1): jiecothin)—D a = 0.556 S ,coth(d,) -D & 3 grin oa) —1) = 0 sd 7 (0.59,)" (0.54, coth(0.54,) | 9, coth(g,)-1= oss (0.5¢, coth(0.5¢,) = » G, coth(g, )—1 = 2.222(0.5¢, coth(0.5¢,) - 1) 0=1.1114, coth(0.5¢,) ~¢, coth(g,) ~ 1.222 «Using excel, 4, =11 oh =55 E, = 0.248 For case 1: Tray 0.09 _ mol E, 0.248 geat —hr True rate of equation = For dy =0.lem, Therefore, diffusion is still important.Question 8.8 on} >, 0.3 flO 1.5 60x10" 10° .987 rite = kp,S,E,C,(—6,) ky = kppS,E,(\-#,) kyr = kppS,E,(~e,)e 4p DP penn? = 0.948Eternal fusion telson Heterogeneous Rascton ‘ooh Lea Hain 20 atm ro nw 1 ao oer he slave importance of tauipase don ud spe eee ee ie oft Teactln? (Caliornla Profesional sa) Pa mcunaber extinct «humans tal tue op, J Ne edit sal arg of is lin were expove 10 mvOH68 gt. Ag sees espn sre becue eh, with sal ster ety Akin, Morte! the skin as consisting of to adjacent layers, one OF thiknes 9, saa verity of Be If souveritfiskon o He ot th essen Ft a iy acs tt the sin a ha ptt he by Tre ea ote rl pesires maxi? he saturn pan Nese Mth gres 101 Pac ea he ser esl of ese Aree well prosunes exceeding te satura pal eu ae py ‘coming out of the solution (Le, the skin)? re aoewerng any of these Gusti les oe Ny a ee an ayes, He 1 durve the concentration po jee Side Note. Diftusivity of He and Na i the inn skin layer = 5% 10 YemYs and 1.5 % 10-? ems, respects Ditfusviy of He and Ny inthe outer skin 10-3 ems and 3.3 X 10-4 Ta ka D nypisition of eyefohesane to benzene sd yogis ss ied at high temperatures, The reaction is cari out ia a Som 1D WR The dee fort in fei The pellet ‘ao costed with the eatalyst only om the aatside tring volumetsc Mow eat is 60 min tyelchexane from an entering gas stream of 5% eye! at 2 wim ane 500°C (0) Plot conversion as # fanction of length ue number of pipes necessary to achieve 99.9% conve Ihap. 14 Puts, Puite PIS, Questions and Problems 805: (©) How much would your answer change ifthe pellet diarneter and length were each eut in half? {@) How would your answer to part (a) change if the feed were pure cyclo- hexane? (e) What do you belive is the point of this problem? ‘Assume the raiuimam respiration rate of a chipmunk is 1.5 micsomoles of (Ogimin, The corresponding volumetric rate of gas lake is 0.05 dmn¥inin at str, (@) What is the deepest a chipmunk can burow @ 3m diameter tole beneath the surface in Ann Arbor, Michigan? Dag = 18 x 10 mis (&) In Boulder, Colorado? (©) How would your answers to (a) and (b) change in the dead of winter when = 0°F? (@) Critique and extend this problem (e ., CO poisoning). Cachon disultide (A) is evaporating ito air (B) at 25°C (Pygg = 510 mm Hg) tnd 1 atm fom the bottom of a 1.0 em diameter vertical tube. The distance frow the CS; surface to the open end is 20.0 om, and this ie held constant by continuous adition of iguid CS, from below. The experiment is aranged so that the vapor concentration of CS, at the open end is zero. (a) Calculate the molecular difusivity of CS, i air (Dy) and ts vapor pres sure at 35°C, (ans. Dyy = 0.12 cris) (b) Find the moiae and mass Buxes (My, me of CS,) in the tube (©) Caleulae the folowing properties st 0.0, 3.0, 100, 15.0, 18.0, and 20.0 cm (roma the CS; surface. Areange columns in the foliwing onder on one Sheet of paper. (Additional columas may be inchaded for compatational purposes if desired) On a epacete sheet give the relations used Wo obtain Each quanti. Try 40 put cach relation into a form involving the mini mun computation and the highest accuracy (1) yn andy Cole fractions), Cy @) Va. Va, V8, V mass velocity) Q) Inde (2) Blow etch of the groups of quantities in (@(1), (2), and (3) on separate sgapbs, Nanve all vaiables and show units, Do'nor plot those parameters in parentheses {@) What isthe cate of evaporation of CS, in erway? {Discuss the physical meaning of the value of VY, and Jy at the open end of the tube (@) Is malecutar difsion of aie taking place? AA device for meusuting the diffusion cuefReient of « gas mixtre (Figure PLI-R,) comsiats of two chambers coneetel by a small tube, Initially the chambers contain different proportions of two gases, A and B. The tote ps is the same in each chamberFogler Problem: P11-5 Renetion is CgHiz > Colle + 3H A > B +3C Assume: = Isothermal Ideal Gas - Perfect plug flow - Constant P a) Mol Balance: Mole Balance Inital Change Final A Fw “FaX4 — Feo(l-X,) Bo Fy FX, Foot FX, BF eX, 3a, BFoX, Fro (143% 0X4) Start with the mass balance for @ PER: dk, a” Need to get r, (rate per unit volume) in terms of mass transfer 14 = kat (Car~Cur) 4, is the area of catalyst per volume of bed ‘mass transfer limited, so C,, = 0. aX, RIX) dV” v(1¥0.15X,) a, RIX) dz U,(1+0.15%,) X,)Use Thoenes & Kramers correlation (or similar) for km: Sh’ = (Re’) *(Se') * kad, ( oC Late Loss Caloulate the effective diameter ofthe particle: 10 aos? 4, ($) [ena 203) -osv Caloulate the diffusivity of cyclohexane in hydrogen: oor (& as M, De = + PUPP) Fuller, Schettler, Gi (Perry’s Handbook) ings for binary mixtures, low pressure, non polar ‘My, My = molecular masses = 84 and 2 g/mol, respectively V4, Va = diffusion volumes = 122 and 7.07cm*/mol, respectively o.oox(773.13)( 42) EY, 0.857 mts 2{(122)" +(7.07)" | Duy porosity, = 0.4, 1.146 Initial velocity: % 60000 A adi 60 =50.9 em? /s Expression for velocity: i (1+ 3¥40%,)=50.9(1+0.15%,) thet vy w(+0.15X,) (1+0.1S%,)jal density: (840.05 + 20,95) 202.65 y= Mada? , Marr? _ ( +2%0.95)202-65 «919 kein? 0.00019 ple? RP ORT 83145x73.15 p= Oper p/om.s (Hz , 500 K, 2 atm) 9.8001} te _509%(14. 0:15, )x0.572%0.00019 _ yo 5 0.00017 (1+ 0.15, )x(1— OA) xt. 145 — 0.00017%(1+0.15%, =1.044(1+0.15%,) 0,000190.857 a (=5)7 patiggn 4,6, 17.98(1+0.15¥,)” (note the typing error, ke should be kz) 577x6.88%1.014x(1+0.15%,)” ‘Need to calculate a, for a non-porous clyndrical catalyst: ws) (1-8 )(2a7,b4 207) ab 29 om’ aK, X,) _17.98x(1-X,)!" x6.29%(1-X,) de O,(1+0.15X,) 50.9% (IF 0.15X,) a, -x,) 4-22 _ “5 eG osK,) Plotting in excel. Only 3.3em required to reach 99.9% conversion. Much less than one tube, (b) Plot(©) Can use the same mass balance from before: dx, R(I-X,) de U,(140.15X,) Need to find new effective radius and shape factor: 6v,)” _(6xx0.125 0.25)" 4(%) (2 0.125 2) = 0.286 = x a 2 228 snd 27225 5 90.25%0.25 p= 4 its ad 10.286" Assume porosity remains unchanged, find new Re (Sc unchanged): __S09(14 045%, )x0.2864 0.00019 5g 00017 (140.15. Jx(I Oat 4S Dy (I=: p Pall) nese as 195% 4.866x1.014x(1+0.15%,)" k, =25.43(1+0.15%,) (note the typing error, ke should be ky) Calculate new a: 3 1-6,)(2mr,L+2r2 (eal “ ) 21259 em aL aX, ka,(I-X,) _ 2843x(1-X,)" «12.59«(1-X,) “dz U,(1+0.15X,) ——-50.9x(1+0.15X,) ws (4) dz (140.15x,)" Integrating the equation again in excel shows that only 1.16 cm of reactor is required. About 123 of the previous length required.wns cower eal P1239 Hatt Fame the temperate were ines iil (3) 1 Bn vel iipled? (2) He peti wore dee Dy 8 fh 9 Ny ‘Would the rector Heng ehange in each exse? (5) What ley 2” Pe, {quire to achieve DDG conversion oF the pollutant NOP” MH What it. (e) yo applied the Meaes and Weisz-Prter criteria to Examples 1.4 12-4? What would you fwd? What would you Team if yg, Md kcal/mol, f= 100 BeufheM%E and £ = 20 keal/mo!? 2s would your effectiveness factor change and the rate of reaction a iow powitive or negative effects that oeeur? t CO+3H, > CH HO H,0+C0 --—> CO, +H, hae ‘emporature in CDROM Example 812.2 were inreased” Yow woul felative resistances in the sly reactor change (4) you were asked fr ll che things that cauld go wrong inthe operation uf slung reaeing, what would you say? Te eataytieresetion AB cakes place within # xed bed containing spherical porous eatlyst X22. Fi te P12-3y shows the averll rates of reaction at a point in the reser a5 function of temperature for various entering total molar flow rates, Fre (a), Is the renetion limited by external diffusion? {b) if your answer to part (a) was “yes,” under what conditions [of tse shown (ie, J Fy] is the reaction litnited by external dlfusion? (0) Is the seaetion “feation-te-limited"? {@) If your answer w pat (c) was "yes," unr what conditions [oF those shaw (ie. T, Felli the reaction limited by the sate of the surface reaction” (e) Ts she egation Hinited by internal ditfusion? (I your answer to past (6) wax “yess” under what conltions (of Hes ‘07, Fr) isthe reaetion nied by the rate of internal Cision (2) For a flow rate oF 10 g mul, determine (Hf possi) the overall iveness factor, £2, at 360 K. (h) Estimate (if possible) the intemal effectiveness fret, at 367 K G@_ Ir the concentration atthe extenal eatalyst surface is 0.01 mot" ¢ ‘late (GF possible) the concentration at y = A/2 inside the porous Iyst at 367 K. (Assume a fistrder rection)(chap. 12 Questo na Problems as7 29 Fg = 1000 g mam 0360 a¢0 3700 “00 TH) Figure P1233, Reueton ste in extalyst bod Addlvional informatio: Gas properties: Bod properties: Diffosivty: 0.1 ean's Tortwosty of pellet: 1414 Density: 0.001 fem? Bed permeability: 1 millidarey Viscosity: 0.0001 glem's Porosity = 03 PI24,. The reaction es) Ae Ii is carried out in a differentia) pucked-bed reactor at different temperatures, flow HH ii ané price son. To ela shows In Figen nes nd Figure P24 Resotion rte a etalys ed (a) What regions (ie, conditions d,. 7 Py) ave externa mas eansfer Hite (b) What regions are teaction-ate limited (6) What region is imteral-diffusion-contrlled? (4) What i the intra effectiveness factor at 7 = 490 K and dy = 08 en! bmFogler Problem: P12-3 (15 mark (a) Yes (im) (b) All temperatures for Fro = LOmol/hr and for T > 360 K for F7o = 100mol/hr. That the reaction is mass transfer limited is shown by the fact it increases with flow rate and increases linearly (as opposed to exponentially) with temperature. (im) (© Yes (im) (@) At low temperatures and at high flow rates: T'< 363 K, Fro = 1000 mol/hr, 5000 molar 1360 K, Fro= 100 mol/hr ‘as shown by independence to flow and exponential increase with temperature of the rate at these conditions. (im) (Yes (un) (O At high temperatures and high flow rates T > 363K, Fro = 1000 mov/hr, 5000 mol¢hr tas shown by independence to low and non-exponential (surface reaction control) and non- linear (mass transfer control) increase with temperature of the rate at these conditions. (im) (g) As stated above for Fro = LOmol/hr, the reaction is mass transfer limited. So its overall effectiveness can be obtained by comparing the rate against those at high flow conditions: actual rate of reaction =r, (T =360K, Fy =10) rate of reaction without mass transfer limitations —r3 (T" = 8, =975 036 07 2m) (hy As stated above for Fro = 5000mol/hr, the reaction is diffusion limited above 363 K. So its overall effectiveness can be obtained by comparing the actual rate at 367 K against a rate extrapolated from the region where there is negligible diffusional resistance: actual rate of reaction =r, (T = 367K, Fy = $000) 7, extrapolated from 360K ro 367 K 'r, without diffusion limitations 12 0.86 (2m)(i The internal effectiveness factor can be used to determine the Thiele modulus of this system at 367 K, We can use the effectiveness factor from part (h) since it is the internal effectiveness factor (i.e. no external limitations). Using the equation for E;: 86 = (Bes) -1) solving numerically $=16 ‘Now use the equation for the concentration profile of a spherical pellet: Cx(a) _ sind) Cy nsinh(g) : =Ze05 TR Nd —SinhO.8) 9.75, C, _ OSsinh(1.6) => C,(r = R/2)=0.0075 mol/ém? (3m) (2m)PID Agno nde or Probl i Curves A. Band C in Figuce 12-5, show the vatatins in ae ee on cea lols pela. Figure PI2-5, Tenpeine dependence of thes teatons, A fintorder inteiogoneons itevnible rastion WY ling place wy gap wich ped wt pati hago ge spre « {Gee Figure 12-0, The reaciant concentration halfway betvcen th Sune and the eentce ofthe pelle (Le, 7 = KF2) is equal tw ny * plat’ exter yurfoes. "The concentration ti voter (2R) is 2% 10" em coneetttation oft Surface is 0.001 gama? the sion coefficient i 0.1 em2/s A—>B (@) What is the concentntion of reactant ata distance of 3% from the exteral pellet surface? (Ans. Cy = 2.36 % 10 + m () ‘To what diameter should the pelle be reduced i te effective is to be O.8? Uns. dy = 48 10° em, Critique this answe atalyst auppart were not ye plated ith platinuin, how st thatthe catalyst support be pel afte i had been ate ofa sonll gain 1, Theoret, Mis 264 1 the energy released y the hydrolysis of adenosine i telat ATP) 49 adevosinediphowphate (ADP). The nite of hyucoysis tae of effusion of ATP feom the mice to thecal (ase Pagan ieient of ATP in the midpiece a tail 3.61 ierted ATP an the eit, where its Tine ofusysectonal ae OF Ue Nal Figure P12 7 Swimming ofan organs (a) Derive equation for difuston and reaction in the til (b) rive ais equation For the effectiveness tactoc in the tl {e) “Taking the ration in the tll (o be of zer order, eakeate the tail, The rate of reaction bythe tall fs 23. 10. mols (a) Compare your answer with the average tall Iength of 41 possible sources of error? 8 yon he en Wet the extern whe dt, 10 em in wld) ‘weal ym (19703 4 phase th yh The su, ADE iw 10 ny, WhaFogler Problem: P12-6 Assume: = Isothermal a) For a first order reaction in a spherical pellet, we can use the equation: “Ca sinh(9) From the data we are given: n=Z=05 09) 91 O=6 sinh(0.56) Seinnggy *0ig nunecoally At the new radius: = C,(r = 7x10" cm) =2.36x10 movdm? 'b) Use the equation for internal effectiveness factor: A $= (GeomK@)-") solving numerially o=2 ‘Now the Thiele modulus is proportional to the radius (and hence diameter) of the particle. Since it is 1/3 of the ‘Thiele modulus above, then: This is a very small catalyst particle!