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Kinetics 3
Reaction Kinetics
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Reaction Kinetics
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MIXED FLOW REACTOR PERFORMANCE ‘The elementary liquid-phase reaction A+2B==R with rate equation mol 12.5 liter*/mol’- min)C,C ~ (15 min)Cx, [i is to take place in a 6-liter steady-state mixed flow reactor. Two feed streams, one containing 2.8 mol A/liter and the other containing 1.6 mol Blliter, are to be introduced at equal volumetric flow rates into the reactor, and 75% conversion of limiting component is desired (see Fig. E5.3). What should be the flow rate stream? Assume a constant density throughout. be introduced at equal volumetric low ratesinto the reactor, and 75% conversion of limiting component is desired (see Fig. E53). What should be the flow rate of each stream’? Assume a constant density throughout. hon 28 mol Mlitar {Gio= 16 no Biter ame v= 6lite 75% somerson ot 6 Fiore F3SOLUTION ‘The concentration of components in the mixed feed stream is Cyy = 14 moliliter Cu = 08 moliliter w= 0 ‘These numbers show that B is the limiting component, so for 75% conversion of B and « = 0, the composition in the reactor and in the exit stream is Cy = 14 = 06/2 = 1.1 molllter Cy = 08 ~ 06 = 02 moll \3 mollliter or 75% conversion Writing the rate and solving the problem in terms of B we have at the conditions within the reactor Writing the rate and solving the problem in terms of B we have at the conditions within the reactor (=n) = RX LSNCAE} - 2X LICR mol) (q5mol\?_ 05 ni9-1) (94m! 2s lice) (1124) (a2@2)'— caminry (oa) —o2—_mal Titer-min Hence the volumentric low rate ino and out of the reactor isFor no density change, the performance equation of Eq. 13 gives Hence the volumentric flow rate into and out of the reactor is Ven) Cw Co (liter)(0.2 mot/lter- min) (08 ~ 0.6) mol/liter | 53. STEADY-STATE PLUG FLOW REACTORPLUG FLOW REACTOR PERFORMANCE ‘A homogeneous gas reaction A > 3R has a reported rate at 215°C t= 10°CX, — [mollliter-sec] Find the space-time needed for 80% conversion of a 50% A-S0% inert feed to a plug flow reactor operating at 215°C and 5 atm (Cp = 0.0625 mol/iter). Hig) 32) Seam a Bam ~. igure ES4a SOLUTION For this stoichiometry and with 50% inerts, two volumes of feed gas would give four volumes of completely converted product gas; thus, 4-2 in which case the plug flow performance equation, Eq. 17, becomes rey AX, ax, C18 pos (14-X, = Cag fae c,, fv Xa q 72 Co [A= Cw ft val wae Bee f) ax a0) Treks ‘The integral can be evaluated in any one of three ways: graphically, numerically, or analytically. Let us illustrate these methods. ELOX's Conmunity0 1 1 12 02 as" 5 1.227 04 23 1528 06 4 2 a8 9 3 Graphical Integration. First evaluate the function to be integrated at selected values (see Table E5.4) and plot this function (see Fig. E5.4b). ‘Average height = 1.7 ‘Nea 1,7(0.8)= 1.36 0s Xs Figure ES Counting squares or estimating by eye we find AX, = (1.70)(0.8) =Numerical Integration. Using Simpson's rule, applicable to an even number ‘of uniformly spaced intervals on the Xq axis, we find for the data of Table E54, 1s (14+ X)!2 f ( Tot) @Xq = (average height)(total width) o WN _ [1 + 40.227 + 201.598) +40) + 108) | r es 106 Chapter 5 teal Reactors foro Single Reaction Analytical Integration, From a table of integrals 14+X,)"2 LEX, Ie) a xs = (wen x08 7) | = 1328 ‘The method of integration recommended depends on the situation. In this prob- lem probably the numerical method is the quickest and simplest and gives a ‘good enough answer for most purposes. So with the integral evaluated, Eq, (i) becomes (6.0625 mot/lites)!? GO? motfiter'®- sex) (133)(ERIM r106 row neacron vou ‘The homogencous gas decomposition of phosphine APH4(g) > P.(g) + 0H proceeds at 649°C with the first-order rate (10741) Cr, What size of plug flow reactor operating at 649°C and 460 kPa can produce 80% conversion of a feed consisting of 40 mol of pure phosphine per hour? ho Ro 6S. Plug iow 40moime y= 08 age 74 ~ 460 Fa Figure ESS SOLUTION Let A = PH,, R = P,, § = Hy. Then the reaction becomes 4A>R+68with =r = (lOMhr) Cy ‘The volume of plug flow reactor is given by Eq. 21 va feareomtg aa] Evaluating the individual terms in this expression gives 40 ml/h k= 10/hr Pao 460 000 Pa T~ (&314Pa- m/mol- KY(22K 1-6, ean toons 60 mol/m* X, 08 hence the volume of reactor 40 mol/hr Y= GoThe)(60 mela) [cron -on4oyTEST OF A KINETIC EQUATION IN A PLUG FLOW REACTOR We suspect that the gas reaction between A, B, and R is an elementary revers- ible reaction A+B==R % and we plan to test this with experiments in an isothermal plug flow reactor. (a) Develop the isothermal performance equation for these kinetics for a feed of A, B, R, and inerts. (6) Show how to test this equation for an equimolar feed of A and B. ELOX's Communit 108 Chapter 5 Heal Reactors for a Single Reaction SOLUTION (@) Feed of A, B, R, and inerts. For this elementary reaction the rate is NyNo VV Ny v H ry = kiCaCn ~ Ce = hy ‘At constant pressure, basing expansion and conversion on substance A, NwoXn Noo NaoXn _ 5, No + Nun, ViL# baka) VoL + eaXa) Vo (1+ @aXa) Letting M = Cy/Caq, M’ = Cyo/Cay We obtain (1 = XM = Xq) _ (1+ e,Xq) ta = ihoHence, the design equation for plug flow, Eq. 17, becomes (1+ eaXa)'dXq ryiKa _ ru | 0 EyCu = RAM =X) — KAM EHNA eX) In this expression ©, accounts for the stoichiometry and for inerts present in the feed. (b) Equimolar feed of A and B. For Cy = Cao, Cy = 0, and no inerts, we have M = 1, M’ = 0,6, = ~0.5;hence the expression for part a reduces to yy (1-05%,F dX, ‘ell [hy 1 Rea HFK = 08K) ae Jireoex, Having V, vo, and X,, data from a series of experiments, separately evaluate the left side and the right side of Eq. (i). For the right side, at various XY, : ° zs Se is (0 pedis a aif sro ine 7 Wep Figure E56 2 guemayroue rung rium meucivn awe evaluate f(X,), then integrate graphically to give Jf(Xq)dXy and then make the plot of Fig. ES6. If the data fall on a reasonably straight line, then the suggested kinetic scheme can be said to be satisfactory in that it fits the data 5.1. Consider a gas-phase reaction 2A —> R + 2 with unknown kinetics. If a space velocity of Limin is needed for 90% conversion of A in a plug flow reactor, find the corresponding space-time and mean residence time or holding time of Muid in the plug low reactor.Bl By the definition Vote thet bxouiag = eee teh GH) te Ent etua e 5.3. A stream of aqueous monomer A (1 moVfiter, 4 liter/min) enters a 2-titer mixed flow reactor, is radiated therein, and polymerizes as follows: ASR s—S 7, In the exit stream C, = 0.01 mollliter, and for a particular reaction product W. Cw = 0.0002 moliter. Find the rate of reaction of A and the rate of formation of W.. An aqueous feed of A and B (400 liter/min, 100 mmol Alliter, 200 mmol Biliter) is to be converted to product in a plug flow reactor. The kinetics of the reaction is represented by AS BR, 1 =200C,C, 701 Titer-min Find the volume of reactor needed for 99.9% conversion of A to product. 5.7. The off gas from a boiling water nuclear power reactor contains a whole variety of radioactive trash, one of the most troublesome being Xe-133, (half life = 5.2 days). This off gas flows continuously through a large holdup tank in which its mean residence time is 30 days, and where we can assume that the contents are well mixed. Find the fraction of activity removed in the tank. 59. A specific enzyme acts as catalyst in the fermentation of reactant A. At a given enzyme concentration in the aqueous feed stream (25 liter/min) find the volume of plug flow reactor needed for 95% conversion of reactant A (Cxy = 2 molliter). The kinetics of the fermentation at this enzyme concentration is given by je pea ley __mol ®~ 7405 C, liter-minSL. Enzyme E catalyses the fermentation of substrate A (the reactant) to product R. Find the size of mixed flow reactor needed for 95% conversion, of reactant in a feed stream (25 liter/min) of reactant (2 mol/liter) and enzyme. The kinetics of the fermentation at this enzyme concentration are given by _ 1, __mol "ST405C, liter mi 5.13. At 650°C phosphine vapor decomposes as follows: APH, + P(g) + Hy, Fa = (LD HC a What size of plug flow reactor operating at 649°C and L1.4 aim is needed for 75% conversion of 10 moVhr of phosphine in a 2/3 phosphine-1/3 inert feed?5.15, A gascous feed of pure A (1 molliter) enters a mixed flow reactor (2 liters) and reacts a follows: 2ASR, r= 005, —2 ier: sec Find what feed rate (liter/min) will give an outlet concentration Cy = 0.5 molliter, S.I7. 1 liter/s of a 20% ozone-80% air mixture at 1.5 atm and 93°C passes through a plug flow resctor. Under these conditions ozone decomposes by homogeneous reaction 203303, —rewoe = KChones k= 05 ter ‘What size reactor is needed for 50% decomposition of ozone? This problem is a modification of a problem given by Corcoran and Lacey (1970).5.19. Pure gaseous A at about 3 atm and 30°C (120 mmollliter) is fed into a 1- liter mixed flow reactor at various flow rates. There it decomposes, and the exit concentration of A is measured for each flow rate. From the following data finda rate equation torepresent the kinetics of the decompo- sition of A. Assume that reactant A alone affects the rate. iter/min | 006 048 1S 81 tos ABR Cyymmovliter | 30 60 80‘S21 We are planning to operate a batch reactor to convert A into R. This is ¢ liquid reaction, the stoichiometry is A->R, and the rate of reaction is given in Table P5.21. How long must we react each batch for the concentra. tion to drop from C,) = 1.3 mollliter to C4y = 0.3 molfiter? ‘Table PS.21 Cay moliliter ray mol/liter min 1 on 02 03 03 os oF 06 os os 06 025 o7 0.10 o8 006 10 0s 13 0045 20 0042 521 the approach which probably fiat comes to rmind & te finda rate eqvahin fo repr the date, ft onder, second, ete iF to ge the tie; os —— pases AS edata. shows thak ne smple Bok a quik plot of A rate forn er ® will Al the data, s cy With a Wik more thought we coe that we stirs nah ated to fl rake equahin,wa were {ust aclead for t, and that th pole Yi olan by aot jemed dlemgy aqachin Sy dwacty by qraphca yrotecluyes, het vs clo anf ma * henna 25.23, (a) For the reaction of Problem 521, what size of mixed flow reactor is needed for 75% conversion of a feed stream of 1000 mol A/hr at Cay .2 molliter? (b) Repeat part (a) with the modification that the feed rate is doubled, thus 2000 mol A/hr at Cy) = 1.2 moliiter are to be treated. (©) Repeat part (a) with the modification that C,y = 2.4 moVliter; however, 1000 mol A/hr ate still to be treated down to Cy = 03 moliter.525. The aqueous decompesition of A is studied in an experimental mixed flow reactor. The results in Table P5.25 are obtained in steady-state runs. To obtain 75% conversion of reactant in a feed, Cay = 0.8 mollliter, what holding time is needed in a plug flow reactor? Table P5.25 Concentration of A, moVliter_ Holding Time, In Exit Stream sec 0.65 300 os 240 1.00 250 056 110 1.00 om 360 0.48 oan 24 048 028 200 048 0.20 560125 for a inal flow Teackor, with GO, we find the tate of teachin. From Eq ( This we talvlate ax follows on 2 doe oat 1000 ate 1500 Halding hime. for gli Plnes Fine v 4208} Gros rag mes by aig emvrning oo WSR wit the tat Whee oe ro Cont the ve of concenrahons gates no praens Lat us use this, Then he performance expression is Ey oF re- (“3 So lataate 4 nit oe tale above Nowa plot Bf Chee =Ty ques a fore bke diss | / is mdicaes that no simple rate exprestion,say 7 wh order, wil fF te doo, here abe grep This is done by patsy Gos Mem) ond mtegmtng ig fle rant Pot = 200 oe eg 5.27. HOLMES: You say he was last seen tending this vat . SIR BOSS: You mean “overflow stirred tank reactor,” Mr. Holmes. HOLMES: You must excuse my ignorance of your particular technical jargon, Sir Boss. SIR BOSS: That's all right: however, you must find him, Mr. Holmes.Imbibit was a queer chap; always staring into the reactor, taking deep breaths, and licking his lips, but he was our very best operator. Why, since he left, our conversion of googliox has dropped from 80% to 75%. HOLMES (tapping the side of the vat idly): By the way, what goes on in the vat? SIR BOSS: Just an elementary second-order reaction, between ethanol and googliox, if you know what I mean. Of course, we maintain a large excess of alcohol, about 100 to 1 and HOLMES (interrupting): Intriguing, we checked every possible lead in town and found not a single clue. SIR BOSS (wiping away the tears): We'll give the old chap a raise—about twopence per week—if only he'll come back DR. WATSON: Pardon me, but may Task a question? HOLMES: Why certainly, Watson, WATSON: What is the capacity of this vat, Sir Boss? SIR BOSS: A hundred Imperial gallons, and we always keep it filled to the brim. That is why we call it an overflow reactor. You see we are running at full capacity—profitable operation you know. HOLMES: Well, my dear Watson, we must admit that we're stumped, for without clues deductive powers are of no avail. WATSON: Ahi, but there is where you are wrong, Holmes. (Then, turning {o the manager): Imbibit was a largish fellow—say about 18 stone—was he not? SIR BOSS: Why yes, how did you know? HOLMES (with awe): Amazing, my dear Watson! WATSON (modestly): Why it’s quite elementary, Holmes. We have all the clues necessary to deduce what happened to the happy fellow. But first of all, would someone fetch me some dill? With Sherlock Holmes and Sir Boss impatiently waiting, Dr. Watson casually leaned against the vat, slowly and carefully filed his pipe, and— with the keen sense of the dramatic—it it. There cur story ends, (a) What momentous revelation was Dr. Watson planning to make, and how did he arrive at this conclusion? (b) Why did he never make it?Sty Since the vat codous ~14% ethane! | ques that Iwloibit fell—dead drune— mtv the vat Ther woud decrease the yolome aveitable fr flid. Lets see’ aie eoald account for the decteass is conversion of goegiion Cewordly, cmce ethanol 1S 4 Voy faige exces We can venconably assume peewse Firar order Evietes tot tecgect te Seager > Se Be tmed loo Eqt® gues, forbove Ha bY, = a Naf 7h we hove Wy =100 (HITE Imp gat Sethe decwaco'n wlvne ie AY = \oo-7E = 2E (up ga! Gs od (TENS) Gaver) = 42.8? Ua sn oon' ABS yolumas bith his every berg C2r0/A Wmbibts vole ts “hese obmes qgtee co Init auld wall beta he sat: } — This hypothesis, guese doce At the facts b thy did Watson never come up tith Has explanation? Eeause tweaking near He alhel tae Net really coal <—— Hole + Ween was: indt kainate on peklng. Yeo ose dal for prting m bine, net ckauol + Of costse euerjone kamvos shat { lag gah Wa velome BE ICH MSO, ara chat {aime waghe ot$28 The data in Table P5.28 have been obtained on the decomposition of gaseous reactant A in a constant volume batch reactor at 100°C. The Table P5.28 see Pay atm 1 90e Pay atm 0 1.00 140 025 20 080 200 oa 40 0.68 260 0.08 60 056 330 0.08 80 04s 420 0.02 100 037 ELOK’s Community. Problems 119 stoichiometry of the reaction is 2A -* R + S. What size plug flow reactor (in liters) operating at 100°C and 1 atm can treat 100 mol A/hr in a feed consisting of 20% inerts to obtain 95% converson of A? 5.29, Repeat the previous problem for a mixed flow reactor.B2Y Cegtension OF problem 5-28) Given a goe phase reackon ZA=R4+S M2 Liat ‘ Cpe t00 mone —— Senivone Avo works infeed 1. Bas =100(2) «125 0tYnr —— Flmabe gen fe sate Tyg2 Hehe Far med Flow we must Sus the cate at the ont eomdtione then tie enn procerd to Puecbing tha tenctor ye Sodhaw ar accuvahe fj oe t ease Gud find Hee stage Chevee vate) of fu~ Ootat t aats, 208, £0 sbw, raleslope = Goo = SES ty Te ate The performace expiahim Sr cimed flow, Eq \%, on precewse nite ie eM 2 feof. 08-04 tr” Catfvod abel. Rut Tall so evauate ov fiom per=nRT Thee wat &T _ (25 Ko0eret P ay “y = 21504 = 21S| Example 3-7. Determining C; = hy(X) for a Gas-Phase Reaction ‘A mixture of 285 SO, and 72% air is charged to a low reactor in which SO, is oxidized, 280,+0, ——+ 280, First, set up a stoichiometric tble using only the symbols (Le, @,, F;) and then ‘prepare a second stoichiometric table evaluating aumerically as many symbols as [Possible for the case when the fotal pressure is [485 kPa and the temperature is con- stant 227°C, Solution ‘Taking SO, as the basis of calculation, we divide the reaction through by the sto- ichiometrc coefficient of our chosen basi of calculation 30,440; — 50, ‘The inal stichiorsewic tuble is given as Table E3-7.1, Inilly, 72% of the total umber of moles is sir contaicing 21% 0, and 79% N,. Fro = (028) Froh 0.72021) Fx) 072.021) _ 4.54 028 = Fe _ (072)(079) _ OnE, 028 72° ‘To write concentration in terms of conversion, we must express the volumetric Low rate as a fuuction of conversion. FLY 80, mV; 40 ‘Therefore,Liquid Phase Gas Phase xosenpemsteMentrnes venaoa( YE) Cu(0 2x Figure 3.3. Expressing concentation as a function of conversion,Fy _ Fag X) a= 7 Recalling Equation (3-44), we have =wuren (2) a Neglecting pressure drop in the reacion, P= Py, yields tent voit ven E Tf the reaction is also carried out isothermaily, T= T,, we obtain v= ettex) = Full=X) uy ex) "s © =x Trex, ‘The concentration ofA initially is equal to the mole fraction ofA intially multiplied by the total concentration. The total concentration can te calculated from an equa tion of state such as the ideal gas law: 00 Gia ene SE) = 01 movi? “The total concentration is= = = natn totiny Ons 7 ce em Se ‘ig ca sagan anrane 8 Calin gris Cone Burret nr toro sp 0, ae 0, a0, ‘Ra ASO Tecoma boas tna 0H SOT pat, (a Eaten serie o 04 0) GiSinte itsim omesone NO, at ete | Setvemiceemerermeretmme — i cin oot mag cet oe ace | ‘SSUES etme Ae ' esd ‘ Re eo eT a Pee ean chet cca ou eal et was a oan Can aE” Ta en pel TRS feel 1= 3 nl wens in 42) 4 sate 1 ES ‘eo UN ne ep oeion nd he (Bie ston CYR ome Seamer =e pense) +405 ‘he FOLYMATH pop nd ta ies 2 a KS ‘Recut omen coms a oteuae 3) Me em ef ot Fie ats coir merry ion Sd Bap No, 280, | Senet eee remit eaiemsie Mae Bon wr Son ea ar ~xeufel all ess, eee ao i hn ok m9 Cong Enos ES) a 8.63 win yi 1asian) 00) a ol Sa) sate 05 — ene ie, ie i Egon 2-19) 8 Epon 010 an aie Sociee caneufeafa} as | | |‘Sj ce G01) we deen Cy dC, . cabs FAM as eycrma eA eosein AO as HytT=aeg "MES 8 ce Be SFA aioe oP araiviaas SOI d tee IE seme eee cnaasicoon ER | ein RES n= ate IS“ MASTS FLS— BY DIO) Meld mow me oD Fe = Fa Fofa™ Fel 786-058) fa onto et Dk a te wi oe
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