ASBHH Assume a rate-limiting step; start with surface reastion, ASHSTB SHH S BS +5 HOSTH+S juniting step; start with surface teaction Cas Come up with ways to find Pay Pas An Pg Ces = Kay PCy Find the expression for C, C=C, + Cast Cars tC Combine all of those to get the following rate law suggestion. EES HPs KP + Key + KyPy) (KB KP + KP, Checking to see if it fits, we see that for high P,, increases in P, cause decreases in the rate. We see thar if P, or Py increase the rate will go down, which is consistent with the rate law. P10-11 (b) Now using POLYMATH’s non-linear equation regression we can find the values for the parameters. We find that In the problem it is given that K, is 1 or 2 orders of magnitude greater than K, and K, which is true so this is a good answe: 10-304.000 o aeqr ersten ramod ane 20 + eale-iaes ee zaco Ly neo | | =e ie o.800 | Wf 1 | { coco 1 Lt cia iain i ee mien sata hogel: 6 aaexPar€) -KamPankomPD-KHHEM~2 x = 0.00137022 xe = 0.289982 ka © 4.76094 xn = 0.42359 P positive residuals, 3 negative residuals. Sum of squares = $.27033e-15 P10-11 (c) The estimates of the rate law parameters were given to simplify the search techniques to make sure that it converged on a false minimum, In real life, one should make a number of guesses of the rate lw parameters and they should include a large range of possibilities P10-12 (a) Assume that the second reaction is the rate-limiting step. R= k2Csn, 5 Using PSSH, we know that =k C, ity s Sik 1031Perform a site balance: c v + Csi, s “TER C Sin Combining all of these we find: KiCsizCy KC, TF KCgy1, LP KCgi, This rate law is consistent with the data. As the concentration gets larger, the rate change gets smaller which is consistent with the rate law as given. P10-12 (b) No answer is right or wrong, but the points will probably be higher than the ones given to see that the change in rate becomes even smailer. P10-13 KR; Assume the rate law is of the form 1p, =—— #2 — 1+ KB ipo Athigh temperatures KL as T T and therefore KRijpg <1 At low temperature and low pressure 2 Tow = Fino 10:32Run2 2915 9.375 (02) These fit the low pressure data At high pressure KP},p. >1 iro K This fits the high pressure data ee k Tbe = KP? At Pyripo = 1.5, 1 = 0.095 and at Pyro = 2, r= 0.1 Now find the activation energy Atlow pressure and high temperature k= 11.2 At low pressure and low temperature k = 0.4 (22) Inf —= 04 (ee 1 Sy Sus = ll KB) PLP : Fett Ke . P= KePim Pr = KsPrKy O° TSP Rr 10-33Fro, = EsSias I fy Sus > HA1+ KP) Py Per 2, ae + P= Ke Pim Pr 1+ (Bhp / Pu) Po Low Pr: Rxn is second order Since = 1 >> K Phyp/Ppy High Pr: 1< ol 010308693, Precision R2 0.7852809 R'2adj = 0.787565 med 0.0372861 Variance = 0.022441 a=0.184 B=-0.031 k=1.148 Q) POLYMATH Result 10-34Model: rT = k*PMi(1+KMAPM) Variable Ini guess _Value 95% confidence ® r iz.256278 ~ 21574162 aM 2 9.0251862 18060287 Precision R2 19800096 R2adj = 09780108 Rmsd 000113769 Variance = 0.0018638 12.26 Ky =9.025 GB) OLYMATH Results Nonlinear regression (L-M) Model: FT = k*PMYPH2/((1+KM"PM)*2) Variable Ini quese _value _ rR r ¥-4090333 x 2 2iasosoaa 4.257098, Precision Rt2 = -4.9698952 R-2adj = -4.9002187 med o.1863588 Variance = 0.5001061 k=8409 Ky =2.83 (@ POLYMATH Results Nonlinear regression (L-M) Mod PMIPHO/(1+KMPM+KH2"PH2) Variable Ini guess __Value 958 confidence ® T Toi.99975 ~-dvetaios x 2 3.608202 7.161591 ri 2 67.213622 5.934327 Nonlinear regression settings Max # iterations = 300 Procisinn R2 -32021716 R°2adj = -4.1959875 Rnsd 0.1649487 Variance = 0,4353204 k 02 Kw 3.6 Kip = 67.21 P10-15 (b) 10.35We can see from the precision results from the Polymath regressions that rate law (2) best describes the data. P10-16 Using Polymath non-linear regression few can find the parameters for all models: See Polymath program P10-16.pol. @ POLYMATH Res Nonlinear regres Model: = k*KNO*PNO*PH2/(1sKNO*PNOsKH2"PH2) Variable Ini guess _Value __ 95% confidence k i 9;0030565 3. 7028-05, ENO 1 37.237684 110353031 ru 1 101.9967 212670513 Precision Re 09709596, R2adj = 0.964506 Rnea 5.2556-07 Variance = 4.436612 k=0.0031 Kyo = 57.23 Q) POLYMATH Results Nonlinear regression (L-M) Model: ¢= k°KNO"PNO*KH2/(14KNO*PNO1KH2"PH2) Variable Ini_ guess 95% confidence R ot 1257 NO 16 49334604 mu z 2la7en-o5 Nonlinear regression settings Max # Hterations = 300 Precision R2 6842898 Retedj — — 12,058576 Resd O1E-05 variance = 1.632E-09 k= -0.00000471 Kyo =-1084 Ky = 0.00001046 @) ‘Nonlinear regression (L-M) 10-36Model: r= k*KNO*PNO"KH2*PH2I((1+KNO"PNO+KH2"PH2)2) Variable Ini guess _Value 958 con 2 i on Syisae-0d ~ 2-242 NO 10 13.187119 7.659298 KH2 1 1g.4e7727—7.7652667 ‘Nonlinear regression sottings Max # iterations = 300 Procision RD = 09809761 Re2adj = 0.9767486 Rnd 4.262E-07 Variance = 2.906E-12 k=0,000519 Kyo=13.19 Ky = 18.49 ‘The third rate law best describes the data. P10-17 (a) Mole balance: a Cae Evaluate the parameters: ene POLYMATH, Equatior A(x) /d(w) =a" (ra) /£a0 (a) /2(w)=-kavavea/us kas faoea000000 10-37us=250000 fe) Noving-sed Reactor ke90 eae caos.8 ~s eps. 8 =< caseaot (1-2) /(Leeps"x) was-krea Mos % Me = soa00 P10-17 (b) ‘Mole balance: x 1 A(oa) /e(e)2ea4/eau-{ ((Leyat) /(24ea/eto}} sEautark) teafeme 0.8 Acad) /6(¢)=ca3 /eau-(((Leye3}/ (Lreat/eto)} stautark) tead/t 0.8 Aca) /alt)=ca0/tan- ( (21780) /(Aveal/oto}) ytautatk) teai/e 0.8 lead) /dtt) seal /tau~(( (Level) / (24ea2/et0) )+tautatk) tea2/t 0.8 ead} /A¢t)2ea2/eau~ ({{2eya2) / (teas aro) Joraurara)*ea3/e 0.8, kao 10-38eaus0 004 eto=1 eas caos0.8 yasscag/cto yaiscai/eto ya2eea2/ero ya3=ca3/eto x= (ca0-ca) /c20 yaoscao/cto to = 0. tee os P10-17 (c) ‘The only change from part (2) is the decay law: 4024000000 kas us=250000 ae veax=50000 es apee.8 cascact {1-)/ (teps*) ras-ktea arexp (hel*oa/U5* (wows) ) vy = 0, Me = so0a0 P10-17 (d) 1039To find the Time-Temperature Trajectory we need to use the following equation for first-order decay ae Kay {ex £4(4-34) Ft RT 300, Siiee no initial temperanae was given, we assumed one of 300K. ‘This isthe graph of that equation 1000 800 600 400 200 Temperat ure. (kK) P10-17 (e) ‘The two energy of activations ate switched and this is the new graph made. Temperature-Time Trajectory jg 1000 panne = <300 5 S500 E gio E "200 0 Oe ape 9.08 ‘The graph looks the same just the time is much smaller. P10-18 (a) 10-40For all of the parts, the mole balances and rate laws are the same. They are: ant ty =kaC, Find the equation needed for a. 4 ac, at a=exp(-k,C,t) ‘a=1 when t=0 Assuming values for Vo, k, and ky come up with the following graphs according to the cases described. squations ated) fate tea) fatei=rarvo oat cx20 ket ranktaten MeO Mpa so fa) case tro es? | 10-41P10-18 (b) Find the new equation for a: Cy ae LEK, Cyt Using same values come up with these graphs: Bava (eb) /a(w) e200 dea) /2(u) s2arvo vorlo ka 001 e200, ket ay (askarcatel(bi Case III @ ts19 100 xe Ca oem ~ &b | wo . + OX = iv P10-18 (c) Find the new equation for a: da ~ ay hele a=exp(-k,C,t) ‘The following graphs are made: equazions: (ce) /a(w) #carvo aleb) aw) arb-vo vo=10 ka=.001 000 (el case 1 @ ex1000 ket = - Po =| ; sbokrarca Bae | heaven oa ee | 10-43hoc P10-18 (d) Making a into a differential equation we come up with this: 10-44Equations: saitial value dten)ratutaeove ° tay ature kavaveasus t we a= 001 (a) case T FS me ] eo \ + a) case tr KEX a ta ans S = (a) case rrr P10-18 (e) 10-45Everything from part (d) is the same except for the decay law. sletat ya atep) sage) aeptz0 ° vort0 kana : ke.002 we wnaxel0 Te asexp(kttca/d5" (wimax) ) . asvkatea wt 10-46P10-19(a) dW =U,dt Activity is zero for W > 2.5 kg, so the catalyst weight only goes to the effective weight.= ku 1-xX % X=02 x =H P10-19(b) P10-19(¢) For infinite catalyst loading a = 1. AX _KC yg (1X) P10-19(d) X__ ky kW? I-X % Beo[s- 1-04 v, 1548 : P10-19(c) kW Us kW 10-48U, =kyW =0.2*5 P10-19(f) a= 0 means there is no reaction is taking place. Activity can never be less than 0. P10-19(g) U= when W=W,, a=W yc s SMe Us kW, kW, FoWe 4) ko, Us Us Now find We. KW, EW, O22 41 ot a We we Ww * -oa{(s-25)(1-22 5) 38 625] 05 2 = 1875 X =0.65 P10-19(h) $=160F,.X -10U, 10-490. cm dU, P10-19(i) No solution will be given P10-20 (a) Start with the mole balance for a batch reactor ax _-5W Rate taw Baka Decay lave da at Stoichiomeny: zB Poll» X) Plugging those into POLYMATH gets ‘graph following pr ram and the follow! 10-50Equation: raitial Ae) /d(e)=-rerwince ° ata) /Ae) da“? 1 wes ke=20 kasi 6 & prost vel e082 ptspto* (1-x) erecketpeta ntosptory/ (RT) =o, Se "2 = 0.001 P10-20 (b) For the moving-bed reactor the mole balance now becomes a aW Fy ‘The decay law now becomes: ae a kee aw U; Everything stays the same. Plug into POLYMATH. ‘The conversion achieved is X = 0.266 Equations atic fate) =-2e/f20 lai £8) = Rdta2/U8 eeeza £02600 eae 6 wane se2 ea 2 st duns 3S Bee y Rome sen ree kerpera a a feo M2 Mee 50 ae i Be P10-20 (c) ©) Increasing U, will get us a higher conversion. Looking at this summary table, U,= 10 kg/h and X 50.6 10-51x a.ss96a oo 0. $9968 f20 600 600 600 ra 16 16 Ls os 10 10 ro ke 20 20 20 pee 3 2 a z pe 2 2 9.800525 0, 90625, ae wo sherry 40 1.77917 P10-20 (d) For second-order decay: 7 off 2E, +E, (1 dex 5 kn @-24E,/E,) Ku Ea/Ey For E, = 25 kcal/inol and E, = 10 kcal/mol ~ (610/251) \T 735 Use this equation in Excel to generate the following graph: nfl of al “Temperature -Time Trajectory Eat0aed 5x5 a © For E, = 10 kcal/mol and &, = 25 kcal/mol: exp 25 10 (1. 0.001987 T 1.6(25/10~1) Pdf aiso(t-af Use this equation in Excel to generate the above graph. t= P10-20 (e) 10-52In part e, the only thing that changes from (b) is the decay law and the decay constant: 2 Plugging into POLYMATH we get the following summary tables for U, = 2 and 10 kg/h. X= 0.50 and 0.88 respectively. X will again increase as U; increases. Bquations: value lx) /€oe)=-ra/E20 ta) fal) =-karper2a°2/08 1 kas? se? Leo ° Ps a so faces : finan 9 orsoze3s = ‘ C Saewas tts peepter(1-x) 2 2 : 2 —— wea fea ee foo “ore - : a > 10.256 able woxinun value 0.818709 478708 2 ess3s22 9 $5322 a2 ea o.2 » » rs 600 00 00 20 2 2 2 2 2 2 2 0.240501 0.240582 « ass 0 -2.7509 P10-21 (a) AB __ Elementary reaction with 1“ order decay. co ‘kya a a=exp(-k,t) P10-21 (b) 10-531.0 t ‘The activity is never zero for first order decay. When a= exp(-k,f) there is no t such that a= 0. P10-21 (c) Mole balancé Decay: a=exp(-kpt) Stoichiometry: C,=Cw(I-X) Combi Fm exp(-fot)(1-X) wy) =< [1-exp(-kt)] ie ten (HEN ~exp(-tu)]] P10-21 (d) 10-54P10-21 (e) Decay rate increases more rapidly with temperature than does the speci conversion decreases with increasing temperature. reaction rate. Therefore, P10-21 (f) uel ae X =1-exp(-0.57[1-exp(-5.3)]) =0.43 P10-22 (a) In order to get a high conversion the entering pressure should be as high as possible since the rate is a second order function of the pressure. U should be kept low since the conversion is an indirect function of the flow rate. P10-22 (b) ‘The problem with such a low flow rate is that the activity will remain low P10-22 (c) We can use the same equations that are given in example 10-7 with a few exceptions. For example the rate law, we use the one given in the problem: -g=kPE The activity will be different b wuse the equation given is different: DC coke a = KpaCcoks a 0 To find the concentration of coke we use stoichiometry: We find that the value that gives the best conversion (X = 0.337) and uses the ‘whole reactor is U = 7. See the following POLYMATH program. 10-55squacior aia /402 aver/ae yo/ea9 a aon 22 waxinom valun wniann value Zeta value rhonde oo Poa am SS imam cecoke=peoke/R/t asis34e-07 -0.0072 aise tot tenis P10-22 (d) ‘To find this the only change necessary was the values for the k's because they change with temperamure. Ex/ to kg =5x10° Fa ( | amon elit on T Epf_t _1)] kp =100 [Eo( +) 2-10 Rar TT The POLYMATH program below shows the results, The temperature is 485K and the conversion is 0.637. 10-56Equation: inicial value (x0 /a(2) =-ra/u/eao a Ala) (A(z) =-katarecoke/T 2 caoe.22 0H2.5 pao=i2 rho=80 ka=100"exp(15000/1.987"(1/673-1/7) ) kprine=Se~5vexp(3000/1.987"(1/573-1/7)) Uso" (.repstx) paspac* (1-x) / (1+eps"x} peokerpaotx/ (1+eps"™) cookespeoke/R/ saprime-a* (-kprimepa"2) factho*raprine 72% teas variable audziad value pain vais Maia val : a oes 2 sia : F : ccosssso.eoses? oe : 28 2s 2s a i i : : 7 fut ¢.082 9 oa 082 : a os ss aes = 2 2 2 ¢ a a “ fe & fas basse an] Laase worine «2 gassdened 2 0955s0-05 T.a98Hae-o5 2 09s8t0-08 2 bs ap 2s pacer = 2 2 hese eset: fee ° coms a Cores coke ° oor ¢ eprine 0, 00001753 “a stoaieros o.abnei7e2 a P10-22 (e) 10-57‘To find the temperature-time trajectory, use equation (10-119) and add C. where necessary: T 4) R Kao(l 8 + Ea/E4 Cooke ser E82 sea Ba( ‘The following curve is generated from that equation. ole 0000s pgs, 00150 | P10-23 (a) —> Design equation; =r Eat Assume W = . on ~» — Propene + Benzene ® s Fag (LX) Frank Ak ‘The amount of cumnene hydroperoxide does not contibnte significantly co the total number of moles, 7 Fak Fag l-X) + FaoX + FaoX 1058X]_0sT ores (-DRELI) /Urepa-tacrepa) fa035 42 ee oo ee — a : ae by ‘ke 33 exp (Be (1/450-2/T)) a ae : Mon % Mee 50 P10-26 (b) Using the same program we can see that the maximum conversion is 0.887 P10-26 (c) Everything is the same except the energy balance: T= T)+ ha, (7, ~1 FaoCpa We also need an energy balance on the catalyst particles. Choose values of h and a). We find that T, needs to be slightly higher than T in order to get a latge conversion. ‘The maximum conversion will be different for each T, thar Is used. CDP10-A 10-65Given: ‘The eatalyi oxidation of edanot (CH CH; OH + 4.0; CH; CHO + H,0 Denote: A {=} CHs CH OH , B[=]CHs CHO , W[=]H,0 . AS “Mechanism is belived to be the following: 5} CHs CH O-S A +28 2 AS+HS ta=kalPa Ch~Cas Cus/Kal O +28 & 25° -to= ko[Po, C&- Chg/Ko] AS +05’ 2 B+OHS'+S t80= kno [Cas Cos’ Ps Cons C0] OHS +HS @ W+S+S" -tw= kw [Cons Cres - Pw Cs Cs/Kwv] Itis given also that Cys = Cass ‘With reaction (-r49) controlling: Cas Cs = Ka Pa C3 or Cas = KA Pa Cs B20 Che=KoPo.Ch of Cog =VROF Ge FEs0 Cons Cas © with Ces = YRAPA Cs kw Pw Cs: Cons: Kw VKaPa Cras + Cus + Cas =Cs[t + 2YRAPal a + ROP. RB] Cp = Cy + Cos: * Cons: Pa Cons Cs] Px Ro Po. Cs Cs: f = tag = kao {Cas Cost =F} = kao YR —PaPy * Ka Kw Kao ¥Rol Kay = Ka Kw Kao VRS Px Pw] Kea | kao 1a Ro Cr Cr [Pat Po YPx(1 + 2YRXPALI + TRAP + ep Initially Pa = Pw =0 ko 1a PARG Po: Cr Cr (1 + 2VKxPa{1 + 21Ro Po, “.0= 10-66 a(b) With reaction 3 imreversible, -t49 = kao Ca.s Cos”. Since A-S, H-S, OH-S' are created (and destroyed) only at the reaction surface. A stoichiomemic relationship exists berween them: Cus = Cas + Cons @ ‘The same equilibrium expressions for reactions (1), (2) and (4) exist as before: Cas Cus Ka Pa CE b) Pts Cy Cons Ces = © Pw Cs Cs PwCs Cy + (Cres - Cas) Crs = Be Chs = Rah + Kw RES oF Cag = KyPa Che ge Kw Cag KaPah 3 4 NSC ‘V KaPach Expressions for Cr and Cy become Cre Cs + Cis + Cas 12 yy SuCs with K,PC3 >> Cr=Cs[1 + 2YKXPa] 1+ (KB, + | TEE ic Ge 10-67Rate expression become += kx0 Cars Cog: = Kao Ko YPo, Cy YRAPA es lessee | | << 1RoFo, | | KegKoy PoP, CiCh lt ue Ce 1. 2VRSFE) a aeRO waa cree Cg Hg + Ha iy ey On Quanticative data suggests reaction rate is of the form Ay Pe TURSBS Cay Where At Az, As are constants The fact that (re) is independent of Hz suggests that the reaction i irreversible, and that Hy is not adsorbed on the catalyst surface. Also, the above expression for (-rg) suggests that both E and St are adsorbed on the surface <. Try the following reaction scheme. EvSoEes “ta=kalPeCs -CosiK, EoS eoSieS+H, al a] Cea ts=ks(Cas Coos PayKe] 1p = ko [Cses -PsCo/Kp] 10-74To insure that Pi, does not appear in the rote expression assume thatthe surface reaction controls: Kp Then: Crs Ces + Cos s[t+ Ka Pe + Bi] Coes Pi Ps: Pi, | And 5 = ks [Ces - ca Cs([Pe- $ ss 5K | K of EO RAK Kp «where Keq=K,Ks Kp 1 Kare Bt with Ks >>> 1, reaction can be considered irreversible, and its dependence on Paz drops. Pe Ts KaPe+ ee + Where k=ks Cr Evaluation for k, Ka and Kp Rearranging the rat ion: PE ing the rate expression: Pex =. Point | Peon) | Crp) emovimin-gmen | Pets | m= 1.00. a3 210° 7067 | 2 0.01 0.214 x 103 46.73 Pe\ 2 Ls Lepe ana (PE =. 11 (pp (3), ky beh na Fe, eKy eee promabove: al fh $613 7067 . 556 EMBER e"ekoPen 60 mole ol = 1.50 x 103. = 10-75and —L~=[Fe| 1p, = 666.7 = 49 SRSA cin PH Lite, =7067-5657 = Kas 166haee! ow. ing apn a3, nic canst hale oR Laan ee Kp can be determined: For poin: 1: (Bape bear (Psth_ wks beeen + Ph EK, TEE ROKR Soisaceng. and solving for gt ing tat Pe =P 1o[——-J ~ 5| we 2 lags<103 14155005) gaex-min Eoeky” Pak Pah 10-50 eal 925 Fs ( Pe + 1327 Ps 1 16.64 Pa += gm cat mia G) (OW) = 106.1 S85. (MW = 18 SEE. (Mie. = 1081 Then 9, = Lemele 20 Lo 5 gmoie E yeo=-—L.. =0.833 ; P=P,=0415 ; Xp=0.60 1; T=903°K 1+ 8 © =ye95 = 0833 Pe = cert = Fel FgRT Pap = Ca . 10-76‘Rate expression for any X is: ons (ues?) . YeoPa 1+ 1664 [2ST , wk Design expression for a CSTR (fluidized bed) is W = ~=2 T+exX ae FouXe [1 +exe 4 16.64 4 327 Xel 0.025 Xe [veo Po (I-Xr) Xe 19.2103 gmoi 1 dav |_ 1 +-0.833 (0.45) cay 232.7 (0.45)] I day = 16.64 + 12270-4511 , Lay _ 54S 1" 360 asia W = 7.06x104 g ‘ost = 7 x SLLes77 Cost = 70.6 kg x SLL-= S17 (©) Plug flow reacwor. expression for Yeo, Fey Pe, Ps, and -re are the same as fort CSTR, The design equation is: [tex = 1327K 16.64 + 132; Veo Po (1-X) “ 1 1 Ly (aX [Loe] nL L-X)) + 16.68% # 132.7 (X- scvxall” = {hat “ Xp) + +132. + In(1- w aatxs chao (Ie) In{L-Xe]) + 16.64Xp + 152.7 [Xe In(-Xel wa 92410 gmoi cay + 16.64(0.45) 152.7045 +101 0.45) x 54a ggee cus = ar x Elbe 52 tx Bibs sass CDP10-G Given: reduction of CO with hydrogen over Ni catalyst: CO +3 Hy ~> CHe + 20 10-770.0183 Px: Peo | Kinede given by: T=“ SB (erete ce eran From the above expression: 1) The appearance of Pi in the denominator suggest that Hl is adsorbed on the surface, 2) The fact that CO does not appear in the denominacor suggests that it reacts as 2 ges phase species. 3) The square root dependence in the numerator suggests that Hf splits. Therefore, suggested mechanism is: ky Hho + Sa Hrs kj; [Pig Cs - Crys/Kil ie ao ‘HyS + So 4 2HS [Gnas Chas 1X) 3 HS + CO. CHOS “15 = ks [Css Peo - Crros/K3] ke CHOS + HS 1, CS+H,0+5 t4 = ka [Conos Crs - Cos Pro Cs/Ka) Cee coe 15 = ks (Cos Pha Pos, CK] Pou. Piso Cs KGKsPi. Cus Ka Ks VRP Kr PR Pow. Pu Cs __] Hs Peo Cs PCO CS Ka Ks¥Ki Ba PR CraCs+ Cus + Cos + Conos Cr=Cs|1 + Ki Pa, + YR Ra Pg + 10-78Kinetic expression becomes wy FRAT Cet Pn-g EaenD n=— if, + Ky PIR + YRY RG Ph + Reaction is irreversible ~. let Ks —> o° Thea ks YKy Ri Cr Ph, Poo ks YR Ky Cr Pf Poo PCL + Ki Pa, + YK Ra Pig) 1 +X Pr, + YR1R2 PI with Ky Py, >> YRi Ko Pik, we get 5 ERS EE SEE Eco. “This expression implies that at moderate pressures, most of the Pi active sites are occupied by the Hy molecules. (a) Design for a plug flow reactor. Denote A{=] CO, B[=] Ha; then yao =0.25, yao = 75, Op = EBO u YB 75, Oy = ERO = YB. 0.75, Op = Fe = 20. = 3, Xp = 0.80 bal4-2-1 2 e=yagd= 0.75 = = tb, ibmoie . 25 Ibmol Fag Xe= Fen, = 2000 1» lama «25 ba 2125 Ibmal «156.25 lama Fao Og day 985 "ay Design equation Fag dX =-1, dW or 0.0183 PA PE 10-79— +15 yao PALER ax Fa” on183 5 iexd TS yh | fu sto2sncP 5 75/1-0.2sxprl A cramtcan| SEP ost eer a Tre incegral can be solved using Simpson's nile xy 3" | too | w_| wooo T0001 4.730[ 1 | 4.750] 1090] 3.430] [367 “123s fea30 T2112. 860 Tse es0d [438357 2000 75.5001] 15.300 [ AXX = O2 £4 750 + 21.679 + 12.860 + 34.257 + 15.500] = 5.936 day aan Sm eat" min, 156.25 tbmol . 454 gmol 1 day tbe (24x60 min () Design of aCSTR CDP10-H 10-80Runs 1.2.4 Runs 4.5, at-P, (b) Numerator: Pa and Ps Denominator: Pa and Pe Power of Denominator: 1 (©) Proposed Rate Law: (d) To find the rate law parameters, rearrange the rate law so that i can be plotied as a line with the rate law parameters as the slope and intercept of the line. 10-81Parameter Evaluation with Parameter Evaluation with 1.6025, y-~ intercept = ESF. Using the four equations above to solve for k, Ka, and Ke, we get: S13S2amm". Ky =4 1665 am” (e) A and C are adsorbed on the surface of the catalyst. (© Proposed Mechanism: AASeAsS A+S+B=B+C-S C+Saces The irreversible reaction step was assumed to be the limiting step. We check this mechanism and rate limiting step by rearranging and combining the rate laws for each step. If the mechanism is correct, we will obtain the rate law proposed in part c. 10-82“te = Cou | ik, is much smaller than ka and ke, therefore, Cus =KyP.Cy and Cos Also, Cy =Cy + Oxy +Cog After substitution, C, = ce “ T¥K,P, +KP Next, substitute the above equations into the reactions step to get KP.Pa AP, FKP Because this is the same as the rate law in part c, the rate law and limiting step assumptions have been verified. (g) Ratio of sites of A to sites of B at 80% conversion: CDP10-1 10-83a) To determine the mechanism and rate-limiting step we must come up with the rate law. Looking at the rate dependence of A we see that between runs 1 and 2, Pa increases from 1 to 1000 atm while the rate law oaly increases from 1 to 115. This telis us that as A gets larger it changes the rate law a good deal less. This tells us that A is both in the numerator and the denominator ’ Py ™ “1+K,P,, Looking at the rate dependence of B we see that between nuns 1 and 3, Ps increases from 1 t0-4.5. This tells us that the rate law is directly related to B. Kae Looking at the rate dependence of C we see that between runs 7 and 9 Pe increases from 0 to-4 atm and the rate increases from 4.5 to 4.8, Also in these runs we sce that P, increases from | to 4 atm. So one of two things is true either Pe is both in the numerator and denominator or just in the denominator. Since C is a product it will not be in the numerator in an irreversible reaction, Pee Vek ePe So the rate law becomes 414K Py t KP ‘With that rate law the following mechanism exists: Adsorption AHSOAS Surface reaction A S#BE)9C-S Dissociation CS9C+S “The surface reaction is the rate limiting step. 10-84b) In evaluating the parameters we can also see if our rate law is a good one. Plugging into POLYMATH we can come up with the parameters, eet 1) ES HI | | | ‘We find that the rate law is a good one. ¢) The best places to add points would be where Pc is changed, but P, and Pp are not changed. 4) No solution will be given. CDP10-J 2. C) Hs OH ~> C2 Hs O C2 Hs + HO “ ®) ow) A+s ZAS 11 = kPa C5 -CasiKi) AS+ AST ES+ WS 12 = ki [Chs- Ces Cws/Ka) ES ¢ E+s y= ky [Ces “Pe CK] eee 14 = ke[Cwes - Pw CK) Atsteady sater=-2E8 <> rary = rp = dey =2tu {sutice reaction is controlling, 10-85where k= 2k; CE K} Keg = Ki Kz Ky Ky Using points 9 and 13,Pe=0 . Pw=0 Alot fF vs pL paducra sig ine wih sloe [Land interop slope = fF = 4.945 2 k=0.0409 + KS 731 Using point 10, P = 0 2 Ky= 0.0399 Check Using point 1, Pe =0 => Ks = 0.0368, close enough Using pointe 6, Pw =O => K; = 0.659 anally, using point 12 => Key = 0.0975 Pa + LSUT Pe + 25.05 Pub? Note: Kugimay aso be calculated using RTIn Kg = AG". Inmxested readers are ouraged to check the goodness of fit of this rate law with the data 10-86CDP10-K CDP10-L Rate law: KCooCacCwrort (1#KxcCac) Proposed Mechanism: Pd+Co* tac 4-CO Pd-CO+NaOH* Pd -CO- NaOH AC + Pd ~» AC- Pd AC-Pd +Pd-CO- NaOH --~->C;HsCOOH + NaCl +2Pd Neither of the first two reactions can be limiting because they are reversible. The rate step must be irreversible because there is no subtraction function in the numerator. We will first try the third equation as the rate-limiting step: Th KC Pye Then CG, + Cosco + Copacomnsons + Creeae Find equations for Cyacor Cocoon Ad Cyysne Taco = Kaco Cea co = CxCooKco FACO.NaOW - Cpaconaon = KooKysouCyCrsonCco ky NaOH fac. ene Cease Combine to find C, C. 7 _——— _ 14 CcoKeo + KeoKxsoxCcoC aot ‘This is definitely not what is supposed to be on the bottom of the rate law so reaction 3 can not be rate-limiting. Trying reaction 4: 1, = K,CrueacCraconnon Ceage Cannot be found so therefore this rate law is also not rate-limiting so none of the mechanisms reactions agree with the rate law. 10-87CDP10-M a) Start with a mole balance: aw, We then come up with the equation for the profit: P=160*(F,)~10* (U5) Where Fy Fg *X “Then plug into POLYMATH and get the following program. The feed rate of solids that gives a maximum profit is 4 kg/min a(x) /€ (4) =-ra/fa0 £0 ae soetaors . : s160*#-10"06 : : . ve MoO ped tao 2 2 b) As seen above: X= 0.75 and a=5 10-88¢) The only equation that changes is the rate law: da da _ kaw aw” u Integrating we get this: Bguacions: ix) (2) = za/fa0 0 eres #208) ka? vase wmaxel Sool (xe) ehen (20%) else!) anit (kd/Us* (smax-w) <1 p=i50rs>-10*UE on (1-k#/US* (wax) e2s0(0) Yon Mee We find U 8 to maximize the profit. X = | and O exiting the reactor. CDP10-N 10-89 —@ Design Equation For n™ order kinetics. Assume att=0, a(0)=! and X «2 3 FO)=FuoX=Fyy =105 > Now Ta(t)=FaaX)=RON() x= 106 RON(0) Second order kinetics and second order decay rate fit the data very well. kC4 a Caa-Ca = ltkgt= 190200300, 400500 + dn) Fromthe graph: intercept=1/k = 0.0835 =k =11.98 slope=ky/k=0003 => ky =0.00025 () Activation Energies both for rate constant and decay constant can be estimated from the temperature-time trajectory CDP10-0 10-90Given AR+S Baich constant volume reactor, P increases with time Nao dX = ar, Wde Assume a=eat tn (1-X) Les) Assuine that dere is very litle deactivation inthe frst 10 see n(x) = Bas = Pt (For small‘) BaLin( Lela tn ohas)=3.7 x 10° see B 3.77 x 108 (Jer 1x 008205 (2734420) k = 6.63 x 105 sec! 10-91At trefatively large, = B Ea aw(ixy ae Pg 38710" 1) * int a) Gaal cn (-X) = 0.728 (1-05-1807, 1B x 103 sect [rT x x a 0 3 TOL 0.037 0.0356 2 0.07 0.069 30 0.102 0.097 30, 0.130, 0.137 (600180. O17} 800333 O21 TOO 9 0.255 [150 0.330 0325 0.379 0375} Oadt 0.857 0.493 T0490 0 Ostz—|0310_] COST 031s} tion Of a first onder reaction kinetics and 2 first order decay Kinetics is justified CDP10-P n= pentane cyclopeniane < coke Batch mole balance : -rW =k,CW LW ov a°C] = ka, with C, constant 10-927 a 7 LE | Sorte il a = 00x om oa From the above graph, all ines are saight lines. Therefore, q = 2 is a good assumption. ‘We need to cxamiine the dara to see which value of n having *¥ = constant n= anda =2 a will have similar behavior of because: LXed.y xX f 4 bal and At = 20 min 30081; _.; 0.0797 = 0.094; 0.087 ; 0.087 ; 0.084; Therefore, *% is decreasing gadualy. Its nota constant 10.93Lar i07 | 1.35103 n=2: Slope is negative. It is unreasonable n=O: Sb vs. ¢ isa straight line. ‘The reaction is zero-order: -r4 = kaa 10-94i He BoE | @ (ex) duax Oavdx om wm Ee t Cao = 0.03 kok = W =0.01 kg/m? t ml 2208 asin 135x103 kmovinin (mF (bo) The order of decay is q=2 fi=4 109 = Kj3% 109 mint (©) Moving bed reactor: Fag =2kmnol ; x a=) ew Sultans ina equation (1). ~~ Ka? = Baw 10-95eet) my ooxse yf i =a W455 ke @ cDP10-Q 10-96a) Mole balance: aie aw Fg Rate law: Kak ‘Decay law: ole aw su, Stoichiometry: C,=Gall-X) Cy = Cyo(O, +X) Evaluate the parameters: (e) (at) ea" (za) /fa0 aia) /A(w)=-karcb/U a8 2350 aon. shetas.t eaneaot{2-x) ebecaot (chetasn) ras-keteateb % Menon 10-97'b) The only change isin the stoichiometry: Cy = Cus(Oy# XI a POLYMATH eareaot (1x) *(oalptw*S eonsaot (ehetaen) *(1-alptw) 0. rar-keeateb CDP10-R Cumene —> Propylene + Benzene a) (6) ) (a) We find a relationship becween a and Ca, aX Fao Wows Run |: Pa=iam t O° 60 120 180, a 1075 0598 0491 Ca 0 0.0L 0.018 0.0243 Run 2: P,=04 am - 0 100 200 300 400 a 1 0.833 0.733 0.65 0.583 Lore 0 0.0057 0.0106 0.0148 0.0184 10-98Plot of Ina vs. Ca gives a straight ine passing through the origin with slope & azeets . 2228.9 ~EiKalPa- Pr PoKeg) Re i face ntrollin TEER Pad Ra Pe (Single ste asorbed, surface reaction conzolling) initial rate are used, Py = P50 and 1 >> KP, (adsorption is small at high temperature), thea ro kr KPa Using data at time 2eo from rons I and 2: Ky Ky = 3.2x109 Fence, overall apparent rate law is KyKaetPa 5 Kj Ka =32x103 a= 289 @® r=an He -kyamf(Pa, Pa, Ps) kya PR Trym Since P, is almost constant, during runs { and 2 (low conversion) LeiekyPar Run 1: kgP§ = 5.767 x 103 Run 2: kaPh = 1.769 x 10% Pas iinzunt => ky= 5.767 x 103 Pa=04inrun2 = n=129 KKaPa oe aoe Th Sey § ¥/ Ka=32000 ky = 5.767103 n= 12 tin mites, 10-99(© Overall conversion [2.8 mollzec cumene | {42 malice propene )Z = 15.2 mol see 14.2 motisec benzene) Cumene > Propene + Benzene “Fiat Ree Bor to molsee 3 molisee cumene = 7 molisec Conmposition at reactor outlet Ya fy 025 yasys= 32 = 0375 i Composition a: reactor inlet, F, =7+3= 10 mol/sec Fao = 7 + 3(0.25) 5 yas 0.775 Fro = 3(0375)=i125 => yn = 0.1125 Fp = 3(0.375) = 1.125 ys= 0.1125 Let Xy = conversion per pass ‘Total flow at reactor outlet before the recycle seam is: Fao(I-Xi} +2 FaoXe » Fao + Fao = Fad(l*+X:) + Fro + Fo == 0.25 => X;= 0.542 o> Fso " ‘Atany point along the reactor Fao(tX) LX tX) + Feo + Foo Bex PaSYAR= YA CG Fro + Eso +Fao . 10 am Fao 7757 29 Assume sam aw in leo for fe moving bel opraon (may ot be uci ee sreak Kaeo HEPA i+ksPat ‘Moving bed reactor: t= W Us Fag dX = 1d W 10-100= HS 161s10" (yg04 KP wy, 775 (1:22) 3.2x1032000 3.2103 = 698 «10° (L283 vst With X= Wao If X=0542, using digital computer W = 3.1 kg CDP10-S a) Mole balance: ax dw i Stoichiometry: ‘o(l X)0~ aw) 10-101ata) (aw) ska ape 0055 te pon com fot (x) *(Loalpti* a q ae b) POLYMATH CDP10-T ax , ign Equation: Fy =a(WY- Design Equation Sy ROE) Rate Law Decay Law (forsintesing) a(W)= z Swoichiomeuy: T=, ax. bine: : Comt aw 1 i =~ fr = 8. rx) From the problemstatement. aq, ==—-do- =! ew 4 Plugging in 100 kg for W, we can solve for Kt 1 43 cx xX =0.708 10-102CDP10-U ‘The heat of activation is given in the problem as a function of the carbon ‘number so we can just graph that: Heat of adsorption ve carbon | number —— To graph the activation energy we need to find its equation. It is the Arthenius equation. k= Ae E/T Solving for E we get: can We know that as the temperature increases when n < 15, the rate increases so kk still gets larger with greater temperature so E is stil positive. When the temperature increases when n > 15, the rate decreases so k decreases making E negative. So we can come up with some equation with the above equation that fits this criteria and we can come up with the following graph Activation energy vs carbon number ay Activation, ‘The reason for this unusual temperature dependence is due to the fact that the higher the carbon number the less it wants to add another carbon 10-103CDP10-V @) ‘= O at the end of the reactor: the catalyst is inactive. In theory a can be negative, but in reality, once the catalyst is inactive there can be no further decrease in activity. (©) Foracatalyst feed rate of Us = 0.5 kg/s: ax Mole Balance Rate Law : Decay Lat Se Te Todas TONKS! > a=LOAW Stoichiometry: (Assume =',,P = P,,and v= v,) Saal X) -oaw) kez, -xF] (ileal ee > Gels 10-104From part (b) we know that the maximum catalyst weight (the point where a = 0) is 25kg ‘We will find the conversion at this point : (02) (5-se2 2} 0.25 0.667 =1-23 3 1G xX) =, ae Ww ) 2)w=(025)=1 > x=050 CDP10-W Design Equation Rate Law : Decay Law: 10.05 ‘From this we can see that the maximum reaction time is 20min. We will find the conversion at this point Stoichiometry: (Assume constant volume) Combine 10-105,CDP10-X a) Mole balances: rate laws: =n = akC, stoichiometry: Evaluate the parameters: nome (5-4) ¥ veng{ 2000/1 k= 001* ex aly Plugging all of this into POLYMATH we can change values of Us, T, and v, (Py) that will give us the most of product B ‘We find dha ata troperatine of 396K, a solids velocity of 1Okg/s and gas volumetic velocity of (0.633 dm'¥s at comesponds fo a paral pressure of 31 3 aun we ca the maximum eld for 8 (28) /a =z £01 186 la) 8 savas : alpsd. 86-3 : ete, OBexp(25000/2 98701240010) oe vea= oL¥exp{20000/1,987°(2/400-1/91) ve tes oan sebe-02tonp(20000/1 987 (1/400-1/1)) Ebene bose Stee Geen = S Shas Genes ereas cessor ovsnenen Sie o tiie tate gots 10-106») Using the same program we can find what it takes to get the most of C possible. We find that at T = 396K, U, = 10, and v, =.03 we can get Lmol Cis. Pyo= 1082.4 atm. Minin valoe final vetue 1 a 2.062502 1.42629e-23 ° osm 6 a ssouze-0 . a asm hese ws o.osenas 9 o6sin08 o.osen349 @ o-eor7ssse 75354 @ 00775554 6 00775884 a eave 9 17602 2 oven3t ° ° 17.2686 6.36s950-10 so.seriog 1 es05re-24 o.sarioe =i ee05te 24 fe a ones 9 56333 «) To get the Time-Temperature trajectory we can use the following equation to create it 1 ele als) ‘This will give us the following graph: Temperature-Time Trajectory Temperature (Ky 4) For this we just add an energy balance We have to assume a heat capecity of the ‘catalyst since bone is given Here iti assumed to be 100 Ikgest AT | (OH y+ (OH) ‘Plugging this into the POLYMATH gives the following program, ‘We find chat he temperature is 388K, U,= 10ky/sandv, = 0.51 dis. Pyg am. 10-10781 fa) /atei ere (em sao erb ate} fateh are 2a) 3) =a ts a(t) fae = (2a (-26000) +25" (~32000)) /(ep* (Usseareoete)) ede 08*expi15000/1.987"(3/400-1/2)) beei0 pero k2= oxtexp(20000/3.$87*(1/400-1/2)) Jens 02*exp (1000073 987%(1/400-1/2)) vow Si caster ner” $/¥0 cheer (L-algtw* $/¥0 Fosvar(azreb-x2*ea) ae et lun tatoo valag tininun value 10-108Solutions for Chapter 11 - External Diffusion Effects on Heterogeneous Reactions PI1-1 individualized solution P1l-2 (a) ZA, yn 28,0 gy, Wa = Dan G+ YaCWa +Wz) Wp =-2W, =2Pap dyn “"Cya) & Integrating with y, =0 at 2=8 D, (+ya) =-cDapdin YA) Ne wm @ Taking the ratio of Equation (1) to Equation (2) to eliminate Wa and solving for ya In(l+ ya) _ Int yao) Sa 7 meres Ya=l~ (4 ya0)Yad ya P11-2 (b) () T,=300K T,=350K 2137. 6/4, U2, 2 a (ee) (2) 4 () ae Ka (Dani) (v2) (U1) (dpa. Asa first approximation assume Dap2 5/67, Wr. \U2 (2) (3) wy 02) \dpo \U1 AtT, = 300K pty ~0.883cP AUT) = 350K pz = 0.380cP ‘Assume density doesn’t change that much, v= p 42232 My Ueenres 2’ dp 2 4.61x10" m/s 61x10 m/s [2.32 iy ty 65x10 m/s = kal =(4.6110% m/s) (10° mol/m’) = 0,00465 mol/m* /s 12P11-2 (c) (hb) A.S0-50 mixture of hydrazine and helium would only affect the kinematic viscosity to a small extent. Consequently the complete conversion would be achieved. Increase diameter by a factor of 5 y2 y2 d 1 Keg =k] PL] =2.9. (2) males) cowl =13m/s X=l- ox 13019895] =1-exp(-4.6) X=1-0.01=0.99 again virtually complete conversion. P11-2 (d) Liquid phase :e.g.water Re = Bited . 100001005 _ B ere ee ‘Sce margin notes on page 786 and 787 for solution. P11-2(c) oe vimm{ th os a) yP11-2 (f) Co Cu ba ‘Assume concentration in blood is negligible (C4 =0 at 82). Assume quasi steady state d(V,C,,) Plow into the blood Cpa Fxp=—"4mol/time , R= [time ‘AB Ry mo" ] constant =Cpao CragB t If Cap varies ep Vy dt fae Cy ‘ . Fy=S2 8; and 82 are given in the side note. a t Pul-3 Mol balance on oxygen: Fo:-0-+102=0 constant liquid composition. kCo;* where n is the reaction order. Pr Acouming ideal gas law applies : Fo: whore ve oxygen uptake rate mL/hr RT Assuming that # constant. by corection of v, to some reference, then Fos Assuming Henry's law applies (low pressures) Coz = H.Po where H is Henry's constant and Por is the oxygen partial pressure‘Substituting into the moi balance ket Inv, = nln Pox + In = ic A plot of ln v, vs la Po: will give n as the gradient As the system pressure, P, given in the data is absolute: P= P,+ Poy if in the reactor, the xylene is at boiling point and dissolved oxygen and oxidized xylene are at low levels, then P, = | atm (open to the atmosphere) Tn oxder to deduce the cortect kinetics of the oxidation it is necessary to find the partial oxygen pressures for the conditions where the rate is limited only by the reaction Kinetics and not by diffusional mass transfer: Plot of stirrer speed, W, vs oxygen uptake rate, Uy , for each cua will show the conditions at which diffusion is negligible. Ie can be seen that at stirrer speeds above 1200 rpm that OUR is insensitive to W and hence the reactor is well mixed ie. no liquid diffusional limitations. OUR: Oxygen Uptake Rate Hence using the system pressure data at 1600 cpm for the plot of la v, vs In Pos will give n uniafluenced by diffusion Po: ~Py=P AL 1600 pm.PL-4 Diffusion in adjacent skin layers Skin taver interface Pst Poa Outer layer Inner layer Strotum Epidermis comeum for each diffusing component in each layer 2: Outer layer: boundary conditions 2=0,Ca= Cao z=8,C ea Fe CroProfile Ca = Cro =(Cro ~ Cu) Inner layer: boundary conditions. z= 8; ,Ca=Cu t=h, Cas Profile Total partial pressure profiles Outer skin layer: Pa + Pa = Pao~(Pao- Pa). = 1010 ~-(1010-- 1008) = = 1010 ~1000.z + 5000.2 = 1010 + 4000.2 Inet skin layer Put Pa= Pu + Pa (Pao~ ey = 1008 (224 £) -s10-(s10 vof 5 001-0002 01 - 0.00: = 810+126000(0.01 -100000(0.01 ~ :) = $10 + 26000(001 ) outerlaver = innerlayer Pot Po Pot Pa Check AL interfaée (2 = 0.002 em) 1010 + 4000, 10+ 26000(0.01~ 2) 1018 = 1018 correct! Plot these two profiles across the skin from z = Oto =00lemHe: Inner layer: boundary conditons Profile Outer layer: boundary conditons K Profile Total concentration profiles : Outerskin layer: Cat Ce Inner skin layer = Evaluation of Cy and Cyr: [Cx0~ Cu] 5-3-1 Conversion of kPa to kg/cm*s* 101kPa=101000Pa=101000kg/ms"=1010kg/ems” ». 1kPa=10kg/ems? 119He: Outer layer Wa SxlOe~ 2kg /cm*s b-8 O = 1008kg / cnt.s* Wa _ 5xl0e “i 0002. = 10kg / om.s* 1110‘The maximum sum of partial pressures occurs at the skin layer interface z=0.002em Prout = 1018 kgfem.s* Pya= LOL KPa = 1010 kg/em.s* < Pras = 1018 kg/em.s* Hence the maximum sum of the partial pressures is slightly greater than the saturation paral pressure and so gas wll form bubbles atthe skin ayer interface causing blisters. P11-5 (a) Part (a & b) Packed bed, mass tranfer limited, gas phase Mol balance : where Fa=U.Ca.Ac U = constant superficial gas velocity Rate law Mass transfer limited boundary condition ca’ = ke (Ca-Cas) but Cas = 0, rapid reaction Stoichiometry Assume constant T, P, gas phase Gao Ca = Gl a0.5 = 0.05 x3=0.15 Combining Wo.tt+ 015%) Use Thoenes & Kramers correlation for ke : Sh” = Re')!2(S0?)"” [sae yt? wo a7 | Dab wenParameter evaluation =0.238em hee Diffusion of cyclohexane in hydrogen (assuming constant T, P) Fuller, Schettler, Giddings for binary mixture, low pressure, non polar (Perry's handbook chem.eng } ‘Ma, Mc = molecular masse Va, Vb = diffusion volumes = 4.2 respectively 22, 7.07 em’ mol respectively of LY? 0.001(73) li Al Dab= ——-- HSE 2 = 0857em" /s af 122)" + (707)" T $204 05" 05.05) 22 a 1b 0572 Yo = Ys. = 000-50 9em 1s 12p= 0.00017 g/cms (Hz, 500K , 2 atm) 50.9(1 +0.15X)0.572x0.00019 (0.000171 -0.4)L146 4713(1+ 0.15%) = 9000190857 (i = aa} [473(1+015x)}"[Loaay” = 17.981 + 0.15X)* *) 2 6.29cm" 0.572 = 0.00017 g/em.s (Hz , 500K , 2 atm) pe’ = SO.ML-+ 0.15X)0.572x0.00019 = 4731+ 0.15X) 0.000170 - 0.4)1.146 0.00017 _ (0.0001920.857 os } oas7\1-04 : (4730. +-015x)}"[Loaa}” = 17.9801 +0.15%)"" 1 1146 = 0388.ke 038 04) 5 629¢m POLYMATH P11-5 (b) 1-13equazion:, Initial value Ux) (42) =2.22° (19) (12 ASHI ° p27 % teas variable nistal value Maxim value Minimue value Final value 2 ° 5 o s x ° 0.99957 ° 0.99997 KEY: eco e.e00 o.200 Paso asieie aewrs a.sseuseia : ognize. 2.0538 oase34853 canara oss9e3579 osssnas2s ovspsaisea The results show thar only 33 ces of the tube is required for conversion of 99.9%, much less than the ful 20.m P11-5 (c) 1dsoe )t [eae sl Dab (1-0)7 [nl-o7} |p Dab. Assuming the porosity remains the same, factors in the correlation affected by the size of the catalyst pellets are: 0286/04 TL be 194 ke } it as (23.6801 +0.15x)}*[Losay” = 25.39(1+0.15x)" <= 12.59¢m4 309 (+ 015x) aU POLYMATH (+015x)" 811-48 part arb “TY As can be seen from the above graph, the affect of reducing the dimensions of the pellets by half results in the conversion reaching 99.9 % 1.18 cm from the entrance. This seems reasonable because reducing the size of the catalyst particles is one of the methods for increasing mass transfer and hence ke. ALASP11-5 (d) IF pure cyclohexane feed were used at the same volumetric flowrate 60 dm*/min , then the initial bulk concentration would be greater and there would be a greater concentration gradient across the stagnant film on the pellets. However the mass transfer coefficient will be reduced as the products must diffuse away from the surface which will be harder in higher concentrations of cyclohexane. the equations used in Part (a) do not incorporate Cao, the initial cyclohexane concentration (Cao is cancelled out), so the only affect this change would have is to alter the physical properties of the bulk flow : RMMP _ (8452) RT 0821x773 = 2647gm/1 = 0.00265g /em' =?g/ems (cyclohexane , 500 K 2 atm) P11-5 (e) ‘This problem gives an indication as to how changes in parameters may affect a packed bed. PLI-6 Given, © Minimum respiration rate of chipmunk, Fa. = 15 pmol O,/min Ss ‘* Breathing rate of Chipmunk, SSSsssss vo= 0.05 dm* gas/min SSS =3em SS © Diameter of hole, Assuming, SSS + Atepresents oxygen Ss © Brepresents nitrogen Ss ‘© Chipmunk has a constant breathing rate of 0.05 dm’ of gas/min SSS ‘Minimum flow rate of oxygen to the bottom, Far SSP PS = Minimum respiration rate of chipmunk oat = 1.5 pmol of Oymin 11-16Flow rate of A down the hole = Flux of AxCross- sectional Area ----(1) = 0.18 cm? /s =0.18x10m?/s 2 _ x (003m)? = 7.06910 m? Fy, =1.50X10° mol / min = 2.5x10" mol/s PI1-6 (a) At Pasadena, Clifomia B Cy =—hXy, — (deal gas Rr (deal gas law) where, P, =1.013x10° N/m? at Pasadena, California (situated at sea level ) R=8314J /mol.K T = 25°C = 298K ¥4 20.21 (Mole fraction of oxygen in air) 1.013x10°. N/m? 314—2_x 298K) mol.K 0.21 £-Cyy = 8.59 mol /m’ Now, Flow rate of A= (Concentration of A atthe bottom) x (Volumette i Fu = Cu X% 05 dm’*/ min =0.05x10°m* gas/min Fu 2.5x10Smol/ s 2 ae u (005.10 ‘aie | min 60s Solving for the length from (1), of gas) .03 mot m* 1-17(8.59 0.030) mol /m’ 25x10 mol /s Leotsst0-nt 1 0610? 2 L= 436m P11-6 (b) At Boulder, Colorado Boulder, Colorado is 5430 feet above sea-level. The corresponding atmospheric pressure is 0.829 x 10° Nim P, =0.829x10° N/m* at Boulder, Colorado 0.829 10° N/m? Cy 2 {sa 298k) mol.K "49 = 7.03 mol /m? Solving for the length from (1), (7.03 ~ 0.03) mol { m° 7.06910 n> 25x10 ®mol/ s =0.18x10™m? to 3.56m P11-6 (c) ‘During winter at Ann Arbor, Michigan 1 =0'F =-17.78°C = 255.37K “g= ae Nim aa 8314 ——_x255.37K ( mmol? 9537 ) £+ Cyy =10.02 mol [mt Solving for the length from (1), 1sss\t s 5 L=0,18x10m? /sx{ 222) x{ 40.02 0.03) mold m5 9695104? 298 25x10" mol/s 2 L=3.87m During winter at Boulder, Colorado 255.37K PB Cy =ZEX In 10 Rr oe ae Nim egy 8314 apn 2s5a7K | mol.K Co = 8.20 mol /m? Solving for the length from (1), Cag 15 _ : 18310"? J yx{ 298) xf 6:20 —0.08) moll m7 969 10-4 m? 298 25x10" mol /'s /L=3.17m P11-6 (€) tndiviguatized sotation PI1-7 (a) Given: P, = 510mm Hg @ 35°C (from plot of InP, vs U/T ) InP,=A -Gs ° ‘Antoine Equation Day= 0.120 em*/sec (from equation of Fuller, et al) Faller Equation where V, and Vp are the Fuller molecular diffusion volumes which are calculated by summing the atomie contsibutions This also lists some special diffusion volumes for simple molecules Fuller diffusion volumes ‘Atomic and structural diffusion volume increments c 159 =F 147 fe ie Cln 210) (Ope 611) Br e219) N 454 1 298 11.19Ring -183 S229 Diffusion volumes of simple molecules He 267 CO 180 Ne 598 CO2 269 Ar 162 N20 359 Kr 245. NHB .207 Mey 210) 13) 2 612 SF6 71.3 D2 684 «C2382 N2 185 B2 690 02 163 S02 418 Air 197 P11-7 (b) By CS; molar flow rate balance oy —— Z-20em Fick’s First Law ( For Nam = 0) t N, =-CDyy ay X,(N, +0) __ kz KS} oem Day Oy o LJ 1-X, dz [| Rosen Equating the results of Fick's First Law and molar flow balance, then rearranging and writing in the integral form K, ]ae=CDy “fama-x,) o Xe CDyy ft Exe a LI-%,. Evaluating for 7 =20, X2=0 (atm (82.6) =3.95*10° gmol /cm* X, = th =< o6n1 760 nyo, = 29971073012) f 1-00 ] (20) 1-0.671. = 2.64 *10 7 gmol /cm?.sec P11-7 (c) 11-20For any value of z between 2 = 0 and z= 20 x, C,=X,C M=X,M,+X,M, V,=N,IC, Cp = XC 1 axy=a-xoy, 1-Xy, IX), = (4,7 Ip = CyV -V)= Ng ~XpNu = XoNq Jy =CyVq ~V")=-XgNy =I, cio) z Xe Xa Cy Ca Pe oO 0.329 0.671 1.3 2.65 0.376 5 0.434 «(0.566 1.71 2.24 0.495 10 0.573 0.427 2.26 1,69 0.655 15, 0.757 0.243 2.99 0.96 0.865 18 0.895 0.105 3.54 0415 1.02 20 1 0 3.95 Oo 1.44 lserenesurntteet (= (J) Sane oenntoeen Zz Ve. Va v v 0 0 © 89 7478.92 5 0 «18 717 905 10 oO 15.6 7.17 10.25 15 oO 27.5 717 12.5 8 0 635 717 149 20 0 1E+06 7.17 17.5 P11-7 (d) Cy =X,C V, =Ny/C, = (10°) Pa Py 202 24 0.158 171 2.21 0.226 129 1.95 0.338 073 1.6 0.544 0316 1.34 0.764 o 4144 10%) 10%) neta eee 316 87 452 11.45 677 15.15 109 20 149 236 20 26.4 ai % 0.842 60.7 0.774 56 0.661 49.4 0.456 40.5 0.236 «34 0 28.97‘Mole fraction Z (om) Concentration, Concentration (105) amo! Diffusion Flux sslon Flus(*10"6, "10°8) ‘mass/oms-sec it P11-7 (e) Evaporation Rate of CS:_ (pi; @ 20°C = 1.26 gmice) 11-22(2.0*10° 1B3600 #24) 1.26 cm (@20°C 075: P11-7 (f) No solution will be given P11-7 (g) Molecular diffusion of aris taking pace Ng =Jg+X5(Nyt+Ny) O=J, + Xy(Nq) ~X,(N,)=Q-X,)N, P11-8 (a) ‘Quasi-steady-state — no accumulation in the capillary tube or in either chamber. Volume 1: Accumulation = in — out. acy dt Hy _APaie, c.) avg (on See Subuaction ives us: d(Cu-Cra) __ AcDas( 1, 1 (Ca-Ca) 7 ZL ly ty, (CaO Now integrate: 11-23In(Cu Car cons P11-8 (b) (Cy ~ Car) = KAIC Ink +InAIC =-Ada(t +} + Constant ty D, 1 narc=-4e2e{1 1 |rec, L \Y, Vy In AIC =—D,g (0.01025) +C, it we plot InIC) as a function of time and find the slope, that would give us -Dap See Polymath program P11-8-b.pol. POLYMATH Results Linear Regression Report Model: InDIC = a0 + at*t variable _Value_ 958 confidence a0 37024708 3-0078035 al -010307008, 9838-05, General Regression including free paramoter Number of observations = 9 Statistics o.9998944 0.999873 0.0015013 Variance= 2.608E-05, Dap = 0.0107 Pi1-9 Dissolution of monodisperse solid particles in excess solvent pDi-D+ (oF - DY) =a 3 Define conversion in terms of volume dissolved: X gives D=DI(L-)""Substituting for: DI-Di(L =)!" +55; (+ xy?Pysas ean | term 2 Surface reaction controls: D* is large, term 2 is small cf term 1 Di-Di(L = XY? sat ae 1-(- x)? Ce Di Mass transfer controls: D* is small, term 1 is small cf term 2 1 uP) = a [pia - 0 Py=ar Di any 2 Ot gph ODM) = Both regimes apparent; Term | and term 2 apply v3], [BE _x»)]2% fi-a- x») 12 xy | Di P11-10 (a) Mass transfer limited Wake Cro Ain excess, Ca = Cao ‘The reaction rate is equal to the mass transfer rate - ta." = keCas® ke.Cao 2.De For small particles and negligible shear stress ken re 2.De D CxoMol balance on solids nix s AS J. . dt 6 dt For t mole A dissolving 1 mole B then - ra" =~ ea.” = Ke Cag as Cay i undefined Time for dissolution, tc , at D = 0, and assuming particle density, p = 2000 kg/m’ =5? 200 x (198 2X. = 0125s Bec0e 10) «(20065 ~°" ie. viewally instantaneous dissolution P11-10 (b) Surface reaction limited =r" =k. Cao Mass tcansfer effects are not important when the surface reaction sate is Hiiting D? fre) ‘Mol balance on solids = ral. DE _2 ae For | mole A dissolving I mole B then ~(!” =~" 11-26x08 3) sctoei2s 10) x (2000) a very long time. P11-10 (c) . Att=0, total moles A in tank = 0.1 x 100 0 mol A i.e. there is just enough mols of A to completely dissolve all of B in a well mixed tank. Acid aot in excess and dissolution is mass transfer limited (Ca,# 0 and Cy # Cao) War = ke(Cy~ Ca.) =~ tas! ke Cas assume zero order in B 2.De ken BBE Mol balance on solids ae For { mole A dissolving { mole B then ~ ra." | (re") ? Dkr Cal 1 11.27Boundary conditions, Di-D+ Asa function of radius ‘Time for complete dissolution, te, at r= 0: | Dit least DkrCr assume p= 2000 kg/m! and ct = = Bale = 18)x(0.165) =10e-19 gives Ie ~5)+ |- 1el4s ~ wal 2x(2xl0e 8) again a very long time. P11-10 (a) | ‘To reduce te, increase C, and / or decrease Di. To inerease te, decrease C, and / or increase Di Dec P11-11 (a) Irreversible, gas-phase, adiabatic. no pressure drop. packed bed. Isothermal Mot balance : mol/gcat s 11-28where Fao = Cros = 10e-3 x Le4 = 10 moliem" Rate law oy SRC But Cx is unknown. Assume reaction rate is mass transfer limited. Was ke(Ca- Ca) = Ca cm mol s.gear cm TOFem! s = 29 10 \" O1 0.02 J converting : 70.7 x a= 70.7 x 60 242 em'/s.geat O01x4242xC4 4242 +001 Stoichiometry gas-phase, constant pressure and temperature where €=yao5=0.5(1-1) =0 Cx =Cro(1-X) and Cao = 1 mol/dm? = 10e-3 mol/em? POLYMATH emanions: sicinl value za (ekerea)/ Ore) 11.29Lvalue Mactan vaiue Misisu value Zins) value “ 1er06 ° ase * ° 9.60232 ° 0 6sa12 * 0.08 2.0 0.02 0.02 fa0 10 10 10 Fo ke 242 azar a on cao o.00, 0.002 o-oo 0-001 om 0.002 2.002 0.00036788 ka -3.999980-06 -3.67879e-06 -3.999980-06 | P11-11 (b) Adiabatic operation Mol bulunce and rate faw as in Part (a) 7 4000/ t L }| with = 417) =00b nt ee : oe SPL T9g7\ 300 T Stoichiometry Cao{ = \ where =O and To = 300 K Use xT 11-30and Cxg = 10e-3 mol/em’ -W,-S F.C. = (~, Enecuy batance: SF TMs DECOM) Fuk CAM a 0) a dt ENC, Y Fio Cpi.(T - Tio) = (10 x 25 (T - 300)] + (10 x 75 (T - 750)] = 1000 (T - 300) 1000 (7-300) + 10.X.(10000) = 0 POLYMATH ena2a2 ‘eao=0 002 ‘ro=300 ‘p2120"x"10000/1000) +0 eaccao® (Ze) *(70/T) ras-(erka*ea) / (eRe) Mga Me = 1.20006 Yaitiat value vaximn value Minimum value Float value * a 4. 2a006 ° L.zeo6 x ° o.eseazs a 0. 6s4e25 x o.er 0.08 2.01 oor fae 1 10 10 10 we saz aa 242 a2 eo 9.001 o.c0, 0-002 9.001 0 300 300 300 300 7 300 263.402 300 365.483, ca o.aa, 000283331 9.000283931. -2.0333e-06 -9.999980-06 | -2.83238-08 e020 131For a conversion of X = 60% . W, vp = 1020 kg Scale: 103 g & got P11-11 (c) Tris possible to generalize that the addition of temperarure variation in adiabatic operation does not affect the conversion, concentration profiles in form, but the numerical values are slighily different. Because the reaction is exothermic, isothermal operation enliances the conversion profile along the packed bed, so that for a given bed diameter less catalyst is required. It is clear that adiabatic operation inhibits conversion as heat is not removed from the systern so more catalyst is needed for the required conversion. The removal of the heat generated in the reaction allows a reduction of 85 kkg of catalyst in the bed. More detailed economics will indicate whether isothermal operation is worth it, P10-12 (a) Dissolution of pills. ‘Complete dissolution 1132Cs Relate C, to time Three pills. each with different thickness outer layers, the inner cores dissolving at different times (but ax the same rate) t0 each other, will each contribute to Cy in the stomach, Pill | D:=5mm,D,=3 mm Time for outer layer to dissolve 1 Bx(6xt0e~4}x10 Pid: D:=3.5 mm, D, =3 mm Time for outer layer to dissolve 1) = 2.9354x(035' = 03°) Sx(6x10e—4)1.0 24min Warners aAttat mol balance on drug ren DE where W = mass of drug in stomach, ¢ ‘V = volume stomach fluid , cm? 1200 = 4.17x10e-4 g/m? 11-33Outer layer : Mol balance on outer layer: 00 +71'".#.D' lund 14°" rate of dissolution of outer layer = rate of mass transfer from pill surface Wa Wa = ke Sou = t2"” Boundary conditions : where t= time for outer layer to dissolve 0035. = 2035 52min Sx(6el0e 4) x10 Inner core: Boundary conditions ime for inner core to dissolve 11-340.035403" O Se(6xl0e--4)<08 L66min time for complete dissolution , tr = ty + t= 0.52 + 1.66 =2.18 min P10-12 (b) biood stream | stomach “adsorption Cocone. in blood €s cone. in stomach dissolution stomach wall Let rate of adsorption into bloodstream ta =k Cy Relate concentration in stomach C, , to concentration in blood Cp ‘Mol balance on drug in bloodstream : ee kaCa san w= {f\ =| \ vo | Zh ee woes 11-35Scale: 108 P10-12 (c) ‘The graph of Ce against time shows how the drug concentration in the bloodstream initially varies with time and then becomes independent of time as all the drug initially jn the stomach has absorbed into the blood (consumption of the drug withia the bloodstream has not been modelled, unrealistic but no data). If a certain drug level is specified, and assuming a constant size of inner core (drug) and that the pills were to be taken similtaneously, then the way to achieve this would be to use pills of different outer layer thicknesses -to maintain an even stomach concentration and hence absorption rate over the whole period Relate D with time: 12 2.24 S2_ 4 Dar Sa dr ° Dp and boundary conditions: t=, D =D, 2. D=0 Using logic to obtain the correct timing for the drug concentration profiles inside the stomach for each pill, the total profile is used in the relation with the concentration profile in the bloodstream. 11.36P11-120 squations: UBL) /4( =) =L€ (e>0.24) chen (3 (D1>0-00001) chen |~4*Dab*sin/( Ditrho} jelse(9) )elze(0) CB) Fa¢ ce} ekarcarvrimody 4caa) /a(e) =L£(t>0.52) chen (2*bab Gin"3.14°02/¥) else(0) 402) /4(c) =£€(e>0.52) eben if (5220. 00001) ehen{-4*Dabrsin/ ( D2-zho} )elsa(0) Jelse(0) ° Acat) /A(2) #i£(e>0,24) chen(2-Dabrsinr3 14-DL/Velsela) 0 a aicad) /a(e) it (toi. 18) then(2*Dabrsints LADI/VVelse(0) 0 41033 fad “LE (end, 1a) than (LE (9529, GG001) eMea(-AeDabsia/ (0-4 Da+zho} }else(0)}els6(0) pabe0 0005 Sineaoo mon3S.4 ean0. 166867 ve1200 mbody=75000 CascalCa2~Cad- (Coribody/¥) ss kaicial value Haxinun value Minimum value Final value ° 4s ° s 0.3 03 9.9965e-08 | 9.99650-06 ° 2.aoisse-0s 0 2,00164e-05 ° e.caaa7378 0 0.000817378 a 0.000417373 0 .000417373 0.3 0.3 9.99774e-06 9.997742-06 ° 2 nea ° 9 ,900817364 bs 0.3 D.998dle-06 9.998420-06 Dab e-ao0s 9.0008 0008 sin 400 420 400 = 354 as.4 35.4 a o.1ssss7 6.1588 0.166687 v 1200 x200 3200 3290 woey 75000 75000 75000 ‘75000 ca ° aooassize 0 1.os0ste-06 Relate D with time :, 22 2 24:54. _4-Du Sm a p DP and boundary conditions; t=) ,D =D, t=h,D=0 Using logic 0 obtain the correct timing for the drug concentration profiles inside the stomach for each pill, the total profile is used in the relation with the concentration profile in the bloodsteam. P10-12 (d) 11-37‘To maintain constant drug level by maintaining a constant stomach concentration, time needs to be allowed for the dissolution of the outer layer. for a given period of say 3 hours, a size distribution of outer layers is needed, with thin layers for initial response and thicker layers for delayed response. This distribution would be back aleulated given the necessary stomach concentration for the required bloodstream, “Concentration accounting for bloodstream diug consumption, Optimization of the stomach concentration will indicate the times at which complete dissolution of the: Outer layer of the ‘next’ pill is required to maintain this level. ‘The range of pill sizes depends on the number of pills which can be reasonably consumed in one siting, the period for effect and the limits of practical pill size. P11-13 The plot ofthe data is shown below Particle Diameter vs Time ] Initially the rate of incineration of the droplet in terms of diameter, is non-linear, but apparently becomes linear after ~ 50 time units. The linear form of the data indicates that the diameter is directly proportional to time and the rate of deerease in diameter is constant and hence not a function of diameter. This relationship should make it easier toestimate the required ixcineration time for complete destruction (zero diametei). ‘Assuming that rate of diameter decrease continues at the linear rate until complete destruction (at time ty and hence complete decomposition of the POHC's, the ‘equation for the linear relation indicates tg ~ 160 units. Pi1-14 11-38Mol balance on layer of earth control volume: Fl ~ Fils de SE but a= ALWa de Ws =~Dia St a Gives: Let Boundary conditions : TSU (present day) (surface), y=0 zee, =0(end of glacial) ,z>0, Gives the error function : It is defined that at y= 1.82, Cq=0.01 Cao and for) > 1.82 , Cais negligibly small. ‘This defines the penctration thickness, 5 (as a function of time): 182 =-—® Concentration Profile "y — : | ie 11:39But the graph gives at, C,=001 Cy -» 2=04 hence 5=18-0.4m, the penetration thickness after time ¢ The time taken for 5 to seach this thickness, is the time since the diffusion started (ie. ai the end of the last glacial) 176)" t L « 1=(25) scsechacww wan cares "toe (12) PebBixide 10 3éo0 aes CDP11-A CDP11-B CDP11-C CDP11-D CDP11-E CDP11-F CDP11-G CDP11-H CDP11-1 CDP11-5 CDP11-K CDP11-L CDP11-M 11-40Solutions for Chapter 12 - Diffusion and Reaction in Porous Catalysts P12-1 individualized solution P12-2 (a) @ t=5 1 T D. ~Dap ~ Pp 1.75 oan 8f P\T, (ines and angles not to scale) P12-2 (bh) (1) First Order Reaction Kinetics @&c c z D,—A-kC,=0, w==* , A= ysl n=O ae AO 2¥ pay=o Dax Xe oe De w= AcoshyDaa +B sinhyDaa i Rel ay a GL7 Ava sinh Vad. + Br/Da cosh. ay symmetry Y=0 @ A=1 «. pymmetry a sinha =-A TanhyDi coshyDa ae w=1@A=0 1211= A coshYDa az—t_.B TanhyDa coshyDa " ~ cosh/Da _ cosh Da 2 TanbyDa ipa a coshyDa cosh Da 2 Monod Kinetics HmaeCaCe _ gl Use Ks+Cq [Quasi Steady Co _HnaxCaCe 9 [State We KytCa (Analysis No further solution to Monod Kinetics will be given. Q) Variable Diffusion Coefficient dF, Solution the same as before Equation (E12-2.13) 122The flux of O in does not depend upon De which is not uprising since this reaction is zero order. For the build up of material that hinders diffusion Fy =kvt From a quasi steady state approximation as time goes on Fy increases D. decreases and 9 increases. However, the point at which the oxygen concentration is equal to zero has to be found. We can parallel the analysis used in P12-10 switching the coordinates of 4 =0 and A= 1 (see solution to P12-10(c) in which the solution manual) we will find he 10 =05 - Increasing t 0 Hea Jey A= We see that as t increases Ae decreases, that is the point at which the oxygen concentration is zero moves toward the top of the gel. P12-2(c)(1) ForR; 1 =0.182 18.2% Surface reaction limited and 81.8% Diffusion limited ForR2 1=0.856 85.6% Surface reaction limited and 14.6% diffusion limited —t4 (0bs)p.R? (2) Cyp =A DER «ng? 259) DCas =(0.95)(0.9) =0.77 which is less than 1 sv there are no significant diffusion limitations. P12-2 (d) il Q2=—e 14 RSP Keile — “T KS.0p nN ke Q=0.059 So 5.9% surface reaction resistance and 94/1% external and internal diffusion limited 0.941 0.941 OAL %R=——z— = — 1 k’S.0, 6.0+10.96 16.96 nN keile % Internal diffusion reaction 0.941100 «300 = 33.3% % External diffusion resistance = (0.94 1100) i058 60.8% Summary of Resistances External Diffusion 60.8% Internal Diffusion 33.3% Surface Reactor 5.9% 100.0% Increase temperature significantly. Surface reaction % resistance decreases. Increase gas velocity external resietance decreases decrease pellet size both internal and external resistances decrease For 99.99% Conversion In(0,000 =0,16!0(10.000) 1n300 Ly =Lyh Beas P12-2 (e) 124) From Mears's Criterion AH C14 )PoRE! hT’R, The value from the question AH gy =—25kcal/mol = ~104.6kI /mol h=100BTU /h- ft2.°F = 0.567KI /s.m? -K E = 20kcal/mol = 83.682kI /mol Rg=8.3144*10~kI/molK From example 12.3 <0.15 » ~th = KS.Cxo k=4.42*101m? /m? -sec S, =530m?/g 1 6)p, = 1 -0.5)(2.8*10%) = 1.410% g/m? 10m 17K At the inlet of the reactor the fraction of NO =0.02 From ideal gas law <> = 10.39mol/m? 3144 * 117: .02* 10.39 = 0.2078mol/m> Substituting all value in the first equation 04.6)((4.42 *101)(530)(0.2078))(1.46*10%)(3* 10-2 )(83.682 (0.567)(11737)(8.3144 *10™) As the calculated result is lower than 0.15, there is not the temperature gradient. The bulk fluid temperature will be virtually the same as the temperature at the external surface of the pellet. =2.88*10 P12-2 (f) (&) For'y=30 use Figure 12-7. If you draw a vertical line up from >, =0.4 it should be tangent (or very, very close) to the B=0.4 curve. Any slight increase in temperature will cause the reaction to go to upper steady state. P12-2 (g) ® 1 1+ Kot > O For large 1253 Pe _3 [De RVkK RYk?S, vo Sa 1+kpt Area2 Area 1 (1) Pore closure. Consider De As t > pore throat closes B= <0, 6,90, D, 90, and de 30 (2) Loss of surface area S. As t > then S90 then —>0 m1, but 14 = 48, 30 P12-2 (h) (tn) The activation energy will be larger than that for difusion control and hence the reaction is more temperature Sensitive. I the apparent reaction orders greater than one half, then the rate of reaetion wl be less sensitive to Concentration, I tis es han one ha the tue order wl be negative and the rate wil inrease significantly at low concentration. P12-2 (i) In example CDR12-1, the reactor is 5 m in diameter and 22 m high, wheteas the reactor in CDR12-2 is only 2m in volume. The charge is much different. In CDRI2-1 the charge is 100 kg/m? and in CDR12-2 itis only 3.9 kg/m* P12-2 (j) No soltion will be given at this ime P12-2 (k) ‘With the increase in temperature, the rate of reaction will increase. This will eause the slope of C/R vs Vm and, therefore, the resistance to decrease P12-2 (1) No sotation wil be given at his time P12-3 (a) Yes P12-3 (b) {All temperatures, Fyy = 10 moV/n. The rate of reaction changes with flow rate and increases linearly with temperature P12-3 (c) Yes P12-3 (d) 1 <367K, Fr 7 362K, Fr = 1000 mol/ir, 5000 molar P12-3 (e) Yes P12-3 (f) T > 367 K, Fro = 1000 mol/hr, 5000 moV/hr 12-6T > 362 K, Fyo = 100 mor P12-3 (g) _ actual rate of reaction ideal rate of reaction 0.26 (at362.K, Fy, =10mol / hr) 7 17, (at 362K, F;, = 5000 mol /hr) =0.37 0.70 P12-3 (h) At Fy» = 5000 mol/hr, there is non external diffusion limitation, so the external effectiveness factor is 1. ___actual rate of reaction (at 362K, Fy = 5000mol/ hr) 7 cxtrapolated rate of reaction (at 362K, F,, =5000 mol /ir) = 0.86 1 P12-3 (i) _3[ cosh 9-1] a by iterative solution @ =1.60 1 sinh (ga) a 0.86 P12-4 (a) External mass transfer limited at 400 K and dp = 0.8 em. Alos at all Fry <2000 mol/s P12-4 (b) Reaction rate limited at T = 300 K and dp = 0.3 cm. When T = 400 K: dp = 0.8, 0.1, and 0.03 cm, P12-4 (c) Internal diffusion limited at T = 400 K and 0.1 < dp-<0.8 P12-4 (a) tate with dp 08 10 _y gs rate with d, =0.03 16 P12-5 Curve A is reaction-rate limited. This is so because of the way the curve bends, implying an exponential function which is the equation form for the specific reaction rate with respect to temperature. Curve B is inner-diffusion limited. This is because it has a dependence on temperature, but that dependence is small 127Curve C is outer-diffusion limited. This curve has a much larger dependace on temperature than curve B. P12-6 (a) c. 2 _ MRS. pp CAS! Ig = £8 4 do 2 Pb Ca’s Cas : De Then @ = (sehen Boundary 9 =(4=1)=1 A) sinh conditions: = (A = 0) = finite Effectiveness factor: 1 = 2-(0; cosh 6y- 1) first orderreaction. or r=R ic arr = By oe »Ca = 0.1 Cas where Cas = 1x 103 mole Rh Tx 104 1x103 R=1x103cmi Ol 2/ ° jie a WW sinh oy 1s JU 60 =o ° a7t sinh6 | Ca =f FS] 1x103 O71 e6-e6 | Ca = 2.36 x 104 ial P12-6 (b) n= Fires] = 0.80 => ¢; = 2.04 i 2_ KR*Sapg or = —> Ath = 4, @ = 01: o = 6 (eepar(a)) P12-6 (€) Individualized solution 128P12-7 (a) Start with a mole balance: WAL, .WAl,.,. + mAAz=0 Divide by AAz and take the limit as z > 0. Combining the two equations we get: ald] yoo Dividing by -D, we get: d[-D, d BC): C,=Cy @z=0 ‘We can then solve for the concentration profile: dC, _kz “aD, o Using boundary condition (1): 0 Bagk kL Cap pte From boundary condition2 Cy) = C, P12-7 (b) 7 a 7 = Fate of reaction without diffusion 2D(Ca - Cao) z(z-2L) __ 2D(Ca-Cao) n= rr = sie) Kz(z-2L) P12-7 (c) Boundary conditions: Cy = Oarz=L O= L(G -L}+ Cao Cao = KL a0 = - 105 mol/em?) 7 cm?) (Lem) LI? = 0.0640 L = 0.0041cm = 41pm P12-7 (a) The answer in part (c) is equal to the average tail length. 1 = Lin this problem. If7 = 1 , then it contradicts the assumption of diffusion being rate-limiting. P12-8 12-10e ze aL 5 Cas First-order irreversible reaction: A>B A =k Ca Wi, = Dota nglsWa no Mole taiance: -H-d2(S¥a)+ndxg = 0 dofESs]-ne, =o Cas (wy) pak HEF whee 2 k L2 =e SE cos h{ (1 - (Concentration distribution: cx = og =H cosh > L = 107m, 2L = 2x103cm Cas = 103g mole D = 0.1 cm/sec bfo(1-4j feet cya das» Guy[ eel Eh) : cosh id=. —1_ 10 cosho $=29932 12P12-8 (a) cosho Co (0.001 (£2212-29330 51) [cos b{2.99320.5)]}) i) cos h (2.9932) Ca = 2.345 x 104 g mol P12-8 (b) o= ays => 9a(2L) tanh oa _ tan h(2.9932) Tod = = 03324 ua 2.9932 Tinew = 0.8 = Sth _ 4 = Osseo Onew new Ane oa a= =(2 x 10) (0.8889) 5.993 x 104 cm Soia P12-8 (c) =Lc, = Cs = 0.001 4 Atz = LC, = oar * Gosh (0.8880) 7.038 x 10+ g mo ‘Thus minimum C, is now 70.38% of ‘Cas. Therefore the suggestion is plating entire surface of the inside of the pore. P12-8 (d) individualized solution P12-9 (a) 12-12Define Wa > 0 in direction of increasing z. ‘Material balance: Wa Apt, - WaApl,..+-taa Apa: = 0 RT ECA: Wa = DEEQV = -D_SEA for small Ca Taking Az + 0: Ap Was chap =0 A (p, da} _ S Ard (DSS}-ecgaar = 0 Forconstant De; D.SCA - KCya = 0 Boundary conditions: z = L Ca= Cas z=0 oso O by symmenry SEs oF Ca = 0 wherea? = © oF Assume Ca = e%, then r?-q2 Ca = Ape + Ay eae Atz = L: Cas = Aye-tl + Ay eal Maj | = 0 = -aA;+eAz =0 az Al = Az From above: A, = —CAs ooh y eal = ot + ect | Ca = Cas (eS + eck 12.13Therefore, concentration profile can be written as: = cos h (az) CA = Casal] > = -D, (2a! B65 sin h (coz) Waar = DA(REAL.) Ap = - Ard. Cas of SHES Wa Ap = -ApD. & Cas tanh (aL) By the sign convention: -Wa Ap = NraaApL = -nkCasaApL. 2 1kCasaApL = ApD.a Cas tanh (aL) 1 = (EBs = fF Blea) n= (VE geenen/ EY Overall effectiveness factor: -W, Ap = 2k CagaApL = 1kCasaApL on Qa Sas nN Cao -Wa Ap = kc Ap(Cao- Cas} = @ Ap De Cas tanh (aL) Cao = Cas[1 +82 anh (at) Gos 5 f—__1__j Cao [ee mae oe — . (Vee dant VEE 1+8Bs anh(aL) + 4/€32s tan(,/EE 1] P12-9 (b) ADB Wyarl|, -W,rl|,, +7,zrArL =0 14 rar =0 rdr 12-14EMCD therefore, W, =D, aia da Ada OD, dy idy ay LW yuo aaa dy Ath=Ly=Landath=1, We Lye and athe t 6 Bessel Function Solution (n) P12-10 (a) (© eMcp W, =-p&Ca dz. 1 tye-k In—Out +Gen=0 Wael, ~WaAclesae ttaAz Ae =0 Day ot) A=L wel dz’ LY Cao ae i 3 Slt Using the symmetry B. dy A=0 —=0 ah G=0 12.15Integrating equation (1) KU? = +C; V"oD.Ca ath=l yal kL? ve aoe lw=1+ 06 [2 P12-10 (b) (p) Now let's find what value ofthat, For 99=1 : O=1+1p?—1]=1+2 O for different Gp Therefore the concentration is zero (i.e., y= 0) at For $3 =16 : O=1+ P- 141622 -16 = 2 =0.938 Seems okay, but let’s look further and calculate the concentration ratio at 4 = 0 for Jo = welt lof. 2) 1+ 1+16[0.04-1]=-149 Negative concentration. @ P12-10(c) () Let's wy again with o = 10 w-1+(10)'[o.12-1]}-1. 107.99) y=1-99=-99 not possible 'y will be negative for any value of Oy greater than one. P12-10 (d) 12-16(8) We now need to resolve the problem with the fact that there isa critical value of A, Ae, for which both y= 0 ay and —~=0 da - a= 4 Ge TBH Cy y= 09 +C)A+C, AtA=1, y=l 1=95+C,+Cp Ath=he , w=0 O= ORR + Cae +Cy Subtracting 1= 09-094 +Ci(l-Ac) Solving for Cy o, tila) 1-Ac Solving for Co 2 &-%i(-%2) a (- 96 At A=Ac then Fx 0=2H6hc CHE) c O= 5A -25%c~(-08) POLE) a Heras LE 265 205 205, 12.17‘Sketch of concentration profile for different values of 60 = 1 then Ae =0 60 = 2 then Ae = 0.5 That is for @ = 2, the concentration of A is zero half way (2, = 0.5) through the slab w= 05% + [0~98(+ Ac) fe 1-95 - [00-950 +Ac)] | = 0327+ foo 95-03 + 4 +165 -240 + 268 Y= 95H? +240 (1~ oA +1- 209 + 95 For > he P12-10 (e) te ae fh [inacdes [I Age+0 ty Ade Srna © 4 0 iq =0 fore, <2B+2C k = 50 m/g sec mol; dp = 0.4cm; U = 3mys; T = 250°C = 523°K; P = SOOkP, = 4.936 atm; X = 0.80; D. = 2.66 x 10% ms; Eb = 0.4; Po = 2x 108 g/m}; Sa = 400 mg. Cao = Ee = 4. = 0115 £0 RT ~ (oog2 —lam_lsa3oq 7 OLS > { 08: qum,| 3 K Rate law: -t, = k Ch Mole balance: £C, a . Dap @SA- USCA +r, py =0 LG yd Das 2S - USA ax sa pach = 0 Neglecting axial diffusion with respect to forced axial convection, we have: 12:19a. -(P S420] 3 . “Sf a, feng Ca? u 'h 1 ah - (Resse), Atz=L: ag = (bgt) = PES L=(—U___1_ -1) 2. pp k Sa Cao}! -X Imemal effecive factor: 1 = (25)! oi mheren =2 he af ente {50 atm (009 «10k B fons ELOY 2.66 x 19 m2 2 = 02x10%m $2 = 2.63% 10 very large = (2 }2 = 8 a=(3) er 9.313 x 10 Internal-diffusion limited: Q = n = 9.313x 10-4 Reactor length: 3m/s(—t—- 1) © (9313 %104)2x 108, [gio (00% |[us 228) L = 2.80x 10m P12-12 (a) 12-20Start with the mole balance taken on a shell W,,2ar|,- W,,2ard, + 1{p,2arlar = 0 Divide by -2nlAr and take the limit as Ar approaches zero to get: atte) = tips =0 Next find the equation for equimolar counterdiffusion and plug it into-the above equation: A-0%)) Next differentiate to get the following differential equation: ~rpr=0 aC, , et We can then set the following: Cy r aha ask anc R go, 1d —HaeS Re 2 = FP SR ae D, . D, read. 0329 =0 ae Solution: 9=C\I,(@A)+C,K, (4) Boundary Conditions: =1@a=1 do B-o@a=0 7 = 0@A 12-21#e =@(C1,(64)-C,k,(02)] 1,(0)=0 K,Q)=0 as ae 705C,=0 9 =Cylo(@A) 1=CI,(@)=C, = Ze 1,(@a) 1,(@) p= P12-13 (a) d © bo(PhT)remoew=0 34 ay ea)ageo Q) Pdr Dividing by AF and using Equation (2) o substitute for —r4 L 4 te 4 #0, 2 —AHpy Jr? (dr! dr)? dr d| jd kT a) a{ eT 6, Ho ae lat Hig) a Integrating 2d] kT ar DE Alig) dr k,T ¢ Cyt =-=1 +, “"D.CAla) =0 because T & C must be finite. kT *D.Calin) r=R Cy =Ca, and T. Cy 12.22P12-13 (b) No solution will be given P12-15 (a) Cas c, ! Ae Be z=0 4 L I Given: A ¢+B on the walls of a cylindrical catalyst pore. 2 = length of poisoned section = kCa In the poisoned section: Wane l, - Want, +r,P dz = 0 For0SzS2,, tq = 0, Since this area is poisoned. Warrl, - Wamtl = 0 o Maso Wa = = CDap XA + x4 (Wa + Wa) 12.23But Wa =-Ws, since, for each mole of A consumed, one mole of A is reacted. eX Wa = - Dan HA and (CD, A) = 0 or Sa =0 Atz=0, Ca= ae = Cas Atz= 2, Ca = Xa= Ca Integrating: Xai = Ki z+Kz Atz=0, Xa = Ss: k - Ss Cai -C atz=z1,Xa = Xai = = +S = ki = = = Cas Car-Cas, Cas XZ thet Ca = (Car -Cas)(Z) + Cas The fax is Wa = -CDap SEA = -Dap SEA (Cat - Cas) P12-15 (b) oni tanh +2 Before poisoning, 1 = where) = $ = L{2k-] o Bal After poisoning, the differential equation and boundary conditions are the same for the unpoisoning region of the pore, 21 ko = 578.25 AL= 146515 =0 At Ti = 237C = 510K: ky = A ae *A 2- 6.097 Me , = oso) = 53.38 = ky CLS where: = FaoX where x = 2-20.097) _ 9 9499 = Pao 82 gm Cao = Rt ToaxsTo = 9196-5 0.196 (1 - 0.9490) _ ons £2 T - 0.5(0.9490) ky = —53.38_ < 2035 x 104 (0.019) ky = kyexp (EGs-a 2.035 x 10¢ = 578.25 exp Pcie aul 5 lL E = 755x109 P12-16 (b) Neue = 2Mgpp- 1 = 21.5)-1 = 2: second order Egue = 2Exp = 15.1 x 10° P12-16 (c) ; 5 [ESepeCuo _ / (1x 10F (2.035 x 104) 49(2.3 x 105) 0.196 ark De 0.23 x 10+ 12.272 = 1.40 x 106 | 2 2/3) ye = 4 n=(-35] G}- (3) areas 1.75 x 10 P12-16 (d) TTomake the catalyst moe effective, we should wse a smaller diameter P12-16 (c) Ca = 0.01 £221; = 527C = 800K k= toewp (E(t = 57825 emp [ AI k = 219 x 1032 om = KCAS = 2.19 x 102 (0.01)'5 = 2.19 x so Emole P12-17 dy n ww) | csr © ©A A — A >[_ Pre > > >[ PR csTR or M | PER > Recycle ® (10) a) (12) P13-2 (c) ora PrRAsTR Series E(1) = 13.2wee esr 0sF P13-2 (d) X=0.75 For a PER first order reaction: 1 Da= uf J In(4) = 1.39 where Da = kt x For a CSTR first order reaction: pax (Ay)-1=3 where Da = kt For a LER first order reaction. Solving iteratively Hilder approximate formula with an initial value Da? (ie. DayrxeDa’< Dacsrx) Dacxy 22s Da 7.4 where Da = kt 0.15 = Bi 4+ acne 4) Da Da=258 ‘The ratio ofthe Damkohler numbers i equal tothe ratios ofthe sizes V; vi Relative sizes: —™*. = 00.46, —®_ = 0.86 cSTR Vester P13-2(e) Fora PER, =5.15min, first order, liquid phase, irreversible reaction with k=0.1min™ X =1-e* =0.402 133Fora CSTR, t=5.15min, first order, liquid phase, irreversible reaction with k=0. min" kt = 0.402 1+kr x, Xen Xcsm 0.385 0.402, 0.340, Page 851, only the RTD is necessary to calculate the conversion for a first-order reaction in any type of reactor. Not good when the RTD has a long tail that is difficult to interpret or interpolate. P13-2( Decrease of 10% in temperature See Polymath program P13-2-pol POLYMATH Results Calculated values of the DEQ variables Variable initial value minimal value maximal value © 0 0 7.0B404 baz 0 0 06023637 x 0.025446 0.025406 00025446 cao 0.75 0.75 0.75 x o ° 0.9744692 tau 1000 1000 1000 tl 500 500 500 2 5.0B+10 6.258-08, 5.0R+10 z ° a (00023564 ODE Report (RKF45) Differential equations as entered by the user (2) d&Xbandl) = XE Explicit equations as entered by the user = .00493"exp(13300/1.9872"(1/828,15-1/313.15)) Cao =.75 K'Cao"t(1+k*Cao"t) tau= 1000 tt = taw2 1w'2/2/(%8-+.00001) (ett) then (0) else (E2) 13-4 016023837 010025446 0.75 019744692 1000 500 6.258-08 6.25E-08070) 0.36) on 028| 0) 40008000, 12000 16000 20000 temperature has the effect of reducing the mean conversion by 14%, Decrease in reaction order from 2" to pseudo 1 ‘See Polymath program P13-2-F-2 pol LYMATH Results Calculated values of the DEQ variables lue minimal value maximal value final value Variable initial va = 0 0 ~OEFOE 7 OBYO4 xbar ° ° al9391084 09391084 & 0.006 0.008 0.004 0.004 cao 0.75 0.75 0.75 0.75 x 0 ° 1 1 tau 1000 1000 L000 1000 a 500 500 500 500 2 5.0B+10 6.256-08, 5.0B+20 6.255-08 =z 3 0 0.028925 5 .25z-08 ODE Report (RKF45) Differential equations as entered by the user [11 dXbarjia(t) = XE Explicit equations as entered by the user [11 k= 0.004 [2] Cao =.75 [1 X= epee) (4) tau = 1000 [5] tt =tau2 [6] E2=tau'2/2/(¥%G+.00001) [71 E=if (tet) then (0) olse (E2) 13.5“Go00 8000, 12000 16000 20000 ‘The decrease in reaction order fiom 2% to pseudo 1" has the effect of increasing the exit conversion by 20%. The smaller the dependency of the rate on C, means that when Cy is below 1 moVdn then the rate of consumption of A is larger and hence resulting in a larger conversion. Exothermic reaction in adiabatic reactor: ‘See Polymath program P13-2-f-3.pol, POLYMATH Results Calculated values of the DEO variables Variable initial value minimal value maximal value final value r 0 0 2.0B+04 2.0804 Xbar a ° 01999375, 01999375 x 0 ° 1 1 T 323.15 323.15 823.15 823.15 cao 0.75 0.75 0.75 0.75 tau 1000 1000 1000 1000 ct 500 500 500 500 = 5.0R+20 6.2995-08 5.0B+10 6.2998-08 E ° o O.a0z21a2 «6 .2998-08 K 0.02 0.01 19.337202 -19,337202 ODE Report (STIFF) Differential equations as entered by the user 1), dlxbarVat) = X°E (2) dQXyat) = (1) Explicit equations as entered by the user [1] T= 323.15+500°X (21 GB) (3) 15] E2 = tau*2/2/("+.00001) (6) E=if (tet) then (0) else (E2) (7) k= 0.01exp(8000/1.9872"(1/828.18-1/7)) 13-610 os. 06 a4 02 9) Fava 8000, 1200016000 20000 ‘The mean conversion Xbar, the integral, is estimated to be 99.9%. The reaction is adiabatic and exothermic as the temperature increases to a maximum of 1373.15 K once the batch conversion within the globules has reached 100% which occurs after only — 4 seconds. Hence, the adiabatic increase in temperature considerably increases the rate at which conversions increases with time and hence also the final value. P13-2 (g) For a PER, 1=40min, second order, liquid phase, irreversible reaction with k=0.01 dm? /mol-min'' kre, X=——* =0.76 1+KTC,, 01 dm’ /mol-min" For a CSTR, t=40min, second order, liquid phase, irreversible reaction with x (-x) ‘Maximum Mixedness Model and Segregation model are given in E13-7 kr, > X = 0.58 Maximum Mixedness Model ‘See Polymath program P13-2-g pol POLYMATH Results Calculated values of the DEQ variables Variable initial value minimal value maximal value final value 2 0 ° 9 200 ° ° 0.5938635 05632738 8 8 8 8 0.01 0.01 0.01 0.01 200 ° 200 ° 0.1635984 0.028734 0.1635984 0.028004 #2 2258-04 2258-04 9.015011, 0.015011 FL 516332387 ° 5163333870 ¥2 0.997002 0.381759 019970002 0.381769. ra -0164 -0164 -0,1055646 — -0.122067 EB 2.25B-04 2258-04 0028004 0.028004 F 0.997002 ° 0199700020 EF 9.075005 0.020689 9.075005 0.028008 ODE Report (RKF45) Differential equations as entered by the user(21 doidl2) = -(raleao+£/(1-F)"») Explicit equations as entered by the user [11 ca0=8 (2) k= 01 (2) lam = 200-2 (a :20°(1-x) (s .446580-10"lam\4-1.18026-7lam"3+1.953580-5"lam"2-.000865652"lam+.028004 [6] E2=-2.640-0'lam’G+1.9618e-6"lam*2-.00024069"Iam+.015011 i 448580-10/5"larn"S-1.18020-7/4"lam/4+1.953580-5/3"lam’G-.000865652/2"Iam/2+.028004"lam [8] F2=-(-9,30769e-8"lam*3+5.028460-5'lanv'2-.00041"Iam+.618231-1) i) car? [10] E= if (lam<=70) then (E1) else (E2) [11] F=if ame=70) then (F1) else (F2) (22) EF =E/(1-F) 0.60 0.48} 036] 024 oan] 0.00 0% 80, 120 160 200 Xue x Xv Xesw 56% 61% "76% 58% P13-2 (h) Liquid phase, first order, Maximum Mixedness model C yok = 0.08min™ Rate Law: ~t_ = C4 = Cag (I-X) 1Cq where ky = See Polymath program P13-2-h-1 pol 138POLYMATH Results Calculated values of the DEQ variables Variable initial imal value maximal value final value 2 ° 0 200 200 x 0 ° 0.782932 —-0.7463946 cao a 8 8 8 k 0.08 0.08 0.08 0.08 Lam 200 9 200 o ca 8 1.7365487 8 2.028435 EL 0.1635984 9.0028731 0.1635984 0.028004 2 2.258-04 2.25B-04 0.015011, 02025011 FL 516333387 a 516333387 0 2 0.997002 0.381768 019970002 0.382769 za 0.64 0.64 011389236 | -0.1623075 E 2.258-08 2125m-00 0.028008 0.028004 F 05570002 a 019970002 0 EF 0.075005 0.0220691 0.075005 0.028004 ODE Report (RKF4S, Differential equations as entered by the user [1] d(x)id(2) = -(ralcao+E/(1-F)*») Explicit equations as entered by the user [1] cao=8 [2) k= 0.08 [3) lam = 200-2 4} ca=cao"(1-x) (5) E1 = 4,446580-10"lam4-1.1802e-7"lanV9+1 35968e-5*lam/2-.000865652"lam-+.028004 2.640-9"lam"G+ 1.96 180-6"larm”2-.00024069"lam-.015011 ‘446580-10/5"lam/6-1.18022-7/4"lam4+ 1,353580-5/3"IamS- 000865652/2"lanv'2+.028004"lam (-9:30769e-8"lam*3+5.028460-5"lam/2- 00941 "lams.618231-1) koa (lam<=70) then (Et) else (E2) (lam<=70) then (F1) else (F2) (12) BF = B(1-F) 0.80 ood 0.3 0.34] ors es OT) ‘Atz=200, ie. 4= 0 (exit), conversion X = 75 %. The decrease in reaction order fiom 2 to 1* has the effect of increasing the exit conversion by 19%. Once the concentration of A drops below I moVdm’ then the rate of consumption of A does not fall as rapidly (as the 2™ order | reaction) and hence resulting ina larger conversion iquid phase, third order, Maximum Mixedness model Rate Law: — 14 =kC,* 139Where k'C,,” =k =0.08min™ ‘See Polymath program P13-2-h-2,pol Pol H Result Caleulated values of the DEQ variables Variable initial value minimal value maximal value final value z 0 0 200 "200 x ° ° 0.4967311 04614308 cao a e a 8 x 0.08 0.08 0.08 0.08 lam 200 0 200 0 ca 8 41061501 8 43085534 EL 0.1635984 0.002873 0.16359¢4 0028004 = 2.258-04 2258-04 0.015021, 0.015021 FL 516333387 6 5163333870 F2 09970002 0.381769 0.9970002 0.381769 zB 2258-04 2258-04 0028004 0.028004 F 09970002 0 0.9970002 0 EF 01075005, 0.020689, 0.075005, 0.028004 ODE Report (RKF45) Differential equations as entered by the user 1) dlsydl2) = k(x S4EA 1-F)) Explicit equations as entered by the user a (21 1) 1a) ca=cao"(t-x) 5] E1 = 4.446580-10"lam’4-1.18026-7"lam/G+ 1 35958e-5"lam/2-,000865652"lam+.028004 [6] E2=-2.64e-9"lam’3+1,96180-6"lam'2-.00024060"lam+.015011 [7], Ft = 4,446680-10/5"lam'6-1.18026-7/4"lam™4+1.35358e-5/3"lam/G-.000865652/2"lanv'2+.028004"lam [8] F2=-(-9.80769e-8"lanv'3+5.02846e-5"lanv'2-00941"lam+.618231-1) [3] =i (lame=70) then (E1) else (E2) [210) F=f (ame=70) then (F1) olse (F2) fu) EF =E(1-F) Atz= 200, ie. 4=0 (exit), conversion X = 46.1 %. The increase in reaction order from 2nd to 31d has the effect of decreasing the exit conversion by 10%. Once the concentration of A drops below 1 mol/dm’ then the rate falls rapidly and C, is not consumed so quickly, resulting in a smaller conversion. Liquid phase, half order, Maximum Mixedness model Rate Law: — 1, =K'C, 1? 13-10Where k=k'Cy/? = 0.08min™ Bare rx Ox ‘See Polymath program P13-2-h-3 pol POLYMATH Results Calculated values of the DEQ variables variable initial value minimal value maximal value final value z 0 3 200, 200 x ° ° 0.934778 0.3038179 cao 8 8 8 a k 0.08 0.08 0.08 0.08 dan 200 ° 200 ° ca a 0.532208, e 0.7694568 EL 0.163984 0.002873 0.2635984 0.028004 2 2125R-04 21258-04 oloiso11 0015011, FL 516333387 516333387 m2 019970002 0.381768 019970002 0.381769 z 2258-04 21258-04 01028004 0028008 F 0.997002 0 019970002 EF 07075005 0.0220677 0.075005. «0.028004 ODE Report (RKF45) Differential equations as entered by the user [LT dxydle) = +k" (1-2) 5)+E/(1-F)%) Explicit equations as entered by the user [1] cao=8 (2) k=008 [3) lam = 200-2 [a] ca=cao'(t-x) [5] Et = 4.44658e-10"lam4-1.1802e-7"lamv'3+1 35358e-5*lan/’2-.000865652"lam+. 028004 [6] E2-=-2.640-0"lanv'G+-1.3618e-6"lam/2- 00024068"Iam+.018011 [71 Fi = 4.446580-10/5"lan5-1,1802e-7/4"lanv4+ 1 35958-6'S"lam*3-.000865652/2"lam’2+.028004"lam [8] F2=-(-9.30769e-8am'3+5.028460-6*lanv’2-.00941 “lam. 618231-1) [91 E=if (ame=70) then (E1) else (E2) [10] F=f (amz=70) then (F1) else (F2) fa) EF = B/-F) 13.1ww, 10160 200 Atz=200, ie. 4 =0 (exit), conversion X = 90 %. TThe decrease in reaction order from 2" to 44 has the effect of increasing the exit conversion by 34%. The smaller the dependency of the rate on C, means that when Ca falls below 1 moV/dm’ then the rate of consumption of A does not fall as rapidly (as the 2“ order reaction) and hence resulting in a larger conversion. P13-2 (i) Assymetric RTD: See Polymath program P13-2-+4.pol POLYMATH Results Calculated vaiues of the DI e ° a 2.52 2.52 ca 1 0.0228578 1 00228578 cb 1 02840809 fl 012840909 ce. ° ° 0.3992785 93992785 cabar ° ° 01513598 01513306 cbbar ° ° 014543234 014539723, cobar o ° 03570959 03566073, ca ° ° 03178411 02612331, ce. ° ° 013166306 03166306 cabar ° ° 013029636 03026417 cebar ° ° 0.1782569 0.178722 . 350 350 350 350 kL 1 1 a i 2 1 a 1 1 EL -0.004 -27.414373 0.958793 -27.414373 22 -27.402 27,402 019557439 -0.0272502 ze 1 0.0064937 1 0,0064937 3 2 1 a 1 ra 2 2 0.029355 -0.0293515 E 0.004 ~0.0272502 01958793 00272502 > ae al 010807076 00807076 sea ° 0 415284379 115284379. sée ° ° 42.398031 —_0.8250406 zd 1 ~0.0522658 1 ~0.0513561 ODE Report (RKF45) Differential equations as entered by the user (1) dfeayiatt) = ra [2] dlebyatt = rb 131231, dlecyatt) (4) dlcabaratt) = cate 5) dfebbara(t) = obME 6) dlccbanyatt) = oc" (7) dleayatt) = rd [21 dlceyatt) = re [9] dlcdbarya(t) = od"E (10) d(eebaryia(t = ce" Explicit equations as entered by the user (1) T=50 op ((5000/1 987)"(1/380-177) =p{(100011.987)(1/350-17T)) [a) Et =-2.104"Me8. 1677-1 596"'2+0.953"-0.004 104:¥\4417.037'19-50 247°V12462,964"127 402 ‘reatcb p{(800011.987)"(1/860-17T) (g] 1a=-kI"cateb-k2"ca [11] tb =-kt*cateb-k3*ebted [12] Sed = ce/{ed+.000000001) [13] Sde = edi(ce+.000000000001) [14] t= ke*0a-k3"eb‘ed If the temperature is raised, the conversion of A increases. The selectivity S.q increases with temperature and Sie decreases with increasing temperature Bimodal RTD See Polymath program P13-2+-2.pol POLYMATH Results ‘alculated values of the DEQ variables variable initial value minimal value maximal value ue 0 o 6 “6 ca i 02660482 1 0. 2660482 ob a 0.5350642 i 015352659 cc ° ° 0.2672257 0.274576 F 0.99 0.003987 0.99 -0.0033987 ea. ° ° 02692177 0.269217 ce. ° ° 011929233 0.190615, bo 2 1 1 1 cao, i 1 1 1 eco, ° ° ° 0 edo. ° ° ° ° ceo, ° ° ° ° lan 6 ° 6 ° 2 a i Fl 1 kL i 1 1 1 re 1 0.1424065 a 0.1424065 m3 a 1 1 1 =L 346.34561 0.2019474 346.34561 0.20909 #2 6737-4446 0.0742397 6737-4046 925.46463, #3 0.00811 0.006156 1.84845 1.84445 ze ° ° Oiesaara 0. 144103 za 2 2 -0.4084547 0, 4084547 => a a 0.28635 7012865096 5 0.00911 0.006256 016288984 0.20909. EF 0.911 0 2083818 iise94a36 02083818, 13:13ra a 0.1219452 a o.azi9452 sea ° ° 1.0856272 10198908, sde ° ° \7.ese981 © 1.4157322 ODE Report (RKF4S Differential equations as entered by the user [1] d(cay/d{z) = -(-ra+(ca-cao)"EF) (21 d{ebVa(2) = -(-rb+(cb-cbo)EF) [3] d(ce)/d(z) = --re+(co-cco)"EF) (4) atFyde) [5] d{edyd(z) (51 dleoyde) d+(cd-cdo)"EF) re+(ce-ceo)"EF) Explicit equations as entered by the user (1) 1 21 a @ [5) ce0=0 (6) lam =6-z (7) T=350 [8] k2= exp((1000/1.987)"(1/850-177)) [9)_k1 = exp((6000/1.987)*(1/850-1/7)) (20) w=kt cared [12] k3 = exp((9000/1.987)*(1/350-17)) [12] Et =0.47219"Iam-1,30733"lanM3+0.81728"lam’2+0,85688"lam+0.20909 [131 E2 = 3.89999"lam'6-68.16185*lam5+366.2097 lam'4-1224 66963"lam*G+2289,84857"Iam"2- 2265.62125Iam+925.46463, [14], E3 = 0.00410"larW4-0.07599"lam*3+0.52276"Iam/2-1.59457"iam+1,84445 [15] re=k3tebted [16] ra=-k1"ca'eb-k2"ca [17] tb =-kt*ca"eb-k3"cb‘ed fel £82)then(Et)else(itlam<=2.8)then(E2)else(E3)) (19) EF sE/(1-F) (20) rd=Kecaka'cb‘ed (21), Sed = e(eds.0000000001) {22}, Sde = ed(eer-0000000001) Ifthe temperature is raised, the conversion of A increases. The selectivity Sw increases with temperature and Sue decreases with increasing temperature P13-2 (j) Exothermic Reaction: E=45Kj/mol ‘See Polymath program P13-2-j-1.pol POLYMATH Results jod values of the DEQ variables ble initial v mini ° 0 x ° 0 09628524 0. 9579239 cao 8 8 a e ? 320 320 464.4279 463. 68658 dan 200 0 200 ° ca 8 0.2971785 8 0.366089 EL 0.1635984 0.0028744 0.2635984 0.028004 2 2. 258-04 2258-04 9.015011 0:035031 FL 516333387 0 5163333870 F2 09970002 0.381769 0.997002 0.381768 13140.01 0.01 1.924805 E 2.25m-04 2258-04 0.028004 F 019970002 ° 0.997002 BF 0.075005 0. 0220681 0.075005 ra -016a 018227063 © -0.1699892 ODE Report (RKF45) Differential equations as entered by the user (1) dixyld(z) = -ta/cao+E/(1-F)"x) Explicit equations as entered by the user 1) cao=8 [2] T=920+150"% [3] lam = 200-2 993687 028004 o2s00a 2140759 [4] ca=cao'(t-x) [5] E1 = 4.446680-10"lan4-1.1802e-7"lanV9+1.35958e-5*lam/’2-.000865652"lams.028004 [6] E2-=-2.64e-0"lamn’G+1.9618e-6"lamv2-.00024069"lam+.015011 [7] F1 = 4.446580-10/6"lanv-1.1802e-7/4"lan/4+1.35958e-5/3"lanv"3-000865652/2"Iam”2+.028004"Iam [8) F2=-(-9:90769e-8%am’3+5.02846e-5"lam/2-.00941"lam+.618231-1) [9] k= 01*exp(45000/8.314"(1/820-1/7)) [10] = if (ame=70) then (E41) else (E2) [11] F=f (ame=70) then (F1) else (F2) (2) EF =E/(1-F) [13] ra=-k'car2 ow 7 ao 16200 Endothermic Reaction: E=45Kj/mol See Polymath program P13-2,j-I.pol POLYMATH Results Calculated values of the DEQ variables variable initial value minimal value maximal value z 0 0 200 x ° ° 0.3017158 cao, 8 8 8 ° 320, 289.82835, 320 lan 200 0 200 ca. 8 5.5862683 8 EI 0.1635984 0.028733, 01635984 = 2258-04 2258-08 9.015011 FL 5.633387 ° 516333387 13.15 final valus "200 0. 2860515 8 291,39485 0 7115879 1028004 5 ° 0.015011 °Fa 0.997002 0.381769 0.9970002 0.381769 x 0.01 0.0017191 olan 00019006 E 2125B-04 21258-04 0.028008 0.028004 F 0: 9970002 ° 019970002 oo =F 0.075005 0.020579 0.075005 0.028004 za 0164 -0.64 010536459 0.062023, DE Report (RKFAS) Differential equations as entored by the user [21 doxid(2) = -(raleao+E/(1-F)*») Explicit equations as entered by the user (1) cao=8 (2] T=820-100% [3) lam = 200-2 [4] ca=cao%(t-x) [5] E1 = 4.446580-10"lam\4-1.18020-7"lam\@+1.953580-6'larn’2-.000865652"lam+.028004 2.640-9"lam'$+1.9618e-6"lam/2-.00024069"lam+.015011 ‘446580-10/5"lam"S-1.1802e-7/4"lam/4+-1,353580-5/3"Iam'S-.000865652/2 lam’2+.028004"lam (-9.307690-8"larn"3+5,028460-5"lam/2-.0094 1"lam+.618231-1) .01"exp(45000/8.314"(1/320-1/)) (lam<=70) then (E1) else (E2) oa} 00) a= e300 P13-2 (k) Base case: ‘ODE Report RKESS Diferenial equations as entered by the user (1) d(Ca)/d(t) = ra/vo (2) d(Cbyd(t) 13] d(CoV/d(t) = revo: Explicit equations as entered by the user [11 vo [21 (31 (a1 (5) (6) 13.16(7) Ca (2) x=1-CalCao [9] t= KI°Cake"Cb PER Ky/K=1 KiKe=2 KK =05 CG 0.284 0.080 0.284 G 0.357 0.406 0.203, Co 0.359. 0513 7 0.513 a 0.716 0919 ‘0716 ‘See Polymath program P13-2-k-2 pol POLYMATH Results NLES Solution Variable value fix) ca O-aa2a779 4.704810 eb 012466912 -3.531R-10 0 ce 0131083080 ° cao 1 tau 1.26 cho 0 eco ° ka 1 2 1 ra 0.442479 re 02066812 » 0.1957867 LES Report (safenewt) Nonlinear equations [11 (ea) = caosravtau-ca = 0 [21 {eb) = cbostbvtau-cb = 0 [31 flee) = eco +rettau-ce = 0 Explicit equations m (a) (31 core MK a1 KiK=05 Cy 0.443 [0284 0443 Cy 0.247 0317 0158 C 0.399 0.399 x 0557 0716 See Polymath program P13-2-k-3 pol POLYMATH Results Calculated values of the DEQ variables 13.17variable initial value minimal value maximal value final value c o 0 2.52 2.52 ca 1 0.004596 i 0: 0804596 ob ° ° 0.367866 02027582 ce. ° ° 017367822 © 0.7167822, cabar ° ° 0.3050685 0.304964 chbar ° ° 013350218 03347693 char ° ° 013876989 03468313 kL 1 1 1 a ka a a i a cao 1 1 i i BI -0.008 27462382 0.9523809 -27. 462382 = 727.402 27.402 019568359 0272502 za 4 4 -0:0800586 (0204596 re ° ° 013678269 12027582 x 0 ° 019195408 19195404 xb 1 -0.1353314 1 11222986 z 0.004 010272502 0.9568359 10272502 ODE Report (RKF4S) Differential equations as entered by the user (2) d{cala(t) = ra (21 dlebydtt (31 d(eoyia(y (41 dlcabaryd() = ca*E (5) dlebbaryalt) = ob*E (6) decbar\d(t) = cote Explicit equations as entered by the user Ti) kt=4 (2) ke=t 13] cao=4 [4] Et =-2.104"444,164°N8-1.596°"210.953"10.004 15] E2=-2.104°N4+17.037°%3-50.247°'2+62,964"-27 402 [6] ra=-k1"ca 17] t= ke'eb 18] x= (cao-caycao [9] b= K1cak2%eb [10] E=ilfte=t.26)then(Et)eIse(E2) Asymmetric RTD ‘Segregation Model _| Ky/K= Cc 0.306 Ce 0.335 Co. 0.347, x 0.694 See Polymath program P13-2-k-4,pol POLYMATH Results Calculated values of the DEO variables Variable initial value minimal value maximal value final value e 0 8 OT ca 2 9.1198-04 a 9.1198-04 cb 9 ° 0.3678325 00063832, ee. ° ° 0.992709 0.927049 cabaz ° ° 013879174 (03879174 1318cbbar ° o 0.2782572 ecbar o 0 o.3271713 ki 1 i 1 ra 1 i 1 cao 1 i 1 EL 0.20908 0.1017293 707.06582 707.06552 2 925. 46463 0.074462 3.0728+0¢ 3.07 28404 ta a “1 -511198-04 | -9.1198-04 re 0 ° 013675087 0 .0063832 x 0 0 019990881 0. 9990881 xb 1 =0.1353022 i 0.054713 Ee 6 9 0 ° B 1.gaaas, 0.061369 1.34445 9.08781 z 0.20808 0 v ezuue7 0 ODE Report (RKF45) Differential equations as entered by the user [11 d(cayid(t) = ra d(ebytt) = [31 dfecyatt) = 10 [4] dlcabaryatt) [51 d{cbbaryatt [61 d{ocbar/a( Explicit equations as entered by the user t1 kt=4 2) ki [3] cao=1 [4] Et =0.47219'Y'4-1,30733"1N3+0,91728'"'2+0,85688"t+0.20909 [5] E2-=3.89999°V'6-58,16185°1'5+366.20970"NN4-1224 66963°N3+2289.84857°1"2-2265.62125t+925.46463 (6) ra=-kt"cal (7) r= kateb is} x= (Ca0-cayeao Bimodal RTD Segregation Model Ky =05 © 0213, 0.388 Cy 0.350. 0.175 C (0.430 0.430 = x a 0787 0.612 Asymmetric RTD Maximum Kit Kk? KK =05 Mixedness on 0306 O10 0306 Gh 0.335 —_ [0390 0.195 Co 0.347 0.486 0.486 x 0.694 089 0.694 P13-2 (1-1) No solution will be given at this time. 13.19P13-3 Equivalency Maximum Mixedness and Segregation model for first order reaction: Maximum Mixednss Model; 4&4 = "dh Rean Hey ene Using the integration factor: feet je Ble G -f 1-F() A eet __ pl Bete sterile es etal 9/2 es Fay by definition E(A)d(A)= dF (A) gives: D = edltat-F(2Nl = (1 F(A) ‘changing the variables from 2. to tin the RHS integral: “(-n(a)= f[ AO FO, ray Fe Je Mat @ =C “1-F) Exit concentration is when 2=0, F(0}=0 hence eqn (1) becomes: C,= Cu [ BWe “ae This is the same expression as for the exit concentration for the Segregation model. 13-20P13-4 (a) ‘Mean Residence Time ‘The area of the semicircle representing the E(t) is given by A E By definition [E@)adt = 3 2 For constant volumetric flow f,, = 7 x 08min t P13-4 (b) Variance o? = t—z) B@ar = feEz@a-c é a =r kos (x)+2cos(x)+ 3 Using Polymath: See Polymath program P13-4-b pol POLYMATH Results Calculated values of the DEQ variables initial value minimal value maximal value o 0 1.596 T signa ° 0 011593161 0.593162 tau 0.790869 0. 7980869 017980869 0.790869 ea 115961738 115961738 115961738 1.561738 E2 ° 6 0.798064 00166534 z ° o 0.7980614 0 .0166534 ODE Report (RKF45) Differential equations as entered by the user (1) dfsigmayat) = (Mauy'2"E Explicit equations as entered by the user TL) tau = (218.1405 12) W=2ttau [3] B2= (@ttautyyn1/2) [4] E sf (tet) then (E2) else (0) 1321020 ors oy] 0.08 oo OMyoy 032 061, 096 1281.60 P13-4 (c) Conversion predicted by the Segregation model ¥ Jx (E(e)dt a X(t)=1l-e" 2 fem? —(-2P) ar a ‘See Polymath program P14. pol x val Variable initial value minimal value maximal value final value e 0 0 1.596 1.596 xbar ° ° 0.4aa7s6s 0. dad7s65, tau 0. 7980869 0.798069 017980869 0. 7980869, el 115961738 115961738 115961738 115961738, 2 ° a 017980671 0. 0166534 E ° ° 0.7980671 00166534 x 0.8 0.8 ole ole x o ° o.7210716 07210716 ODE Report (RKF4S 13-22as oa 03 02 4 °° p00 0319 06H 0958 1377 1.596 X =44.5% P13-4 (d) Conversion predicted by the Maximum Mixedness model Sce Polymath program P13-4-d pol POLYMATH Results ‘Calculated values of the DEQ variables initial value minimal value maximal value ° o 1.596 x ° ° o.4aasze9 F 1 5.0538-04 1 kx 0.8 0.8 0.8 lam 1596 ° 11596 tau 07980869 0. 7980869 07980869 EL 00166534 ° 0. 7980666 E 00166534 ° 017980666 ODE Report (RKF4S Lirerential equations as entereu by te user TL) dtaQldte) = -Ck° (x) E/(1-F)X) (2) (Vda) = -E “Explicit equations as entered by the user my 596-2 (23.1408 (iau’2-(lam-tauy2)0.5 (ame=2"tau) then (E1) else (0) (3) 13.23 final y T a 5 0 ° ° 0 ° 7596 14445289 0538-04 ta 7990869os o4 03 02 4 © (00 0319 06409881277 1.596 X =44,5% as for the Segregation Model, but we knew this because for first order reactions Xseg= Xvae P13-5 (a) The cumulative distribution faction F() is give: 1 r Fo) ost °o 20 4 ‘The real reactor can be modelled as two parallel PERS sl |—+ r > pi The relative E(t) = {tow - +25( -%) ‘Mean Residence Time far = (10min*1) + (20min*0.75) = 25min a 13.24t= feta 5 i (7) fae -t ] 3 4, +=1, = 25min 4 P13-5 (b) Variance Je =) Beat = fr ta} ft = 75min? P13-5 (c) For a PER, second order, liquid phase, irreversible reaction with k = 0.1 dm’ /mol min, t= 25 min and Cao= 1.25 moV/dm? For a CSTR, second order, liquid phase, irreversible reaction with k= 0.1 dm* /mol-min'', ¢= 25 min and Cyy= 1.25 mold? x =ktCy,>X = 572 (x) 10 min and t)= 30 min, Fag, = 1/4Fay and Fag = 3/4Fap , second order, liquid phase, 1 dm’ /mol-min' and Co 1.25 mol/dm’ For wo parallel PER, irreversible reaction with k = k yp REE 80_€,, = 0.556mol din? 1FkECy, kes Caz = Cy -— 0.263mo/ dm? ae Ne TC me x= 4 4 031 P13-5 (d) 1-Conversion predicted by the Segregation Mode! 13:25i iat me ute FLFR gh 414KCg,T pe ee eens a) 1- Fa) LYMATH Results Calculated values of the DEQ variables variable maximal value final value z 40 40 x 0.7125177—0.7061612 F 0.9993 -L.osix-o4 0.9383, -1!0818-04 cao 1125) 125 1125 1125 x 2 oa 0.3 on lan 40 ° 40 0 ca 1.25 0.3614311 1.25 0.3672986 a 10 10 10 10 2 30 30 30 30 3 ° ° ° a ra 0.15625 -0.15625 -0.0130632 -0.0134908 #2 1125 1125 1125 1125 EL 1.25 1125 1125 4125 z ° a 1125 0 BF ° ° 2186049310 ODE Report (RKF4S Differential equations as entered by the user (1) d(xW/d(2) = -(ra/eao+E/(1-F)*x) fa dlFyae Expitont equations as entered by me user (1) cao = 1.25 [] ra= [3] E2=0.75/(2*2"(1-0.99)) [10] Et =0.25/(11°2"(1-0.99)) 13-26111) E = if (lam>=0.99"t1)and(lamet.01°t1)) then (E1) else if (lam>=0.99°t2)and(lam=t1)and(lame=t2)) then (E41) else(0) (10) EF =E/(1-F) ‘The conversion shows an inflection point in correspondence of z = 1, where start the pulse P13-8 (b) Introducing in the Segregated Model and in the MM Model (200001/300-177) k= kyo -e' ‘See Polymath program P13-8-b-L pol and P13-8-b-2.pol 300K 310K 320K 330K, 340K 350K. Xo 0.530, 0.82. 0.933, 0.974 | 0.989 0.995 Xue (0.521 0.806, 0.924 0.97, 0.987 0.994 ‘The discrepancy is greatest at 300K P13-8 (c) Adiabatic Reaction Introducing the enthalpy balance: pay + Cater) y = 305 4 40000 y YACm 50 ‘See Polymath program P13-8-c pol POLYMATH Results Calculated values of die DEQ vartables variable initial value minimal value maximal value final value bar ko. aL 2 2 cao B x 76864651 7.6864651 7.6364651 76864651 To. 305 305 305 305 8949502 3948702 8949502 8948702 3948702 13-34° ° 0.9430621 —-0.9430622 x . 308 308 1059.4497 1059. 4497 ODE Report (RKI Homy Differential equations as entered by the user sao] [1] d(Xbarjd(t) = XE Explicit equations as entored by the user reo} [11 ko = 0.3*exp(20000°(1/300-1/305)) (2) t=1 8) ta) (51 460) (61 my [8] 300, [9] X= 1142" Ca0r eS ° (10) T= To+800"% P13-9 (a) 3" order, k=175 dm’ Amol min), Cpo=0.0313 dim'/min (LER, PFR, CSTR with t=100s) PFR aX 2 Design equation v,C,,——=kC,C, ign equation VC ay Fy =KC4Cy C,=C,,(1-X) 0.168 = 0.832 ‘The conversion for a PFR X=83.2%csrr Design equation v,(C,, ~ 1 =kC,C," C, =Cy(l-X) Cy =Cuoll-X) =x x =k, xh ‘The conversion for aCSTR X=66.2 % LER (completely segregated) E@=0 for tu at Rt for p=w2 ‘t= VWv=1000/10=100s=1.67min reat See Polymath program P13-9-a pol POLYMATH Results Calculated values of the DEQ variables Variable initial value value maximal value final value t T.0B-05, 1. 08-05, 100 100 bar 0 ° 0.1827615 0. 1827616 ebo 0.0313 0.0313, 0.0313, 0:0313 x 175 175. 275 175 tau 1.67 1.67 1.87 1.67 EL Li3e4gsa5 21 4038-06 iisgagias 1 4038-06 * ii7iae-o6 a!714n-06 alaaisnng =a /aaasonn s 0 0 O14g0215 1.403E-06 ODE Report (RKF45 Differential equations as entered by the user 1) dlxbaryia(t) = ee Explicit equations as entered by the user 13:36taur2i(2""3) -(4(1+2"k*cbor2"))"05 i(t>=tau2) thon (E') else (0) ‘The imegral X= JX (E()de gives mean conversion=185% 3 P13-9 (b) (Segregation Model and Maximum Mixedness Model applying RTD of Example 13-1) Segregation model —aNa dt =-1V Batch reactor Similarly 1+ 2kC,, | be Jx@EWar and E(t) from the given data, fitted using Polymath See Polymath program P13-9-b-regression.pol POLYMATH Results Polynomial Regression Report Model: Cuz = arG0! + a2 GOIM2 + u3'CO1"S + atCO1s Variable _value 95% confidence al 970889237 9.0424295 22 ~0.0157181 0.016371 3 7.9268-08 0,0019617 ad -8 1632-06 2888-05 General Order of polynomial = 4 Regression not including free parameter Number of observations = 13 13.37Statistics 0.8653673 0.8204897 0.0085707 8.107E-04 POLYMATH Results Calculated values of the DEQ variables Variable initial value minimal value maximal value final value t ° 0 Ta 14 bar ° ° 0.106313 -0.4106323, F ° ° qlais7eaz «13237842 cho 0.0313, 0.0313 0.0313 90313 ® 175 15 475 175 x 6 6 0.5ea7a98 0.547898 E ° ° 01566631 00199021, ODE Report (RKF45) Differential equations as entered by the user [11 d(xbaryd(t) = Ex (21 dFya() =E Explicit equations as entered by the user {2} cbo = 0.0313 (2) k= 175 13] x= dz eDO OS [4] E = 0,0899297"-0.0157181"1'2+0.000792"1'3-0.00000863""4 os 04 03. 02 “oo” te 86, a4 a2 140 X =41%. Maximum Mixedness & 4, BY) y dA Cy 1-F(A) Rate Law:— 1, =kC,C,” 13.38Cy =C,,(1- X) C,,(I- X) KC 4 Cp," (1— XJ" where ke175 dm“/mol? min =B(z) where 2-1 See Polymath program P13-9-b-2.pol POLYMATH Results Calculated values of the DEQ variables value min. value maximal value final value 0 Tt 1d ° 0.3536026 03536026 F 0.9999 0.113884 019999 011238842 cho 0.0313 0.0313, 910313 0.0313, k 475 175 175 115 lam ia o 1 ° cao 0.0313, 0.0313 0.0313, 0.0313, ca 0.0313 00202322 0.0313 00202322 E 0.0199022 ° 0.156664 ° =F 199.0212 ° 199.0212 0 cb 0.0313 0.020232 0.0313 0.020232 ra -010053663 00053663 -0.0014493 00014493 ODE Report (RKE4S) Differential equations as entered by the user Explicit equations as ontored by the user a (21 Gr (a1 [51 Ca=Cao%(t-x) [61 E = 0.0899237"Iam-0.0157181"lam*2+0.000792"larn’-0.00000863"larn4 (71 EF =EN1-F) [81 Gb = Cbo"(1-x) [9] ras -kCa'cb2 XH35.4% P13-9 (c) Exit time(t), internal age(a) and life expectancy [ewe rj 0 at) win (9 is bined fom the polyoma fin Pat @) 13.39Ha)=Fl-Fla)] Intensity Function P13-9 (4) Adiabatic reaction Segregation model ax KCp." (1X) ac,,MI-X) Where Hr) = koexp| =( : =175exp] 200 i RUTo T 8314(320 T ~AHrx Os and r(x)=t04[ x =0s150x X= [x(E()dr and BW» from the given data. See Polymath program P13-9.4-L pol POLYMATH Results Calculated values of the DEQ vartables Variable initial value minimal value maximal value final value e 0 0 Ta Ta bar o ° 0.7585435 0. 7585435, F 9 ° 3l1a37882 111137842 x 0 0 018973303 08973303, cbo 0.0313 0.0313 0.0313 0.0313 ? 320 320 454.59954 454.5954 E ° ° 0.1565966 0.019021, ® 175 175 4931.8727 493.8727 ODE Report (RKF4S) Differential equations as entered by the user [1] disband) = E*x (21 arya Cebor2"(1-x)°8 Explicit equations as entered by the user 0.0313 320+ 150"x (0.0899237"1-0.0157181"'2+0.000792"1'9-0.00000863"1N4 '75*exp(30000/8.314"(1/320-1/T)) 13-40in) = E(1_1)|_ 3000/1 1 swe (¢)= hoes BL B)-rrsen| 2 ( 3] and T(K) toa(=2e 320+150X Ps See Polymath program P13-94-2 pol POLYMATH Results Calculated values of the DEQ variables Variable initial value minimal value z ° ° ~ x ° ° 0.7189248 0. 7289248 F 0.9999 -0.1138842 019939 -0.1138842 cho 0.0313, 0.0313 0.0313 0.0333 T 320 320 427,93873 © 427.63873 lam 4 ° 4 ° cao 0.0313 0.0313 0.0313, 0.0313 ca 0.0313 0.008797 0.0313 0.008797 E 00193021 ° 0.1566233 EF 199.0212 ° 399.0212 ° cb 0.0313, 0.008797 0.0313 0.008797 kK 175 175 3001.8809 301.8809 ra -0.0053663 0.007411, 0.020441 -0.0020442 ODE Report (RKF45) Differential equations as entered by the user [11 d0Qid(z) = -(ralCao+E/(1-F)°X) [21 dF yale) = -E Explicit equations as entered by the user [1] Cbo =.0313 (2) T=920+150°* (2) lam= 14-2 Cao = 0313 Ca =Ca0"(1-x) E = 0,0899237"Iam-0.0157181*lanv'2+0.000792"lam/3-0.00000863"am 4 EAI-r) Cb = Cbo"(1-x) 178" exp(30000/8.914*(1/820-1/T)) K°Ca’Ob2 1341080 064] 0.3 032 os} “Go a8 86, 4 M2140 ives Ifthe reaction is carried out adiabatically the conversions are more than doubled. P13-10 Irreversible, frst order, long tubular reactor, constant volume, isothermal dX —=kC,,(1- X. sw Gy = #Caolt- X) ax _k ——=— [av 1-x a For X = 0.865 => kr For laminar flow with negligible diffusion (LFR), the mean convetsion is given by X= peo JE (tat = fx E(t)ae x()=I-e E() forlaminar flow=—— where #2 = 2° “2 Therefore X= fle \Ear= joa We can apply the approximated solution due to Hilder: 13.42= 00.782 - (4+ Da)e*™ + Da where Da=ke=2 a (4+ Daje®** + Da-4 ¥ $0,782 < X pop = 0.85 P13-11 (a) First Moment about the mean: by definition is always equal to zero. r-T=0 m= fc sel a = feet fel Imesin = Pion = Mure =9 P13-11 (b) Second-order liquid-phase reaction Da= tkC,y=1.0,1=2min and kCy,=0.5min". csTR x Second-order ~ 1, x ‘ KCL Cy, (1X)? Solved 7 Fa (1+2Da)-ViF4Da _5 455 2Da 13.43(=x) (+ex) x vary [ee meen Cle Liquid-phase « = 0 and integrating 1 [ x Jax= Da KC, LI-X 1+ Da LER In the ring globule of radius + dy 2 <4 = 1, Where — ry = KC’ renee) ra = RCA, (order batch) 0 for t<1min E()= LER) © |4120°)min for t>1min « 2 Kay [* + ACao) KC fs = xX XE =fic cree 5 Nee w | os 20 bP WemC,) + ial 2 . . Okay ~etc of HEE) ~odi-Ben(4 “pei 2 t t eid 2 Dal2 Evaluate for Da=1, X = 0.451 ‘See Polymath program P13-11-b.pol CSTR = PFR ‘LFR 039 tos 0451 P13-12 KC, -r =H “GRY 13-44<0 XigXva “The following figure shows the reaction rate as function of the concentration. oor 0.005 4 ° ‘The second derivatife is initially Wgative (X 466.) then pORitive (Xing>May). The flex point is for Ca=8moVdm? (%iq=XMM). Ca In the limit of low concentration = ry =kCy+0(C4)> First order) and Xeg=Xnne in the limit of high concentration Fed or ee Ky, Cy P13-13 No solution will be given P13-14 (a) Liquid phase, Segregation Model, second order, non ideal CSTR, adiabati: Xie xt.r)ee\ar=0 67 E() lw) and ‘feletar = img sin dn’ fel ° E(t)=IF (t<=1) THEN (1) E (IF (t>=2) THEN (0) ELSE (2-1) ax For abatch globule: Cy =—ry at 13.45-rm =k? C4 =Caoll-X) aX KC, (1- XP a 7 RCaoll-X) Where C4,=2 molidm? Ea 1 1 =0.5exp) —22-( H(r)=05ex f(s 2 T=To+ eX ©, +ACPX whete Cy, = BC y = Cy, +0= 50S /mol- K 100/250 ACp =1/2C, -C, T=300+150X Iterate with Ea, using the ODE solver for values of X(t:T) and substitute these into the polynomial regression to evaluate the integral X Jx(.r)e@ar =0.67 a An activation energy Ea of 10000 J/mol gives approximately the correct mean conversion, X =0.67. Inaccuracy lies in the polynomial fit and hence the integral area. See Polymath program P13-14-a pol POLYMATH Results Calculated values of the DEO variables Variable jal value maximal value finel value e o 3 3 bar ° 0.6673438 © 0.6673438 x ° 019198721 0.198721 ca0 2 a 2 r 300 437.98082 437. 98082 BL ° 5 3 E 2 a a z o 0.9933851 0 x 05 24247011 2.247011 ODE Report (RKFS Differential equations as ontored by the user [11 doxbaryid() = Ex [21 d(xyd(t) = krea0"(1-x)*2) Explicit equations as entered by the user (11 ca [2] T=900+150"% 13-46(1 et [4] E2=ot [5} E = if (Le=1) then (Et) else (i (t-=2) then (0) tse (E2)) 6} Ea= 12500 [71 k= 0Stexp(Eals.314"((1/800)-(177)) P13-14 (b) Parallel reactions, isothermal, segregation model atch globules Exit concentrations dC, te. =C Bt) Maver. CyE(t) Achar — at = CoE lt at = CoE) E()=IF (t<=1) THEN (1) ELSE (IF (t>=2) THEN (0) ELSE (2-1)) Selectivity S Iteration with kycuntil $= 2.38 gives kae= 0.3755 dm? /mol min ‘See Polymath program P13-14-b.pol P13-15 Reactor: fluidised CSTR (V=1m?; F=10dm'Ys, C-?=2 Kmol/m") += 1000dm’s/10dm?= 100s ‘The system of complex reactions for the Kentucky coal n 9 is given by ae SE 2 -kyCp -bC, 7 phy Meo KC +kiCy— byl dr 13.47Ms 2 be h,Cp —haCy ss dy dt P13-15 (a) Segregation Model See Polymath program P13-15-a pol POLYMATH Results Variable initial va! imal value maximal value final value t 0 20 20 ca ° 900.42918 900. 42918, os ° 68961265 68961265, ce 2000 1383.5708 2000 1383-5708 cabar 0 o 137.10239 © 137.10239, cpbar o ° 4.011527 46.011527 cebar 2000 2000 398.5578 3988.5578 co. 6 6 466.78695 466. 78696, cobar ° ° 91391124 9.1391124 ka 0.012 0.012 0.012 0.012 2 0.046 0.046 0.046 0.046 13 0.02 0:02 0.02 0.02 ka 0.034 0.034 01034 0.034 XS 0.04 0.04 0.04 0.04 re ° -49.695094, ° ~49..695094 ra 92 10.804749 92 10.804749 24 24 37,5424a5 331425188 tau i667 1.667 1.667 1.667 ro ° a 36.017167 -36.017167 E 0.59988 3.6958-06 0.59988 3.695B-06 Spo 2.4B+08 19280349 214E+08 019280349 ODE Report (RKFS5) Differential equations as entered by the user i) (2), dlep)/d(t) = mp 13) dleoyatt) = (4) dleabarya() 15]. dlepbar)d(t) = op" {6} d{ccbar)a() = core (7) dlcoyiat) = ro {8}, d{eobar\a() = co Explicit equations as entered by the user Th} kt =0.012 (2 BI (41 (1 (el i (8) [11) B= exp(ttauytau 13.4812] Spo = rpi(ro+0.0000001) The exiting selectivity is 0928 P13-15 (b) ‘Maximum Mixedness model ‘See Polymath program P13-15-b pol POLYMATH Results Calculated values of the DEQ variables Variable initial value minimal value paximal value final value 2 0 0 20 20 ca ° ° 75.1273 875.1273, ce ° ° 631.80972 63180972 ce 2000 2463.3111 2000 463.3111 co 6 o 40843732 40843732, P 1 6 1498-06 1 6.149B-06 kL 0.012 0.012 0.032 0.012 x2 0.046 0.046 0.046 0.046 3 0102 0.02 0.02 0:02 ka 0.034 0.034 0.034 0.034 KS 0.04 0.04 0:08 0.04 re ° ~47.836902 ° 47836902 za 92 15.190182 82 15,190162 =» 24 24 37.327161 34.6737. tau 1.667 i667 3.667 1.667 ro 0 ° 35.008509 —-35.004509 zB 0.59988, 3.6958-06 0.59988 3.6958-06 Spo 248408 0:9906544 2.4m+08 019906544 EF 5.999807 36958-06 519998407 -3.6952-06, sigma a a 3 3 cao a a 6 6 po o ° ° 0 ceo 2000 2000 2000 2000 coo 6 6 ° ° ODE Report (RKF45) Differential equations as entered by the user [11 a(Cayiala) = --ra+(Ca-Cao)"EF) 12) d{(CpV/d(z) = --1p+{Cp-Cpo)EF) (3), d{Ceyd(2) = -(10+(Co-Coo)"EF) 4) d{(CoVid(2) 5) dlFYal2) = -E r0+(Co-Coo)EF) Explicit equations as entered by the user (1) kt =0.012 (8) p=kt*Coskd*Caks'Cp (9) tau= 1.667 KeCa »xp(-zfauytau [12] Spo = rp/(ro+0.0000001) 13) EF=E(1-F) 1349(27) Ceo = 2000 (18) Coo=0 P13-15 (c) ‘The selectivities are reported in the following table: SMMpre XMMcsia Xsmore Xsmesre 483 099 4474 0.92 P13-15 (d) Normal Distribution with t = Smin and o = 3min Segregation Model See Polymath program P13-15-d-1.pol POLYMATH Results Calculated values of the DEO variables Variabl al valve minimal value maximal value final value e 0 2 2 ca ° 171.75027 —171.75027 a ° 52.079376 52.879376 ce 000 991.2989 2000 1991.2989 ‘cabaz ° li.iie671 11.1667, cpbar ° 3.268987 -3.2689487 ccbar ° 221.39065 -221.39065 co. ° 7,0306771 7.030671, cobar ° 013200147 03200147 kL 0.012 0.012 0.012 0.012 pe 0.046 0.046 02046 0.046 x3 0102 0:02 0102 0.02 a 0.034 0034 01034 0.034 xs 0:04 0.04 0.04 0.04 re 0 85350648 0 85350648 ra 82 79.947816 92 79.947816 rp 24 24 28.677508 —-28.677508, signa a 3 3 3 ro 0 0 6.8700107 68700107 tau 5 5 5 5 Spo, 2.408 4.1743032 2.48+08 4.174032 EL 10 10 10 10 E 0.031675 00331675 0.080674 00806774 ODE Report (RKF45) Differential equations as entered by the user (11 d(cay/a(t) = ra (21 d{epyd(t) = rp [3] d{ce)/dit) = re [4] d(cabar)/d(t) {5}. elepbar)at) [6]. dlccbar/d(t) = co*E (7) eoytt {£5} aleobaryat 13.50