CHAPTER 1 1.1. For the thermal cracking of ethane in a tubular reactor, the following data were obtained for the rate coefficient at different reference temperatures: Tec) 702 725 734 754 773 789 803 810 827 837 Kis") 0.45 0.273 0.933 0.595 0.923 1.492 2.138 2718 4.137 4.665 Solution ‘The Arrhenius expression E k = Aexp| -—— ter) is transformed logarithmically into: E Ink =InA~ For each data point Ink and 1/T is calculated: x= IT 108 y=ink 1.025 1.897 1,002 =1.298 0.993 =1.100 0.974 0519 0.956 0.080 0.941 0.400 0.929 0.760 0.923 1,000 0.909 1.420 0.901 1.540 ‘The slope and the intercept (In A) are calculated by linear regression: pre Ro Oy N na = DYE N with x= 1/P and y = Ink,So: -= = 28497. or E = 56623 keal/kmol or 2.37-10° ki/kmol. In A= 27.245 or A=6.800-10"' st 1.2. Derive the result given in Table 1.2.4.2-1 for the reaction A+B>Q:+S. Solution A+B >Q:S ‘The continuity equation for species A reads: ac ST RCAC a To integrate (1), Cy has to be expressed as a function of Ca’ Cy = Cp, (Cay Cad Hence, & dc, k AENEn, Cn FOG or Expressing the concentrations C, and Cy as a function of the conversion of the reactant, Xa Cx =Ca,(l-x4) Cy=Cu, —(Ca, Ca) En, Ca, Calla) = Cy, —Ca,Xa Hence Cp, Cn, 1-X4) OG, Cara)or with 1.3. Derive the solutions to the rate equation for the first order reversil in Section 1.2.3. le reaction given Solution or This is a standard form, with integrating factor expl fk, +k)dt] = exp[k, +k,)t]} Thus and Ca= Cao, leading to ky KE, BC Q, tu ste = (Cy, + Cg, Ra + Bt Hat thst (+64, Kk, +k, ktk, ° which is the solution given in Section 1.2.3. ‘The alternate approach in terms of conversions is somewhat simpler:Then or 1.4, A convenient laboratory technique for measuring the kinetics of ideal gas phase single reactions is to follow the change in total pressure in a constant volume and temperature container. The concentration of the various species can be calculated from the total pressure change. Consider the reaction aA +bB+... > qQ+sS+.. (a) Show that the extent can be found from: Vp, -P..) = RT(Aa) where a =q+...-a-b- (Note that the method can only be used for Aa +0.) (b) Next show that partial pressure for the j" species can be found from Fb.-p..) P; (c) Use the method to determine the rate coefficient for the first-order decomposition of di-t-butyl peroxide(CH,),COOC(CH,), > 2(CH,),CO+CH, ‘The data given below are provided by J.H. Raley, R.E. Rust, and W.E. Vaughn [.A.CS., 70, 98 (1948)]. They were obtained at 154.6°C under a 4.2-mm Hg partial pressure of nitrogen which was used to feed the peroxide to the reactor. Determine the rate coefficient by means of the differential and integral method of kinetic analysis. (min) __py(mm Hg) ° 173.5 2 187.3 3 193.4 5 205.3 6 211.3 8 222.9 9 228.6 1 230.8 12 14 15 7 18 20 24 Solution a) For 0=)oa,A; Thus,V (rp) RT da b) Use akc, kPa KI, CDG ake, eB El, + 2 6, | or Sb, ~p,)= ain, 4b, -P, Integrating yields: Pay -4b, -p,) Pay In} kt The integral method uses a plot of In [ ] vs. t, and the slope gives the value of k. Alternatively, a linear or nontinear regression method could be used: k = 0.0193 min", ‘The differential method utilizes slopes from the (p, ~p,, ) data plotted vs. [> 7 30. Pa, )} the slope of which, or regression techniques, gives the rate coefficient:0.5 0.4 0.2) Slope = 0.0193 min" 0.1 0 5 10 15 20 25 time(min) 1.5. The results of Problem 1.4 can be generalized for the measurement of any property of the reaction mixture that is linear in the concentration of each species: a, =K,C, s in Problem 1.4) various spectral properties, ionic The A, could be partial pressures ( conductivity in dilute solutions, and so on, Then the total observed measurement for the mixture would be: a=YA=UKC, a) For the general single reaction, Bs show that the relation between the extent of reaction and 2 isb) After a long (“infinite”) time, the extent E,, can be evaluated for irreversible reactions from the limiting reagent, and for reversible reactions from thermodynamics. Use this to formulate the desired relation containing only measured or determined variables (see Frost and Pearson [41]): wok EL ‘The total observed property for the mixture is given as n=DKC, 7 a) For the general reaction Lady =0 the concentration at reaction extent & is -YKC, ay ka }é constant volume b) For infinite time, either €,, can be found from the thermodynamic equilibrium constant, Ke ufc, ou’) or from the iting reactants: g O= Coun Fae == In either case from part a)& Ros hot LGK Solving for the extents, _Anay Vo Lak, and f. _enho Dividing the two gives the desired result: — AAA 1.6. Show that the general expression for the concentration at which the autocatalytie reaction of Section 1.2.3.3 has a maximum rate is Co if 14 e| Coo max 2 Cao Note that this agrees with the specific results in the example. Solution From Section 1.2.3.3, the rate written in terms of only Co is: =k,(Cy-Cy Eg - KC}, ‘The maximum rate will be at 6r/6C, {Cp 2k Cg -2k Co or where K is the equilibrium constant. This can be written asfor the irreversible case with K — 00, as in the numerical calculations. 1.7. Derive the concentration as a function of time for the general three species first order reactions: 1 A => Q 2 Xe f s These should reduce to alll the various results for first order reactions given in Sections 1.2 and 1.3. Also determine the equilibrium concentrations C aes Coca: Csea in terms of the equilibrium constants for the three reactions. Solution ‘The general solution method is best explained in terms of the complex reaction network notation where the rate for the j" species is given by: dy, x Genki t kava +E y+ - a t A solution is assumed of the form: yi Q) where Y; and 4 are constants to be determined, Substituting (2) into (1) gives YC rJe* = kyYo" +. CD 'k, Ve" +. or kiY) tkp¥s+-+1- Yk, aly, +..=0 @) If equations (3) are written out for each of the j = 1, 2, ... N species, they form a set of N equations for the N unknown, Y;. Note that they are homogeneous algebraic equations (RHS =0), and so they only possess solutions if the determinant of the coefficients is zero.(De) ken kw Ky OD) ks kay (@) k, k, o we Kw Dk When multiplied out; (14) will be an N" order equation, with N-roots. For each of these roots, a set of the constants Y; can be found from (3): Yjr Then the general solution will be 6 YE LOY ert 6) where C, are constants of integration to be found from the initial conditions. For our specific problem, the determinant, (4), is: P- (Kk) ky ky ky An(ky+ke) ke © ky ks A-(ky +k, which when expanded gives: ak, +k, +k, +k, +k, +k,)+k(k, +k, +k,) +k,(k, +k, +k,)+k(k, +k, )+k,k, or aQ? -aar+B)=0 a Thus, the roots (eigenvalues) are (8) (Note, Wei-Prater would number these 2y,2,.23-) Then the solutions will have the form Cy =CyYq) CY yet $C, Ye 9) Cy =CyYqy + CzYqe + C3 Yq3e (10) Cy = Cig) + CY ge + Cs Ye ap where the Yjp are found fromPry (ky +a IM, HRY, +I Yoe KY, +L, -(k. +e Wn +k eYa, =0 (12) KaYie thsYas +L hy “(ks tks Va, =0 for each of the ), (actually, only two of the equi the Yj-can be found in terms of the third), jons will be independent, and so two of Finally, the integration constants, C,, are found from the initial conditions: Cay = CY qi HCa¥ar +CsY us Coo = C1Vq) +CrYon $C Yor (13) Cu =CVYe, + O2Y qo $CYey Clearly, these manipulations are most casily done utilizing matrices. The equilibrium concentrations will be found from (9)-(11) for t > 2 Carey =CiV at 4) where Y1 and C; are known in terms of the ky and initial concentrations. From the principle of microscopic reversibility, it is also time that each reaction is individually at equilibrium, leading to: (as) with KKiKy (16) The total mass balance is Cy FC g #Ey = Cay + Coy HOw = Cy an Then, ing (17) and (15):or Similarly (18) 1.8. For the complex reactions aA +bB—15qQ 4'Q+b'B— 458 (a) Use (1.1.2-15) and (1.1.2-17) to express the time rates of change of N,, Nuy Nos and Ng in terms of the two extents of reactions and stoichiometric coefficients a, b, b’, 4, 4’, and s; for example, a 8 gy fee dt dt dt (b) In practical situations, it is often useful to express the changes in all the mole numbers in terms of the proper number of independent product mole number changes—in this case, two. Show that the extents in part (a) can be eliminated in terms of dNo/dt and dNe/dt to give aN, dt ay, dt This alternate formulation will be often used in the practical problems to be considered later in the book (©) For the general reaction‘The mole number changes in terms of the extents are or dt where N is the N-vector of numbers of moles, & is the M-vector of extents, and a" is the transpose of the M x N stoichiometric coefficient matrix. Show that if an alternate basis of mole number change is defined as an M-vector ane dt that the equivalent expressions for all the mole number changes are vast Boone where a” is the M x M matrix of the basis species stoichiometric coefficients. Finally, show that these matrix manipulations lead to the same result as in part (b) if the basis species are chosen to be Q and S. Solution aA+bB>qQ & (a) dQ+bBoss &, Thus, o @ a) a (b) Rearrange for & and E> in terms of No, Ns:© () (6) a) Ne= (8) For the general reaction x 0= Yaya, i=1,2....M o a ‘The change in mole numbers is: N=[al"é (10) If the new M-vector basis species are N i) the M x M matrix of basis species stoichiometric coefficients is part of the total stoichiometric matri: e=[e'ne:] oy) (The stoichiometric coefficient matrix can always be arranged to have the new basis species coefficients first.) Now the subset of the mole number change equations for the new basis species are: N {err fi: (13) which is equivalent to (3)-(4) above. Then solving for the extents gives IZ E={err}' (14) which is equivalent to (5)-(6) above.Finally substitute (14) into (10) to give the desired results: > Setal"{taty fs as) This general result can be used to define any conversion basis in a complex reacting system. It is instructive to use (15) for the simple example of part (b). aA +bB > qQ dQHDB ss as in part (a). Now choose the alternate basis vector: wi =|Ne Ns and [ss] Then, working out the intermediate matrix steps: pr _|d -o [el [i “]and -a 0 ce tie hy = qo-q 0 s aq’ —bq'-b'q ag-da ws —alq —aq'/qs _| =blq_ ~(bq'/qs) — b/s “| 0 o 1 Finally, or1.9. Show that the overall orders for a free radical reaction mechanism with a first order initiation step are 3/2and 1/2 for a BB, respectively [JH termination. Solution (a) BB termination A,—*52R} Rj +A,—S>RiH+ +k ype RU POR} +A, RJ +R{—>A, Disappearance rate of reactant Ay Am hy +l y Cy, —KiCR 1 Ge THs, aCe, Ca, —KiCh, wo Steady state for the intermediate radicals R} and R3: Cp, Gen ARCs, “KCe,Ca, HRaCa, ~2RCE, = 2 dCy Gera BaCa.Ca, “KC, =9 ey From (3): kCp, =KiCy, Ca, Elimination of Cy, from (2) yields: Cy, —KyCy, Cy, HRICR, Ca, —2KCe, =O (4) (5) since k; is negligibly small() pH termination A, 9 2R} RJ +A, —2>5R,H+R} Ri >A, +R) R3+R3— >A, Disappearance rate of reactant Ay -aC, at 1Ca, +K2Cx Ca, Steady state for the intermediate radicals Rj and R3: ac, = 2KiC4, —kaCa, Ca, +hsCe, dt aC, KCy, Ca, —KiCe, = 2k sC2, = 0 Solution of (7)-(8) for Cy, and Cy, yields: ky ky Vs (6) a) (8) (9) (10)1.10. The thermal decomposition of dimethyl ether CH,OCH, > CH, +CO+H, or CH,OCH, > CH, + HCHO is postulated to occur by the following free radical chain mechanism: CH,OCH, —*>CH; + OCH; CH; + CH,OCH, —* >CH, +CH,OCH; CH,OCH; —" >CH; +HCHO cl 1,0CH; —*>C,H,OCH, (a) For a first order initiation step, use the Goldfinger, Letort and Niclause table [1948] to predict the overall order of reaction. (b) With the help of the steady state assumption and the usual approximation of small initiation and termination coefficients, derive the detailed kinetic expression for the overall rate: _a(CH,OCH, dt .(CH,OCH, and verify that the overall order, n, is as predicted in part (a). Also find ko in terms of ki, kas ks, Kee (c) If the activation energies of the individual steps are Ey = 80, Ez = 15, Es = 38, Ey = 8 Keal/mol, show that the overall activation energy is E, = 62.5 Keal/mol. Solution (a) _ The termination is of the type BH. Hence, for a first order initiation, the overall order of reaction is 1. (b) Disappearance rate of CH3OCHs a(CH,OCH,) t ~k,(CH,OCH, )- k, (CH; \CH,OCH,) wo Steady state for the intermediate radicals CH OCH and Cl cts) k,(CH,OCH, )- k, (CH (CH,OCH,) \ 2 +k, (CH,OCH3)~ k, (CH (CH,OCH;)=0AICH.OCHS) _ (cus )cH,0cH,)-k,(CH,OCH) dt GB) —k,(CH3)(CH,OCH; Solving (3) for (CH,OCH%) yields: 4) Substituting (4) into (2): k,(CH,OCH,)~k,(CH})CH,OCH,) th, k,(CH3\CH,OCH,) __k,(CH3}, (CH; \CH,OCH. Kk, +k (CH; k,+K,(CI kaki (CHS) Kk, (CHS) ky =0 or ‘The terms k,k,(CH;) may be dropped because ky and ky are small compared to the other k’s. Hence +) kiks (cH;)=- 2 5 (cus) 2k:k, ” Substitution of (5) into (1): ~MEROCH) 4 (cH0CH,) Hk, ah H,OCH,) 6) The apparent rate coefficient reads: KKK (©) The overall activation energy is determined by means of (7):£(@0-+15+38—8) =62.5 keal/mol Ll. K. Laidler and B, Wojciechowski [Proc. Roy, Soc., A260, 91 (1961)] provide the following table of individual rate constants for ethane pyrolysis: Reaction a E (Keal/mol) 1 10" 85.0 1 order initiation la 107 70.2 2" order initiation 2 2.0 10" 10.4 hydrogen abstraction 3 3.0 104 39.5 radical decomposition 4 34 10" 68 H’+C,H, oH, +C,H: 5 16 108 0 H’ +C,Hz > termination 6 16 10% 0 I: + C,H; — termination sins or em’ mot! s" (a) _ Derive the overall kinetic expressions for the four combinations of the two possible initiation steps (I or La) and the termination steps (5 or 6). (b) Compare the overall rate constants at T = 837°K with the experimental value of 8.4 107s" (c) Show that the ratio of the rates of reaction 5 and 6 is given by: ry kike 1 r, kk, C,H, (4) Calculate the “transition pressure level” where terminations (5) and (6) are equivalent (rs = r4) at T = 640°C, and compare with the measured value of 60 mm Hg. At this point, the overall reaction is changing from 1 to 3/2 order. Solution (a) Reaction scheme: 1. C)H, > 2CH} la. X+C,H, —“-52CH3 +X 2. C,H, +CH} —2>CH, +C,H} 3. C,H} —*>C,H, +H"4. C,H, +H’ 9H, +C,Ht 5. C,H} +H’ —*>5C,H, 6. C,H} +C,H} —*>C, Hy, Case 1: initiation | + termination 5: Disappearance rate of CsHe: 4080 emg -aenens)-e4es He) + ks(CzH)H") Steady state for radicals CH3,C,H3,H" : AC 2 fe) ke Hen) =0 MEME) 4 (cor) Cat) 4 (Ca (") dt —k.(C,H; (Ht MO) (eH) CaH ARE) -KGQHEH")=0 dt From (2) From (4) k, (CoH, (H") (C,Hz = tr) Substitution of (5) and (6) into (3): kk, (CoH, }H") (cso, SECHOM fes er) Since ky and ks are small: a Q) 3) @) (5) (6)(er)- fe Kiks and [ek (cH) Vik Substitution of (5), (7) and (8) into (1) yields: (cus a(CH,) _ [KiKaky (CH de - (C,H) Case 2: initiation 1a + term i Disappearance rate of CoH¢: alC,H,) =-ki,(CH,)*-k. +ks(CH3)H") Steady state for intermediate radicals acH) __, at Balances for (C,H3)and (H") are equal to (3) From (11): (c= (C,H) ky Substituting (6) and (12) into (3) yields: (CH, )2k,.(C.H,)~ Neglecting the terms in kiks: aH, xe Hi) kk.(CoH,\H") |’ 2(CoH,XCHS)}-k,(CoH,\H") Pk (CH,) — ky (CH,(CH3)= 0 and (4), +k(CHH") oO (8) ) (10) ay (12) (13)Substitution of (13) into (6): Peeks (ey Vksks or ‘Substitution of (12), (13) and (14) into (10) and neglecting terms in ky yields: Steady state for intermediate radicals: For (CH3) see equations (2) and (5): sles) =-k,(C.H, (CHS )—k, (C,H (CHS) k.(CH, XH) ~k (CoH; =0 AW) (ca)-kenottr dt From (18): Substituting (19) and (5) into (17) yields: en (c.u3)= Hence (4) ) (16) a7) 18) (19) (20)2D ‘The rate expression thus becomes: (C,H, 2k, 2k, (cs = hy (CoH) kalGH,) eta oH)” Neglecting the terms in k; yields: 22) Case 4: initiation 1a + termination 6 : Disappearance rate of CoHe: ee = ky (CoH)? ke (C. Hg \CH3)-k, (CH, XH" 23) Steady state for intermediate radical For (CHS) see equations (11) and (12). For sear) and ster) see equations (17) and (18). ‘Substituting (12) and (19) into (17) yields: (c.Hs)= [Evea) (24) Substitution into (19): (w)-© [Ph (25) ORV Rs Hence, the disappearance rate for C3Hg becomes MEME) (CH) 2 (CHF “ky ACH) 6 After neglecting the terms in ki:(26) b) Case 1: [KKK ks Case 2; _[Kiakika ks Case 3: [RK ks Case 4; fk k, First calculate the rate constants of the individual reactions at 873°K. ky 5.296 10° ks 6751 10'° Ki 1746 10° ks 16 10" ks 3.890 10° ke 16 10° With these individual rate constants, the overall rate constants become for: Case 1: 9.3 107 st Case 2: 1.19 10"! em“? mol? s Case 3: 1.00 107 cm *? mol Case 4: 1.82 107s" from (8) : (C,Ht)= Hence:(@) i _keky 1 Te Keky (CoH) ks and ke are equal. At 640°C, ks is equal to 1.05 10° and ky is equal to 8.01 10". Hence: (C,H,)= = 1.31 10° moVem? 8.01 10° = 0,098 atm =74mm Hg Experimentally, 60 mm Hg is observed. 1.12. ‘The overall reaction for the decomposition of nitrogen pentoxide can be written ast 2N,0, > 4NO, +0, The following reaction mechanism is proposed: N,0, > NO, +NO, NO, +NO, +N,O, NO, +NO, > NO, +0, +NO NO+NO, +2NO, If the steady state approximation for the intermediates is assumed, prove that the decomposition of N,O, is first order [Reference: R.A. Ogg, J. Ch. Phys., 15, 337 (1947). Solution In steady state:a(NO,) at =k,(N,0,)—k,(NO, (NO,)—k,(NO(NO,)—k,(NO\NO,)=0 or k,(N,0,) aw k, +k, (NO,)+k,(NO) atx) sf, =k, (NO, (NO, )—k,(NOXNO,)=0 or ky (xo) = (wo, ) @ Substitution of (2) in (1): k,(N,05) No, )=——SitN20s) 3) (wo, k, +2k, (NO) ° ‘The rate of decomposition of (N,O,) is given by a(N,O;) ‘dt (N,05)- k(NO, (NOs) (@) Substitution of (3) in (4): (N05) __ 2K Oy 0.) 6) dt K+ 2k; ‘The previous reaction was carried out in a constant volume and constant temperature vessel, to allow the application of the “total pressure method” outlined in Problem 1.4. There is one complication however: the dimerization reaction 2NO, N,O, also occurs. It may be assumed that this additional reaction immediately reaches equilibrium, the dimerization constant being given by: logK,, = 26 —logT - 9.132 (T in °K; Ky in mm") The foll data were obtained by F. Daniels and E.H. Johnson [J. Am. Chem. Soc., 43, 53 (1921)] at 35°C, with an initial pressure of 308.2 mm Hg:t (min) 40 50 60 70 80 90 100 120 140 160 130 200 240 280 320 360 Determine the first order rate coefficient as a function of time. What is the conclusion? Solution For a first order reaction: _ SP y.0, =k x Px,0, The solution is PaO. _ gop =n PM w Px,o, t Py,o; The problem is to express Py.o, 8 a function of py P. =Pxo, + Pro + Po, +Pw,o, + Pro, + Pro, From the apparent reaction, the terms pyo and pxios drop out. The complete structure reads N,0, > 2NO, 4Let abe the degree of dissociation of N,O,: when a= 0, no dissociation is taking place. When I, dissociation is complete. At time t, let the conversion of N2Os be x. The composition of the reacting mixture on the basis of one mole of N,O, is then: N,O, Ix NO, 2ax N,O, x(1-a) 12x +(a+1/2)x. ‘The total pressure reads: pr i (eb) io By definition: oo Pho, — Prog @ Pros ‘Substitution of (2) in (1): @ The dissociation degree itself is a function of p, and is found by introducing the equilibrium relationshiy x(=a)phu.o, p Pro [+ Q+12)x)pro, Pro, depo, [+ @HIAsF Ro) or k=) 4 AXa’PN,0, Substituting (2) in (4) and replacing py,o, by (3) in the resulting equation yields: ()Further _ 2866 logk, — log? -9.132 Which gives for 35°C: K, = 0.00484 Hence (5) yields 0.5 +J2.25 + 0.03872(p, ~ Pho, a= tes © 2+0.03872(p, Pho, Hence, for each t, the corresponding p; can be introduced in (6), giving the value of a, which in turn is substituted in (3) to give the actual pentoxide partial pressure . From (1) point values for k are calculated: t k t k 10 0.010670 120 0.008010 20 0.009618 140 0.007940 30 0.008980, 160 0.007931 40 0.008622 180 0.007880 50 0.008460 200 0.007825 60 0.008360 240 0.007767 70 0.008308 280 0.007623 80 0.008235 320 0.007446 90 0.008166, 360 0.007446 100 0.008080 Conclusion: k exhibits a trend as a function of time. Hence, the order of reaction is not exactly 1. Mean value of k: 8.0005 10% min’ (8:10) (J) is based on t = 0 as reference value. Any other value, ty say, can evidently be used. Writing (1) for two times t and t yields: Pro, Pre gk)from which k= The ty/p1 now serves as reference point. This possibility may be of interest when the initial iIt to measure, due to temporary non stationarities, caused by inflow of pressure is di the reactant. tin (-t) Pp Graphical Solution From (1), itis seen that the data can be plotted also in a graph If the reaction is first order in N2Os, the graph should show a straight line with slope equal tok. 1.14. Reconsider the data of Problem 1.13. Determine the order of reaction together with the rate coefficient that best fits the data. Now recalculate the value of the rate coefficient as a function of time. Solution _ 4Pr,o. at = kp’ log ty,o, = logk +n log py,o, Px,o, is calculated as in the previous problem. In the following treatment, the data points at t= 10, 20 and 30 are discarded because of possible inlet effects. 40 50 60 70 80 90, 100 Pro, 218.297 201.89 186.63 1723 159.49 147.79 137.38 120 140 160 180 200 240 280 320 360 Px.o, 117.87 1014 36.646 74.62 64.435 47.786 36.46 28.45 21.81logry.o, Px.o, log Px.o, 50, : 0.1995 201.89 2.305 70 1 0.13258 1723 2.236 90, 1.10! 0.043559 147.79 2.1696 120 0.8995 -0.046 117.87 2.0714 160 0.6695 0.174 36.646 1.9377 200 0.4472 -0.3495 64.435, 1.8091 280 0.2417 -0.6167 36.46 1.5618 Linear regression yields: k=4.71 10° n= 1.0985 =1.1 Using this value for n, point values for k can again be calculated by the integral method of kinetic analysis: Pwo, a — Pwo, dt Pn,o, we atlono J 0.5633] This yields: t k (min") 50 4.87 10° 70 4.82 10° 90 4.77 10° 160 4.76 10° 200 4.78 10° 240 4.8110" 320 4.74 10° 360 4.75 10° ‘Mean value: 4.79x10° min’, ‘The value of k is now constant as a function of time.CHAPTER 2 2.1 Derive the basic equation (2.3.1-7) for a single reversible catalytic reaction. Solution For the single reversible reaction A <> B, the following elementary steps can be written: D Ate Al K,=K, (2 wo 2) Ale RI @ 3) RIOR+I 8 Reaction rates of elementary reactions: = rate of adsorption: 4 = rate of surface reaction: o - ( CR = rate of desorption: Pes (6) (Ke ) When adsorption, surface reaction and desorption are simultaneously rate determining, all rates are identical: oer o The problem is to express ¢,,C,, and Ca as function of measurable quantities, From (4): C4, (8) From (6): Cry O} ‘These concentrations are su ©, =O, + eq HOR, (10) from which c, is determined:ay Substitution of (8), (9) and (11) in the rate equation for the surface reaction and solving for r yields: Pe KK AG Pa ~ Jk.s(n.-) kaka, kak, K It Ka Rf Kapa HRP) -) Rearranging the denominator in a constant term, a term in py and aterm in py leads to: (, Pe KK 4e1| Py — «Kae Pa | 1p Keka , Keke +K,l 1+ KaKe , keke Pa + Kal 1+ KeKy Ky key kp ky (Or equivalently, since k-Kake 1 K.Ky iol 1 (1K 1 GK + +K, + Ip, +Kx + ky kK KK, kK KK, kK, 2.2 Consider the catalytic reaction: A+BoR+S a) Derive the Langmuir-Hinshelwood-Hougen-Watson kinetic rate expression, assuming that adsorption is rate controlling. b) Compare the result of part (a) with that found from Yang and Hougen Table 231-1. Solution For the reversible reaction A +B <> R +S, the following elementary reactions can be written: NA+e Al K,=K, + a) Pati2) B+1@ BI Q) 3) Al4+ Bl<> RI+SI 3B) 4) RIGR+1 (4) 5) SloStl (5) ‘When the adsorption of A is rate controlling e.g., the reaction rate is given by: ab (rac CO} Reactions 2-5 are assumed to reach chemical “equilibrium”, so that use can be made of the corresponding equilibrium relations to determine the unmeasurable concentration of adsorbed Hence, ¢ PaPs oa PePse, since o K,K,K,K,K, = K (overall equilibrium constant). The reaction rate equation (6) becomes PrPs (Ps —PaPs |, ®) Kpy ‘The unmeasurable concentration of unoccupied active sites, ¢, , is determined from an overall balance on all si 6, =e, Feq Hep Hy He 0) The unknown concentrations of adsorbed B, R, and S are solved from the equilibrium relations (2), (4) and (5) respectively: From(2): Cy =KaPacr (10) From (4): eq =KpPeey ay From(5): ey =Kspse, (12) ‘Substitution of (7) and (10) - (12) nto (9), followed by solving (9) for c, yields:(13) 1 Ke Pap. ee Dy 7 KaPat Kua * Ksps ‘Substituting this expression into (8) yields: m= A Ky Ps 144 PRPS + Kypy + KgPg + KsPs Ps which is exactly the result found by Yang and Hougen and shown in Table 2.3.1-1. 23 Ina study of the dehydrogenation over a brass catalyst of see-butyl alcohol to methyl ethyl ketone, CH,CHOHGH, -» CH,COC,H, +H, L.H. Thaller and G. Thodos [AIChE J., 6, 369 (1960)] obtained data that appeared to show two different steps controlling, depending on the temperature level. At low temperatures, surface reaction was controlling, while at high temperatures desorption of (perhaps) hydrogen seemed rate controlling. A selection of their initial rate data is given in the table below. a) Using the data at 1’ = 371°C, determine the parameters of the appropriate initial rate expression. b) Using the data at 7'= 288°C and 302°C, again determine the parameters. TCO) P, (bar.) Tao (kmoV/kg cat. hy 31 1.0 0.195 371 2.0 0.189 371 40 0.188 371 9.0 0.198 a1 120 0.190 315.5 10 0.0392 315.5 70 0.0416 315.5 40 0.0416 315.5 10.0 0.0326 315.5 146 0.0247 315.5 55 0.0415 3155 85 0.0376 3155 3.0 0.0420, 315.5 0.22 0.0295 315.5 1.0 0.0410 302 1.0 0.0227 302 3.0 0.0277 302 50 0.0255 302 70 0.0217 302 96 0.0183 288 1.0 0.0115 288 3.0 0.0161 288 2.0 0.0146Note that the intermediate temperature level results should presumably depend upon both surface reaction and desorption steps, since at some point both steps will have equal rates (see Problem 2.5) Solution A@R+S Surface reaction controlling A+1@Al Al+ 1 RI+SI RI@R+1 Sloss Total active sites: C=C, + Cy + Cy + Cy =C(1+K ap, + KyPe + KsPs) =k, 2{c,¢,- Sa CQ K ‘Then, Ss Kepaksp. =k Zi Kyo, Saeses) =(k,Cs)K, (PaPePs!K) . OME KPa + Kuda + Kap Initial rate Pa Ky (1+ Kyra) Desorption of R controlling same as above, except CuCs ond Ky 2% exc, Cpe Then KK PAC C=C, + K pac, + APA + Kp, “ Kops . and1 ~4-h| 2c {K.Ky z “50 Re] ) KPA_p, | cq teem) [1+K.n, *Kak PAs Kap} . Ps For the initial rate, multiply through by ps, and let py. Ps > 0: To a) At high temperatures, if desorption controls, a plot of ry vs. p should give a horizontal line, from which (kg/K, ) can be determined: Tho = (Ky/Ky) From the data at 371°C, the plot on Fig. 2.3-1 shows random scatter about a horizontal line, to give kmol ky/Ky) = 0.19 (n/Ke) kg cat-h Intercept 192-8 (FE Tao ’ (cite 20) Tear 8 1012 prelate) Figure 23-1 b) At lower temperatures, with surface reaction control, a straight line should result from plottingThen, k, = [[stope)tintercept)}" K, =(slope)/ (intercept) Figure 2.3-2 shows these plots for the two lower temperatures, with the results; T=302°C k,, =0.113 kmol /kg cath K, =0.403 atm" T= 288°C k,, = 0.064 kmol/ kg cat h K, =0.299.atm" 2 * 2 2 20 18 s VET | see ccs san 14 s. some VS a? Intercept =p a 8 nen VG ® kes Bioper niercepy gt ssa BopereepT > K j= [Slope!/Cinterept) pelatm) Figure 2.3-2 Note that K,, increases with temperature, the reverse of the usual behavior of adsorption equilibrium constants. Finally, Fig. 2.3-3 shows the good agreement with the data of the surface reaction controlling rate equations using the above values for the parameters.0.05 asec Kg 035, K 0.58 (aK = 0.182 ° 0.08 ks 0.191, K 053 (eA he 0.892 ° 5 10 Figure 2.3-3 2.4 The Michaelis-Menten mechanism in enzyme kinetics is based upon the following reaction scheme between the reactant (substrate S), and the catalyst (enzyme E) to give the produet, P: S+ESESSP+E a) Use the steady state hypothesis for the enzyme-substrate complex, ES, to derive the Michaelis-Menten kinetic expression: _ a(S) _ (KE 9))(S)—(PYK) _ a(P) dt Ky, +S)+(k/k,P) dt Where (E,, ) = (E) + (ES) represents the measurable total enzyme concentration the “Michaelis constant” b) Show that the maximum initial rate is given by: a(s)| - =k,(E, ae Solution hook SHESESOP+E a) Disappearance rate of S.-o =k,(S\(E)-k,(ES) Formation rate of ES. d(ES) at =k,(S)(E) +k, (PE) ~ (k, +k, )(ES) Steady state for ES: se) MES) <9 + (k\(S) + ky (PME) (ky +k, (ES) =0 from which: es)- +P Substitution of (3) in (1): 8S) _[ (gy 4, HD+ KAP) [py at k, +k; From the total balance: _ _() kS) +k) (Eo) = (B) + (ES) = ! MOO ley from which: ®©=- (Eo) 1 KS +P) Ky +k; Substitution of (5) in (4): _ aS) _ (6) -k, HS) EAP) at 1 k, +k, _ Mk, +k XS) —ky/k[kS) +k PE) k@) a Q) B) (@) ()Kiks k,(Ep)| (S)-(Py- k,Eq)[(S)- PK] Hs 4 Km K,+6)+ ®) 1 : : b) Initial rate is obtained when (P) = 0: _ AS) _ ky VS) _ ky(Eo) dt K,+(S) Ka yy (S) ‘This is maximum when the denominator is minimum or when (S) is maximum. In the limit: (S) = o Hence ats) ee de (Ey) 2.5. (a) For the reaction in Problem 2.3, show that the initial rate expression, assuming that both surface reaction and desorption of R are rate controlling, is ki (1+K,p,)° ki (1+K,p,) " rye =[e, REO Kapa) | |i Rt Ot Kapa | ye | Ike KAP, 2ke KPa j See Bischoff and Froment [1965]. (b) Show that the result reduces to the proper Yang and Hougen Table 2.3.1-1 results for each of the special eases (ky/k,,) > and (ky /Ky) >. (©) Using the combined results of Problem 2.3 and the above results, compare the model with the data at the intermediate temperature level, T = 315.5°C. (See also Shah and Davidson [1965] and R.W. Bradshaw and B. Davidson, Chem. Eng. Sci., 24, 1519 [1969},) Solution A+lQR+4+S Cy A+1eAl Kye 0 Al+1@ RI+SI Kk, +a. Q Cu, RIOR+I Ky =Se 8SloS+l K,=—- a) Rate of surface reaction Total sites C=C FCy + Cy + Cy Substitute (1) and (4) into (5): Substitute (1) and (4) into (7) and rearrange: C, = — 2:2 Cu = 11+ K apa + Ksps Now substitute (9) into (6) and (8) T+K yp, + K gps) . Ky 1+ Kapa + Kops k cH ~keJe -K Cw ‘* af . lien Atsteady state, 1, = tn c+ ( C=Cy } Cuksps (C= Cui) Gk) KoPal rp + Kone kK oe 1+ K,ypa + Ksps Ky 1+ K4pa + Ksps J Su (Cu) | For initial rates, py =0,p, =0: & (5) (6) fa) (8) @) (10) ay (12)s G-Cy | _ 2k. K,p,| <1" |} = Sec, 13) q | (ee K, " ” For initial rates, from (11) k ke Fy = tno = AE Cy = he Se Ky" KRG where kyC, =k, — ky has been used. ‘Substituting this into (13) gives 2 1-1 K g/k sof. (!=8eat |. % or , : {ke ae{ Ke \leKypal |, ,( ke) 9 Ky \ ke KK APa Ky Solving, Kg/Ky \(+K pa) |_| wy oR ty (Note that the result in the book has further grouped a ky). R b) Show that the result reduces to the proper Yang and Hougen Table 2.3.1-1 results for each of the special cases. ky/K, w@ For desorption control, —"“—~® 5 0. ‘Then the initial rate becomes: which is the correct limiting form (e.g., Problem 2.3). 7 . k, 7 a (ii) For surface reaction control, —*— —> 0, and the initial rate expression must n/ Kp be rearranged by squaring within the radical:ke [,, Ke/Ke(+Kypa)_ke/Ky (1+ KPa) k, 2K Px ee ee A eaPal {14 2—s__——aPa Ky k, 2K Pa 2KyP, | ky /Ke (1+ Kp, Then expanding the radical to three terms gives: ty = 82 {(0)cboth term, cance+ Ka 2KaPa | Rak ara Ky 2ky/Ky 1+ KyPal) 1+ Kapal which is the correct limiting form (¢.g., Problem 2.3). ) Using the combined results of Problem 2.3 and the above results, compare the model with the data at the intermediate temperature level, T = 315.5°C (also see Shah and Davidson [1965] and R.W. Bradshaw and B. Davidson, Chem. Eng. Sci., 24, 1519 [1969].) An Arrhenius plot of the rate coefficients found in Problems 2.3 is shown in Fig. 2.5-1. Only k,, and K, are known at two temperatures, and the activation energy for (ky /Ky) cannot be found. Thus, an assumption must be introduced for (ky /K,) at 315.5°C. One possibility is to me E, = 0 (merely for lack of information), which makes it equal to k,, at 315.5°C; in this situation, both steps would surely be rate limiting. Another possibility is to assume the activation energy for (ky /K, ) is similar to (k,, /K,.), which leads to a smaller value at 315.5, and which is the same as that estimated by Shah and Davidson; however, their activation energy was much smaller (and wouldn’t be at all correct at 317°C). Note that the former value (0.192 = const.) is similar in value to k, at 302°C, and only at 288°C is there an order of magnitude difference. Therefore, probably both steps are still rate controlling at 302°C. The fact that a good surface reaction control only plot was obtained in Problem 2.3 is possibly similar to the illustration of Bischoff and Froment [1965]. In any event, Fig. 2.5-2 shows the results of using the extrapolated rate parameter values in the combined initial rate formula of part a), and it is seen that agreement is not obtained. The even smaller value of (ky /K,) would give worse agreement. However if the value of k,, = 0.35 is used, reasonable agreement with experiments is obtained. This extrapolated value at 315.5°C could have been obtained if the value at 302°C was 35% larger, as shown on the Arthenius plot. Since surface reaction was probably not truly rate controlling at 302°C, this could be a reasonable value, as shown in the illustration of Bischoff and Froment [1965]. This problem illustrates the difficulties in using rate expressions with more than one rate controlling step, even though meaningful kinetic parameters can only be found in this way. When this situation occurs, precise data covering a large temperature range is essential in elucidating the details and parameter values,ou a om ean ta Figure 2.5-1 9.08 ssc ker 0.25, K 053 (eK he 0.192 o 2 @ ° oot |S y= 04191, K 053 (ak fe 0.182, 003 0.02 r,gerotig cat he 288 001 ° 5 70 Figure 2.5-22.6 Consider the reaction A < R +S, occurring on dual sites. Determine the rate equation in the case that all four elementary steps are simultaneously rate determining. Solution ARES The following steps occur: A+l@Al AL+1@ RI+SI RIGR+I SlOS+1 Rate equations: In steady state conditions (1) = (2) = (3) = (4) =3)=4) Fea te + es) (5) A possible procedure is as follows: c),€,1.qi¢s; are calculated from (1), (3), (4) and (5) and then substituted into (2). (1) ey =Kylegei—m/ka) @) 60-45] LeKy ke ks TK yey + Katy + Koc, c+ Ka Ke_Ks +Mn D=14K 4c +Kut +Kses Substitution of c, into (1), (3) and (4) leads to: Equation (2) becomes lee Kaen 4e,Mry 2) rode ka KBE KsKr coc, ¢cgMr, ~782 | ccc, +eMr, — a2 st keh ks or 2, KaMD_KsKp yy, K,MPe,— aes + ky ke | KsKe pos KsKe pe! Ky ks Ky Kuks K,De,_KsKy K Mee, + K ye,Me, ~ This is a quadratic equation in 1, : Arg + Br, +C =0KsKy K, s (kc + kycp )-—* Kokyky Se BSH) | > Sats) Kykgk, akaks A = KSKu_ (hc, + kgea) K+ , , Kl K is the overall equilibrium constant, ~*~ Ks 2.7 The following data were obtained by Sinfelt and co-workers [Sinfelt, J.H. et al., J. Phys. Chem., 64, 1559 (1960)] for the dehydrogenation of methyleyclohexane to toluene. In addition, they found that the product toluene had essentially no effect on the rate. Tc) (bar) __pH2 (bar) 315, 0.38 14 315, 0.38 30 315 0.07 14 315 0.24 14 315, 0.72 14 344 0.36 14 344 0.38 a4 344 0.08 14 344 0.24 14 344 0.68 14 372 0.38 44 372 0.36 44 372 14 44 372, 22 44. (a) Discuss which of the steps—adsorption, surface reaction, or desorption—might be rate controlling in view of the data in the table above. (b) Show that a rate expression based on the mechanism A+1@Al Ale RI RI>Q+S+1 fit the data; also estimate the activation energies. (c) Discuss the results of (b) in view of (a). ‘The react+ 3m Solution (a) The rates at T— 315°C show: 1. Rate is independent of Hp pressure. 2. Rate increases with py, but approaches saturation; no maximum. ‘The rates at T ~ 344°C show: 1. Rate is nearly independent of Hz pressure 2. Rate increases with py, possibly approaching saturation. ‘The rates at T = 372°C show: 1. Rate is nearly independent of Hz pressure. 2. Rate increases with pat The conclusion is: Since toluene and Hz have no effect on the rate, the final step is irreversible, and the other steps possibly in quasi-equilibrium-thus try desorption control. (b) The suggested kinetic steps are: A+l@al K ALO RI K, RISQ+S+1 Ks ‘Then and =G(1+ K+ K, py) ‘The rate is: P= K,Cu/Ky = BKK P\Cy/Ky —_(KCK)K,/K,)py kp ~ 1+K,(1+K,)p, 1+ Kpy oONote that (1) has the features observed in part (a), The parameters could be estimated from a plot of 1 (‘J () 1 Ky fly r Uk) (KJ py ‘The plot shows that the slopes at all three temperatures have essentially the same value, and so the “combined activation energy” (E, +Q, + Q, ~Q,) is zero. The rate coefficient has a value k = 0.4 kmol/kgeat h atm, From the intercepts, the following are found: re. Kik K, atmet 315 80 32 344 28 10 372. Z 28 A semilog plot gives 31 keal/gmol lope of 15.6, and so the “activation energy” of K,(I+K,) is (©) Since the postulated kinetic scheme of irreversible desorption control reasonably fits both the qualitative observations of the data, plus yields quantitative consistent parameter estimate plots and activation energies, it will be accepted. The original reference then uses this for further postulates about the catalyst behavior. 2.8 The isomerization of n-pentane was considered in the text, where several rate expressions were stated. Derive the final result for desorption of i-pentene controlling: KKK K,(p, ~Py/K) y— KKsKoKe(P, —Pa/K) Pu, +KsKp(1+K,)p, Solution The global isomerization A <> B can be decomposed in the elementary reactions shown in Chapter 2. When desorption of i-pentene is rate controlling, i., the 7-th reaction, the overall reaction rate is given by: fou K | wo From the equilibrium relations with respect to the fifth and sixth reactions: xo = KsKePutoCue = KsPate @ Total balance on acid active sites: HE y#Eyy +p = (14+ Ks(14+ Ky Pw ky 3) Hence: koe Kok Py -B| ok, 1+ks(1+K, py, (4) where K, is the equilibrium constant for M <> N on acid sites. The unmeasurable gas phase partial pressures of the pentenes, py and py, are expressed as a function of the gas phase partial pressures of the pentanes by making use of the assumption that the hydrogenation and dehydrogenation stages are in equilibriu K.K;KK, KK KK, Substitution of (5) and (6) into (4) yields: KK pK K(P, ~Pp/K) Pu, +KsKy(1+K, pq where K=K,K.Ky k=ke, 2.9 For the isomerization of n-pentane, derive the rate expression if the surface reaction step of the dehydrogenation reaction were rate controlling. Contrast this with the correct rate of Problem 2.8, especially regarding variations with total pressure. Solution When step 2 is rate determining: owFrom the equilibrium relations with respect to reaction(s): (Ds &y =Kipae, @ @) Pee, @) By having considered reactions (4) - (11), cy is expressed directly in terms of the observable partial pressures py and py, A total balance on all Pt sites: 1 Oey + Oy Fay + Op + CH (6) requires still cy, and cp, to be determined. From the equilibrium relations with respect to reaction(s): 1 (11: cm = Pats (6) @)-a i) Hence: 1 ¢=|4— (8) TIK ‘Substitution of (2) — (4) and (8) into (1) yields: 4, (r—P) 1 1 Py 1 1 ete cp bp TAK eK Pp, Pin KP KP where K is the overall equilibrium constant of the overall reaction A <> B.Obviously, this rate equation is not independent of total pressure. 2.10 For the isomerization of n-pentane, the following experimental data were collected by Hosten and Froment [1965]: x y___| W/FAO (kg cat. h/kmol) 0.4025 4.858 5.92 0.35 5.253 3.84 0.2784 5.29 2.84 0.2001 5.199 1.75 0.3529 6.833 5.74 0.2728 7.33 3.84 0.2028 7.344 2.66 0.8248 7.638 5.28 0.2571 a5i4 39 0.2011 8.135 2.65 0.3017 10.598 5.73 0.2413 11.957 437 0.1734 10.227 2.65 yis the molar ratio Hz/n-pentane. The pentane feed consisted of 92.65 mole % n-Cs and 6.37 mole % i-Cs. The overall equilibrium constant is 2.07, while the selectivity for isomerization is nearly constant and equal to 0.91. Estimate the parameters in the adsorption model by means of the integral method of kinetic analysis. Both W/F 4g and x can be used as dependent variable. Comment on this choice. Compare the results and the computational effort for both cases. The reaction network for the isomerization of n-pentane (A) into i-pentane (B), accompanied by the cracking of the n-Cs into Ci-Cs (C) to a small extent can be written: When the adsorption of n-pentene is rate determining for the isomerization, the reaction rate equation for isomerization is given by: kKp(p,—Pp/K)___ k(P, ~Ps/K) w K a (3 ote Pu, +KaPs (It is assumed that the cracked products are not adsorbed on the acid sites). The integral method of kinetic analysis makes use of the continuity equation for species B. For an ideal tubular reactor with plug flow:Q) (1) has to be substituted in (2), which is then integrated. This requires the expression of the partial pressures as a function of xp. The feed contains P mol % n-pentane, Q mol % of i- pentane and R mol % of an inert I, cyclopentane. The following balances can then be written: Number of moles Conversion of A: XA Component Feed Conversion into B: XB) A P P (1 XA) B Q Q+PB L R R He Py P ly - (A - XB) c ° 2P (XA - XB) Y=100+Py Y= 100+ Py It is hereby assumed that | cracked mole of A gives rise to two moles of cracked products C. Tis seen that cracking does not give rise to expansion or contraction. Since the selectivity for isomerization, 1) = xy x, , is constant, the partial pressures read: —Ply-(W/n-txo], @ 100+ Py _ PU xp/nt * "100+ Py Integration of (1) can now be carried out analytically: w Kn {ta+Kee} (4) Fo PUK +m)\k k in which: ing the given data pairs x | W/F ao, ¥- If W/P4p is used as dependent variable, the criterion reads:Notice that (4) is linear the groups 1/k and K , /k, so that linear regression will surface to estimate these groups. Values of k and K,, are unambiguously determined afterwards. If xy is used as the dependent variable, the appropriate least squares criterion, Db. requires non-linear regression. Moreover (4) is implicit in the conversion xq, so that this implicit equation has to be solved for %g, for each experiment. Since W and Fyo will ‘generally be precisely known, W/Fag is likely to be considered as a discrete rather than a random variable, so that criterion (5) seems to be inappropriate. The conversion on the other hand seems to be the true observed variable, subject to experimental error and hence, estimation should be based on criterion (6) indeed. 2) > Min } Res Dependent variable WIFAO. x Kk 0.89) 0.89 K 6.57 25 Both criteria yield estimates which agree very well. Clearly, required computational effort is much higher when x, is the dependent variable. 2.11 A catalytic reaction A <> B is carried out in a fixed bed reactor. Comment on the concentration profiles of adsorbed species as a function of bed depth for various rate determining steps. Solution A+I@Al K, =a. Paty AL@ BI k, == en Blo B+I > Adsorption rate determining: orGB) and . * 4) K,, or the ratio is constant. > Desorption rate determining: From an identical reasoning, the reverse is obtained for c, and c,, when the desorption is rate determining. © The ratio <8 remains constant. ou Surface reaction rate determining: Lp KP All kinds of profiles are possible. In the case that the denominator is nearly constant or, at least, varies slower than p,, or Py, Cy is decreasing, cy, increasing, and c, nearly constant as a function of bed depth. Also with, strong product inhibition, this means that ->>K, ,c,will be decreasing. So will cy, at an even greater rate since not only the denominator increases, but also the numerator decreases. 2.12 The dehydrogenation of ethanol was carried out in an integral reactor at 275°C with the following results: Xx__ pr (atm) _W/Fa0 (kg eat. wkmol) | __x pt | WiFao | x pr_| W/Fao O24 One, om 302 | 092 4 16 O44 0.196 o2 | 3 04 ond 7 02 ost 0.262 02 3 08 013 7 04 0.88 1 0.339, 02063088 01e4 7 |. 1531 0.446, oss2 3 16 0214 7 0.88 161 0.454 om 4 02 | 0258 7 16 2681 0.524 oie 4 04 ot 4221 0.59 024 0604810 4541 0.60 O27 40.88 0175 10 |. 0.188 100.88 ozo 0 | 168 The overall equilibrium constant is 0.589. The feed consisted of the azeotropic mixture ethanol-water, containing 13.5 mole % water. Water is not adsorbed on the catalyst. Estimate the parameters of the adsorption, surface reaction, and desorption models, using conversion as the regression variable. Comment on the feasibility for the estimation of the parameters. Which model is the best? On what basis? Solution As shown in Chapter 2, the continuity equation (a) has to be integrated after substituting the appropriate rate equation and expressing the partial pressures of the reaction partners as a function of conversion and independent variables. The result is an expression of the form: wii Fal itPetDs) w for all three rate equations with D,,D,,D, given in Chapter 2. The functional dependence for Cand A,,B,,C,,A,,B,,C, are different for each model, however. They are shown in Chapter 2 for the surface reaction controlling rate model. They are given below for the two other models: Adsorption controlling: C=k A\= 1.334 A,= 1.155 p, B,=2.31 +(Ky+Ks)p, B, =-0.155p, C.=1+Kypi/K+(Ky+Ky)p, C= -p,(+ p/K) Desorption controlling: C=kK A= 1155 Ky Age 1.155B= 1.155+K,p,-0.155 KK, B= -0.155 C= 1+ Kyp,- KK p+ Kop, C= -(I+p,/K) ‘The parameters are estimated in all three models by means of the least squares criterion based on the conversior > Min Q Thi and all models. The objective function (2) is minimized e. technique again necessitates the solution of the implicit equation (1) for &, for each experiment by means of the Marquardt Results The next table presents the point estimates for the parameters and their 95% confidence limits, as well as the residual sum of squares. Adsorption | Surface reaction| Desorption k tts (k) 05514014 4.964058 0.205 + 0.2 KA sts (KA) 12.4642.4 0.4340.052___-0.0937 + 0.19 KR £ ts (KA) 0.321 + 0.36 KS £ts (KS) 1.329 £2.32 KRsKSits(KR+ KS) 5.69421,75 2.895 0.6 Residual sum of squares 0.0086 0.0021 (0.0036, Note that the parameters K, and K,, can be estimated separately in the desorption model. even when pure feed, i.c., containing no reaction products, is used. This is not possible in the adsorption and surface reaction rate models: only their sum is estimable. Compared to the differential method of kinetic analysis, discussed in Chapter 2 the estimation technique discussed above is undoubtedly much more laborious. From this analysis, it is clear that the surface reaction model is the best: 1) Ttis the best fitting model and has a residual sum of squares which is only % of that of the adsorption model. 2) All parameter estimates are positive and significantly different from zero. 3) The adsorption model fits much worse to the data and contains a significantly negative parameter estimate; this is in conflict with thermodynamic requirements for adsorption constants; hence the adsorption model must be discarded. 4) The desorption model fits relatively well to the data, but none of the parameter estimates is significantly different from zero from the statistical point of view. 2413 Boolean Relation Matrix and Label representation of molecules and ions. a) Write the Boolean relation matrix and the label representation of (i) 3-Me-pentane -2+ carbenium ion Gi) Naphthalene Gii) Cumene (i-Propylbenzene)b)What are the Me-shift isomerizations and the B-scissions that the 3-Me- pentane -2+ ion can undergo ? What are the products ? Hint: For the B- scissions first construct the matrix M’-1 in order to determine the 3 -carbon atoms. Solution 2,4 | autrixs (010000 2 Lipa 5 10 L900 123211 ofolol gssees 901010 6 e00100 oo1ov0 matrix: (0100010001) 0 rorooo0009| 3222232222 0101000000! 1444414444 9010100000 9001010000 1000101000 2000010100 9000001010 oao0000101 1900000019 mais: (010001100) 9 ro10900e0| = 322222311 010100000 444444888 001010000 000191000 190010000 ioovooorr 900000100 900000100CHAPTER 3 34 The cracking of cumene into benzene and propylene was carried out in a fixed bed of zeolite particles at 262°C and atmospheric pressure, in the presence of a large excess of nitrogen. At a point in the reactor where the cumene partial pressure was 0.0689 atm, a reaction rate of 0.153 kmol/kg cat. h was observed. Further data: My = 34.37 kg/kmol; Pg = 0.66 kg/m’; [= 0.094 ke/m.h; Cy = 0.33 keal/kg.°C; Pr = 0.846; an = 45 mveatlkg cat; (-AH) = -41816 keal/kmol. Show that, under these conditions, the partial pressure and temperature drops over the external film surrounding the particles are negligibl Solution a) The partial pressure drop Apa over the external film is given by: where jp is obtained from: 68Re*' (Re < 190) or jp= 7.50 Pia is defined by: 0. +54? )-(, +84(Pa — APs) a +D4p wf P,+54Pa | P.+54(P,~ APs) For the reaction aA +bB +... + qQ+sS +... the expansion is defined by 9, -dtstacacbe. For cumene —> propylene + benzene: 141-1 1The pressure drop is calculated according to the iterative scheme presented in Chapter 3: 1) Assume Ap, =O > py 0689 BPA Ap, = _0:153%3437 ( 0.094 45 x 56.47 = 7.50\ 0.66 + 0.096 or Ap, = 3.836% 10 atm 2) With this new guess, an updated film pressure factor is calculated: La 1n 140.0689 (140.0689 — Ap, Pa = 06863 This value is sufficiently close to the previous value, so that no further cycles are required. Hence, 5p, = 3.836% 10~ and —P* x10 = 0.56% which is negligible. Pa b) The temperature drop is given by rCAM) Any in AT= From the figure given in Chapter 3: ju =5.49 Hence: = OIS3x 41816) 69 946)29 43% 0.3342 x 36.47 x5.49 =-1.228°C and 200 =0.34% which is again negligible 3.2. The solid density of an alumina particle is 3.8 g/em', the pellet density is 1.5 g/em', and the internal surface is 200 nr/g. Compute the pore volume per gram, the porosity, and the mean pore radius. Solution A catalyst pellet consists of the solid phase (catalytic material + support) and the void phase:1 em? catalyst = X em’ solid + (1 —X em) void In weight : 15 g=XX38g+(1-X)X0g 1s Hence X = <= = 0.395; 1X =0.605 0,605 cm’ pores/em? cat 15 g.catfem>cat volume void (pores) total volume (pores + solid) X mean pore radius = X pore volume /g cat = = 0.404 em? pores/g cat X porosity = = 0.605 em? pores/em? cat assume a pore to be cylindrical with length L, then: pore volume = volume of cylinder = RL surface area = surface area of cylinder wall = 2nRL pore volume R _ 0.404cm*gcat _ 0.404% 10 m3 surfacearea 2 200m%gcat —- 200m? or R=40.4x 10" m=40.4 A. 3.3. Turning to a general description of pore diffusion, the "dusty gas" theory of Mason et al, [1969] utilizes the results from the formal kinetic theory of gases, with ‘one "species", the "dust", having a very large "molecular weight". Their final results can be clearly visualized in the form utilized by Feng and Stewart [1973]: N,, = (diffusive flux) + (viscous flow flux) + (fluxes caused by other driving forces) (1) =NO EN 4. where the viscous flow flux is found from with Bo = D'Arcy constant, a function of porous media geometry, = 77/8 for a long cylinder of radius r, and the diffusive flux is found from the extended Stefan ‘Maxwell form hyp, Sony NDZ 8) RT BD OT DgEquations (1) to (3) can also be combined to give a single equation containing only the total flux resulting from both diffusive and viscous flow mechanism: Carefully watching how the various fluxes combine, derive (4) for the molar flux in a porous medium. Solution ‘The total mass flux is the sum of the diffusive and convective flows N)=NO EN” (a) where the viscous convective flow is Vp. (b) The diffusive flux driving force, the partial pressure gradient, is utilized by both bulk and Knudsen diffusion: -1 Kod Ny ay, Noy nm), Rr 2p," ?—y,NP) Das © The diffusive flux is N® =N,-N? w and Ni xy Q ‘Substituting (1) into (c) gives two parts to each of the terms on the RHS. The Stefan-Maxwell term with the convective flow term is 8 z (yj-yv)=0 ik since diffusive intermingling of species is separate from convective motion. However, convective and Knudsen flows are similar, and both terms remains. Thus, the final result is: “1 No N, | yy (p.B. ay, ——(y,N, ~y,Ny)+ Pe ly, ar 2p, ON Np tp olay) from which the total flux of species j can be found.3.4 A catalyst considered by Satterfield [1970] has a void fraction of 0.40, an internal surface area of 180 m’/g, and a pellet density of 1.40 g/em, Estimate the effective diffusivity of thiophene with hydrogen at T = 660 K. Solution The first step is to estimate the bulk di dense gas kinetic theory result for diff usivity. From Bird, Stewart, and Lightfoot [2] the ity is M. M, 2 Dy = 1.8583 1079 —1 4 SO Platmor,Q, Ss where the “collision diameter” o and integral Q,, (which is a function of the “interaction energy” eT/k) are found in tables: Ho, o = 2.92.A , e/k = 38°K. For thiophene, Satterfield [40] user correlations to estimate o = 5.25A,, e/k = 447°K. Then mn =30, +04)= 7625+ 2.92)=4.08A E qy/K = VE xey /k = 447038) = 130°K, Then KT/e ,y =660/130 = 5.08 > Q,, = 0.84 Finally, 11 .00185: ft > _ 001858 (600) e4°2 “ p(4.08)7(0.84) _ 1.612 cm/s P A at p= 1 atm, Dap = 1.612 cm/s at p = 30 atm (Satterfields value 0.054 cm?/s) Das = aa = 0.0537 cm*/s (assuming ideal gas behavior at 30 atm!) With this value, then, 04 0.677 (1.612)The Knudsen diffusivity depends on the average pore radius, which is: 2e, 204) pS, 1.40 (180) 10° =31.8A=3.18nm ‘Then from Chapter 3, (3.4-4): [2 (8.314) 10° 660 " 84 = 0.865 x10 m/s = 0.865 x10 cm/s 4 Dua =33 18 107] _ 0.346 “ot x10? cm/s 1 1 =(—_4 Dexa (0.677 anoaas) D, A or D, 0,00344/r = 0.00115 em*%s (t= 3) Note that with the relatively small pore size of 3.2 nm, at | atm the Knudsen diffusion predominates. At p= 30 atm, using Satterfields value of Dan = 0.054 cm/s { ryt 0.0216 ” 0.00346 or 0.0010 ems (x ) Again, the Knudsen diffusion is most important. Only at p = 200 atm would the bulk diffusion, be of the same magnitude (at this pressure more comprehensive correlations would be needed to predict the bulk diffusivity Dap).3.5 Calculate the diffusion flux for ethylene diffusing in hydrogen at 298 K in a porous medium with the following properties: thickness = 1 em, ¢s = 0.40, pg = 1.4 g/em’, Se = 105 m/g. The conditions are steady pressure p of ethylene on one side and hydrogen on the other, for 0.1

where t has been arbitrarily taken to be 1.0; other values merely decrease the flux by t= | ‘The average pore radius is needed for the Knudsen diffusivity 2c, 2 4) — OA = 54.4.4 =5.44nm pS, 14 (105) 10° From (34-4) 2 (8.314) 10° (298) Day = 25.4410 3 x 28 = 1.72210 mes = 0.01722 em*/s xa = 04 (0.01722) = 0.00689 cm/s Now the above formulas can be applied. (The remainder of this problem will be done using S.L units.)_ p (bar) kmol “24.78 m3 (o9sek) 2478 a 0.237104 m p_(kmol) 1p (1.01325) s 24.78\ m3 /0.0lm — 1—/28/2 «10~/1,01325 p —(l— 28/2 )(0) + ——___ a ( i 0.689 x10 0.237 x10 /1.01325 p TL (=v 28/2 JC.0) + (8 0 e510 = 3.445 x 1077 In 42 * 34-0/P 1+340/p Itis scen that for large pressure, the maximum diffusion flux (bulk diffusion) is: > kmol sm 445 x 10° In (3,742) = 4.54 x10 In general, it is useful to have the limiting forms for both high and low pressures. In the former case, Dn /D.xq > 0, and. Pern, 1=(- MAM Wu, a I Ul yM My) (JM Ay Yay Yq =1 For the present (common) case of Y.4y cD, Ny= {eA tn Ma fen(p) L{l- JM, /My My cp, «ps. P since For very low pressures, careful expansion of the log terms by multiplying numerator and denominator by D.xx/D.an leads to: — Ra] Bt lb riia H-t- 5G = Beg Ya)

(Litzy,) or (1.0,0.1) ¢> (0.0039, 0.225) ‘Therefore: ose [Ee \D. and fone 0.225 KyCoge Ky (2107) o1 Solving these gives: k, = 112x104 =3.lem/s em} hem3y D, = 4.72x10° cms (liquid?) Also note that the smallest particle is almost in region of no diffusional effect 2.40 2107 12x10"b) Fora finite cylinder, a L= 252M _ 9.0833 em and @ = 0.0833, | —*!__ 442(1) V4.72x10 and =k Coy =0.046 (3.1) (2x10) = 3x 107 = nol ems orig Lem Figure 3.8-1 3.9 The following rates were observed for a first order irreversible reaction, carried out on a spherical catalyst: For d, =0.6cm, r, = 0.09mol/geat. hz For d, =0.3em, r,, = 0.162 mol/geat. hsIn both cases strong diffusional limitations were observed. Determine the true rate of reaction. Is diffusional resistance still important with d, = 0.lem ? Solution mita(Ca) _ 9: Tota Tao Mat (CA) > The last equality holds in the region of strong pore diffusion limitation, An iterative cycle is set up, in which use is made of Fig. 3.6. From “#t From Fig. 3.6.1-3 From St Teo To n+» % ___, % ___,¢ __,m t { => This cycle is continued until the value for ®,, is converged. The following cycle is then obtained: m=] ——» 1) =056 ——+ 6,=15 ——+ 6, =083 ‘These values for 1, are in sufficient agreement. Hence n; =0.64 ., _ 0.162 _0.09 1, = 0.36 0.64 = 0.25 kmol/kgcat h. ‘To check for eventual pore diffusion at a particle diameter of 0.1 em, the modulus is: ol 0. (1.22) = 0.407 which from Fig, 3.6.1-3 gives n, =0.92.3.10 A second-order gas phase reaction, A > R,, occurs in a catalyst pellet, and has a rate coefficient k ps =3.86mYkmol s The reactant pressure is 1 bar, the temperature is 600 K, the molecular diffusivity is Dx =0.10¢m*/s, and the reactant molecular weight is M, = 60. The catalyst pellets have the following properties: Radius of sphere R= 9 mm Pellet density p, = 1.2 g/em* Internal surface area S, = 100 m?/g Internal void fraction ¢, = 0.60 a) Estimate the effective diffusivity. b) Determine if there may he pore diffusion limitations. ©) If part (b) results in pore diffusion limitations, what might be done to eliminate them? Justify your answer(s) with quantitative calculations. Solution a) The mean pore size is found from: es 2 (0.60) psS, (1.2 g/cm) (100 10*cem*g) =10%cm =10*m(=100A) Then the effective Knudsen diffusivity is: \2 28. & ps2 581600) oun 123) x (60) = 6.135107 ms also Dee =< Da =So 1) =2«10%m*%s 1 ‘Then for the 1:1 stoichiometry: or470x107 m/s = b) If the given rate coefficient is directly used in the generalized modulus: For pure reactant c, = 2. -_tam or spr = 0.0203 kmol/m* RT {sau ‘pam 000") kmol°K ‘Then 9x10" [3 (3.86) (0.0203) 3. V2 4.70x107 and 1 = 0.6: significant pore diffusion limitation. Alternately, the value could be taken as an observed rate coefficient, and the extended Weisz-Prater criterion for a second order reaction gives: 3UiyJooL? _ 3 (ky )ana(CRL? 2 D.C D. 3 (3.86) (0.0203) (3%10")? 2 470x107 2.25 >1 Again, there is likely significant pore diffusion limitation, ©) The most straightforward way to reduce pore diffusion limitations is to reduce the pellet size — a factor of two or three should suffice from the numbers in part b. 3.11 A gas oil is cracked at 630°C and 1 atm by passing vaporized feed through a packed bed of spheres of silica-alumina catalyst with radius = 0.088 cm. For a feed rate of 60 cm' liquid/em,;-h, a 50 percent conversion is found. The following data are also known: Liquid density = 0.869 g/em* Feed molecular weight = 255 g/mol Bulk density of packed bed = 0.7 cat/em,? Solid density of catalyst = 0.95 g cat/em* cat Effective diffusivity in catalyst = 8 x 10“ em*/s Average reactant concentration = 0.6 x 10° moV/em*.Assume a first-order reaction and treat data as being average data of a differential reactor. a) Show that the average rate is 3.9 x 10° mol/em’ eat s. b) Determine from the data whether or not pore diffusion was important. ¢) Find the value of the effectiveness factor. d) Determine the value of the rate coefficient. Solution a) The catalytic reaction rate computed from the data (emt 2 Vimo 602} o.g69-2_{ tml co) ( mol conve em 3h em? }\ 255g 36005 | 0.7 Be | 1 _emcat bem 095g ‘gmol em cat volume — time or 85x 10° b) The observable, or Weisz-Prater, modulus can now be determined: ® > 2 108 L hase ( 0 es) 3.85% 10 = 6.90 (dimensionless) — C.D. (3) @.6x10%) (8x10) ‘Therefore, diffusional effects are important. ©) Inthe large $ , or ®, asymptotic region, 1 1 =—=—=0.1449 oe d) Then k=—*- (if first order) AC, 3.8510 © 0.1449 (0.6% 10) = 44.38" (orem/cm',s) Note: Units of D, are em/em,s.Chapter 4 4.1. Derive (4.2-3) by using simple geometric arguments. (Also see Kim and Smith [3] and Wen [2]). Solution ‘The solid concentration of species j is Cjs kmoly/m,$ (based on the total pellet volume—sce the notation), the molar volume is vj, mj3/kmol and the solid fraction is (1—es )m}gq/m} . Then for the reaction A(g) + B(s)—> P(s)+ Q(g), the initial solid fraction is given by: =Cy¥y, $C, Yi, @ where C,, represents the concentration of the inert solid material. Ata given conversion level, the solid fraction is Co,Me, +Cn¥e, +OM, @ For 1:1 stoichiometry and constant overall pellet size, Cy. Thus, vis, -G We, 8 = Coa (¥e, ~¥9,E-Co, (Cag) With obvious change in notation, this is (4.2-6), but without the term (I~, ) which would actually only be needed if the reactive solids concentrations were based on the total solid rather than total pellet volume. 4.2. Consider the general model with the reaction first-order in fluid phase concentration: D.V?C,, ~akC,f akC,,f(e,) where f(C,) is the rate dependency on the solid reactant concentration; (e.g.,a grain model or mass action form). The simplest boundary conditions would be:Cy C,=C, ,att=0 and ", on the pellet surface. (a) Show that the new variable V(x,t)=ak{C,.(%,t°Ht (cumulative concentration) is also defined by the formal integral This result can he solved, in principle, for C, =H Wiutke, | (b) Then, the new variable can be differentiated in space (V ), and these results combined with the original mass balance differential equation to yield: 6, 2 = 0.v3 -akfey HC, J Prove this result. (c) The boundary conditions can similarly be transformed to: W=0 att=0 YW =aC},kt on the surface. Prove these addi jal results, (4) The results of parts (b) and (c) show that the original two coupled partial differential equations can be reduced to solving one diffusion type equation, with a time-dependent boundary condition—a much simpler problem. For the special case of rectangular (slab) geometry, and where the pseudo steady statewith YW =akCi,t on the surface (z= L) and ow <-=0 at the centre, z= 0 (symmetry) % ‘Thus notice that the results of Chapter 3 can be utilized to solve the transformed problem. For a zero order solid concentration (£(C,) = Cy), show that the following results are obtained: cosh(Dz/L) gy [AKCw Cu = Cw cosh() D, = Cy) 1- OAL) .es.t) os cosh() which are the type of results obtained by Ishida and Wen [9] in (4.2-13) and (4.2- 14), (€) Finally, for the slab geometry of part (¢), show that the conversion is given by which is based on the generalized modulus concept of Chapter 3. Thus, it is seen that the complicated gas-solid reaction problem can be reduced to an analogy with the simpler effectiveness factor problem of Chapter 3. For more general results, see DelBorghi, Dunn, and Bischoff [6] and for extensive results for first- order solid reactions, f(C.) = C,, see Dudokovic [25]. Solution (a) The cumulative gas concentration is defined as: ak/C,.d" a ‘Then, using the solid mass balance in rearranged forma Ha 2) J ie) ak [Cua y @ If the left hand side of (2) can be integrated (e.g., if f(C.) = C,> In (CYC) then an explicit expression can be found for C; (e.g., Cs = Coo exp [-¥]); this can always be done in principle, even if only implicitly or numerically, to give H,[¥(x,0;C,, ]- (b) Using the definition of W, the spatial derivatives are: vs ak[VC,.d¢ @) VW =ak[V°C,d0 = af | . a + sic ste, 4 ak lye = Bleu Con) fe les(Cx, Cao)“ (C, - Co) Also, from the definition (1): ov Te ake 5 a 7G as 6) ‘Therefore, combining (4) and (5): WW =ake,Cyy +ak(C, -Cy) (6) Using the solution of (2) for C,, HOV; C.o). yields the final result from (6): 0, 21.99 —aklCg- HC )-2.C yo] a Where the last term usually has ayy = 0, as in the problem, (c) The B.C. can be similarly transformed by using the definition (1) and the result (3):© Atthe surface, Cy, = Ci, Whose = ak | Cydt = akC),t (8) © Atthe center, VC,, =0 o Yer = ak [Ost = 0 0) at zero time, the definition (1) always gives W(x;0) =0 (10) for any value of Caw. (d) For pseudo steady state, the left side of (7) is taken to be zero, and if Cas) = 0 and slab geometry is used, (7) becomes =ak[C, -H(¥;c,, J] ap ‘The B.C. (8) (9) are used to solve (11), For zero order solid reactions, the function H(¥) can be found by using (2) “Ws fac. =C,-Cy or H(W:C, )=C, =(Cy-¥) (12) Then, (11) becomes =akW =ak' CoP (13) which has precisely the form of a first order reaction diffusion problem, but with the B.C. (8). Note that we have changed to the modified rate constant k’, k= K'Cyy Therefore, the solution can be taken directly from Chapter 3, and is cosh(9z/L) ‘cosh() W= [ak CC, $= (14)Finally, the gas concentration profile can be found from the definition (1) by recognizing that, in general ow " Fh nak C y= Ak CC 5 ‘Thus, C=C, SosnlealL) L) (15) cosh() The solid concentration profile is found from (12): c,=[1- See Mavessien (16) cosh(o) These results are the same as those of Ishida and Wen, but for slab geometry. (©) Since the entire problem is reduced, in general, to (11) with B.C. (8) (9), all the results of Chapter 3 can be utilized with the "rate" being taken as [Cy —H(:C,, Jak. The conversion is defined as te D. [ote cq Co a7) ~ Lake, 3 Oz where (11) was used as in Chapter 3. Next, (11) is partially solved as in Chapter 3: pt on = pfpaalce woo (18) lartace where Vo is the value of W at the center of the pellet, which can be found for asymptotic cases as in Chapter 3 (¢.g., Y @ ~ 0 for large ® and irreversible reactions). Finally, combining (17) and (18) and B.C. (8) gives: ge feel Hee sel (9) which is the (corrected) form of the result given in the text, with dimensionless $7 =Lakf(Cy)/D,.4.3. a) Derive the results of (4.2-13 to -15) by directly solving the appropriate differential mass balances. b) Compute the conversion-time results of Figs. 4.2-3 for 9 = 2.0 (first stage onl Solution a) The differential equations to be solved for the first stage are: ‘The zero-order rate form permits the uncoupling of (1) from (2), and the standard substitution of Cas = w/t leads to: GB) @) with =0, one readily finds B = 0. Then at r= R, 0 xh} =k, C,—Asinna From this, the constant A can be found and substituted back into (4), with the result: Ca _ 1 sinh og Sw 5 aa 6) where E=0R and eal (ocoth¢-1)Next, (2) is used to find the solid concentration, and by direct integration gives: CCact or sinh bE 0 canbe, © where 6 =ak'C,t and (5) was used. Finally the conversion is found by integrating over the spherical volume: oe). esi x a ae = fine ” “3 (pcoth 6— oe b) A few calculated values for =2.0 are given for the conversion (note that in Fig. 4.2- 3, be= Land also that 8 o th 2 ~1)6 = 0.8068 8 0 02 04 0.6 x 0 0.161 0.322 0.484 4.4 — The secondary steam reformer of an ammonia plant has to be opened to replace the Ni/alumina catalyst. This requires the prior careful reoxidation of the pyrophoric Ni-catalyst. Simulate the reoxidation by means of an oxygen/nitrogen mixture containing 5 volume % oxygen. Use the general model of Section 4.2 to calculate the evolution with time of the concentration profiles of oxygen (A) and Ni (S) in the catalyst particle for various values of the rate parameters and for conversions based on S of up to 50 %. The initial Ni content of the catalyst (Cso) is 0.00624 kmol/kg cat. ‘The rate equation for /2 02 + Ni into NiO is ry =kKypaC’s/1+KP, [mol Nifem’ cat. s] with k= 21.7 exp(-3520/T) Ky = 0.305 exp(3070/7) The particle is isothermal at 300°C. Is there a transition between uniform and shrinking core situations ?‘The porosity of the particle, ec, is 0.45. Neglect the change caused by the oxidation. Calculate the effective diffusivity of oxygen for a random pore model with only macropores. (In Chapter 11 this operation will be dealt with at the reactor level.) Solution Atmospheric pressure is assumed. The density of the catalyst is 1515 kg/m’ and the catalyst particle diameter is 1.4 cm. Variations of the value of the diffusion coefficient by a changing porosity do not have to be accounted for. The molecular diffusion coefficient can be found in Perry et al. [1984] or can be estimated from the Fuller, Schettler, and Giddings correlation also found in Perry et al. [1984] worn et r MoM, Ply), (Ev)? where T'is in K, p is in atm, and D in em’/s. The values of the atomic diffusion volumes ‘Lp can be found in Perry et al. [1984], for 0, Lp = 16.6, for No, Yp = 17.9. A value of 0.65 cm’/s is found. The diffusion coefficient for Knudsen diffusion depends on the pore radius. For macropores, a pore radius of | jim is considered (see Chapter 3). The diffusion coefficient for Knudsen diffusion is then calculated from (3.4-4): 2r [RT Peo Sem A value of 4.1 cm’/s is found. Applying the random pore model with only macropores, the effective diffusivity can be found from: Then, D,o, = 0.114 em’/s, where the contribution of the Knudsen diffusion is minor in this case with macropores only. The species continuity equations to be solved are (4.2-9) and (4.2-2): Co. [. 2p, 42 ous ot r orwith initial and boundary conditions (4.2-3)-(4.2-5): (R= Co,(8) ‘The latter implies the absence of interfacial transport limitations. The spatial derivatives can be discretized with a finite difference method. The equation is then solved in time using a 4th order Runge-Kutta routine. ‘Two results are shown in the figures hereafter: (1) for an initial oxygen partial pressure of zero and (2) for an initial oxygen partial pressure equal to that in the gas phase, i.c. corresponding to a 5 volume % oxygen content. Figures 44-1 and 4.4-2 show the evolution during the first 10 seconds of the Ni concentration in the catalyst and the partial pressure of oxygen in the catalyst pores, for the case where the initial oxygen partial pressure is equal to that in the gas phase. Figures 4.4-3 and 4.4-4 show the evolution during the first 10 seconds of the Ni concentration in the catalyst and the partial pressure of oxygen in the catalyst pores, for the case where the initial oxygen partial pressure is zero. The longer-term evolution is not shown here. x10? a 5 Cy, (mol/em? cat) a Ere) a7 03 os 05 08 Contor r(em) 07 Solid surface Figure 4,4-1. Evolution during the first 10 seconds of the Ni concentration in the catalyst ‘The initial oxygen partial pressure is equal to that in the gas phase.08s 005| onus a] aca 01s ona| Pog (bar) 0025 0.09] oop oot 108 omar 07 03 04 05 06 97 Conter (em) Son Figures 4.4-2. Evolution during the first 10 seconds of the partial pressure of oxygen in the catalyst pores. The initial oxygen partial pressure is equal to that in the gas phase. x10 ‘oo; 02030405 06 a7 Contor r(em) Son surface Figure 4,4-3. Evolution during the first 10 seconds of the Ni concentration in the catalyst ‘The initial oxygen partial pressure is zero.006, 0s| a] ona| Pog (bar) ona| O18 oot Os o ot 02 03 of os 06 97 Conter (em) Son Figures 4.4-4, Evolution during the first 10 seconds of the partial pressure of oxygen in the catalyst pores. The initial oxygen partial pressure is zero.Chapter 5 5.1. For shell progressive poisoning, the “shrinking core” model of Chapter 4 was utilized to derive the time rate of change of poison deposition, (5.2.3-6); complete the steps leading to this result. Solution Equation (5.2.3-6) is obtained by elimination of C5, and C}, from the set of equations (5.2.3-1) - (5.2.3-4): alCp Ch) a (3) Setting [on fale? ef. x, @) yields: Sek Bo aterky Substitution in (2) gives : 4n D, 6 x (Cart from which : C}, is now eliminated from (1)or with Replacing t by ” = tref. yields (5.2.3-6). 5.2. The effect on the reaction rate for shell-progressive poisoning is based on (5.2.3.8), (- 9) and (-10). Use these to derive the effectiveness factor relationship (5.2.3-11).. Solution Derive:(5.2.3-12) where Poisoned Shell: (5.2.3-8) Unpoisoned Core (5.2.3.9) Boundary conditions : ac Dy—* @r=R (5.2.3-108) chor ¢ ) @r=r, (5.2.3-10b) @r=0 (5.2.3-10¢) @ @r=R )using B.C. (5.2.3-10b) with (c), (d), and (e) KR? 3 sin fka/Daat =A (C.-C )+C, © & Dak also, B ian [Bey 4B [Ba cogn, [Re Ka (RY 6 ce |B BoB [Be coun fi | = vage(®) cc.) © From (g) kaR?(C, -Ci) Dgasinh Belek pect fe -| k kat [ea Le ore Np ee D,,sinh (396) [396 coth(39E)— 1] (h) From (f) Kea * 6 sinh(39e)+F#*®(c, -C3) KyR(Cy—Ci) Ke Rie, c.) @ Dit, BoEeoth(39E)= 1] Duy =(c,-c,/ et ows Dr 3oE coth(3GE)-1]+Sh,Combining (©) and (h) c kR2(C,-Cy) ©" Dapsintl oe TREcouL (396) a r Combining (d), (e), and (i) k AR 1 Cy, =(C, - Cy, } —j —*—___— + Sh,,| = w= n= iat amE 1] { & Now, n is defined to be: Combining (1) with (5.2.3-10a) fan'tles-Cu)_3 a eR ln “Fl FAR Cy Rk @ r=R.Cy=Cy From B.C, (n) and (k) -cy iam aoe si(2-1}} et os) a RT 1 kyaR? 1 Cu Donel Ge com) t] vse ' k,l R? Cn vesi,( a} DaclOd5 eoinH—)=] 1 ie Kea J Djar-[o8)coth(3o2)=1 Combining (n) and (0) I a (kK) oO (m) (a) (0)(5.2.3-12) 5.3. Obtain a plot of the deactivation function ® vs. dimensionless time w for the shell progressive model: For $= $' (D,, =D,,) and Sh, >, from Problem 5.2:a 2) B) 4) Ow ny 2(308) coth(39e) — 1] For Da >» and Sh, >», the dimensionless time is found by integrating the results of Problem 5.1 (or (5.2.3-7)): “bsecal yee) tels (le-geqp -L ete ®) Plot four lines subject to the conditions: o=0 3 10 100 (0)=1 0.67 0.27 0.03 ¢, Pick value of o (0 to 10 by 0.1 increments) Pie c VY! Determine € =| 1} —*- Gc, Pe Determine w from (B) or Figure 5.2.3-1 Determine @ from (A) or Figure 5.2.3-2 (Note: ® = & for @ 0) Plot @ vs.4 =I o)=003 a q a 5 i i é W Dimemionles Tine Figure 5.3-1 5.4. Derive (5.2.4-5) and (-7) for poisoning effects with consecutive reactions. Solution stan A—>R—>5 : ' ‘ Unpoisoned | Poisoned (Both Rxn’s Poisoned) ! npoisones ' oisone ' zone t zone (a oO Ze L Boundary conditions @Z=Ze BC(7) Ca. =€, BC(8) Cy, = Cyy BC(9) C., = Cy, BC(10) DiyBC(I1) Dig aw BC(12) Dig = Differential Egs. Boundary conditions @Z=L BC(I) Di, Su =n ale, -Cal, ] BC(2) Diy Se = RIC ~Cul,] : S.-C BCG) DS OZ @Z=0 Kuo BC(S) y =0 ee, BC) —==0 Oa LetKjgh sh, = Ds Des General solutions to (1) > (6) are as follows: IAC, =A+BZ 2A Cy, =C+DZ 3A Cy =E+FZ 4A Cq, = Gsinh($,Z/L)+ Hcosh(,Z/L) Applying BC(1) -> BC(3) to general solutions 1A > 3A: z IBC. =A +snyley ~cu, F Ez UL 3B C=E sshifc, - ch 2B Cy, =C#Shy|Cy -Ca Thus @ Z=L |, -BeSiCs Sle 14+Sh,Cy Substitute these expressions into 1B > 3B. ICC, =A4 Shy (c,-ale 1+) 2C C= C+ Shy_ [cx -cé 1+Shy LShy Zz ese} 3C C =E va 8 ET sh: hy L Now applying BC(4) to 4. 4+| =0 only when G=0 FAC C= Host 2) Substitute 4C into 5 ee, @ . yt sa TOu -(2) Cu wz AL The solution is: 5B Cy = taint 9,2) J cost 2 ) + sain 2) «Teos L) = General solution + Particular solution Inserting SB into 5A and equate cosh (by inspection-only the particular solution need be substituted). s(ayomlnc}eat) om(og) (2) fomor) Equating coefficients sin{ 2) terms: $= 0 cont 02) terms: Substitute for $ and T into 5BApplying BC(S) to the above equation: re =0 whenT=0 5 5C Cy =F cosh 2) - Substitute 5C into 6 Da Host Zz De L) ‘The solution is 6B C,,=M+4Nz+ sin, 2) + Ucosh ¢ 2) +Psinh| 6, 2) + Veout{ 2) L EL eL L = General solution + Particular solution Substitute 6B into 6A and equate coefficient (by inspection-only the particular solution with coefficient U and V need be substituted.) ufoale dh ale 4 Des Heoshl 2) HED OL Substitute for U and V into (6B)= MWe oat 6,2] Pa cosh{ to} Ds L) Des $1 - 62 ob. Applying BC(6) to the above equation: 3) <0 whenn=0 2:66 Cy, =M—B8 Je si 2), Ba. Ds L rin Summarizing Ic 2c 3c 4c 5c oc ‘There are six unknowns and six remaining BCs (BC(7) > BC(12)). Applying BC(7) and (10) to (1C) and (4C) La an —Sha_[Ex-A]_ Sc nsinn( (2) o a |, Tan L Cy =¢, Sha_te, = Heosh( 8) hhc =Enlne PAH Tope [Ca AR = Heoshld,6) @) Take the ratio of (7) to (8) to eliminate H and solving for A. C, [1-4 tanh(o,6)] tanh(>,é) ASubstitute A into (7) and solving for H Cy Hea mf E+ gi praanlo) Repeating this procedure gives the following results: Lu} _ Cw B.C.L) @I,, Oh lee Cole Cale Bee 1+ShyD, 7 Call osétanh(9,€))+ Shy Dag a lsinn()—#,cosh(¢,8anh(@8)] sn oi 5 “osh(,8) + af -E+ si, Heme) fit.) 4 ae -t+ sh, snl) il) Finally using x] _ Os @Z\,, OZ lee Cs, = Ele Daw atte +Cy _1+Sh,[ Day _ p= SH[ Patil.) D.e-8 Shy ‘The value of M is not needed for the result since Dy Ce ( | _DaVCx az, Taw PsVOsh py CsSubstitute values for C and E into above expression, rearrange to the form of (5.2.4-5) (good luck!) to get the selectivity of R. 5.5. and 5.6 TO BE PROVIDEDCHAPTER 6 6.1 Derive the rate equation for a reversible first order gas-liquid reaction A ———P using the film theory (D, = Dp) ac, C,, and =" =0 and “yy 4: C, =Cy, and C, = KC, ku (Cy-C, JK) Show that N= 1k fanhy y k, (1+ K)D, where (14K) KK Solution ‘The rate equation of a reversible first order gas-liquid reaction reads r=! ‘The continuity equations for species A and P are 4 (¢ Ge v,Soran(e.-S] Integration of (4) between y and yi, leads to @Cty A (yp -y)+C,, (K41) (5) Substitution of (5) in (1) gives @C, kK (K+) KN, ay K car wate K,C,, (K+1) K (6) ‘The integral of (6) may be written as Cy=Ay soi vfs sin? Zale : a o YA . Dk (K+1) kiK Substitution of (7) in (6) permits the determination of the coefficients P and Q: where (8) o Accounting for the boundary conditions permits the determination of the integration constants A, and Ay. N For y=0 Cy, =AtCy, + ory AHO TE N A,=C, -C, -—A— 10) Ons Te, (10) For y= yu C,=Ascosh +4.sinhy-T Substitution of (8)-(11) in (7) leads to ca{es Saigon} a smn[y2 y Z w(t he, ‘The rate of the overall phenomenon follows from the application of Fick’s law:6.2 Derive the rate integral selecti Solution For complex reactions of type 3 the rate equations are He CC dt dc, C= yey k.CnCy with boundary conditions Cy, =Cpo and Cy=0 at t=0 Dividing (2) by (1) leads to SCoy _ Ke Cun yyy Coy With B.C. Cyy=0 at Cy, tet oa, Cy =x and Cray (3) becomes dy B.C: x =O for yyy ‘The transformation “= leads to y dy “dy and (4) becomes 2 = az-1 dy equation (6.3.6-1). op) 2) (3) @ (5) (6)dz (az (5) and (6) - with B.C 2=Oat y=yy The integral of (7) is or 6.3 A gas is being absorbed into a liquid in which the concentration of the reactive component B is 0.1 M. The reaction between the gaseous component A and the component B is extremely fast. The conditions are such that C, = 0.IM. Further, D, = 10%cm*/s. Compare the enhancement factors based upon the film theory and the surface renewal theory for the cases that a) D, = Dy 3b) Dy = > 30) D, =2D,. Solution 1) Film theory 2) Surface renewal theoryRe —1~ “(| where fi follows from (6.4.1-8). e ) v ) Prerfe| PB |= Lm |Ps Prore| 8. beat epee ao] 6.4 Consider the absorption of gaseous CO; by a NaOH solution. The stoichiometry is as, follows: CO, +2NaOH = Na,CO,+H,O Consider the solubility of CO, to be independent of the NaOH concentration and let the diffusivities of CO2 and NaOH in the liquid be approximately equal. 1) Can the reaction be considered as being of the pseudo first order when the gas-liquid contact time is 0.018 and when a) The partial pressure of CO> is 0.1 bar and the concentration of NaOH 1 mol? b) The partial pressure of CO; is 1 bar and the concentration of NaQH iM? 2) When the gas-liquid contact time is 0.1s and the NaOH concentration is 3 mol/l, what is the partial pressure of CO; above which the reaction is no longer pseudo first order. Take k’= 107 cm'/mol s and H = 25.105 em* bar/mol. Solution Use the Van Krevelen-Hoftijzer diagram. For purely physical absorption, according to the film theory and according to the penetration or surface renewal theorySo that k,_ can be related to the contact time by with kek Cyc (with NaOH in mol/l) Finally, 0 im 4 ‘The parameter on the curves in the V.K.-H.-diagram is the reaction is pseudo first order 2 Ds Cw b) for y=78.5 and for bD, Cy 2,5 itis not when y=50 12.5 Suen has to be larger than 200 so that poo, should not exceed 0, 0.2 bar, 6.5 COz is absorbed at 25°C into a 2.5 M mono-ethanolamine solution in a rotating drum type of absorber. The contacting surface is 188.5 em? and the contact time 0.2 s. The partial pressure of CO; in the gas phase is 0.1 atm, The reaction is as follows: CO, +2R,NH> R,NCOO’ +R,NH} The rate of absorption at these conditions is found to be 3.2610 mol/s. What is the value of the rate coefficient neglecting the gas phase resistance and considering the reaction to obey pseudo first order behavior? Additional data are: Dy = 1.4:10° em?/s3 Dy = 0.7710 ems: Henry’ constant, H = 29.810 atm cm/mol , SolutionThe solution is obtained from (6.5.4-3) or from the two simplified formulae derived from it— for short contact times (6.5.4-4) and for long contact times (6.5.4-5). First calculate N, = 2 = 3:26:10" 73.10% motem?s t 188.5 Then, from (6.5.4-5), Ny=C, DaKe,( 1+ u } 2kKC,T Ny O.tatm swam cl 298-19 mem™ 1 nw! ( 2kx0.2x2.5-10 from which: k= 7.6-10° em’/mol-s By repeating this calculation on the basis of (6.5.4-4) it is scen that KC, largely exceeds the value for which this formula is valid.Chapter 7 7.1. Write (7.3.1.1-6) in terms of &,, the extent of the i-th reaction per unit mass of the reaction mixture, defined by Solution (7.3.1.1-6) reads: and Substituting the above relations into (7.3.1.1-6), we get for the i'" reaction: -o( 2+} «[ +e] -s(ee or7.2. Derive the steady state continuity and energy equations and appropriate boundary conditions for the tubular reactor with turbulent flow, corresponding to the various situations represented in the figure below. The continuity equation for the first case is given by (in cylindrical coordinates): (7) =D, 0S Cr). ry (po Ci], ey ag or , C,(0, with B.C. u(r}Cy = ulr)C,(0,r)-D,, (0) 00") & x r=L S16 Vall on oC; z=0 1 6 ,allz or a z=R 1-6 Vall or Solution 1. Energy equation fort the first case: o.C,ule}er =, (0) ey BC. { no radial dispersion a) entrance: 2 =0 |noreacion ar(o ,C,ulr{T, ~ T10.1)] =A.) oz b)z=L a 4 allr OL o)r=0 aio all z a es ee ee) R,Continuity equation: ul) =D,, BC: a) ult}, =ulr)c,(0.r)-D,,, conditions for: z= L = (asin case | r=R, Energy equation: Cy ulONeE Real) BC: a) xC,ule{t, -T0.r)]=2,. 2 (0.7) b), ©) as in case 1 eT d)r=R dal, =U(T,-T,) D,. Des 3. For a flat velocity profile, u(r) = constant and become corresponding toa dey Rea uniform velocity profile Continuity equation: BC:Energy equation: BC: oT Cully —TO,r)]=2.,5> 4. Only axial dispersion a Flat concentration profile “1 =0 Flat temperature profile = Continuity equation: BC: Since ; the other B.C.’s don’t need to be considered. Energy equation: aT 4U cu + DCA, + (7, -7) ecu Deas Po) 4 surface — in the last term comes from volume BC:5. No dispersion in axial direction D,, =0 Continuity equation: BC: Energy equation: o.cuet =D AH), e -T) BC: Ty =T(z=0) 6. Continuity equation: u(C(z=L)-C,)=R,xL Energy equation: p,C,u(T(z = L)-T,)= (AH, Jy -L+ her, -T) 4, No boundary conditions.CHAPTER 8 8.1 The esterification of butanol with acetic acid, using sulfuric acid as a catalyst, was studied in a batch reactor: o C,H,OH + CH,COOH "8°: 5C,H, -O-C-CH, ‘The reaction was carried out with an excess of butanol. The following data were collected [C.E. Lejes and D.F. Othmer, I&EC, 36, 968 (1945)]. ‘Time (h)_ Acetic acid concentration (moles/l 0 2.3270 1 0.7749 2 0.4514 3 0.3152 4 0.2605, Set up a suitable kinetic model of the homogeneous type. Solution A plot of 1/Ca vs t yields a straight line. Hence the reaction is second order. The slope of the line is the reaction rate coefficient and equals 0.9 liter/(g mole h). Point values for k are also obtained from the integrated continuity equation: ac, kCh boat Geo Introducing the pairs C,/t yields or ‘Time (h) Acetic acid concentration (moles/l 1 0.8608 2 0.8928 3 0.9143 4 0.8523 8.2. The following data on the conversion of hydroxyvaleric a were collected