Gregory Yablonsky Department of Chemical Engineering, Washington University, 1 Brookings Drive, Campus Box 1198, St. Louis, Missouri 63130 Sir: Recentl y, I nd. Eng. Chem. Res. i naugurated a new ki nd of paper cal l ed a Commentary. The concept i s excel l ent. The paper must be wri tten by i ndi vi dual s hi ghl y respected i n the area of chemi cal engi neeri ng. A Commentary i s meant to be cri ti cal and sel ecti ve because i t i s based on a broad perspecti ve that i s both hi stori cal and cauti ousl y propheti c... A Commentary i s not meant to be exhausti ve, on the contrary, i t i s hi ghl y sel ecti ve, a product of the authors judgment (ref 1, p 4139). The fi rst Commentary appeared and was wri tten by Prof. Octave Levenspi el , who i s a worl dwi de wel l - known author of Chemical Reaction Engineering and TheChemical Reactor Omnibook 2 and who i s superbl y fami l i ar wi th the hi story of chemi cal engi neeri ng. I n our ti mes of i nformati on overl oadi ng, one cannot emphasi ze enough the i mportance of i ni ti ati ves such as com- mentari es. The message of Prof. Levenspi el s commentary i s the fol l owi ng: Dont compl i cate a ki neti c model ! Pay more attenti on to the fl ow model ! He i s somewhat sarcasti - cal l y descri bi ng the contemporary practi ce of reactor model i ng wi th some researchers have used as many as 60 i ndi vi dual el ementary reacti on steps, whi l e at the same ti me compl etel y i gnori ng the questi on of l ooki ng for the best contacti ng or fl ow model (ref 3, p 4142). Certai nl y, Prof. Levenspi el i s ri ght. We have to anal yze the si mpl e model s fi rst, usi ng even semi em- pi ri cal ki neti c equati ons for an nth-order reacti on, and resul ts of anal yses of overcompl i cated model s shoul d be vi ewed wi th cauti on. However, i n chemi cal reacti on engi neeri ng there are many probl ems i n whi ch the compl exi ty of the chemi cal reacti on seems to be un- avoi dabl e. I t i s obvi ous that, anal yzi ng sel ecti ve oxi da- ti on reacti ons over oxi de catal ysts, pyrol ysi s, and po- l ymeri zati on reacti ons, we have to take i nto account the change of compl ex chemi cal composi ti on i n ti me and wi th the l ength of the reactor. To cal cul ate these profi l es, we have to esti mate the parameters of the di fferent steps of compl ex reacti ons, parti cul arl y for steps wi th parti ci pati on of the i ntermedi ates (radi cal s or surface substances). Unfortunatel y, Prof. Levenspi el does not pay attenti on to these probl ems. Moreover, he cri ti ci zes an appl i cati on of Langmui r-Hi nshel wood and Hougen-Watson (LHHW) equati ons for descri bi ng het- erogeneous reacti ons (Prof. Levenspi el cal l s thi s the petrotech approach). I n hi s opi ni on, the LHHW equati on (numerator over denomi nator equati on) i s too compl i - cated. However, the compl exi ty of thi s equati on i s unavoi d- abl e too. I ts denomi nator refl ects the fact that some i ntermedi ates occupy the surface of the catal yst. Even Prof. Levenspi el wi l l appl y the si mpl e nth-order ki neti c equati on; the apparent order wi l l be a functi on of the chemi cal mi xture composi ti on and temperature. Another i mportant thi ng whi ch i s not taken i nto account i n Prof. Levenspi el s Commentary i s the speci al correspondence between the model and i ts goal . There i s no model for al l ti mes. For some purposes the si mpl e model i s the best one, and thi s si mpl i ci ty rel ates to the l evel of physi cochemi cal understandi ng. However, for other purposes we real l y need a compl ex model . Typi cal strategi es of mathemati cal model i ng, i n chemi cal engi - neeri ng as mul ti scal e hi erarchi cal model i ng 4 or a mul ti - scal e approach to a mul ti -objecti ve task, 5 are wel l - known. I n our understandi ng, si mpl i ci ty has to be empha- si zed, and i n that Prof. Levenspi el i s compl etel y ri ght. However, we al so have to l earn how to l i ve wi th the unavoi dabl e compl exi ty of chemi cal reacti ons whi ch i s a real l y new trend i n chemi cal engi neeri ng. I t i s al ways di ffi cul t to di sti ngui sh the usel ess fashi on and the new trend. I t i s al so di ffi cul t even for Prof. Levenspi el . Acknowledgment I am very thankful to Prof. Guy Mari n, who brought to my attenti on the new type of Commentary papers i n I nd. Eng. Chem. Res., and Prof. Mi ke Dudukovi c for edi ti ng my comments. Literature Cited (1) Paul , D. R. Commentary: A New Type of Paper. I nd. Eng Chem. Res. 1999, 38, 4139. (2) Levenspi el , O. The Chemical Reactor Omnibook; OSU Bookstores: Corval l i s, OR, 1996; Chapter 31. (3) Levenspi el , O. Commentari es: Chemi cal Reacti on Engi - neeri ng. I nd. Eng. Chem. Res. 1999, 38, 4140-4143. (4) Dudukovi c, M. P.; Larachi , F.; Mi l l s, P. Mul ti phase Reactors Revi si ted. Chem. Eng. Sci. 1999, 54, 1975-1995. (5) Lerou, J.; Ng. K. Chemi cal Reacti on Engi neeri ng: A Mul ti - Scal e Approach to a Mul ti -Objecti ve Task. Chem. Eng. Sci. 1996, 51, 1595-1614. I E001098T 3120 I nd. Eng. Chem. Res. 2000, 39, 3120 10.1021/i e001098t CCC: $19.00 2000 Ameri can Chemi cal Soci ety Publ i shed on Web 05/27/2000 Response to Professor Yablonsky Octave Levenspiel Chemical Engineering Department, Oregon StateUniversity, Gleeson Hall 103, Corvallis, Oregon 97331-2702 Sir: Prof. Yabl onsky rai ses two objecti ons to my presentati on. Fi rst, l et me expl ai n my rel uctance to use the Langmui r-Hi nshel wood-Hougen-Watson (LHHW) equati ons because they are too compl i cated. I f, for exampl e, a researcher comes up wi th a LHHW equati on to represent hi s porous catal yst data, then I probabl y coul d come up wi th fi ve di fferent other LHHW equati ons whi ch coul d fi t the data equal l y wel l . 1,2 Because these equati ons extrapol ate di fferentl y, whi ch shoul d I use for extrapol ati on? I do not know. Even i f I cannot fi nd any other LHHW equati on to fi t hi s data, l et me ask whether he can use hi s equati on wi th confi dence to extrapol ate for scal e-up? Does hi s equati on account for fi l m di ffusi on or how about di ffu- si onal resi stance wi thi n the parti cl es? What about fi l m heat transfer at the surface of the parti cl es? Fi nal l y, how about noni sothermal gradi ents wi thi n the parti cl es? The LHHW equati ons compl etel y i gnore these physi cal factors; hence, they are not useful for extrapol ati on. They si mpl y fi t the data. On the other hand, the chemi cal reacti on engi neeri ng (CRE) approach accounts for al l of the perti nent factors, and that i s why i n the marketpl ace of i deas i t won out over the petrotech approach, whi ch uses the LHHW ki neti cs. The second objecti on concerns my i gnori ng extremel y fast reacti ons. Researchers of such systems use basket- ful s of el ementary reacti ons, hundreds and hundreds of them, 3 to study free-radi cal reacti ons, fl ames, burn- ers, and other such devi ces, wi th computati onal fl ui d dynami cs (CFD) to represent the fl ow and mi xi ng. Thi s type of probl em i s deal t wi th pri mari l y by combusti on speci al i sts. I see thei r goal s as di fferi ng from CRE, whereas Prof. Yabl onsky does not. I suppose that thi s i s a matter of opi ni on. Prof. Yabl onsky al so says that I do not account for the correspondence between model and goal . I thi nk that the goal of CRE i s to come up wi th a good reactor desi gn to produce effi ci entl y what you want to produce. Ki neti c model s whi ch use basketful s of el ementary reacti ons or LHHW mechani sms, but then i gnore perti nent factors and at the same ti me are unnecessari l y compl i cated, are real l y unsui ted to the above-menti oned goal . I n concl usi on, Prof. Yabl onsky says that we have to l i ve wi th unavoi dabl e compl exi ty of reacti ons ...com- pl exi ty of equati ons. I am uncomfortabl e wi th such statements. I feel that we shoul d try to come up wi th si mpl e model s whi ch do account for al l of the perti nent factors. As Denbi gh 4 so wi sel y put i t, I t i s al ways necessary to abstract from the compl exi ty of the real worl d...and i n i ts pl ace...to substi tute a more or l ess i deal i zed si tuati on that i s more amenabl e to anal ysi s. Literature Cited (1) Chou, C. H. I nd. Eng. Chem. 1958, 50, 789. (2) Hougen, O. A.; Watson, K. M. Chemical Process Principles; Wi l ey: New York, 1947; part I I I , pp 943-958. (3) Rojnuckari n, A.; et al . I nd. Eng. Chem. 1996, 35, 683-696. (4) Denbi gh, K. G. The Thermodynamics of the Steady State; Methuens Monographs on Chemi cal Subjects; London, 1951. I E001095G 3121 I nd. Eng. Chem. Res. 2000, 39, 3121 10.1021/i e001095g CCC: $19.00 2000 Ameri can Chemi cal Soci ety Publ i shed on Web 06/24/2000
(Advances in Quantum Chemistry 59) John R. Sabin and Erkki Brändas (Eds.) - Combining Quantum Mechanics and Molecular Mechanics. Some Recent Progresses in QM - MM Methods-Academic Press (2010)