Kinetics of the esterification of acetic acid with 2‐propanol: Impact of different acidic cation exchange resins on reaction mechanism

International Journal of Chemical Kinetics - Tập 38 Số 10 - Trang 593-612 - 2006
Sami H. Ali1, Sabiha Q. Merchant1
1Chemical Engineering Dept., Kuwait Univ., P.O. Box 5969, Safat 13060, Kuwait

Tóm tắt

AbstractThe kinetics of the esterification of acetic acid with the secondary alcohol, 2‐propanol, catalyzed by the cation exchange resins, Dowex 50Wx8‐400, Amberlite IR‐120, and Amberlyst 15 has been studied at temperatures of 303, 323, and 343 K; acid to alcohol molar ratios of 0.5, 1, and 2; and catalyst loadings of 20, 40, and 60 g/L. The equilibrium constant was experimentally determined, and the reaction was found to be mildly exothermic. External and internal diffusion limitations were absent under the implemented experimental conditions. Systems catalyzed by gel‐type resins (Dowex 50Wx8‐400 and Amberlite IR‐120) exhibit some similarities in their reaction kinetics. Increase in reaction temperature, acid to alcohol ratio, and catalyst loading is found to enhance reaction kinetics for the three catalysts. The pseudohomogeneous (PH), Eley Rideal (ER), Langmuir Hinshelwood (LH), modified Langmuir Hinshelwood (ML), and Pöpken (PP) models were found to predict reaction kinetics with mean relative errors of less than 5.4%. However, the ML model was found to be better for predicting reaction kinetics in the systems catalyzed by gel‐type resins, while the PP model was better for the system catalyzed by the macroreticular catalyst, Amberlyst 15. The Eact for the forward reaction is found to be 57.0, 59.0, and 64.0 kJ/mole for the systems catalyzed by Dowex 50Wx8‐400, Amberlite IR‐120, and Amberlyst 15, respectively. For these three catalysts, the adsorption equilibrium constants of the components present in the system increase in the same order as do the solubility parameters of the component. Nonideality in the system is successfully accounted for by the UNIFAC model. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 38: 593–612, 2006

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Tài liệu tham khảo

Simonds M. R., 1943, Handbook of Plastics, 240

Kirk R. E., 1950, Encyclopedia of Chemical Technology

Carey F. A., 1990, Advanced Organic Chemistry

10.1002/9780470772423

10.1002/cjce.5450740409

10.1016/0009-2509(96)00041-3

Bhatia S., 1973, Ion Exchange Membr, 1, 127

10.1016/0926-860X(92)85050-L

10.1039/c39950000203

10.1021/ie940340r

10.1016/S0926-860X(96)00206-2

Krishnaiah D., 1984, Indian J Technol, 22, 268

10.1002/jctb.280370103

El‐Noamany H. M., 1993, Modelling, Meas Control, C, 43, 25

10.1021/ie00033a025

10.1002/(SICI)1097-4601(1996)28:9<649::AID-KIN2>3.0.CO;2-V

10.1016/S0926-860X(99)00081-2

Lee M. J., 1999, J Chin Inst Chem Eng, 30, 117

10.1021/ie0000764

10.1021/ie000063q

Kirbaslar S. I., 2001, Chin J Chem Eng, 9, 90

10.1016/S1381-1169(01)00495-2

10.1021/ie0204989

El Ewady Y. A., 1984, J Indian Chem Soc, 517

Awad M. M. B., 1997, J Indian Chem Soc, 74, 467

10.1016/S1381-5148(02)00086-X

10.1016/S1381-5148(99)00090-5

Leyes C. E., 1945, Trans Am Inst Chem Eng, 41, 157

Petro M., 1983, Chem Zvesti, 37, 461

10.1016/S0009-2509(97)00139-5

Kekre S. Y., 1969, Ind Chem Eng, 10, 115

10.1002/jctb.5040340510

10.1016/0923-1137(93)90064-M

Furniss B. S., 1989, Vogel's Textbook of Practical Organic Chemistry

McMurry J., 1992, Organic Chemistry, 804

Prausnitz J. M., 1999, Molecular Thermodynamics of Fluid‐Phase Equilibria

10.1021/ie9803826

10.1021/ie020925i

10.1016/0009-2509(62)85005-2

10.1016/0009-2509(69)80075-8

10.1016/S0378-3812(96)90021-7

Agreda V. H., 1990, Chem Eng Prog, 86, 40

10.1021/la9607114

Hansen K. H., 1992, SEP 9212, IVC‐SEP

Helfferich F., 1962, Ion Exchanger

10.1016/0009-2509(96)00183-2

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International Journal of Chemical Kinetics

Tập 38 Số 10

593-612

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