Aliquat 336에 의한 액-액 불균일계에서 n-butyl acetate의 가수분해

박상욱; 문진복; 박대원; 신정호

HWAHAK KONGHAK, Vol.31, No.1, 107-117, February, 1993

Hydrolysis of n-Butyl Acetate Using Aliquat 336 in the Liquid-Liquid Interface and Mass Transfer of Phase Transfer catalyst

박상욱, 문진복, 박대원, 신정호

초록

개량된 Lewis cell을 사용하여 상전이 촉매 tricaprylmethyl ammonium chloride(Aliquat 336; Q⁺Cl^-)의 화학반응을 수반한 물질전달속도의 촉진계수를 측정하여 경막설을 보정한 Leveque 모델로부터 구한 이론값과 비교하여 Q⁺Cl^-의 순간 가역 해리반응을 수반한 물질전달속도를 정량적으로 설명하였으며, n-butyl acetate 가수분해 반응에서 물질전달을 포함한 상전이 촉매에 의한 반응기구로서 확산-반응 모델을 제안하여 총괄반응속도의 측정치와 비교하였으며, 이로부터 구한 반응속도상수는 25α에서 36m³/kmolㆍs이며 촉매를 사용하지 않은 경우보다 100배 정도 큰 값이었다.

Constants of the distribution and dissociation equilibria of tricaprylmethyl ammonium chloride(Aliquat 336;Q⁺Cl^-) were measured for the organic phase(toluene, n-butyl acetate)-aqueous phase(water, NaCl, NaOH) system. The enhancement factors of Q⁺Cl^- were measured with a Lewis cell, and compared with those predicted from the theoretical model based on the film theory corrected by the Leveque model. A diffusion-reaction model was proposed to explain the mechanism of n-butyl acetate hydrolysis with a phase transfer catalyst(Aliquat 336), and the overall reaction rates observed were compared with those calculated by the proposed model. The reaction rate constant evaluated by fitting the rate data to model prediction was 36m³/kmolㆍs at 298K, which was about 100 times greater than that of alkaline hydrolysis in the aqueous phase without using a catalyst.

[References]

Starks CM, J. Am. Chem. Soc., 93, 195 (1971)
Starks CM, Owens RM, J. Am. Chem. Soc., 95, 3613 (1973)
Herriott AW, Picker D, J. Am. Chem. Soc., 97, 2345 (1975)
Weber WP, Gokel GW, "Phase Transfer Catalysis in Organic Synthesis," Springer-Verlag, New York (1977)
Gordon JE, Kutina RE, J. Am. Chem. Soc., 99, 3903 (1977)
Starks CM, "Phase Transfer Catalysis," Academic Press, New York, 37 (1978)
Yadav GD, Sharma MM, Ind. Eng. Chem. Process Des. Dev., 20, 385 (1981)
Reuben B, Sjoberg K, ChemTech, 315 (1981)
Dehmlow EV, Dehmlow SS, "Phase Transfer Catalysis," Verlag Chemie GmbH, Weinheim (1983)
Freedman HH, Pure Appl. Chem., 58, 857 (1986)
Starks CM, "Phase Transfer Catalysis-New Chemistry, Catalysts, and Application," Symp. Am. Chem. Soc. (1987)
Wang ML, Wu HS, Chem. Eng. Sci., 46, 509 (1991)
Park SW, Chun BS, Lim GT, HWAHAK KONGHAK, 28(5), 594 (1990)
Park SW, Moon JB, Ko MS, Kim GW, J. Korean Ind. Eng. Chem., 3(1), 119 (1992)
Park SW, Moon JB, Park DW, Shin JH, HWAHAK KONGHAK, 30(5), 612 (1992)
Starks CM, "Phase Transfer Catalysis," Academic Press, New York, 13 (1978)
Davies JT, "Turbulence Phenomena," Academic Press, New York, 51 (1972)
JIS Comm.: J.I.S., K 0101, 107 (1986)
Wilke CR, Chang P, Am. Inst. Chem. Eng. J., 1, 264 (1955)
Hikita H, Asai S, Ishikawa H, Seko M, Chem. Eng. J., 17, 77 (1979)
Ratcliff GA, Trans. Inst. Chem Eng., 41, 315 (1963)
vanKrevelen DW, Hoftijzer PJ, Chem. Trans. Chim., 67, 563 (1948)
Danckwerts PV, "Gas-Liquid Reaction," McGraw-Hill, Book, Co., New York, 118 (1970)
Scott GV, Anal. Chem., 40, 768 (1968)

[Referenced By]

[1] Starks CM, J. Am. Chem. Soc., 93, 195 (1971)

[2] Starks CM, Owens RM, J. Am. Chem. Soc., 95, 3613 (1973)

[3] Herriott AW, Picker D, J. Am. Chem. Soc., 97, 2345 (1975)

[4] Weber WP, Gokel GW, "Phase Transfer Catalysis in Organic Synthesis," Springer-Verlag, New York (1977)

[5] Gordon JE, Kutina RE, J. Am. Chem. Soc., 99, 3903 (1977)

[6] Starks CM, "Phase Transfer Catalysis," Academic Press, New York, 37 (1978)

[7] Yadav GD, Sharma MM, Ind. Eng. Chem. Process Des. Dev., 20, 385 (1981)

[8] Reuben B, Sjoberg K, ChemTech, 315 (1981)

[9] Dehmlow EV, Dehmlow SS, "Phase Transfer Catalysis," Verlag Chemie GmbH, Weinheim (1983)

[10] Freedman HH, Pure Appl. Chem., 58, 857 (1986)

[11] Starks CM, "Phase Transfer Catalysis-New Chemistry, Catalysts, and Application," Symp. Am. Chem. Soc. (1987)

[12] Wang ML, Wu HS, Chem. Eng. Sci., 46, 509 (1991)

[13] Park SW, Chun BS, Lim GT, HWAHAK KONGHAK, 28(5), 594 (1990)

[14] Park SW, Moon JB, Ko MS, Kim GW, J. Korean Ind. Eng. Chem., 3(1), 119 (1992)

[15] Park SW, Moon JB, Park DW, Shin JH, HWAHAK KONGHAK, 30(5), 612 (1992)

[16] Starks CM, "Phase Transfer Catalysis," Academic Press, New York, 13 (1978)

[17] Davies JT, "Turbulence Phenomena," Academic Press, New York, 51 (1972)

[18] JIS Comm.: J.I.S., K 0101, 107 (1986)

[19] Wilke CR, Chang P, Am. Inst. Chem. Eng. J., 1, 264 (1955)

[20] Hikita H, Asai S, Ishikawa H, Seko M, Chem. Eng. J., 17, 77 (1979)

[21] Ratcliff GA, Trans. Inst. Chem Eng., 41, 315 (1963)

[22] vanKrevelen DW, Hoftijzer PJ, Chem. Trans. Chim., 67, 563 (1948)

[23] Danckwerts PV, "Gas-Liquid Reaction," McGraw-Hill, Book, Co., New York, 118 (1970)

[24] Scott GV, Anal. Chem., 40, 768 (1968)