에틸 아세토아세테이트 토토머리즘 평형 상수의 밀도 의존성

박윤국; YoonKook Park

Journal of the Korean Industrial and Engineering Chemistry, Vol.17, No.3, 291-295, June, 2006

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에틸 아세토아세테이트 토토머리즘 평형 상수의 밀도 의존성

The Effect of Solvent Density on the Ethyl Acetoaceate Tautomerism

박윤국^†

홍익대학교 화학시스템공학과

YoonKook Park^†

Department of Chemical System Engineering, Hongik University, Jochiwon 339-701, Korea

E-mail:

초록

본 연구에서는 아임계 및 초임계 이산화탄소하의 에틸 아세토아세테이트의 케토-에놀 토토머릭 평형상수를 후리에 적외선 분광기를 이용하여 세 가지 다른 온도에서 측정하였다. 케토-에놀 토토머릭 평형상수의 용매에 대한 밀도 의존성을 연구하기 위하여 정온하에서 이산화탄소의 압력을 변화시켰다. 용매인 이산화탄소의 밀도를 증가 시키면, 케토 토토머의 양이 증가하게 되어 케토-에놀 토토머릭 평형상수값이 감소한다. 에틸 아세토아세테이트의 케토-에놀 토토머릭 평형상수의 밀도의존성을 연구하기 위하여 변형된 격자유체수소결합 모델을 적용하였다.

The keto-enol tautomeric equilibrium constant, K, of ethyl acetoacetate in compressed and supercritical carbon dioxide was determined by using FT-IR (Fourier transform infrared) spectroscopy at three different temperatures. In order to investigate the effect of solvent density, the CO2 pressure was systematically changed at a constant temperature. As the CO2 density is increased, the amount of keto tautomer is increased, causing the K value to decrease. The modified lattice fluid hydrogen bonding theory has been applied to investigate the effect of density on the K.

Keywords:tautomeric equilibrium constant;supercritical carbon dioxide;ethyl acetoacetate;infrared spectroscopy

[References]

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Gupta RB, Panayiotou CG, Sanchez IC, Johnston KP, AIChE J., 38, 1243 (1992)
Park Y, Ph.D. Dissertation, Auburn University, Auburn, AL, USA (2000)
Kazarian SG, Gupta RB, Clarke MJ, Johnston KP, Poliakoff M, J. Am. Chem. Soc., 115, 11099 (1993)
Gupta RB, Brinkley RL, AIChE J., 44(1), 207 (1998)

[1] Bell PW, Thote AJ, Park Y, Gupta RB, Roberts CB, Ind. Eng. Chem. Res., 42(25), 6280 (2003)

[2] Sarbu T, Styranec T, Beckman EJ, Nature, 405, 165 (2000)

[3] Raveendran P, Wallen SL, J. Am. Chem. Soc., 124(25), 7274 (2002)

[4] Lu J, Han B, Yan H, Phys. Chem. Chem. Phys., 1, 3269 (1999)

[5] Folkendt MM, Weiss-Lopez BE, Chauvel JP, True NS, J. Phys. Chem., 89, 3347 (1985)

[6] Mills SG, Beak P, J. Org. Chem., 50, 1216 (1985)

[7] Powling J, Bernstein HJ, J. Am. Chem. Soc., 73, 4353 (1951)

[8] Schiavoni MM, Di Loreto HE, Hermann A, Mack HG, Ulic SE, Della Vedova CO, J. Raman Spectrosc., 32, 319 (2001)

[9] Henry MC, Yonker CR, Anal. Chem., 76, 4684 (2004)

[10] Park Y, Turner CH, J. Supercrit. Fluids, 37, 201 (2006)

[11] Park Y, Gupta RB, Curtis CW, Roberts CB, J. Phys. Chem. B, 106(37), 9696 (2002)

[12] Fujii Y, Yamada H, Mizuta M, J. Phys. Chem., 92, 6768 (1988)

[13] http://webbook.nist.gov/chemistry/fluid/

[14] Raveendran P, Wallen SL, J. Am. Chem. Soc., 124(42), 12590 (2002)

[15] Kazarian SG, Vincent MF, Bright FV, Liotta CL, Eckert CA, J. Am. Chem. Soc., 118(7), 1729 (1996)

[16] Gupta RB, Panayiotou CG, Sanchez IC, Johnston KP, AIChE J., 38, 1243 (1992)

[17] Park Y, Ph.D. Dissertation, Auburn University, Auburn, AL, USA (2000)

[18] Kazarian SG, Gupta RB, Clarke MJ, Johnston KP, Poliakoff M, J. Am. Chem. Soc., 115, 11099 (1993)

[19] Gupta RB, Brinkley RL, AIChE J., 44(1), 207 (1998)