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Received April 17, 2004
Accepted May 31, 2004
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{1,2-dichloropropane+1,3-dioxolane} 및 {1,2-dichloropropane+1,4-dioxane}계에 대한 298.15 K에서의 과잉엔탈피 및 과잉부피
Excess Molar Enthalpies and Excess Molar Volumes of {1,2-dichloropropane+1,3-dioxolane, and+1,4-dioxane} at the Temperature 298.15 K
(주)대영케미, 718-800 경북 칠곡군 왜관읍 삼청리 1098-5 1국립상주대학교 응용화학공학부, 742-711 경북 상주시 가장동 386
Daeyoung Chemi Co., Ltd., 1098-5, Samcheong-ri, Waegwan 718-800, Korea 1School of Applied Chemical Engineering, Sangju National University, 386, Gajang-dong, Sangju 742-711, Korea
mgkim@sangju.ac.kr
Korean Chemical Engineering Research, August 2004, 42(4), 426-432(7), NONE Epub 14 September 2004
Abstract
298.15 K및 1 atm하에서 2성분계 {1,2-dichloropropane+1,3-dioxolane} 및 {1,2-dichloropropane+1,4-dioxane}에 대해서 과잉 몰부피와 과잉 몰엔탈피를 측정하였다. 과잉 몰부피의 경우 {1,2-dichloropropane+1,3-dioxolane}계는 전체 조성 범위에서 음의 편차를 나타내며, {1,2-dichloropropane+1,4-dioxane}계는 전 조성범위에 대해 양의 편차를 나타내었다. 과잉 몰엔탈피의 경우 {1,2-dichloropropane+1,3-dioxolane}계 및 {1,2-dichloropropane+1,4-dioxane}계 모두 전 조성범위에서 음의 편차를 나타내었다. VmE의 경우 분자구조의 차이 및 분자크기에 따라 이상상태로부터 각각 양과 음의 편차를 보여주었으며, HmE의 경우는 1,2-dichloropropane의 -Cl기와 1,3-dioxolane및 1,4-dioxane의 O< 기 사이의 쌍극자-쌍극자 상호작용에 따라 음의 편차를 보여주고 있다. 또한 그 결과를 Redlich-Kister식에 Nelder-Mead's simplex pattern search method를 사용하여 파라미터를 계산하였다.
This paper reports experimental excess molar volumes VmE using a digital vibrating-tube densimeter and excess molar enthalpies HmE by means of an isothermal microcalorimeter with a flow mixing cell for the binary mixtures_x000D_
{1,2-dichloropropane+1,3-dioxolane} and {1,2-dichloropropane+1,4-dioxane} at 298.15 K under atmospheric pressure. The mixture of {1,2-dichloropropane+1,3-dioxolane} has negative VmE over the entire composition range with exception of 1,4-dioxane, which has been shown to be positive. The cyclic molecular shape of 1,4-dioxane is not ideal to accept the halogenated hydrocarbon, resulting in an increase in the molecular distance. The consequent loosening of intermolecular intersections is also responsible for the positive values of VmE, with the exception of 1,3-dioxolane, due to its smaller molecular size. The excess enthalpies of all these mixtures were found to be positive over the entire composition range. These negative deviations from ideal behavior are probably due to dipole and dipole interaction between Cl and O molecules. The values of excess molar properties were fitted by the Redlich-Kister equation using Nelder-Mead’s simplex pattern search method.
Keywords
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Lopez ER, Garcia J, Fernandez J, Paz Andrade MI, J. Chem. Thermodyn., 25(9), 1127 (1993)
Calvo E, Brocos P, Bravo R, Pintos M, Amigo A, Roux AH, Roux-Desgranges G, J. Chem. Eng. Data, 43(1), 105 (1998)
Ohji H, Tamura K, Ogawa H, J. Chem. Thermodyn., 32(3), 319 (2000)
Park SJ, Lee TJ, Korean J. Chem. Eng., 12(1), 110 (1995)
Park SJ, Gmehling J, Korean J. Chem. Eng., 12(2), 152 (1995)
Bae HK, Song HC, Korean J. Chem. Eng., 15(6), 615 (1998)
Park SB, Kim JS, Lee H, J. Chem. Thermodyn., 31(10), 1265 (1999)
Kim MG, Lee YS, J. Kor. Soc. of Ind., 4(2), 193 (2001)
Kim MG, Lee YS, Kim YW, "Excess Molar Volumes and Excess Molar Enthalpies for {1,2-dichloropropane+2-ethox-yethanol} at T=298.15 K," Proceedings of 2001 KIChE Fall Meeting, 7(2), 3619 (2001)
Kim MG, Lee YS, "Excess Molar Enthalpies for {1,2-dichloropropane+2-alkoxyethanol} at T=298.15 K," Proceedings of 2002 KIChE Spring Meeting, 8(1), 849 (2002)
Kim YW, Kim JW, Kim MG, "Excess Molar Volumes and Enthalpies for 1,2-Dichloropropane+1,4-Dioxane at the Temperature 298.15 K," Proceedings of 2003 KIChE Fall Meeting, 144 (2003)
Kim YW, "Excess Molar Properties of {1,2-dichloropropane+1,3-dioxolane, or +1,4-dioxane} at 298.15 K," M. S. Dissertation, Sangju National University, Sangju, Korea (2004)
Redlich O, Kister AT, Ind. Eng. Chem., 40(2), 345 (1948)
Nelder JA, Mead R, Comput. J., 7(4), 308 (1965)
Riddick JA, Bunger WS, Sakano TK, Organic Solvents, Physical Properties and Methods of Purification, 4th ed., Wiley Interscience Publication, New York (1986)
Isothermal Microcalorimeter User's Manual Revision 3.0, Calorimetry Sciences Corporation (1997)
Sabbah R, An XW, Chickos JS, Leitao MLP, Roux MV, Torres LA, Thermochim. Acta, 331(2), 93 (1999)
Wadso I, Thermochim. Acta, 347(1-2), 73 (2000)
Tanaka R, D'arcy PJ, Benson GC, Thermochim. Acta, 11(2), 163 (1975)
Chand A, Fenby DB, J. Chem. Thermodyn., 10(10), 997 (1978)
Costigan MJ, Hodges LJ, Marsh KN, Stokes RH, Tuxford CW, Aust. J. Chem., 33, 2103 (1980)
Prausnitz JM, Lichtenthaler RN, de Azevedo EG, Molecular Thermodynamics of Fluid-Phase Equilibria, 3rd ed., Prentice-Hall, New Jersey (1999)
