Korean Chemical Engineering Research

The Korean Institute of Chemical Engineers (한국화학공학회)
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Excess Molar Enthalpies and Excess Molar Volumes for the Binary Mixtures {1,2-dichloropropane+2-(2-methoxyethoxy)ethanol, and +2-(2-ethoxyethoxy)ethanol} at 298.15 K

2성분계 {1,2-dichloropropane+2-(2-methoxyethoxy)ethanol 및 + 2-(2-ethoxyethoxy)ethanol}에 대한 298.15 K에서의 과잉몰엔탈피 및 과잉몰부피

  • Kim, Jaewon (School of Applied Chemical Engineering, Sangju National University) ;
  • Kim, Moongab (School of Applied Chemical Engineering, Sangju National University)
  • 김재원 (국립상주대학교 응용화학공학부) ;
  • 김문갑 (국립상주대학교 응용화학공학부)
  • Received : 2005.11.22
  • Accepted : 2006.06.29
  • Published : 2006.10.31
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Abstract

This paper reports experimental excess molar volumes $V^E_m$ using a digital vibrating-tube densimeter and excess molar enthalpies $H^E_m$ by means of an isothermal microcalorimeter with a flow mixing cell for the binary mixtures{1,2-dichloropropane + 2-(2-methoxyethoxy)ethanol} and {1,2-dichloropropane + 2-(2-ethoxyethoxy)ethanol} at 298.15 K under atmospheric pressure. All the $V^E_m$ and $H^E_m$ of the two binary mixtures showed S-shaped forms, being negative for poor and positive for rich 1,2-dichloropropane mole fractions. These show that the excess properties were shown to be negative deviation from ideality due to the strong self-association effect among 2-(2-alkoxyethoxy)ethanol molecules at an early stage of mixing, a relatively high energy then is needed to break hydrogen bonds of 2-(2-alkoxyethoxy)ethanol with an increase ofhalogenated hydrocarbon molecular at high mole fraction of 1,2-dichloropropane. The values of excess molar properties($V^E_m$ and $H^E_m$) were fitted by the Redlich-Kister equation using Nelder-Mead's simplex pattern search method. The Wilson, NRTL, and UNIQUAC models were used to correlate the $H^E_m$ values.

298.15 K 및 1 atm에서 2성분계 {1,2-dichloropropane+2-(2-methoxyethoxy)ethanol} 및 {1,2-dichloropropane+2-(2-ethoxyethoxy)ethanol}에 대한 과잉몰부피와 과잉몰엔탈피를 측정하였다. 과잉몰부피를 측정하기 위한 밀도는 vibrating glass-tube 방식의 densimeter를 이용하였고, 과잉몰엔탈피는 flow mixing 형의 isothermal microcalorimeter를 이용하였다. 측정한 과잉몰부피 및 과잉몰엔탈피는 조성과 상관지어 모두 S자형을 나타내었다. 초기 2-(2-alkoxyethoxy)ethanol 의 강한 자체 회합현상으로 음의 편차를 나타내며, 할로겐화탄화수소 분자의 증가에 따라 2-(2-alkoxyethoxy)ethanol 분자간의 수소결합을 끊기 위한 에너지가 상대적 더 많이 필요함을 보여주고 있다. 실험으로부터 얻어진 $V^E_m$ 및 $H^E_m$ data는 Nelder-Mead의 simplex pattern search method를 이용하여 Redlich-Kister 다항식에 접합(fitting)하였고, Wilson, NRTL 및 UNIQUAC model을 이용하여 $V^E_m$ data와 조성과의 상관관계를 조사하였다.

Keywords

References

  1. http://daeyoungchemi.co.kr
  2. Banos, I., Valero, J., Perez, P., Gracia, M. and Gutierrez Losa, C., 'Excess Molar Volumes of Mixtures Containing 1,2-dichloropropane or 1,3-dichloropropane,' J. Chem. Thermodynamics, 22(5), 431-437(1990) https://doi.org/10.1016/0021-9614(90)90133-B
  3. Barbes, B., Garca, I., Gonzalez, J. A., Cobos, J. C. and Casanova, C., 'Excess Properties of Mixtures of Some N-alkoxyethanols With Organic Solvents, Part 7. $V^{E}$ with Toluene at 298.15 K,' Thermochimica Acta, 257(1-2), 103-110(1995) https://doi.org/10.1016/0040-6031(94)02205-3
  4. Tamura, K., Osaki, A., Murakami, S., Ohji, H., Ogawa, H., Laurent, B. and Grolier, J. -P. E., 'Thermodynamic Properties of Binary Mixtures {an alkoxyethanol + n-octane}. Excess Molar Enthalpies and Excess Molar Heat Capacities at 298.15 K,' Fluid Phase Equilibria, 156(1-2), 137-147(1999) https://doi.org/10.1016/S0378-3812(99)00031-X
  5. Pal, A. and Singh, W., 'Excess Molar Volumes and Excess Partial Molar Volumes of {$xC_{6}H_{5}CH_{3}+(1x)H(CH_{2})_{v}(OCH_{2}CH_{2})_{3}$ OH} (v=1, 2, and 4) at the Temperature 298.15 K,' J. Chem. Thermodynamics, 28(7), 717-722(1996) https://doi.org/10.1006/jcht.1996.0066
  6. Park, S. J. and Gmehling, J, 'Excess Molar Volumes at the 308.15 K for Constituent Binaries of n-decane, n-dodecane, 1-decanol and 1-dodecanol,' Korean J. of Chem. Eng., 12(2), 152-155(1995) https://doi.org/10.1007/BF02705639
  7. Bae, H. K. and Song, H. C., 'Excess Molar Volume of Acetone, Water and Ethylene Glycol Mixture,' Korean J. of Chem. Eng., 15(6), 615-618(1998) https://doi.org/10.1007/BF02698987
  8. Park, S. B., Kim, J. S. and Lee, H., 'Excess Molar Enthalpies (Propylene carbonate + an Alcohol),' J. Chem. Thermodynamics, 31, 1265-1271(1999) https://doi.org/10.1006/jcht.1999.0534
  9. Kim, M. G. and Lee, Y. S., 'Excess Molar Volume and Enthalpies for 1,2-dichloropropane + 2-methoxyethanol) at the Temperature 298.15 K,' J. Kor. Soc. of Ind., 4(2), 193-198(2001)
  10. Kim, M. G., Lee, Y. S. and Kim, Y. W., 'Excess Molar Volumes and Excess Molar Enthalpies for {1,2-dichloropropane + 2-ethoxyethanol} at T=298.15 K,' Proceedings of 2001 KIChE Fall Meeting, 7(2), 3619-3622(2001)
  11. Kim, M. G. and Lee, Y. S., 'Excess Molar Enthalpies for {1,2- dichloropropane + 2-alkoxyethanol} at T=298.15 K,' Proceedings of 2002 KIChE Spring Meeting, 8(1), 849-852(2002)
  12. Kim, Y. W. and Kim, M. G., 'Excess Molar Enthalpies and Excess Molar Volumes of {1,2-dichloropropane + 1,3-dioxolane, and + 1,4- dioxane} at the Temperature 298.15 K,' Korean Chem. Eng. Res., 42(4), 426-432(2004)
  13. Kim, J. W., 'Excess Molar Volumes and Excess Molar Enthalpies for Binary Mixtures of {1,2-dichloropropane + 2-(2-methoxyethoxy) ethanol, and + 2-(2-ethoxyethoxy)ethanol} at 298.15 K,' M. S. Dissertation, Sangju National University, Sangju, Korea (2005)
  14. Redlich, O. and Kister, A. T., 'Algebraic Representation of Thermodynamic Properties and the Classification of Solutions,' Ind. Eng. Chem., 40, 345-348(1948) https://doi.org/10.1021/ie50458a036
  15. Nelder, J. A. and Mead, R., 'A Simplex Method for Function Minimization,' Comp. J., 7, 308-313(1965) https://doi.org/10.1093/comjnl/7.4.308
  16. Wilson, G. M., 'Vapor-Liquid Equilibrium. XI. A New Expression for the Excess Free Energy of Mixing,' J. Am. Chem. Soc., 86(2), 127-130(1964) https://doi.org/10.1021/ja01056a002
  17. Renon, H. and Prausnitz, J. M., 'Local Composition in Thermo- Dynamic Excess Functions for Liquid Mixtures,' AIChE J., 14, 135-144(1968) https://doi.org/10.1002/aic.690140124
  18. Abrams, D. S. and Prausnitz, J. M., 'Statistical Thermodynamics of Liquid Mixtures: A New Expression for the Excess Gibbs Energy of Partly or Completely Miscible Systems,' AIChE J., 21, 116-128 (1975) https://doi.org/10.1002/aic.690210115
  19. Riddick, J. A., Bunger, W. S. and Sakano, T. K., Organic Solvents, Physical Properties and Methods of Purification, 4th ed., Wiley Interscience Publication, New York(1986)
  20. Sabbah, R., Xu-wu, A., Chickos, J. S., Planas Leitao, M. L., Roux, M. V. and Torres, L. A., 'Reference Materials for Calorimetry and Differential Thermal Analysis,' Thermochimica Acta, 331, 93- 204 (1999) https://doi.org/10.1016/S0040-6031(99)00009-X
  21. Wadso, I., 'Needs for Standards in Isothermal Microcalorimeter,' Thermochimica Acta, 347, 73-77(2000) https://doi.org/10.1016/S0040-6031(99)00418-9
  22. Tanaka, R., D'arcy, P. J. and Benson, G. C., 'Application of a Flow Microcalorimeter to Determine the Excess Enthalpies of Binary Mixtures of Non-electrolytes,' Thermochimica Acta, 11, 163-175 (1975) https://doi.org/10.1016/0040-6031(75)80020-7
  23. Chand, A. and Fenby, D. B., 'Enthalpy of Deuterium Exchange Reactions in Water + Ethanol and Methanol + Ethanol,' J. Chem. Thermodynamics., 10, 997-1001(1978) https://doi.org/10.1016/0021-9614(78)90061-7
  24. Costigan, M. J., Hodges, L. J., Marsh, K. N., Stokes, R. H. and Tuxford, C. W., 'The Isothermal Displacement Calorimeter: Design Modifications for Measuring Exothermic Enthalpies of Mixing,' Aust. J. Chem., 33, 2103-2119(1980) https://doi.org/10.1071/CH9802103
  25. Prausnitz, J. M., Lichtenthaler, R. N. and de Azevedo, E., G., Molecular Thermodynamics of Fluid-Phase Equilibria, 3rd ed., Prentice-Hall, New Jersey(1999)