Issue
Korean Chemical Engineering Research,
Vol.44, No.5, 444-452, 2006
2성분계 {1,2-dichloropropane+2-(2-methoxyethoxy)ethanol 및 + 2-(2-ethoxyethoxy)ethanol}에 대한 298.15 K에서의 과잉몰엔탈피 및 과잉몰부피
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
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 VEm 및 HEm data는 Nelder-Mead의 simplex pattern search method를 이용하여 Redlich-Kister 다항식에 접합(fitting)하였고, Wilson, NRTL 및 UNIQUAC model을 이용하여 data와 HEm 조성과의 상관관계를 조사하였다.
This paper reports experimental excess molar volumes VEm using a digital vibrating-tube densimeter and excess molar enthalpies HEm 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 VEm and HEm 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(VEm and HEm) 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 HEm values.
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