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비극성 탄화수소계에 대한 Wilson Parameter의 계산
Prediction of Wilson Parameter for Nonpolar Hydrocarbon System
HWAHAK KONGHAK, April 1987, 25(2), 151-159(9), NONE
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Abstract
Wilson 식은 다성분계의 기액평형계산에 2 성분계의 data로부터 용이하게 확장이 되기 때문에 광범위하게 이용된다. 그러나 열역학적인 비선형모델이므로 Parameter를 계산하기 어렵다. 본 연구에서는 Maximum Likelihood의 원리를 기초로 한 Anderson의 방법을 이용하여 비극성 탄화수소계의 Wilson parameter를 계산하고 두 parameter 사이에는 밀접한 상관관계(상관계수가 0.99∼1.0)가 존재함을 알 수 있었다. 두 parameter의 관계를 plot한 결과 거의 직선으로 표현되며 그 직선의 기울기는 구성성분의 액상몰용적의 비 (v2L/v1L)와 거의 동일하였다. 따라서 다른 성분 사이의 상호작용에너지(λ12)는 동일성분 사이의 상호작용에너지(λ11, λ22)와 v2L/v1L으로 표현되며 이때 직선의 절편만 알면 λ12를 계산할 수 있다. 다시말하면, Single Parameter의 Wilson 식에서 Unlike-Pair Potential Parameter에 대한 새로운 추산식을 제안하였다. 제안한 식으로 계산한 결과와 P, y Regression에 의해 계산된 실측치와의 편차를 비교하여 제안된 Single-Parameter Wilson 식이 기액평형계산에 충분히 이용가능함을 알 수 있었다.
The Wilson parameters of 53 binary hydrocarbon systems are obtained from the vapor-liquid equilibrium data of the systems with regression analysis method proposed by Anderson et al. that is based on the principle of maximum likelihood. The correlation coefficients between two parameters are close to unity and the relationships between them are represented as nearly straight lines. We find out that the slopes of the relationships can be substituted with the ratios of liquid molar volume of the constituents.
In case liquid molar volume and like-pair intermolecular energy(λii) in Wilson parameter can be calculated, we can evaluate the unlike-pair intermolecular energy(λii) if intercept of the linear relationship between two parameters is known.
Therefore, a single-parameter Wilson equation is proposed by the present work. The pressure(P) and mole fraction in vapor(y) calculated by this model are in good agreement with the observed, and deviation of them are plotted in figures to show the agreement between them.
In case liquid molar volume and like-pair intermolecular energy(λii) in Wilson parameter can be calculated, we can evaluate the unlike-pair intermolecular energy(λii) if intercept of the linear relationship between two parameters is known.
Therefore, a single-parameter Wilson equation is proposed by the present work. The pressure(P) and mole fraction in vapor(y) calculated by this model are in good agreement with the observed, and deviation of them are plotted in figures to show the agreement between them.