Group contribution method for Henry's Law constant of aqueous hydrocarbons
Group contribution method for Henry's Law constant of aqueous hydrocarbons
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DOI：
10.1002/aic.690481220
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发表时间：
2002-12
期刊：
影响因子：
3.7
通讯作者：
J. Šedlbauer;G. Bergin;V. Majer
中科院分区：
文献类型：
--
作者：
J. Šedlbauer;G. Bergin;V. Majer
基于水合模型的官能团贡献方案预测作为温度和压力的函数的含水烃的亨利定律常数。它使用的直接链接的亨利定律常数与吉布斯自由能的水合作用，以及其温度和压力的衍生物可从量热和体积数据。半理论模型的灵感来自波动溶液理论与五个可调参数被用来表达的温度和压力的依赖性的10个功能的贡献。在298 K和0.1 MPa的水化性能的一致的基团贡献计划，从文献中约束在参考条件下的模型。烃官能团的参数通过同时关联亨利定律常数的1，000多个数据点和约550个在宽温度和压力范围内可用的衍生物水合性质（焓、热容和体积）的值来调整。由此产生的基团加和性计划可用于预测亨利定律常数的烷烃，烯烃，烷基环烷烃，烷基苯高达570 K和高达100 MPa。预测的平均准确度从20到40%，在环境温度到高温下，分别变化，半定量的估计是可能的水的临界点。
A functional group contribution scheme based on a hydration model predicts Henry's Law constant of aqueous hydrocarbons as a function of temperature and pressure. It uses the direct link of Henry's Law constant with the Gibbs free energy of hydration, as well as its temperature and pressure derivatives accessible from calorimetric and volumetric data. A semitheoretic model inspired by the fluctuation solution theory with five adjustable parameters was used for expressing the temperature and pressure dependence of ten functional contributions. A consistent group contribution scheme for hydration properties at 298 K and 0.1 MPa was taken from literature to constrain the model at reference conditions. Parameters for hydrocarbon functional groups were adjusted by simultaneous correlation of over 1,000 data points on Henry's Law constant and about 550 values on derivative hydration properties (enthalpy, heat capacity, and volume) available in a wide range of temperature and pressure. The resulting group additivity scheme can be used for predicting Henry's Law constant for alkanes, alkenes, alkylcycloalkanes, and alkylbenzenes up to 570 K and up to 100 MPa. Average accuracy of the predictions varies from 20 to 40% at ambient to high temperatures, respectively, and semiquantitative estimates are possible up to the critical point of water.