Aquatic Ecology and Water Quality Management Group, Wageningen University, 6700 AA Wageningen, The Netherlands.
Chemosphere. 2012 Apr;87(2):125-31. doi: 10.1016/j.chemosphere.2011.11.073. Epub 2011 Dec 22.
Abraham solvation equations find widespread use in environmental chemistry. Until now, the intercept in these equations was determined by fitting experimental data. To simplify the determination of the coefficients in Abraham solvation equations, this study derives theoretical expressions for the value of the intercept for various partition processes. To that end, a modification of the description of the Ben-Naim standard state into the van der Waals volume is proposed. Differences between predicted and fitted values of the Abraham solvation equation intercept for the enthalpy of solvation, the entropy of solvation, solvent-water partitioning, air-solvent partitioning, partitioning into micelles, partitioning into lipid membranes and lipids, and chromatographic retention indices are comparable to experimental uncertainties in these values.
阿伯拉罕溶剂化方程在环境化学中得到了广泛的应用。直到现在，这些方程中的截距都是通过拟合实验数据来确定的。为了简化阿伯拉罕溶剂化方程中系数的确定，本研究推导出了各种分配过程中截距值的理论表达式。为此，提出了将 Ben-Naim 标准状态描述修改为范德华体积的方法。对于溶剂化焓、溶剂化熵、溶剂-水分配、气-溶剂分配、胶束分配、脂质膜和脂质分配以及色谱保留指数的阿伯拉罕溶剂化方程截距的预测值与拟合值之间的差异与这些值的实验不确定度相当。
