Yamada Akiyoshi, Yoshida Erina, Eda Kazuo, Osakai Toshiyuki
Department of Chemistry, Graduate School of Science, Kobe University.
Anal Sci. 2018 Aug 10;34(8):919-924. doi: 10.2116/analsci.18P088. Epub 2018 Jun 29.
The standard Gibbs energy of ion transfer at the 1,2-dichloroethane/water interface (ΔG°) was determined for 26 organic cations and 24 anions by means of ion-transfer voltammetry with a micro oil/water interface. Based on the data sets, a theoretical analysis was performed with the non-Bornian solvation model, in which the solvation energy of an organic ion is evaluated from local electric fields on the surface of the ion. The semi-empirical equations thus obtained are available for relatively accurate prediction of ΔG° for organic ions. The mean absolute error was 1.9 or 3.1 kJ mol for cations or anions, respectively, corresponding to the error of ∼20 or ∼30 mV in the standard ion-transfer potential. In this paper, energy decomposition has been performed to discuss different contributions to ΔG° from the "hydrated" (strongly charged) and positively and negatively charged "non-hydrated" (moderately charged) surfaces as well as from the hydrophobic interaction (cavity formation energy).
通过带有微油/水界面的离子转移伏安法，测定了26种有机阳离子和24种阴离子在1,2 - 二氯乙烷/水界面的标准吉布斯离子转移能（ΔG°）。基于这些数据集，采用非玻恩溶剂化模型进行了理论分析，其中有机离子的溶剂化能是根据离子表面的局部电场来评估的。由此得到的半经验方程可用于相对准确地预测有机离子的ΔG°。阳离子和阴离子的平均绝对误差分别为1.9或3.1 kJ/mol，这相当于标准离子转移电位中约20或约30 mV的误差。在本文中，进行了能量分解，以讨论“水合”（强电荷）和带正电与带负电的“非水合”（中等电荷）表面以及疏水相互作用（空穴形成能）对ΔG°的不同贡献。
