Partial Molar Volumes of Ionic and Nonionic Organic Solutes in Water: A Simple Additivity Scheme Based on the Intrinsic Volume Approach
Partial Molar Volumes of Ionic and Nonionic Organic Solutes in Water: A Simple Additivity Scheme Based on the Intrinsic Volume Approach
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水中离子和非离子有机溶质的部分摩尔体积：基于本征体积方法的简单加和方案
DOI：
10.1023/a:1005150616038
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发表时间：
2000
影响因子：
1.2
通讯作者：
P. Gianni
中科院分区：
文献类型：
--
作者：
L. Lepori;P. Gianni
通过一个简单的基于本征体积法的加和图描述了有机电解质和非电解质在25°C水中无限稀释时的偏摩尔体积。假设所有的烃部分在水溶液中具有相同的填充效率，从“实验”CH 2增量确定了烃基团对的贡献。22个带电基团和51个不带电基团被分配为常数，近400个单官能有机溶质的偏摩尔体积被重现，均方根偏差为0.9 cm 3·mol−1。讨论了直链、支链和环状分子的不同体积行为。比较是由不带电的（碳氢化合物和极性）与带电基团，以及与小分子和离子的基团。一个相对估计是givenof的体积效应（空腔形成，疏水水化，溶剂收缩，氢键，和电致伸缩）参与的疏水和亲水基团与水的相互作用。单官能和多官能溶质（包括聚电解质）的加和性偏差从以下方面进行了分析：（1）不同极性中心的水合共球的扩展;（2）分子内相互作用及其对相互作用基团的性质、数量和相互距离的依赖。货车范德瓦尔斯体积Vw被广泛地用作分子描述符。本文给出了带电和不带电基团的Vw的估计值。
Partial molar volumes at infinite dilution,, in water at 25°C for organicelectrolytes and nonelectrolytes are described through a simple additivity schemebased on the intrinsic volume approach. The contributions toof hydrocarbongroups were determined from the “experimental” CH2increment assuming thatall hydrocarbon portions have the same packing efficiency in aqueous solution.Twenty-two charged and 51 uncharged groups, are assigned acontribution and the partial molar volumes of nearly 400 monofunctional organic solutes arereproduced with a root mean square of deviation of 0.9 cm3-mol−1. The differentvolumetric behavior of linear, branched, and cyclic molecules is discussed. Acomparison is made of uncharged (hydrocarbon and polar) with charged groups,as well as of groups with small molecules and ions. A relative estimate is givenof the volume effects (cavity formation, hydrophobic hydration, solvent shrinkage,H bonding, and electrostriction) involved in the interaction of hydrophobic andhydrophilic groups with water. Deviations from additivity for mono- andpolyfunctional solutes, including polyelectrolytes, are analyzed in terms of (1) extensionof the hydration cosphere of different polar centers: (2) intramolecular interactionsand their dependence on nature, number, and mutual distance of interactinggroups. The van der Waals volumeVwis extensively used as molecular descriptor.Estimates ofVwfor both charged and uncharged groups are presented.