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首页> 外文期刊>Biophysical Chemistry: An International Journal Devoted to the Physical Chemistry of Biological Phenomena >Ionic volumes in solution
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Ionic volumes in solution

机译：溶液中的离子量

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The volumetric properties of electrolytes in solutions indicate the interactions of the constituent ions with their environment: the solvent and other ions. The interactions with the solvent alone,are manifested at infinite dilution by the standard partial molar volume, V(salt), obtained from density measurements. To study the interactions, it is necessary to split V-infinity(salt) into the additive ionic contributions, V-infinity(ion), using an extra-thermodynamic assumption. Values of V(ion) for small ions depend cardinally on the electrostriction of the solvent that can be obtained from an iterative shell-by-shell calculation from a continuum model of the solvent. The solvent shrinkage per mol of ions is Delta V-el(ion) < 0. Also, the molar electrostriction of the solvent S-1 Delta V-el(S) < 0, is calculable. The ratio Delta V-el(ion)/Delta V-el(S) = n(infinity) is the solvation number of the ion in S at infinite dilution. The calculated V-infinity(ion)(calc) are compared with the experimental values, showing good agreement for many univalent ions in both single solvents and in some binary solvent mixtures, where no appreciable preferential solvation takes place. Ion pairing sets in under certain circumstances of ionic charge and solvent permittivity. The difference Delta V-ip = V-ip(infinity) - [V-+(infinity) + V--(infinity)] > 0 is obtained experimentally from the pressure derivative of the association constant. The ratio Delta(nip) = Delta V-ip/Delta V-el(S) represents the number of solvent molecules released to the bulk on ion pairing by the diminution of the electrostriction. (c) 2006 Elsevier B.V. All rights reserved.
机译：溶液中电解质的体积性质表明了组成离子与环境（溶剂和其他离子）之间的相互作用。从密度测量获得的标准部分摩尔体积V（盐）可以无限稀释显示与单独溶剂的相互作用。为了研究相互作用，有必要使用超热力学假设将V-无穷大（盐）分解为附加离子贡献V-无穷大（离子）。小离子的V（ion）值主要取决于溶剂的电致伸缩，该电致伸缩可以从溶剂的连续模型逐个壳层式地进行迭代计算得出。每摩尔离子的溶剂收缩率为Delta V-el（离子）<0。而且，可以计算出溶剂S-1的摩尔电致伸缩Delta V-el（S）<0。 Delta V-el（离子）/ Delta V-el（S）= n（无穷大）的比值是无限稀释时S中离子的溶剂化数。将计算出的V-无穷大（离子）（calc）与实验值进行比较，表明在单一溶剂和某些二元溶剂混合物中，许多单价离子均具有良好的一致性，在这些情况下，没有发生明显的优先溶剂化。离子对在某些情况下会形成离子电荷和溶剂介电常数。 ΔV-ip＝ V-ip（无穷大）-[V-+（无穷大）+ V-（无穷大）]＞ 0的差值是从缔合常数的压力导数通过实验获得的。比率Delta（nip）= Delta V-ip / Delta V-el（S）表示由于电致伸缩减少而在离子对上释放到主体的溶剂分子的数量。 （c）2006 Elsevier B.V.保留所有权利。

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