Knowledge of the partial molar volumes of aqueous ions allows accurate calculation of the pressure dependence of equilibrium constants, solubility of minerals, etc., thus being useful for thermodynamic modeling of hydrothermal processes. This study analyzed methods to correlate and predict the values of the partial molar volumes at infinite dilution, V2o, for 1–1 electrolytes and singly charged ions at elevated T and P. Since the precise experimental values of the dielectric constant of water are measured only up to 873 K, we were interested only in non-electrostatic ways to correlate V2o data. First of all, we compiled the V2o values at T > 373 K for the following 1–1 electrolytes: HCl, LiCl, LiI, LiNO3, LiOH, NaF, NaCl, NaBr, NaI, NaNO3, NaOH, NaHCO3, NaClO4, NaH2PO4, NaTr (Tr stands for triflate), KF, KCl, KBr, KI, KNO3, KOH, CsBr, and NH4Cl. Relations, following from the “density” model and from the Fluctuation Solution Theory (FST) were employed to analyze data. It was concluded that at the current state of knowledge of V2o the FST-relations for electrolytes are recommended mainly to reject strongly deviating experimental outliers. However, the “density” model provides a simple and fairly accurate way to describe the compiled set of data with only two parameters for each ion, n and Vhc, values of which were evaluated for the following singly-charged ions: H+, Li+, Na+, K+, Cs+, NH4+, F-, Cl-, Br-, I-, OH–, NO3–, H2PO4-, HCO3–, ClO4-, Tr- (Tr = triflate). Following Mesmer et al. (1988), we consider the fitting parameters Vhc and n to be related to the intrinsic volume of the ion and to the number of water molecules transferred from the bulk water to a hydration shell around the ion, respectively.

中文翻译：

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高 T 和 P 时 1-1 电解质的部分摩尔体积：相关性和预测


了解水离子的偏摩尔体积可以准确计算平衡常数的压力依赖性、矿物的溶解度等，因此可用于热液过程的热力学建模。本研究分析了关联和预测 1-1 电解质和升高 T 和 P 时单电荷离子在无限稀释 V2o 下的部分摩尔体积值的方法。由于水介电常数的精确实验值只能在 873 K 以下测量，因此我们只对关联 V2o 数据的非静电方式感兴趣。首先，我们编译了以下 1-1 电解质在 T > 373 K 处的 V2o 值：HCl、LiCl、LiI、LiNO3、LiOH、NaF、NaCl、NaBr、NaI、NaNO3、NaOH、NaHCO3、NaClO4、NaH2PO4、NaTr（Tr 代表三氟甲磺酸盐）、KF、KCl、KBr、KI、KNO3、KOH、CsBr 和 NH4Cl。采用“密度”模型和涨落解理论 （FST） 的关系来分析数据。得出的结论是，在目前的 V2o 知识状态下，建议电解质的 FST 关系主要是为了拒绝强烈偏离的实验异常值。然而，“密度”模型提供了一种简单且相当准确的方法来描述编译后的数据集，每个离子只有两个参数，n 和 Vhc，其值针对以下单电荷离子进行评估：H+、Li+、Na+、K+、Cs+、NH4+、F-、Cl-、Br-、I-、OH–、NO3–、H2PO4-、HCO3–、ClO4-、Tr-（Tr = 三氟甲磺酸）。根据 Mesmer 等人 （1988），我们认为拟合参数 Vhc 和 n 分别与离子的固有体积和从体水转移到离子周围水合壳的水分子数量有关。