Second cross virial coefficients for interactions involving water. Correlations and group contribution values
Second cross virial coefficients for interactions involving water. Correlations and group contribution values
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DOI：
10.1021/je034047m
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发表时间：
2003-11-01
期刊：
影响因子：
--
通讯作者：
Wood, RH
中科院分区：
文献类型：
--
作者：
Plyasunov, AV;Shock, EL;Wood, RH
提出了一种估算水分子相互作用第二维里系数的简单方法。它是基于Tsonopoulos对应态相关性，并包括一个半经验方程，用于评估该相关性的特定混合物参数k（12）。这个方程的一般结构是由一个基于理论的关系，这是有效的球形非极性分子之间的相互作用。通过用化合物在298 K和0.1 MPa下的水合吉布斯能的函数替换“能量”项，完成了涉及水的相互作用的这种关系的经验扩展。这种相关性得到了水和许多化合物之间相互作用的实验B-12值的支持，这些化合物在水-溶质相互作用的大小和强度上有很大差异。这种经验相关性的局限性进行了简要讨论。此外，可用的B-12数据的水和正构烷烃之间的相互作用，从乙烷到辛烷，强烈建议的适用性的基团贡献方法来预测水和有机化合物之间的第二交叉维里系数。对于水和大有机分子之间的相互作用，基团贡献近似是B-12预测的选择方法。这些发现用于预测水与许多无机和小型有机化合物（甲烷和乙烯的卤代衍生物）之间相互作用以及许多有机化合物官能团之间相互作用的（275至1200）K范围内的B-12值。
A simple method is presented for estimating the second cross virial coefficients for interactions involving water. It is based on the Tsonopoulos corresponding-states correlation and consists of a semiempirical equation for evaluating the mixture-specific parameter k(12) of this correlation. The general structure of this equation is guided by a theory-based relation, which is valid for interactions between spherical nonpolar molecules. An empirical extension of this relation to interactions involving water was done by replacing the "energy" term with a function of the Gibbs energy of hydration of a compound at 298 K and 0.1 MPa. This correlation is supported by experimental B-12 values for interactions between water and numerous compounds that differ greatly in size and strength of water-solute interactions. Limitations of this empirical correlation are briefly discussed. In addition, available B-12 data for interactions between water and normal alkanes, from ethane to octane, strongly suggest the applicability of a group contribution method to predict the second cross virial coefficients between water and organic compounds. For interactions between water and large organic molecules, the group contribution approximation is the method of choice for B-12 predictions. These findings were employed to predict the B-12 values from (275 to 1200) K for interactions between water and many inorganic and small organic compounds (halogenated derivatives of methane and ethene), as well as for many functional groups of organic compounds.