Clegg Simon L, Seinfeld John H
School of Environmental Sciences, University of East Anglia, Norwich, UK.
J Phys Chem A. 2006 May 4;110(17):5692-717. doi: 10.1021/jp056149k.
Atmospheric aerosols contain a significant fraction of water-soluble organic compounds, including dicarboxylic acids. Water activities at approximately 298.15 K (including data for highly supersaturated solutions) of oxalic, malonic, succinic, glutaric, maleic, malic, and methyl succinic acids are first correlated as a function of concentration, treating the acids as nondissociating components. Methods proposed by Clegg et al. (J. Aerosol. Sci. 2001, 32, 713-738), and by Clegg and Seinfeld (J. Phys. Chem. A 2004, 108, 1008-1017) for estimating water activities and solute activity coefficients in aqueous mixtures containing both electrolytes and uncharged solutes are then evaluated from comparisons with literature data. These data include water activities, solubilities, and determinations of the eutonic points of solutions containing up to five acids, and solutions containing one or more acids and the salts (NH(4))(2)SO(4), NH(4)NO(3), or NaCl. The extended Zdanovskii-Stokes-Robinson approach of Clegg and Seinfeld yields the more accurate predictions for aqueous mixtures containing dicarboxylic acids only, and for aqueous mixtures of the acids and salts (though by a lesser margin). A number of hybrid modeling approaches, which contain elements of both methods, are outlined.
大气气溶胶含有相当一部分水溶性有机化合物，包括二元羧酸。草酸、丙二酸、琥珀酸、戊二酸、马来酸、苹果酸和甲基琥珀酸在约298.15 K时的水活度（包括高度过饱和溶液的数据）首先作为浓度的函数进行关联，将这些酸视为非离解成分。然后，通过与文献数据比较，评估了Clegg等人（《气溶胶科学杂志》，2001年，32卷，713 - 738页）以及Clegg和Seinfeld（《物理化学杂志A》，2004年，108卷，1008 - 1017页）提出的用于估算含有电解质和不带电溶质的水性混合物中水活度和溶质活度系数的方法。这些数据包括水活度、溶解度，以及含有多达五种酸的溶液、含有一种或多种酸与盐（(NH₄)₂SO₄、NH₄NO₃或NaCl）的溶液的等渗点测定。Clegg和Seinfeld的扩展Zdanovskii - Stokes - Robinson方法对于仅含二元羧酸的水性混合物以及酸与盐的水性混合物（尽管精度稍低）能给出更准确的预测。概述了一些包含两种方法元素的混合建模方法。
