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):5718-34. doi: 10.1021/jp056150j.
Atmospheric aerosols contain a significant fraction of water-soluble organic compounds, including dicarboxylic acids. Pitzer activity coefficient models are developed, using a wide range of data at 298.15 K, for the following systems containing succinic acid (H(2)Succ) and/or succinate salts: [H(+), Li(+), Na(+), K(+), Rb(+), Cs(+)]Cl(-)-H(2)Succ-H(2)O, HNO(3)-H(2)Succ-H(2)O, H(+)-NH(4)(+)-HSucc(-)-Succ(2-)-NH(3)-H(2)Succ-H(2)O, NH(4)Cl-(NH(4))(2)Succ-H(2)O, H(+)-Na(+)-HSucc(-)-Succ(2-)-Cl(-)-H(2)Succ-H(2)O, NH(4)NO(3)-H(2)Succ-H(2)O, and H(2)SO(4)-H(2)Succ-H(2)O. The above compositions are given in terms of ions in the cases where acid dissociation was considered. Pitzer models were also developed for the following systems containing malonic acid (H(2)Malo): H(+)-Na(+)-HMalo(-)-Malo(2-)-Cl(-)-H(2)Malo-H(2)O, and H(2)Malo-H(2)SO(4)-H(2)O. The models are used to evaluate the extended Zdanovskii-Stokes-Robinson (ZSR) model proposed by Clegg and Seinfeld (J. Phys. Chem. A 2004, 108, 1008-1017) for calculating water and solute activities in solutions in which dissociation equilibria occur. The ZSR model yields satisfactory results only for systems that contain moderate to high concentrations of (nondissociating) supporting electrolyte. A practical modeling scheme is proposed for aqueous atmospheric aerosols containing both electrolytes and dissociating (organic) nonelectrolytes.
大气气溶胶包含相当一部分水溶性有机化合物，其中包括二元羧酸。利用298.15 K下的大量数据，针对以下含有琥珀酸（H₂Succ）和/或琥珀酸盐的体系，开发了皮兹活度系数模型：[H⁺、Li⁺、Na⁺、K⁺、Rb⁺、Cs⁺]Cl⁻-H₂Succ-H₂O、HNO₃-H₂Succ-H₂O、H⁺-NH₄⁺-HSucc⁻-Succ²⁻-NH₃-H₂Succ-H₂O、NH₄Cl-(NH₄)₂Succ-H₂O、H⁺-Na⁺-HSucc⁻-Succ²⁻-Cl⁻-H₂Succ-H₂O、NH₄NO₃-H₂Succ-H₂O以及H₂SO₄-H₂Succ-H₂O。在考虑酸解离的情况下，上述组成以离子形式给出。还针对以下含有丙二酸（H₂Malo）的体系开发了皮兹模型：H⁺-Na⁺-HMalo⁻-Malo²⁻-Cl⁻-H₂Malo-H₂O以及H₂Malo-H₂SO₄-H₂O。这些模型用于评估Clegg和Seinfeld（《物理化学杂志A》2004年，108卷，1008 - 1017页）提出的扩展Zdanovskii-Stokes-Robinson（ZSR）模型，该模型用于计算发生解离平衡的溶液中的水和溶质活度。ZSR模型仅对含有中等至高浓度（非解离）支持电解质的体系产生令人满意的结果。针对同时含有电解质和解离（有机）非电解质的水性大气气溶胶，提出了一种实用的建模方案。
