Prediction of activity coefficients in liquid aerosol particles containing organic compounds, dissolved inorganic salts, and water - Part 2: Consideration of phase separation effects by an X-UNIFAC model
Prediction of activity coefficients in liquid aerosol particles containing organic compounds, dissolved inorganic salts, and water - Part 2: Consideration of phase separation effects by an X-UNIFAC model
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DOI：
10.1016/j.atmosenv.2006.04.031
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发表时间：
2006-10-01
影响因子：
5
通讯作者：
Pankow, James F.
中科院分区：
文献类型：
--
作者：
Chang, Elsa I.;Pankow, James F.
提出了一个用于预测含有有机化合物、无机盐和水的气溶胶中颗粒物(PM)形成的热力学模型。中性组分被允许从气相分配到PM，后者可能由主要是水(A)的液体相和主要是有机(β)的液体相组成。允许在没有任何人为限制的情况下进行分配：当同时存在α和βPM相时，离子组分被允许分配给这两个相。X-uniAC.2，一种基于Yanen等人的扩展的uniAC方法。(1999年)用基团贡献概念预测混合溶剂电解质体系中的汽液平衡。流体相平衡(162，97-113)是为了估算活度系数而开发的。X-uniAC.2利用标准的uniAC项、德拜-休克尔项和代表中期(MR)对活度系数效应贡献的维里方程项。已有大量(234)MR参数可从严氏等人处获得。(1999年)。优化了六个额外的MR参数，使X-uniAC.2能够考虑羧酸基与Na+、Cl-和Ca2+之间的相互作用。对于假设的沙宾烯/O-3体系，在PM中含有不同量的氯化钠，预测了PM的形成还对Cocker等人用α-蒎烯/O-3(和CaCl2种子)进行的室内实验进行了预测。(2001年。水对二次有机气溶胶气粒分配的影响。第一部分：α-蒎烯/臭氧体系。大气环境35,6049-6072)；预测的PM质量浓度与室内测量的PM质量浓度之间取得了良好的一致性。(C)2006爱思唯尔有限公司。保留所有权利。
A thermodynamic model is presented for predicting the formation of particulate matter (PM) within an aerosol that contains organic compounds, inorganic salts, and water. Neutral components are allowed to partition from the gas phase to the PM, with the latter potentially composed of both a primarily aqueous (a) liquid phase and a primarily organic (beta) liquid phase. Partitioning is allowed to occur without any artificial restraints: when both alpha and beta PM phases are present, ionic constituents are allowed to partition to both. X-UNIFAC.2, an extended UNIFAC method based on Yan et al. (1999. Prediction of vapor-liquid equilibria in mixed-solvent electrolyte systems using the group contribution concept. Fluid Phase Equilibria 162, 97-113), was developed for activity coefficient estimation. X-UNIFAC.2 utilizes the standard UNIFAC terms, a Debye-Huckel term, and a virial equation term that represents the middle-range (MR) contribution to activity coefficient effects. A large number (234) of MR parameters are already available from Yan et al. (1999). Six additional MR parameters were optimized here to enable X-UNIFAC.2 to account for interactions between the carboxylic acid group and Na+, Cl-, and Ca2+. Predictions of PM formation were made for a hypothetical sabinene/O-3 system with varying amounts of NaCl in the PM. Predictions were also made for the chamber experiments with alpha-pinene/O-3 (and CaCl2 seed) carried out by Cocker et al. (2001. The effect of water on gas-particle partitioning of secondary organic aerosol. Part I. alpha-pinene/ozone system. Atmospheric Environment 35, 6049-6072); good agreement between the predicted and chamber-measured PM mass concentrations was achieved. (c) 2006 Elsevier Ltd. All rights reserved.