Data evaluations and quantitative predictive models for vapor pressures of polycyclic aromatic hydrocarbons at different temperatures
Data evaluations and quantitative predictive models for vapor pressures of polycyclic aromatic hydrocarbons at different temperatures
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DOI：
10.1080/10629360410001665857
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发表时间：
2004-04
影响因子：
3
通讯作者：
X.Y. Huang;J.W. Chen;L. Gao;G. Ding;Y.Z. Zhao;K. Schramm
中科院分区：
文献类型：
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作者：
X.Y. Huang;J.W. Chen;L. Gao;G. Ding;Y.Z. Zhao;K. Schramm
多环芳烃(PAHs)是典型的、普遍存在的有机污染物。蒸汽压可分为固体蒸汽压(P S)和(过冷)液体蒸汽压(P L)，它们是决定有机污染物环境归宿的关键物理化学性质。建立蒸汽压的预测模型具有重要意义。本研究采用偏最小二乘回归方法，结合15个理论分子结构参数，建立了不同温度下多环芳烃蒸汽压的定量预测模型。通过消除冗余的分子结构描述符，采用两个步骤来建立最优预测模型。所得模型的交叉验证值均大于0.975，表明模型具有较好的预测能力和稳健性。结果表明，分子间的色散相互作用对logP的大小起主导作用。除了色散相互作用外，偶极-偶极相互作用在决定对数P的大小方面也起着次要的作用。考虑到某些多环芳烃的化学标准的稀缺性、实验测定的难度和实验测定的高成本，所得到的模型可以作为不同环境温度下多环芳烃蒸汽压值的快速而简单的第一近似值。
Polycyclic aromatic hydrocarbons (PAHs) are typical and ubiquitous organic pollutants. Vapor pressures, which can be classified as solid vapor pressure (P S) and (subcooled) liquid vapor pressure (P L), are key physicochemical properties governing the environmental fate of organic pollutants. It is of great importance to develop predictive models of vapor pressures. In the present study, partial least squares (PLS) regression together with 15 theoretical molecular structural descriptors was used to develop quantitative predictive models for vapor pressures of PAHs at different temperatures. Two procedures were adopted to develop the optimal predictive models by eliminating redundant molecular structural descriptors. The cross-validated values for the obtained models have been found higher than 0.975, indicating good predictive ability and robustness of the models. It has been shown that the intermolecular dispersive interactions played a leading role in governing the values of log P L. In addition to dispersive interactions, dipole–dipole interactions also played a secondary role in determining the magnitude of log P S. In view of the scarceness of chemical standards for some PAHs, the difficulty in experimental determinations, and the high cost involved in experimental determinations, the obtained models should serve as a fast and simple first approximation of the vapor pressure values for PAHs at different environmental temperatures.