DOI: 10.1016/j.atmosenv.2015.03.032
Scopus记录号: 2-s2.0-84925263737
论文题名: Temperature dependence of Henry's law constants and KOA for simple and heteroatom-substituted PAHs by COSMO-RS
作者: Parnis J ; M ; , Mackay D ; , Harner T
刊名: Atmospheric Environment
ISSN: 0168-2563
EISSN: 1573-515X
出版年: 2015
卷: 110 起始页码: 27
结束页码: 35
语种: 英语
英文关键词: Air-water partitioning
; COSMOtherm
; Henry's law constants
; Octanol-air partitioning
; Polycyclic aromatic compounds
; Temperature dependence
Scopus关键词: Air
; Aromatic compounds
; Aromatic hydrocarbons
; Organic pollutants
; Polycyclic aromatic hydrocarbons
; Risk assessment
; Temperature
; Temperature distribution
; Air-water
; COSMOtherm
; Henry's Law constant
; Octanol-air
; Polycyclic aromatic compounds
; Temperature dependence
; Thermal logging
; nitrogen
; octanol
; oxygen
; polycyclic aromatic hydrocarbon
; sulfur
; atmospheric pollution
; nitrogen compound
; oxygen
; PAH
; sulfur
; temperature effect
; thermodynamics
; air
; Article
; chemical parameters
; chemical structure
; COSMO RS method
; entropy
; Henry law constant
; partition coefficient
; phase partitioning
; physical chemistry
; pressure
; priority journal
; risk assessment
; solvation
; statistical analysis
; temperature dependence
; vapor pressure
; vaporization
Scopus学科分类: Environmental Science: Water Science and Technology
; Earth and Planetary Sciences: Earth-Surface Processes
; Environmental Science: Environmental Chemistry
英文摘要: Henwry's Law constants (H) and octanol-air partition coefficients (KOA) for polycyclic aromatic hydrocarbons (PAHs) and selected nitrogen-, oxygen- and sulfur-containing derivatives have been computed using the COSMO-RS method between-5 and 40°C in 5°C intervals. The accuracy of the estimation was assessed by comparison of COSMOtherm values with published experimental temperature-dependence data for these and similar PAHs. COSMOtherm log H estimates with temperature-variation for parent PAHs are shown to have a root-mean-square (RMS) error of 0.38 (PAH), based on available validation data. Estimates of O-, N- and S-substituted derivative log H values are found to have RMS errors of 0.30at 25°C. Log KOA estimates with temperature variation from COSMOtherm are shown to be strongly correlated with experimental values for a small set of unsubstituted PAHs, but with a systematic underestimation and associated RMS error of 1.11. Similar RMS error of 1.64 was found for COSMO-RS estimates of a group of critically-evaluated log KOA values at room temperature. Validation demonstrates that COSMOtherm estimates of H and KOA are of sufficient accuracy to be used for property screening and preliminary environmental risk assessment, and perform very well for modeling the influence of temperature on partitioning behavior in the temperature range-5 to 40°C. Temperature-dependent shifts of up to 2 log units in log H and one log unit for log KOA are predicted for PAH species over the range-5 and 40°C. Within the family of PAH molecules, COSMO-RS is sufficiently accurate to make it useful as a source of estimates for modeling purposes, following corrections for systematic underestimation of KOA. Average changes in the values for log H and log KOA upon substitution are given for various PAH substituent categories, with the most significant shifts being associated with the ionizing nitro functionality and keto groups. © 2015 . Citation statistics:
资源类型: 期刊论文
标识符: http://119.78.100.158/handle/2HF3EXSE/81794
Appears in Collections: 气候变化事实与影响
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作者单位: Department of Chemistry and Canadian Centre for Environmental Modelling and Chemistry, Trent University, Peterborough, ON, Canada; Air Quality Processes Research Section, Environment Canada, 4905 Dufferin St., Toronto, ON, Canada
Recommended Citation:
Parnis J,M,, Mackay D,et al. Temperature dependence of Henry's law constants and KOA for simple and heteroatom-substituted PAHs by COSMO-RS[J]. Atmospheric Environment,2015-01-01,110