title: Air-water partition coefficients for a suite of polycyclic aromatic and other C10 through C20 unsaturated hydrocarbons.
abstract: The air-water partition coefficients (Kaw) for 86 large polycyclic aromatic hydrocarbons and their unsaturated relatives were estimated using high-level G4(MP2) gas and aqueous phase calculations with the SMD, IEFPCM-UFF, and CPCM solvation models. An extensive method validation effort was undertaken which involved confirming that, via comparisons to experimental enthalpies of formation, gas-phase energies at the G4(MP2) level for the compounds of interest were at or near thermochemical accuracy. Investigations of the three solvation models using a range of neutral and ionic compounds suggested that while no clear preferential solvation model could be chosen in advance for accurate Kaw estimates of the target compounds, the employment of increasingly higher levels of theory would result in lower Kaw errors. Subsequent calculations on the polycyclic aromatic and unsaturated hydrocarbons at the G4(MP2) level revealed excellent agreement for the IEFPCM-UFF and CPCM models against limited available experimental data. The IEFPCM-UFF-G4(MP2) and CPCM-G4(MP2) solvation energy calculation approaches are anticipated to give Kaw estimates within typical experimental ranges, each having general Kaw errors of less than 0.5 log10 units. When applied to other large organic compounds, the method should allow development of a broad and reliable Kaw database for multimedia environmental modeling efforts on various contaminants.
authors.affiliation: a Chemologica Research , Moose Jaw , Saskatchewan , Canada.
authors.forename: Sierra
authors.initials: S
authors.lastname: Rayne
authors.affiliation: b Department of Environmental Engineering Technology , Saskatchewan Polytechnic , Moose Jaw , Saskatchewan , Canada.
authors.forename: Kaya
authors.initials: K
authors.lastname: Forest
mesh_terms: D003198:Computer Simulation; D006838:Hydrocarbons / Q000737:chemistry*; D008956:Models, Chemical; D009930:Organic Chemicals / Q000737:chemistry; D011084:Polycyclic Aromatic Hydrocarbons / Q000737:chemistry*; D015203:Reproducibility of Results; D013816:Thermodynamics; D014867:Water / Q000737:chemistry*
chemical_list: D006838:Hydrocarbons; D009930:Organic Chemicals; D011084:Polycyclic Aromatic Hydrocarbons; D014867:Water
keywords: Air–water partition coefficient; enthalpy of formation; environmental fate; polycyclic aromatic hydrocarbons; theoretical study