title: Using extrathermodynamic relationships to model the temperature dependence of Henry's law constants of 209 PCB congeners.
abstract: Our previous measurements of the temperature dependencies of Henry's law constants of 26 polychlorinated biphenyls (PCBs) showed a well-defined linear relationship between the enthalpy and the entropy of phase change. Within a homologue group, the Henry's law constants converged to a common value at a specific isoequilibrium temperature. We use this relationship to model the temperature dependencies of the Henry's law constants of the remaining PCB congeners. By using experimentally measured Henry's law constants at 11 degrees C for 61 PCB congeners described in this paper combined with the isoequilibrium temperatures from our previous measurements of Henry's law constants of 26 PCB congeners, we have derived an empirical relationship between the enthalpies and the entropies of phase change for these additional PCB congeners. A systematic variation in the enthalpies and entropies of phase change was found to be partially dependent on the chlorine number and substitution patterns on the biphenyl rings, allowing further estimation of the temperature dependence of Henry's law constants for the remaining 122 PCB congeners. The enthalpies of phase change for all 209 PCB congeners ranged between 10 and 169 kJ mol(-1), where the enthalpies of phase change decreased as the number of ortho chlorine substitutions on the biphenyl rings increased within homologue groups. These data are used to predict the temperature dependence of Henry's law constants for all 209 PCB congeners.
authors.affiliation: Chesapeake Biological Laboratory, University of Maryland, Center for Environmental Science, Solomons 20688, USA.
authors.forename: Holly A
authors.initials: HA
authors.lastname: Bamford
authors.forename: Dianne L
authors.initials: DL
authors.lastname: Poster
authors.forename: Robert E
authors.initials: RE
authors.lastname: Huie
authors.forename: Joel E
authors.initials: JE
authors.lastname: Baker
mesh_terms: D004785:Environmental Pollutants / Q000032:analysis*; D008962:Models, Theoretical; D011078:Polychlorinated Biphenyls / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: D004785:Environmental Pollutants; D011078:Polychlorinated Biphenyls