Semi-empirical estimation of organic compound fugacity ratios at environmentally relevant system temperatures.
Fugacity ratios of organic compounds are used to calculate (subcooled) liquid properties, such as solubility or vapour pressure, from solid properties and vice versa. They can be calculated from the entropy of fusion, the melting temperature, and heat capacity data for the solid and the liquid. For many organic compounds, values for the fusion entropy are lacking. Heat capacity data are even scarcer. In the present study, semi-empirical compound class specific equations were derived to estimate fugacity ratios from molecular weight and melting temperature for polycyclic aromatic hydrocarbons and polychlorinated benzenes, biphenyls, dibenzo[p]dioxins and dibenzofurans. These equations estimate fugacity ratios with an average standard error of about 0.05 log units. In addition, for compounds with known fusion entropy values, a general semi-empirical correction equation based on molecular weight and melting temperature was derived for estimation of the contribution of heat capacity differences to the fugacity ratio. This equation estimates the heat capacity contribution correction factor with an average standard error of 0.02 log units for polycyclic aromatic hydrocarbons, polychlorinated benzenes, biphenyls, dibenzo[p]dioxins and dibenzofurans.
van Noort
Paul C M
PC
Deltares, Utrecht, The Netherlands. paul.vannoort@deltares.nl
D000465:Algorithms; D001572:Benzofurans / Q000737:chemistry; D000072338:Dibenzofurans, Polychlorinated; D019277:Entropy; D004785:Environmental Pollutants / Q000737:chemistry*; D008956:Models, Chemical; D009930:Organic Chemicals / Q000737:chemistry*; D044367:Phase Transition; D011078:Polychlorinated Biphenyls / Q000737:chemistry; D000072317:Polychlorinated Dibenzodioxins / Q000031:analogs & derivatives / Q000737:chemistry; D011084:Polycyclic Aromatic Hydrocarbons / Q000737:chemistry; D013816:Thermodynamics; D044366:Transition Temperature
D001572:Benzofurans; D000072338:Dibenzofurans, Polychlorinated; D004785:Environmental Pollutants; D009930:Organic Chemicals; D000072317:Polychlorinated Dibenzodioxins; D011084:Polycyclic Aromatic Hydrocarbons; D011078:Polychlorinated Biphenyls