화학공학소재연구정보센터
Journal of Chemical and Engineering Data, Vol.50, No.2, 438-443, 2005
Prediction of subcooled vapor pressures of nonpolar organic compounds using a one-parameter QSPR
A previously derived empirical linear relationship between the average polarizability of chlorinated aromatic and aliphatic compounds, alpha(m), as calculated using density functional theory methods, and their subcooled liquid vapor pressure, log p(L), is tested here for its capability to predict the 25 degrees C subcooled vapor pressures of a diverse set of nonpolar organic compounds, including 12 brominated benzenes, 13 aromatic hydrocarbons, 10 chlorinated toluenes, 3 hexachlorocyclohexanes, and p,p'-DDT. A comparison with experimental data shows generally excellent agreement over a 10-order-of-magnitude range in p(L), with an average error of less than 0.5 log unit. Experimental vapor pressure values were taken from the literature or, in the case of the chlorinated toluenes, were determined using gas chromatographic retention times. Remarkably large differences in the experimental octanol-air partition coefficients for the isomers of the hexachlorocyclohexanes were found to correspond to similarly large differences in the out-of-plane polarizabilities of these substances. This work suggests that a single theoretically derived parameter is sufficient to estimate within 1 order of magnitude the volatility of a wide variety of organic compounds whose primary interactions are dispersive in nature. This includes halogenated and nonhalogenated, aromatic, aliphatic and alicyclic, and planar and nonplanar organic substances.