Estimation of vapor pressures for nonpolar organic compounds by capillary gas chromatography.

The accuracy of a method based on capillary gas chromatography (GC) for estimating vapor pressures of nonpolar compounds was tested by comparing vapor pressures measured by GC (P/sub GC/) with literature values for the subcooled liquid (P/sub L/). Two 1.0 m long fused silica columns were used, a poly(dimethylsiloxane) bonded phase column (BP-1) and a WCOT hydrocarbon phase column (Apolane-87). GC measurements were carried out by using n-C/sub 18/ and n-C/sub 20/ hydrocarbons as vapor pressure reference compounds. Plots of log P/sub GC/ vs. log P/sub L/ were made for 24 organochlorines and polycyclic aromatic hydrocarbons to establish a correlation between measured and literature values. Systematic errors between P/sub GC/ and P/sub L/ were observed whose direction and magnitude depended on the vapor pressure range and the column used for measurements. On the BP-1 column P/sub GC/was too low by a factor of 2.3 at P/sub L/ - 10/sup -1/ torr, and too high by a factor of 3.5 at P/sub L/ = 10/sup -7/ torr. The Apolane-87 column showed more nearly ideal behavior. On this column P/sub GC/ underestimated P/sub L/ by a factor of 1.9 at P/sub L/ = 10/sup -1/ torr and the error decreased for lowermore » P/sub L/. Corrections for these systematic errors were made by relating P/sub GC/ to P/sub L/ through regression equations. The GC method was applied to 30 PCB isomerids containing one to seven chlorines. The average vapor pressure (P/sub L/) decreased by a factor of 4.5 for each chlorine added to the biphenyl core, although large differences in vapor pressure were measured for isomers of a particular chlorination level. Within each chlorination level isomers having the greater number of ortho chlorines had the higher vapor pressures.« less

[1]  W. Shiu,et al.  Vapor-pressure correlations for low-volatility environmental chemicals , 1982 .

[2]  D Mackay,et al.  Correlation of bioconcentration factors. , 1982, Environmental science & technology.

[3]  E. D. Schall,et al.  Vapor Pressures by GLC, Determination of Vapor Pressures of Some Phenoxyacetic Herbicides by Gas-Liquid Chromatography , 1966 .

[4]  F. Schmidt-Bleek,et al.  OECD Chemicals Testing Programme physico-chemical test , 1981 .

[5]  O. Hutzinger,et al.  Reversed-phase thin-layer chromatography of polynuclear aromatic hydrocarbons and chlorinated biphenyls , 1982 .

[6]  R. Bopp.  Revised parameters for modeling the transport of PCB components across an air water interface , 1983 .

[7]  P. A. Small,et al.  The vapour pressures of some high boiling esters , 1948 .

[8]  J. Prausnitz,et al.  Vapor pressures of high-molecular-weight hydrocarbons , 1979 .

[9]  T. Bidleman,et al.  Collection of airborne polycyclic aromatic hydrocarbons and other organics with a glass fiber filter-polyurethane foam system , 1984 .

[10]  D. Mackay,et al.  The predicted environmental distribution of some PCB replacements , 1983 .

[11]  B. Hicks,et al.  Some aspects of the transfer of atmospheric trace constituents past the air-sea interface , 1978 .

[12]  D. Hamilton.  Gas chromatographic measurement of volatility of herbicide esters. , 1980, Journal of chromatography.

[13]  S. Yalkowsky,et al.  Aqueous solubility of polychlorinated biphenyls , 1980 .

[14]  P. Albro,et al.  Quantitative characterization of polychlorinated biphenyl mixtures (aroclors® 1248, 1254 and 1269) by gas chromatograpy using capillary columns , 1981 .

[15]  W. May,et al.  Dynamic coupled-column liquid-chromatographic determination of ambient-temperature vapor pressures of polynuclear aromatic hydrocarbons , 1983 .

[16]  S. Eisenreich,et al.  Chromatographic determination of octanol-water partition coefficients (Kow's) for 58 PCB polychlorinated biphenyl congeners. , 1984, Environmental science & technology.

[17]  G. Briggs,et al.  Theoretical and experimental relationships between soil adsorption, octanol-water partition-coefficients, water solubilities, bioconcentration factors, and the parachor , 1981 .

[18]  H. Miyamoto,et al.  Effects of ambient temperature on aspects of airborne polycyclic aromatic hydrocarbons , 1982 .

[19]  J. J. Murray,et al.  The Vapor Pressures and Enthalpies of Sublimation of Five Polycyclic Aromatic Hydrocarbons , 1974 .

[20]  T. Bidleman,et al.  Determination of plychlorinated biphenyl vapor pressures by capillary gas chromatography , 1981 .

[21]  S. Yalkowsky,et al.  Estimation of the aqueous solubility of some aromatic compounds , 1983 .

[22]  G. Eiceman,et al.  Adsorption of polycyclic aromatic hydrocarbons on fly ash from a municipal incinerator and a coal-fired power plant , 1983 .

[23]  G. Sundström,et al.  Prediction of bioconcentration potential of organic compounds using partition coefficients derived from reversed phase thin layer chromatography , 1979 .