Measurements of relative distribution constants of vaporized hydrocarbons between air and polydimethylsiloxane via capillary columns for the calculation of headspace hydrocarbon compositions

This study focused on the measurements and validity of relative distribution constants of vaporized hydrocarbons between air and polydimethylsiloxane (PDMS) using commercially available capillary columns. Capillary column gas chromatography (CCGC) measurements, using two columns containing a PDMS stationary phase with different film thicknesses, were conducted to determine the relative distribution constants of n-heptane, toluene, n-octane, p-xylene, n-nonane, and 1,2,4-trimethylbenzene between air and PDMS at 90 and 120 °C. To validate the accuracy of the relative distribution constants via CCGC, the compositions of three headspace samples containing different amounts of hydrocarbons were calculated using the relative distribution constants via CCGC and extracted amounts via PDMS solid phase microextraction (SPME) at 90 and 120 °C. It was found that calculated hydrocarbon compositions of headspace samples were comparable to true headspace hydrocarbon compositions via direct vapor analysis, with an average absolute relative error of 3.2%. Our results indicate that CCGC is an alternative method that can provide a reliable and convenient method to determine the relative distribution constants of various hydrocarbons between air and PDMS for quantitative chemical analysis of headspace.