Investigation of sorption and diffusion of hydrocarbons into polydimethylsiloxane in the headspace-solid phase microextraction sampling process via inverse gas chromatography

Inverse gas chromatography was employed to investigate the sorption and diffusion of hydrocarbons into polydimethylsiloxane (PDMS) in the headspace-solid phase microextraction (HS-SPME) sampling process. Six hydrocarbons as molecular probes and two types of non-cross-linked PDMS with different average molecular weights as stationary phases were used in this study. Experimental measurements with columns containing a PDMS stationary phase were carried out to obtain specific retention volumes, molar enthalpies of sorption, interaction parameters, diffusion coefficients, and activation energies of diffusion of hydrocarbon probes over temperatures ranging from 60 to 90°C. The primary driving force of the hydrocarbon sorption into the PDMS SPME fibers was found to be the molar enthalpy of sorption, which depended on the molecular size of the hydrocarbons. As the molecular size of the hydrocarbon increased, the molar enthalpies of sorption became more exothermic. Interaction parameters and diffusion coefficients indicated that both n-heptane and n-octane were diffused into the PDMS matrix and localized to form clusters or aggregates, which were responsible for more negative molar entropies of sorption. However, the diffusivities of n-nonane and aromatic probes were limited due to their large molecular size and lack in the structural flexibility, respectively. The molar enthalpies of hydrocarbon sorption were independent of the average molecular weight of PDMS. However, specific retention volumes, interaction parameters, diffusion coefficients, and activation energies of diffusion of the hydrocarbons depended on the molecular weight of PDMS as well as the molecular weights and structures of hydrocarbons, as shown by the results of the Wilcoxon signed-rank test.