DescriptionMeasurement of Henry’s Law Constant is often slow and difficult, with the standard Equilibrium Partitioning in Closed Systems method requiring extensive sample preparation and external calibrations. A faster method would significantly benefit the greater scientific community in obtaining these values and applying them to critical environmental questions, industrial needs, and safety concerns.
The objective of this study was to explore whether solid-phase microextraction (SPME)-multiple headspace extraction (in which analytes are removed from the solution over a series of iterative extractions as described in detail in Tena and Carrillo 2007) can be used to determine Henry’s Law constant (Kaw), both theoretically and experimentally. If possible, the Henry’s Law constant would be able to be measured with an automated high throughput SPME-MHE method.
Theoretical exploration indicated that if parameters such as sampling time, sample volume, and concentration are adjusted so that the fraction of the compound on the fiber exactly represents the fraction of the compound in the air phase, then Kaw can be measured, as per Equation:
Kaw = (1 − β)Vliquid / βVair
Three sets of compounds were designed and used for the experimental exploration by study the effects of SPME sampling parameters such as sample volume, analyte concentration, and sampling time, on the determination of Kaw and the accuracy of the determined Kaw. The results indicated that sample volume and analyte concentration can be optimized and predetermined so that Kaw can be measured by SPME-MHE. However, the Kaw determined largely depended on SPME sampling time. Too long sampling time led to the overestimation of Kaw, while too short sampling time resulted in underestimation of Kaw. Since it was nearly impossible to predetermine the right SPME sampling time for a given analyte so that the fraction of the compound on the fiber exactly represents the fraction of the compound in the air phase, it was concluded that SPME could not be used as an exhaustive extraction technique for the determination of Kaw by MHE. However, it is hypothesized that SPME could be used as a non-exhaustive extraction technique in combination with MHE for the determination of Kaw. In this case, SPME could be used like a headspace syringe, taking only an aliquot of the headspace for GC-MS analysis, and relying on a purge mechanism to remove the remaining analytes in the headspace prior to equilibration for the next iteration of SPME.