Extending the solid-phase microextraction technique to high analyte concentrations: Measurements and thermodynamic analysis

The solid-phase microextraction (SPME) technique has been used historically to quantify analytes present at the parts per million level. However, the nonintrusive nature of SPME lends itself to other applications involving analytes at higher concentration. In the current work, the possibility of using the SPME technique to measure concentrated gaseous samples was examined. Pentane concentrations between 0 and 100% saturation were studied, over a temperature range of 20-45 degreesC. The results showed that, up to a critical mole fraction in the solid phase, the concentrations of pentane in the polymeric extracting solid and vapor phases were related by a constant, equal to Henry's constant. The temperature dependence of Henry's constant was shown to follow the predicted trend with temperature, as determined from rigorous thermodynamic calculations. Above the pentane concentration in the polymeric phase, the response deviated from linearity. The nonideality was captured in an activity coefficient. An activity coefficient model developed to describe the nonideality was found to be a function of the swollen volume of the SPME polymer phase. The results indicate that the SPME technique can be applied to high analyte concentrations, although difficulties may be encountered when multiple analytes are absorbed.