title: Kinetics of solid-phase extraction and solid-phase microextraction in thin adsorbent layer with saturation sorption isotherm.
abstract: The effects of sorbent saturation in thin adsorbent layers have been much overlooked in earlier research and should be taken into account in both the theory and practice of solid-phase extraction (SPE) and solid-phase microextraction (SPME). The adsorption kinetics of a single analyte into a thin adsorptive layer was modeled for several cases of agitation conditions in the analyzed volume. The extraction process in the adsorbent layer was modeled using a Langmuir isotherm approximated by the linear isotherm at low concentrations and by a saturation plateau at concentrations exceeding the critical saturation concentration. Laplace transformations were used to estimate the equilibration time and adsorbed analyte concentration profile for no agitation, practical and perfect agitation in the analyzed volume. The equilibration time may be significantly reduced at high degrees of oversaturation and/or agitation in the analyzed volume. The resulting models indicated that the adsorbent layer becomes saturated at some critical value of the oversaturation degree parameter. The critical value of the oversaturation parameter is affected by both the concentration of the analyte in the analyzed volume and the sorbent characteristics. It was also shown that the adsorption process is carried out via the propagation of the saturation adsorption boundary toward the inner boundary of the adsorbent layer. These new adsorption models should serve as "stepping stones" for the development of competitive adsorption kinetic models for both SPE and SPME, particularly in cases where fast sampling is used.
authors.affiliation: Department of Chemistry, University of Waterloo, Ontario, Canada. sem@fly.triniti.troitsk.ru
authors.forename: S N
authors.initials: SN
authors.lastname: Semenov
authors.forename: J A
authors.initials: JA
authors.lastname: Koziel
authors.forename: J
authors.initials: J
authors.lastname: Pawliszyn
mesh_terms: D002853:Chromatography, Liquid / Q000379:methods*; D007700:Kinetics; D013696:Temperature