RESUMO
Solid-phase microextraction (SPME) sampling of the headspace above an aqueous micellar solution of sodium dodecyl sulfate (SDS) was shown to be effective for quantifying the equilibrium partitioning of limonene solute between water and SDS micellar aggregates. Concentrations in the headspace were determined from the amount absorbed by the SPME fiber during 1 min extractions, with the quantity on the fiber determined using gas chromatography/mass spectrometry (GC/MS). Headspace concentrations as a function of surfactant concentration were fit to a mass balance to yield the partition coefficient and critical micelle concentration. When the total limonene in the system was low enough that it could be completely dissolved by water in the absence of micelles, a constant value for the partition coefficient of 1700 M(-1) was obtained, independent of the limonene concentration. However, at higher total limonene concentrations, the partition coefficient became a function of the amount of limonene in the micelles, as confirmed by separate experiments in which either limonene or SDS concentration was varied. The observed increase in partition coefficient with increasing limonene likely signals a shift from micelles to swollen micelles and ultimately to microemulsion droplets. The effect of SDS concentration on the aqueous solubility limit of limonene could also be observed in HS-SPME experiments where either SDS or limonene was varied.
