Proposed Models for Subcritical Water Extraction of Essential Oils

Mechanisms that control the extraction rate of essential oil from Zataria multiflora Boiss. (Z. multiflora) with subcritical water (SW) were studied. The extraction curves at different solvent flow rates were used to determine whether the extractions were limited primarily by the near equilibrium partitioning of the analyte between the matrix and solvent (i.e. partitioning thermodynamics) or by the rates of analyte desorption from the matrix (i.e. kinetics). Four simple models have been applied to describe the extraction profiles obtained with SW: (1) a model based solely on the thermodynamic distribution coefficient K-D, which assumes that analyte desorption from the matrix is rapid compared to elution; (2) one-site kinetic model, which assumes that the extraction rate is limited by the analyte desorption rate from the matrix and is not limited by the thermodynamic (K-D) partitioning that occurs during elution; (3) two-site kinetic model and (4) external mass transfer resistance model. For SW extraction, the thermodynamic elution of analytes from the matrix was the prevailing mechanism as evidenced by the fact that extraction rates increased proportionally with the SW flow rate. This was also confirmed by the fact that simple removal calculations based on determined K-D (for major essential oil compounds) gave good fits to experimental data for flow rates from 1 to 4 ml.min(-1). The results suggested that the overall extraction mechanism was influenced by solute partitioning equilibrium with external mass transfer through liquid film.