The pervaporation mechanism of pure components through a commercial microporous silica membrane was studied by performing experiments using water, methanol, ethanol, 2-propanol, and n-propanol in the 40-80 degrees C temperature range. Experimental fluxes were correlated to feed temperature and viscosity. It was found that the permeation mechanism obeys the adsorption-diffusion description, covering both the microscopic models based on configurational (micropore) diffusion and on activated surface diffusion. The contribution of convection was negligible. Size parameters for the permeating molecules such as molecular weight, kinetic diameter, and effective diameter, which are expected to have an influence on diffusion, did not correlate with the flux, thus strongly emphasizing the importance of sorption as the rate-determining step for transport in the pervaporation process. This was confirmed by correlating parameters reflecting polarity with flux: an exponential relation between the Hansen polarity (especially the hydrogen bonding component) and the flux was observed. A similar correlation was found between the dielectric constant and the flux. Furthermore, the flux increases in the same direction as the hydrophilicity of the pure components (log P). The effects of membrane surface tension and contact angles are less outspoken, but experiments performed on glass supported and silica supported membrane top layers suggest an important influence of the sublayers on the flux.