Adsorption of a diverse set of organic vapors on quartz, CaCO3, and alpha-Al2O3 at different relative humidities

Adsorption constants of a diverse set of 50 organic vapors have been measured on quartz (SiO(2)), CaCO(3), and alpha-Al(2)O(3) at different relative humidities at 15 degrees C. For nonpolar compounds we found an exponential decrease of the adsorption constants on a given mineral between 40 and 97% relative humidity. Extrapolated to 100% relative humidity, the adsorption constants of nonpolar compounds on the different minerals coincide and agree with those measured on a bulk water surface. The adsorption constants of polar compounds also decrease with increasing humidity up to 90%, but between 90% and 100% they increase again. We speculate that this effect is due to a change in the orientation of the water molecules that form the surface at which the organic vapors adsorb at this high humidity. The compound variability in the adsorption constants of all compounds on a given surface at a given relative humidity could be described rather well with a linear free energy relationship using Abraham's solvation parameters for the van der Waals and electron-donor/acceptor properties of the compounds. The remaining deviation between fitted and experimental data was found to be systematic, which indicated that an optimized parameter set for the used compounds could still considerably improve the fit.