Air-water partition constants for volatile methyl siloxanes

Silicones are an important class of hydrophobic compounds in widespread use. To evaluate their fate in the environment, an accurate value of the air-water partition (Henry's law) constant is necessary, which, unfortunately, is lacking at present. A static head space and a newly developed dynamic vapor entry loop method were used to obtain the air-water partition constant for six volatile methyl siloxanes. Internally consistent data were obtained. The value of Henry's constant, as calculated from pure component vapor pressure and aqueous solubility, was 10- to 170-fold greater than the experimental values. A correction to the Henry's constant that involves the ratio of the thermodynamic activity coefficient for a methyl siloxane at infinite dilution to that at saturation solubility in the aqueous phase is proposed.