A generic model is derived for studying the mass-transfer kinetics of the pervaporation of multicomponent mixtures Of volatile organochloride compounds. Applying it to the pervaporation of dilute mixtures of trichloromethane, dichloro,ethane and trichloroethylene using tubular polydimethylsiloxane (PDMS) membranes permits: (1) estimation of the representative mass-transfer parameters, that is, solute diffusivity in the aqueous phase and membrane permeability of the individual components; (2) disci crimination of the relative importance of the mass-transport resistances to the pervaporation flux as a function of operation variables; and (3) determination of the selectivity in multicomponent pervaporation. Diffusivity values calculated with the model agree well with predictions by, the Wilke-Chang correlation for nonelectrolyte solutes. Permeability values of PDMS membranes change in the trichloroethylene > trichloromethane > dichloromethane direction. The relative importance of mass-transfer resistances for the considered volatile organic compounds depends oil the operation variables, that is, flow rate of the feed solution and membrane thickness. Furthermore, for trichloroethylene the main resistance is located in the feed solution, whereas for dichloromethane for high values of feed flow rate the resistance in the membrane could avert a major influence oil kinetic control, and the behavior of trichloromethane is intermediate between both compounds.