Pervaporation is considered a clean and energetically efficient process used for a wide range of applications, working separately or integrated into a hybrid process. In this work, a mathematical model has been developed accounting for the mass transport phenomena under non-isothermal conditions with strong contribution of polarization concentration that prevail in pervaporation systems. The mathematical model incorporates characteristics of the module geometry, mass and heat transfer correlations and estimation of the system physicochemical properties. The equation-oriented simulation software g-PROMSO was used in the solution of the final problem. Finally, the model was tested against a representative case study, pervaporative dehydration of cyclohexane, the solvent used in the manufacture of synthetic rubber. Model simulated curves described satisfactorily well the kinetic data of cyclohexane dehydration obtained in a pilot plant set-up. (c) 2006 Elsevier Ltd. All rights reserved.