A new mechanistic model for reactions involving two liquid phases and a homogeneous phase transfer catalyst (PTC) has been developed based on extraction mechanism considering the equilibrium of catalyst and active catalysts at the interface. The proposed kinetic model considers thermodynamic framework based aqueous phase ionic equilibrium and the separate contributions of non-PTC and PTC-enhanced reactions towards the overall reactions. The developed model was then applied to an industrially important reaction of benzyl chloride with aqueous ammonium sulfide for synthesis of dibenzyl sulfide and benzyl mercaptan. The kinetic parameters of the developed model were estimated at different temperatures using an indigenously developed non-linear regression technique based on modified Levenberg-Marquardt algorithm. Sensitivity analysis was then performed under various experimental conditions using the estimated parameters and the results were compared with experimental observations. A good agreement was observed between experimental and calculated values with proper trends of the results. © 2009 Elsevier Ltd. All rights reserved.