Volumetric mass transfer coefficients in liquid and vapour phases in distillation column were measured by the method consisting of a fitting of the concentration profile of liquid phase along the column obtained by the integration of a differential model to the experimental one. The mathematical model of distillation process includes mass and energy balances and the heat and mass transfer equations. The film model flux expressions with the convective transport contributions have been considered in the transfer equations. Vapour and liquid phases are supposed to be at their saturated temperatures along the column. Effect of changes of phase flows and physical properties of phases on the mass transfer coefficients along the column and non-ideal thermodynamic behaviour of the liquid phase have been taken into account. The concentration profiles of liquid phase are measured in the binary distillation of the ethanol-water and methanol-ethanol systems at total reflux on metal Pall Rings and Intalox saddles 25 mm in the column with diameter of 150 rum. The distillation mass transfer coefficients obtained by the fitting procedure are compared with those calculated from absorption data using Onda's, Billet's and Linek's correlations. The distillation heat transfer coefficients calculated from the model assuming saturated temperatures in both phases are compared with those calculated from the Chilton-Colbum and penetration model analogy between mass and heat transfer. The results have confirmed an agreement neither between distillation and from absorption correlations calculated mass transfer coefficients nor between analogy and from enthalpy balance calculated heat transfer coefficients. Also the concentration profiles obtained by the integration of the differential model of the distillation column using the coefficients from absorption correlation have differed from the experimental profiles considerably. (c) 2006 Elsevier Ltd. All rights reserved.