Membrane potential and membrane conductance measurements have been carried out using Dowex-50Kynar membrane, sodium chloride and urea as a hydrotrope, mixture of varying composition to examine the hydrotrope effect on electrochemical character of the membrane. A significant change on membrane electrochemical character is observed in the presence of hydrotrope due to changed co-ion exclusion. The Donnan equilibrium has been incorporated to estimate the activity coefficient of counter ion, y(p)(m), and solute, y(+/-)(m) in the membrane phase along with the parameter, so called Phi expressing non-ideality. Solute rejection performance of the membrane is examined when electrolyte concentration remains constant and hydrotrope concentration varies and vice-versa. In both cases, membrane specific conductance depends on NaCl and hydrotrope concentrations differently. Friction caused through the membrane by the variation in concentration of hydrotrope is greater than friction caused by the variation in concentration of NaCl. Zeta potential is sensitive to the variation of hydrotrope concentration but insensitive to the variation of electrolyte concentration. The membrane system shows the behavior of NE membrane because Pe << 1 is estimated in both cases. (C) 2012 Published by Elsevier B.V.