Beyond the classical transport laws of electrochemistry: new microscopic approach to ionic conductance and viscosity

Abstract

The concentration dependence of the transport properties (i.e., the conductivity and the viscosity) of an electrolyte solution has been a subject of lively debate for a very long time. The foundation for understanding the transport properties of electrolyte solutions was laid down by Debye, Huckel, Onsager, and Falkenhagen who derived several limiting laws valid at low ion concentration. These classical laws have been rederived several times, although their extension to concentrated solutions has proven to be very difficult. We discuss a new microscopic approach toward understanding the transport laws of electrochemistry. This new approach is based on the general ideas of the mode coupling theory. We show that the mode coupling theory approach is appropriate in the present case because concentration effects arise from collective variables (like charge density and current) which are treated correctly by the mode coupling theory. The new theory can describe the crossover from the low to high concentration seamlessly. Our study yields microscopic expressions of both conductivity and viscosity in terms of static and dynamic structure factors of the charge and number densities of the electrolyte solution. The celebrated expressions of Debye, Huckel, and Onsager for static conductance, of Debye and Falkenhagen for frequency dependent electrolyte friction, and of Falkenhagen for the viscosity follow exactly from the present microscopic theory in the limit of very low ion concentration. Recently derived microscopic expressions of Chandra, Wei, and Patey for the frequency dependent conductivity can also be derived from the present scheme. The present theory is a self-consistent theory. For conductance, the agreement of the present theory with experimental results is satisfactory even up to one molar concentration. For viscosity, the theory seems to give the right trend and suggests directions for further improvement to explain the myriad of unexplained behavior known for a long time.