6533b858fe1ef96bd12b5a8e

RESEARCH PRODUCT

Transport equations of electrodiffusion processes in the laboratory reference frame.

Javier Garrido

subject

ChemistryBoundary (topology)ThermodynamicsMechanicsSurfaces Coatings and FilmsIonElectrical resistivity and conductivityMaterials ChemistryPhysical and Theoretical ChemistryElectric currentExperimental methodsDiffusion (business)Volume balanceReference frame

description

The transport equations of electrodiffusion processes use three reference frames for defining the fluxes: Fick's reference in diffusion, solvent-fixed reference in transference numbers, and laboratory fluxes in electric conductivity. The convenience of using only one reference frame is analyzed here from the point of view of the thermodynamics of irreversible processes. A relation between the fluxes of ions and solvent and the electric current density is deduced first from a mass and volume balance. This is then used to show that (i) the laboratory and Fick's diffusion coefficients are identical and (ii) the transference numbers of both the solvent and the ion in the laboratory reference frame are related. Finally, four experimental methods for the measurement of ion transference numbers are analyzed critically. New expressions for evaluating transference numbers for the moving boundary method and the chronopotentiometry technique are deduced. It is concluded that the ion transport equation in the laboratory reference frame plays a key role in the description of electrodiffusion processes.

10.1021/jp055899rhttps://pubmed.ncbi.nlm.nih.gov/16494340