title: Dynamic theory of liquid junction potentials.
abstract: A Nernst-Planck-Poisson finite difference simulation system is used to model the dynamic evolution of a liquid junction from a nonequilibrium initial condition to a condition of steady potential difference, in a linear semi-infinite space. Liquid junctions of Lingane's type 1 (monophasic, unequal concentration) and type 2 (bi-ionic potential; biphasic, equal concentration) are considered, for the sake of simplicity. Analysis of the results shows consistency with known and novel asymptotic solutions. A comprehensive dynamic theory of the free liquid junction potential is presented, having considered the simulated concentration profiles and electric field in the system. This reveals a dynamically relaxing junction in which a diffuse layer continues to expand. This is advocated as physically realistic and shown to be consistent with a steady state potential difference, which arises after 10-1000 ns for typical aqueous systems, when the expanding diffuse layer has a corresponding size of 10-1000 nm. Hence, Planck's concept [Wied. Ann. 1890, 40, 561-576] that a steady state potential difference exclusively implies a static junction with equal fluxes of all species is shown to be false, for an unconstrained system.
authors.affiliation: Department of Chemistry, Physical and Theoretical Chemistry Laboratory, Oxford University, South Parks Road, Oxford, United Kingdom OX1 3QZ.
authors.forename: Edmund J F
authors.initials: EJ
authors.lastname: Dickinson
authors.forename: Leon
authors.initials: L
authors.lastname: Freitag
authors.forename: Richard G
authors.initials: RG
authors.lastname: Compton