期刊
JOURNAL OF PHYSICAL CHEMISTRY B
卷 114, 期 1, 页码 187-197出版社
AMER CHEMICAL SOC
DOI: 10.1021/jp908024s
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资金
- St John's College, Oxford
- Studienstiftung des deutschen Volkes
- Pembroke College, Oxford
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.
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