Anomalous system-size dependence of electrolytic cells with an electrified oil-water interface

Physical Chemistry Chemical Physics : PCCP
Marise WestbroekRené van Roij

Abstract

Manipulation of the charge of the dielectric interface between two bulk liquids not only enables the adjustment of the interfacial tension but also controls the storage capacity of ions in the ionic double layers adjacent to each side of the interface. However, adjusting this interfacial charge by static external electric fields is difficult since the external electric fields are readily screened by ionic double layers that form in the vicinity of the external electrodes. This leaves the liquid-liquid interface, which is at a macroscopic distance from the electrodes, unaffected. In this study we show theoretically, in agreement with recent experiments, that control over this surface charge at the liquid-liquid interface is nonetheless possible for macroscopically large but finite closed systems in equilibrium, even when the distance between the electrode and interface is orders of magnitude larger than the Debye screening lengths of the two liquids. We identify a crossover system-size below which the interface and the electrodes are effectively coupled. Our calculations of the interfacial tension for various electrode potentials are in good agreement with recent experimental data.

References

Dec 7, 2007·Physical Chemistry Chemical Physics : PCCP·Mirjam E LeunissenAlfons van Blaaderen
Sep 4, 2008·Physical Review Letters·Markus BierRené van Roij
May 13, 2010·The Journal of Chemical Physics·Nouamane LaanaitMark L Schlossman
Jul 12, 2012·Physical Chemistry Chemical Physics : PCCP·Dmitry MomotenkoHubert H Girault
Nov 24, 2012·Proceedings of the National Academy of Sciences of the United States of America·Nouamane LaanaitMark L Schlossman
Dec 31, 2014·Langmuir : the ACS Journal of Surfaces and Colloids·Dominik MichlerDaniel Bonn
Jan 8, 2013·Journal of Chemical Theory and Computation·Guillermo Iván Guerrero-García, Mónica Olvera de la Cruz

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Citations

May 26, 2017·Physical Chemistry Chemical Physics : PCCP·J C EvertsR van Roij
Sep 10, 2016·Physical Review Letters·J C EvertsR van Roij
Dec 8, 2016·ACS Central Science·Guillermo Iván Guerrero-GarcíaMónica Olvera de la Cruz

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