Abstract
Within a modified Poisson–Boltzmann theory we study the effect of Bjerrum pairs on thetypical length scale over which electric fields are screened in electrolyte solutions, taking into account a simpleassociation–dissociation equilibrium between free ions and Bjerrum pairs. At low densitiesof Bjerrum pairs, this length scale is well approximated by the Debye length , with ρs the free-ion density. At high densities of Bjerrum pairs, however, we find , which is significantly larger than1/κ due to the enhanced effective permittivity of the electrolyte, caused by the polarization ofBjerrum pairs. We argue that this mechanism may explain the recently observedanomalously large colloid-free zones between an oil-dispersed colloidal crystal and acolloidal monolayer at the oil–water interface.
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