Dielectric exclusion of ions from membranes.
Dielectric exclusion is caused by the interactions of ions with the bound electric charges induced by ions at interfaces between media of different dielectric constants. It is considered as one of mechanisms of nanofiltration. The transport properties of capillary model are expressed through ion distribution and diffusion coefficients. Due to local equilibrium the distribution coefficient is directly related to the excess solvation energy of ion. First, this energy is considered for single ions in single neutral pores in terms of pore size, ion charge, dielectric constants of solvent and membrane matrix and pore geometry. The dielectric exclusion from pores with closed geometry like circular cylinders is shown to be essentially stronger than that from pores with relatively open geometry like slits. Furthermore, the role of finite membrane porosity is analysed for the model of infinite slabs with alternating dielectric constants. The presence of other ions is accounted for within the scope of a mean-field approach, and the screening of dielectric exclusion is thus introduced and considered in some detail. A fixed electric charge is shown to cause additional screening. At the same time the dielectric exclusion makes the Donnan exclusion of ions stronger. Therefore the interaction between those two rejection mechanisms turns out to be non-trivial. Finally, the effect of solvent molecular structure is considered within the scope of non-local electrostatics. It is shown that the solvent non-locality typically results in somewhat stronger dielectric exclusion, however, its most important effect is slowing down the decline of dielectric exclusion with increasing bulk electrolyte concentration.
Yaroshchuk
A E
AE
Institute of Bio-Colloid Chemistry, National Academy of Sciences of Ukraine, Kiev. andriy.yaroshchuk@kfunigraz.ac.at
D002197:Capillary Action; D017136:Ion Transport; D007477:Ions; D008566:Membranes / Q000737:chemistry*; D008567:Membranes, Artificial; D008956:Models, Chemical; D010539:Permeability; D016062:Porosity; D012997:Solvents; D055672:Static Electricity; D013816:Thermodynamics
D007477:Ions; D008567:Membranes, Artificial; D012997:Solvents