English

Ion distribution around a charged rod in one and two component solvents: Preferential solvation and first order ionization phase transition

Soft Condensed Matter 2015-05-13 v2 Statistical Mechanics

Abstract

In one and two component solvents, we calculate the counterion distribution around a charged rod treating the degree of ionization α\alpha as an annealed variable dependent on its local environment. In the one component case, α\alpha is determined under various conditions without and with salt. In the two component case, we take into account the preferential solvation of the counterions and the ionized monomers and the short-range interaction between the rod and the solvent without salt. It then follows a composition-dependent mass action law. Mesoscopic variations of the composition and the counterions are produced around a chraged rod, which sensitively depend on various parameters of the molecular interactions. Furthermore, we predict a first order phase transition of weak-to-strong dissociation for strong preferential solvation. It can occur in expanded states of a polymer chain. This transition line starts from a point on the solvent coexistence curve and ends at a critical point in the plane of the temperature and the solvent composition. The composition change around a charged rod is long-ranged near the solvent critical point.

Keywords

Cite

@article{arxiv.0905.1441,
  title  = {Ion distribution around a charged rod in one and two component solvents: Preferential solvation and first order ionization phase transition},
  author = {Ryuichi Okamoto and Akira Onuki},
  journal= {arXiv preprint arXiv:0905.1441},
  year   = {2015}
}

Comments

17 pages, 15 figures. submitted to J. Chem. Phys