How Multivalency controls Ionic Criticality

Abstract

To understand how multivalency influences the reduced critical temperatures, Tce (z), and densities, roce (z), of z : 1 ionic fluids, we study equisized hard-sphere models with z = 1-3. Following Debye, Hueckel and Bjerrum, association into ion clusters is treated with, also, ionic solvation and excluded volume. In good accord with simulations but contradicting integral-equation and field theories, Tce falls when z increases while roce rises steeply: that 80-90% of the ions are bound in clusters near T_c serves to explain these trends. For z \neq 1 interphase Galvani potentials arise and are evaluated.

4 pages, 4 figures

References in corpus (2)

• Discretization Dependence of Criticality in Model Fluids: a Hard-core Electrolyte
• New mean field theories for the liquid-vapor transition of charged hard spheres

Cited by in corpus (9)

• Gas-liquid phase separation in oppositely charged colloids: stability and interfacial tension
• Universality of Ionic Criticality: Size- and Charge-Asymmetric Electrolytes
• Criticality in Charge-asymmetric Hard-sphere Ionic Fluids
• Self-Consistent Description of Vapor-Liquid Interface in Ionic Fluids
• Gas-liquid critical parameters of asymmetric models of ionic fluids
• Gas-liquid critical point in ionic fluids
• Vapor-liquid phase behavior of a size-asymmetric model of ionic fluids confined in a disordered matrix: the collective variables-based approach
• Phase behaviour in ionic solutions: restricted primitive model of ionic liquid in explicit neutral solvent
• Phase behavior of the Lattice Restricted Primitive Model with nearest-neighbor exclusion