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How Multivalency controls Ionic Criticality

Michael E. Fisher·Jean-Noël Aqua·Shubho Banerjee
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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.

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BibTeXRIS

Michael E. Fisher, Jean-Noël Aqua, Shubho Banerjee. 2005-07-04. How Multivalency controls Ionic Criticality. https://doi.org/10.1103/physrevlett.95.135701

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