Technical Report
 

A dynamic partial order model of electrolyte solutions

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  • The purpose of this work was to develop a dynamic partial order model of II electrolyte solutions which avoids inconsistencies present in the Debye-1-Iuckel and 1n related theories. It is shown that our results are consistent with activity coefficient data in aqueous electrolyte solutions. The main features of our work are a partial long-range order which increase s with concentration due to the increase in the coulombic energy of interaction and decreases with temperature, a contribution from ionic fluctuations because it is shown that displacen,ent:s fro1n average positions lead to a symmetric increase in ene1·g, which is not cancelled out, and .a hydration correction for the effect of hydration upon the effective ionic concentrations. Ions a1·e given partial counter-ion character as a function of the degree of order so that the free energy of ionic interactions can be calculated rigorously, as if the lattice were perfect, without resort to cluster integrals in the case of single salt solutions.
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