Comment on Negative Deviations from the Debye-Huckel Limiting Law for High-Charge Polyvalent Electrolytes: Are They Real?

A work (Fraenkel, D. J. Chem. Theory Comput. 2018, 14, 2609, DOI: 10.1021/acs.jctc.7b01260) was recently published in which, starting from data of activity coefficients of electrolytes determined by Malatesta and co-workers in the years 1992-2000, an incorrect conclusion is reached, i.e., that the negative deviations from the Debye-Huckel limiting law found at high dilution for high-charge polyvalent electrolytes were presumably not real. The present work shows the reasons why we cannot share his opinion. The negative deviations are supported both by the theory and by experimental demonstration.