Reply to “Comment on ‘Negative Deviations from the Debye–Hückel Limiting Law for High-Charge Polyvalent Electrolytes: Are They Real?’ ”

Abstract

In their “Comment on ‘Negative Deviations from the Debye–Hückel Limiting Law for High-Charge Polyvalent Electrolytes: Are They Real?’ ” Biver and Malatesta, citing my respective paper, argue that my analysis of experimental data of their group is wrong and so is my conclusion that negative deviations observed by them are not physically real. Here I rebut their arguments and explain why their rejection of my work is unjustified, and why those authors do not in any way prove me wrong. The core of my study and conclusion remains intact: Negative deviations in the case of high-charge electrolytes with |z + z –| > 3 do not always happen, and so far, such observed deviations are not convincingly supported by theory.

Investigation of the Limits of the Linearized Poisson–Boltzmann Equation

“…Still, negative deviations appearing at molality values higher than 0.01 mol/kg were observed for LiCl, as presented in Figure S7 in the Supporting Information. There is a recent debate on whether negative deviations represent an experimental artifact or not. ,,, However, our aim in this work is not to delve into the experimental discussion but to show that DHLL may not be the limiting law to the nonlinear Poisson–Boltzmann equation, as later presented by other results.…”

“…There is a recent debate on whether negative deviations represent an experimental artifact or not. 16,17,56,69 However, our aim in this work is not to delve into the experimental discussion but to show that DHLL may not be the limiting law to the nonlinear Poisson−Boltzmann equation, as later presented by other results.…”