Solvent and H/D Isotopic Substitution Effects on the Krichevskii Parameter of Solutes: A Novel Approach to Their Accurate Determination

Round 1

Reviewer 1 Report

Review of the MS “Solvent and H/D Isotopic Substitution Effects on the Krichevskii Parameter of Solutes: A novel approach to their accurate determination” by Chialvo and Crisalle.

 

The Krichevskii parameter plays a kay role in near-critical solution thermodynamics, particularly in determining the thermodynamic behavior of dilute solutions near the solvent’s critical point. The thermodynamic behavior of infinitely dilute mixtures near the solvent's critical point completely characterized by the Krichevskii parameter. In this work the authors reported the method for the accurate determination of the solvent effect on the Krichevskii parameter of a solute, based on the contrasting solvation behavior of the solute in the desired solvent relative to that of the reference solvent. The authors showed the fundamentally-based linear behavior between the Krichevskii parameter and the standard solvation Gibbs free energy of the i -solute in an a-solvent and provide a novel microstructural interpretation of the solvent effect on the Krichevskii parameter.

In the present work the authors solved problem of the Krichevskii parameter determination of an i- solute in a k-solvent, when we accurately know not only the solvation behavior of the i-solute in a j-solvent at ambient conditions, its Krichevskii parameter, and the determination the changes in the Krichevskii parameter of an i-solute, when we replace the j-solvent with a k-solvent. This is great result.

 

The scientific and practical merit of the MS is very high. The manuscript is very good organized. The description of the method is very good and clear. The discussion and the interpretation of the results is high quality. The MS is a good contribution to the field.

 

 I believe the paper can be published as is.

 

Author Response

We are glad the reviewer understood our approach 

Reviewer 2 Report

The results obtained are original and will be useful for modern supercritical technology.

Presentation of formulas may be more compact -technical remark only.

Author Response

Regarding the formulas/expressions, we presented the derivations explicitly to make sure the reader does not need to guess any step throughout the developments. Making them more compact might compromise the intended clarity of the outcomes.

Reviewer 3 Report

The manuscript entitled “Solvent and H/D Isotopic Substitution Effects on the Krichevskii Parameter of Solutes: A novel approach to their accurate determination” reports a theoretical study based on thermodynamics of the simple binary solutions. The presented analysis was described clearly but due to multitude of used symbols (as a regular text and as a super- or subscript) the list of them should help to follow the authors considerations.

Author Response

Following the reviewer's suggestion, we incorporated a nomenclature section at the end of the manuscript, where we compiled the relevant symbols and (sub/super) scripts to facilitate the reading and understanding of the presented developments.