Solubility of Rare Earth Chlorides in Ternary Water-Salt Systems in the Presence of a Fullerenol—C₆₀(OH)₂₄ Nanoclusters at 25 °C. Models of Nonelectrolyte Solubility in Electrolyte Solutions

Round 1

Reviewer 1 Report

This is not a student's report, it is a proposed article and the reviews for the journal do this for free (as do everybody else). It is unacceptable that you do not format the manuscript in a uniform way, that figures have wrong numbers (6.1, 6.3, etc), that again the figures are not uniform, the data markers on some figures are absurd, the insets on several figures are unreadable if one does not zoom in, one does not write 1÷3 but 1/3, etc, the references are not properly formatted, you even left comments in Russian in the references section...

The linear models should disappear: if you have a curved sequence of data and over this a change in concavity it is certainly meaningless to use linear models: you can just refer them in the text.

This manuscript is a lack of respect for the journal and specially for the reviewers.

Author Response

The authors carefully read the review of the highly respected reviewer, agreed with his comments and tried to correct the article.

- The numbering of the figures in the article was made through 1, 2, ...18, 19.

- The inserts in the figures are really unreadable due to the small scale of the figures, we generally remove them from the figures, since they are duboated in Table 2.

- Comments in the links in Russian are translated into English (line 404).

- Authors also agree with highly respected reviewer, that  “The linear models should disappear…”. But attempts at linear approximation were specifically abandoned in order to show how inaccurately such a linear equation describes the convex-concave solubility curves of non-electrolytes in an electrolyte solution.

- The authors sincerely regret the unfavorable impression of the design of the work made on the reviewer. Of course, there can be no question of any disrespect, this is our carelessness in the design, and we are sincerely grateful to the reviewer.

- Please, find the improved paper attached to this letter - changes are in red.

Author Response File: Author Response.pdf

Reviewer 2 Report

         The manuscript studies the solubility of rare earth chlorides in ternary water-salt sytems in the presence of fullerenol nanoclusters and models of nonelectrolyte solubility in electrolyte solutions are suggested. This is an interesting paper but clarify some misunderstandings I suggest some corrections.

 

1. The results of the paper are not consequently presented in the paper:

  In the Abstract we read “The four diagrams are more or less accurately approximated by the simple one-term Sechenov equation (SE-1)”.

 On page 11 about the one-term Sechenov equation it is write „The result of the approximation is generally not satisfactory enough.”

In the Conclusion it changes to “All diagrams are fairly accurately approximated by classical one-parameter Sechenov equation.”

I think that the statement on page 11 is correct.

 

2. In the manuscript it is not stated clearly whether the three-parameter Sechenov equation is a new result of the paper or the authors only give new parametrization or demonstration to the

three-parameter Sechenov equation.

 

3 It is not clear what is the relation between the data in the Tables and the Figures. What the first column (N0) means in Table 1.  The data of Table 1. can be found in the Figures 4.1, 4.2, 4.3 and 4.4?

 

4. Why are so many A, B and D parameters in Figure 2? Only one is applied in Figures 6.1, 6.2, 6.3 and 6.4. with changing the notation to P1, P2, P3.

 

I suggest publication of the manuscript only if the authors clarify the above-mentioned remarks.     

 

 

Author Response

The authors carefully read the review of the highly respected reviewer, agreed with his comments and tried to correct the article.
1.    In the Abstract we corrected the phrase “The four diagrams are more or less accurately approximated by the simple one-term Sechenov equation (SE-1)”. Now it is: “The four diagrams can not be correctly approximated by the simple one-term Sechenov equation (SE-1)…” – line 309-310.
2.    “In the manuscript it is not stated clearly whether the three-parameter Sechenov equation is a new result of the paper or the authors only give new parametrization or demonstration to the three-parameter Sechenov equation”. We added the phrase ” As authors know such approximation is original and at the same time forced due to the nontrivial convex-concave course of the solubility branches of the nonelectrolyte in the studied systems” – lines 273-276.
3.    “It is not clear what is the relation between the data in the Tables and the Figures. What the first column (N0) means in Table 1.  The data of Table 1. can be found in the Figures 4.1, 4.2, 4.3 and 4.4?”. 
N0 in Table 1 is just the number of the experimental point on the diagram of concrete system. This data absolutely corresponds to represented in Figs (now 7-10).
4.    “ Why are so many A, B and D parameters in Figure 2? Only one is applied in Figures 6.1, 6.2, 6.3 and 6.4. with changing the notation to P1, P2, P3”.
In Table 2 in every fourth line and in equation (15) there are three variable parameters at once: A, B, D – it is three-parameter model SEM-3. In figures 6.1-6.4 (now 15-18) these parameters correspond to variable parameters: P1, P2, P3 (such designations are used in grater ORIGIN, subprogram Nonlinear Curve Fit. 
Authors are sincerely grateful to the reviewer for careful reading of the manuscript and valuable comments.
Please, find the improved paper attached to this letter - changes are in red

Author Response File: Author Response.pdf

Reviewer 3 Report

1. How is the validity of measurement method assessed? It would be better if the authors measure and report the solubility of known system.
2. What pressure have the authors measured the solubility data?
3. The uncertainty values for the studied temperature and pressure  should be  appeared as footnotes to the Table.
4. The uncertainty of solubility data (molality) should be determined.
5. Have the uncertainty of density values (measured densities  by pycnometer) been considered in the calculation of the molality?
6. The chemical information and the purity and source of used material should be listed in a Table.
7. All symbols in equations and text should be written in the italic form (e.g. Eq. 2).
8. It would be better if authors clarify their explanations more .

Author Response

The authors carefully read the review of the highly respected reviewer, agreed with his comments and tried to correct the article.
1.    “How is the validity of measurement method assessed? It would be better if the authors measure and report the solubility of known system”. The accuracy of the analysis and thermo-stating  is reported in the end of 3 page.
If the content of the article was a message about a new original model, it would probably be appropriate to test it on well-known systems. The purpose of this article is to study solubility in systems containing both nanoclusters and rare  salts.
2.    “What pressure have the authors measured the solubility data?”. Pressure in the experiment was 745-750 mm Hg – line 102-103  (such moderate pressures can not effect on phase equilibria between condensed phases).
3.    “The uncertainty values for the studied temperature and pressure  should be  appeared as footnotes to the Table”. They were indicated in the caption to Table 1.
4.    “The uncertainty of solubility data (molality) should be determined”. Molarity scale – moles numbers of components per 1 kg of solvent is typical for the description and modeling of solubility diagrams in electrolyte systems. For example, the most popular for the modeling in water electrolyte systems Pitzer’s equations namely molarities used.
5.    “Have the uncertainty of density values (measured densities  by pycnometer) been considered in the calculation of the molality?” The densities were used to convert the volume concentrations of fullerenes in g /dm3 (according to the law of Bouguer - Lambert - Ber) into mass-weight percentages, and then the molality of fullerenol.
6.    “The chemical information and the purity and source of used material should be listed in a Table”. We add the phrase (Purity C60(OH)24 – 98.5 mass.% - HPLC, REMCl3 (REM = Pr, Nd, Tb, Y) = 99 mass.%) in the subscription for Table 1 – line 160.
7.    “All symbols in equations and text should be written in the italic form (e.g. Eq. 2)”.
We try to do it in all equations in the text.
8.“It would be better if authors clarify their explanations more”.  We try to do it.
Authors are sincerely grateful to the reviewer for careful reading of the manuscript and valuable comments.
Please, find the improved paper attached to this letter - changes are in red

Author Response File: Author Response.pdf

Round 2

Reviewer 1 Report

I am very sorry that you did not implement several of my correction suggestions, especially the figures.

Your show very interesting results but the article loses impact because of:

a) a lot of bad English sentences; you really need to work on your written english. There is a lot of google translator;

b) lack of uniformity of variables; these should be all  in italic font;

c) figures have to be corrected;

d) You should highlight that the last modification extends the range up to which one can accurately model solubility (4 to 7m)

Comments for author File: Comments.pdf

Author Response

Dear Editor,

Once again, we are grateful to the highly respected reviewer for his valuable comments. So, keeping the numbering of his comments:

a) a lot of bad English sentences; you really need to work on your written English.There is a lot of google translator;

We sincerely apologize for the primitive English language. None of us, unfortunately, is a natural native speaker of English. We use Google Translate wherever we can. We tried to correct the English language somewhat in the text of the article

b) lack of uniformity of variables; these should be all in italic font;

All variables in equation and text are given in italic font (as far as we understand the concept of variables, not chemical symbols maybe?) throughout the text.

c) figures have to be corrected;

We corrected figs 1-5 and 6-10, removed unnecessary inscriptions from the drawings increased the caption to them. Figs 11-20 seem to be acceptable to us.

d) You should highlight that the last modification extends the range up to which one can accurately model solubility (4 to 7m)

We added the phrase: “The last three-parameter SEM-3 allows us to expand the scope of the model for describing the branches of solubility of non-electrolytes in electrolyte solutions to high concentrations of the latter (to molalities range from 4 to 7 mol per kg of solvent)” – lines 306-309. And in the conclusions we also insert: “All diagrams are fairly accurately approximated by classical one-parameter Sechenov equation and very accurately approximated by the three-parameter modified Sechenov equation in the whole concentration range up to 4-7 molalities of electrolytes” – lines 375-378.

Changes are highlighted in red in the attached paper

Sincerely Yours, for the authors