Approach for the Description of Chemical Equilibrium Shifts in the Systems with Free and Connected Chemical Reactions

Round 1

Reviewer 1 Report

I reviewed the manuscript: " Approach for the Description of Chemical Equilibrium Shifts in the Systems with Free and Connected Chemical Reactions" and I found it interesting but not sufficiently well prepared. Scientific value of the article is proper.  Still, the manuscript editorial preparation is on very poor level. I don't understand the structure of the paper. It looks more like a book chapter than actual research paper. There are both minor and major issues on that matter. Moreover there are barely no discussion with other research paper presented.

Please see specific comments about editorial issues below:

It is not understandable for me if authors wanted to present only fragment [36-43] as an introductive part of the paper or add also the further parts to that. It seems like each part has it's own number corresponding to the given section but for some reason "Introduction" [35] was presented as higher tier.

Going further, equilibriums reactions were presented clearly but the explanations seems to lack of any structural order. It makes the paper very difficult to read and comprehend only because of lack of editing skills presented by the authors.

Another examples of flaws in text editing below.

[155-156] equilibrium is illegible by over-lapsing with line numbers

[174]  both equation and it's number are presented differently than the others

[150],[175],[226], [276], [284], [288], [292], [299] - inconsistency of bolding the text. I cannot understand the rules on what basis authors decided to bold some parts of the text. It is not clear for the reader cause it doesn't seem that those part are more interesting nor more scientific input they gave.

I strongly recommend the Authors to majorly revise the manuscript and send it in the form advised by Processes editorial office. Please do prepare the paper according to the rules and recommendation available on MDPI websites - https://www.mdpi.com/journal/processes/instructions. I am more than positive that by following the rules from there you can make the paper more comprehendible for readers. It will also make it easier for reviewers and editors to recommend you proper amendments if still needed.

For now I can accept the paper only after major revision based on previously given comments.

Author Response

The authors carefully read the review of the highly respected reviewer and agreed with most of his comments. The authors are grateful to reviewer.

About concrete comments.

1. Lines [36-43] is an introductory part of the article and we add additional parts to it.
2. Lines [155-156] were corrected.
3. Line [174] was corrected.
4. Bold text highlighting was eliminated in the lines [150],[175],[226], [276], [284], [288], [292], [299]. Also in lines [555], [563], [571, 573] etc bold text was eliminated (new lines elimination). Empty lines were removed. The authors tried to organize the use of a bold font in the text of the entire article. We hope it worked out.
5. The authors tried to streamline the use of numbering in the text of the entire article. We hope it worked out. The numbering hierarchy is not currently assumed.

About general remarks.

6. : “It looks more like a book chapter than actual research paper”. Authors agree with highly respected reviewer. However, they do not understand how unacceptable this is in general and for your respected Journal, in particular.
7. The authors, of course, apologize for their excellent English, they are not natural native speakers, and sincerely apologize to the editorial board and the highly respected reviewer. We shall try how we can improve it if a fundamental agreement on publication is reached. Once again, our apologies.

Reviewer 2 Report

The authors use relatively old references. Perhaps the biggest complaint is that the article looks more like a complex lecture in chemical thermodynamics for students in the second or third year of the Faculty of physical chemistry. I'm not sure how much this article will be cited. Despite everything, the presented results are accurately derived.

Author Response

The authors carefully read the review of the highly respected reviewer and agreed with most of his comments. The authors are grateful to reviewer.

About concrete comments.

1. : “The authors use relatively old reference”. The authors do not argue with the obvious fact, this is undoubtedly true.

Does this mean that the topic of the article has been uninteresting to researchers for many years, or is it something else, the authors can state with certainty. Let us to quote in our presentation the well-known phrase of J. W. Gibbs (multiple translations may somewhat distort the meaning of what was said): Thermodynamics is the only science, that will remain unchanged in its foundations forever…

2. : “Perhaps the biggest complaint is that the article looks more like a complex lecture in chemical thermodynamics for students in the second or third year of the Faculty of physical chemistry”. Authors agree with highly respected reviewer. However, they do not understand how unacceptable this is in general and for your respected Journal, in particular.
3. : “I'm not sure how much this article will be cited”. The authors are also not sure about this, and whether it is possible to be sure about this, the authors also do not know.
4. : “Despite everything, the presented results are accurately derived.” For this conclusion, the authors can only be grateful to the highly respected reviewer.

 

Reviewer 3 Report

I regret to evaluate the article negatively and propose to reject it. The text is not scientific - it does not meet the standards of a scientific article. The purpose and scope of the research were not formulated. The methodology used is not described. The results were not clearly presented, no discussions were held and no final conclusions were drawn.

Author Response

The highly respected reviewer completely rejects the article directly in its essence. Unfortunately, we cannot agree with his opinion. In our opinion, everyone, in particular the reviewer and the authors, has the right to their opinion. However, we will take into account the remarks of the highly respected reviewer expressed in such a categorical form. Perhaps, they will help us in the future.

 

Reviewer 4 Report

The authors have explained different approaches for the Description of Chemical Equilibrium Shifts in Systems with Free and Connected Chemical Reactions.

The appearances and explained approaches are not much interesting.

Very old research papers have been used in the introduction as well as in the entire discussion.

In fact, the title is not looking relevant.

The abstract and conclusions are not explained clearly.

The introduction section is too narrow. The authors should elaborate on this section by taking the latest research outcomes/processes. 

 State the principle and significance of Isolated “free” reaction systems

I don't find any citations for so many equations.

Overall, the quality of this manuscript is not appropriate to publish in this journal.

 

 

Author Response

The highly respected reviewer completely rejects the article directly in its essence. Unfortunately, we cannot agree with his opinion. The specific comments of the highly respected reviewer are reduced, by day, to a complete rewriting of the article with a radical change in meaning. In our opinion, it becomes inappropriate to discuss private comments in the context of a review. However, we will take into account the remarks of the highly respected reviewer. Perhaps, they will help us in the future.

Reviewer 5 Report

 

 

The paper from Zhasulan and coworkers investigates the chemical equilibrium shifts in the systems with free and connected chemical reactions. Especially, the author details the interconnection between factors (temperature, pressure, reagents, input/outputs of reagents/products) and the chemical equilibrium shifts. I believe the work is suited for the journal of Processes. However, some problems in the manuscript need to be addressed before I recommend for publication.   

1.Can the author provide more information in the introduction about the background and importance of the research?

2. Can the author summary the research results and conclusions in the Conclusions part to help readers get the conclusions for the research efficiently?

3. Some of expressions in the manuscript are not clear enough and difficult to get points.

Like, line 317, “Let us number of common components is the 1-st”.

Line 339, “The very result of transferring the condition of extremeness of the composition from one connected reaction to another (although it looks somewhat unexpected) can be explained”.

This is not an exhaustive list and I encourage the authors to take one more pass of the manuscript

4. There are numerous statements made that would require a reader to have deep knowledge of the specific literature in this area for context and in many of those cases no reference is provided. A couple examples where no references are given but are needed include:

Line 337: Unfortunately, in more complex cases of connected reactions, the authors fail to establish the transmission of the extremeness of the composition.

This is also not an exhaustive list and I encourage the authors to take one more pass of the manuscript and make sure that a reader will be able to easily access the necessary prior literature needed to fully understand the statements and claims of the present manuscript.

 

 

Author Response

The authors carefully read the review of the highly respected reviewer and agreed with most of his comments. The authors are grateful to reviewer.

We apologize for our irregular English, it is not our native language.

About concrete comments, кeeping the numbering of the reviewer.

1. The following paragraph was inserted into Introduction. “Let us allow ourselves a digression related to the prehistory of the issue. The principle of Le Chatelier - Brown itself was formulated in 1884 “If a system in stable equilibrium is acted upon from the outside, changing any of the equilibrium conditions (temperature, pressure, concentration, external electromagnetic field etc), then the processes directed to side of resistance to change”. Henri Le Chatelier (France) formulated this thermodynamic principle of moving equilibrium, later generalized by Karl Brown. The principle is applicable to equilibrium of any nature: mechanical, thermal, chemical, electrical. If external conditions change, this leads to a change in the equilibrium concentrations of substances. In this case, one speaks of a violation or shift in chemical equilibrium. The chemical equilibrium shifts in one direction or another, when any of the following parameters changes:

temperature of the system, that is, when it is heated or cooled;

pressure in the system, that is, when it is compressed or expanded;

concentration of one of the participants in the reversible reaction.

All these variants of external influences are considered in this article.

This principle in an exceptionally simple and illustrative form formulates the direction of displacement of the equilibrium state under external action on the system and is truly universal. Despite the fact that the principle itself was formulated a very long time ago and is very well known, the authors dare to assume that they propose some (albeit not too significant) change and expansion of the interpretation of the original principle stated earlier by the authors- Henri Le Chatelier  and Henri Le Chatelier”.

2. The following paragraph was inserted into Conclusion. “The principle itself is supplemented by considering the states of chemical equilibrium, in the case when the reactants and reaction products are mixed into a single reaction phase and are not separated in space from each other. In the considered case, this phase can be arbitrarily imperfect. On the other hand, the article considers cases of equilibrium shift in a system of several related reactions at once. This connection can be carried out by any participants in this system of reactions (products, starting materials or intermediates). The established principle of the joint passage of the concentrations of substances of related reactions through an extreme may, in the opinion of the authors, be of separate interest”.
3. Phrase “Let us number of common components is the 1-st” is changed on the phrase: “Let's assign the number 1 to the common component”.

Phrase “The very result of transferring the condition of extremeness of the composition from one connected reaction to another (although it looks somewhat unexpected) can be explained, if we take into account, that, when the composition changes, there is a redistribution or competition between connected reactions for a common reagent or common product” is changed on the phrase:

”Transfer of the condition of extremeness of the composition from one connected reaction to another can be explained, if we take into account, that, when the composition changes, there is a competition between connected reactions for a common reagent or common product”

The authors once more are grateful to the highly respected reviewer and apologizing for their terrible English.

Sincerely Yours, for the authors, N.Charykov, K.Semenov

Round 2

Reviewer 1 Report

Dear Authors, please see short comments below:

The authors carefully read the review of the highly respected reviewer and agreed with most of his comments. The authors are grateful to reviewer.

I am glad to read that authors decide to follow provided suggestions. 

About concrete comments.

1. Lines [36-43] is an introductory part of the article and we add additional parts to it. approved
2. Lines [155-156] were corrected. approved
3. Line [174] was corrected. approved
4. Bold text highlighting was eliminated in the lines [150],[175],[226], [276], [284], [288], [292], [299]. Also in lines [555], [563], [571, 573] etc bold text was eliminated (new lines elimination). Empty lines were removed. The authors tried to organize the use of a bold font in the text of the entire article. We hope it worked out. approved
5. The authors tried to streamline the use of numbering in the text of the entire article. We hope it worked out. The numbering hierarchy is not currently assumed. approved

About general remarks.

6. : “It looks more like a book chapter than actual research paper”. Authors agree with highly respected reviewer. However, they do not understand how unacceptable this is in general and for your respected Journal, in particular.  agreed
7. The authors, of course, apologize for their excellent English, they are not natural native speakers, and sincerely apologize to the editorial board and the highly respected reviewer. We shall try how we can improve it if a fundamental agreement on publication is reached. Once again, our apologies. approved

After reading revised version of provided manuscript, taking into account that Authors have made proper amendments and sufficient corrections, I can recommend this article to go through the next steps of publication process. 

Best of luck on future research.

Author Response

The authors are grateful to the reviewer for the valuable comments.

Reviewer 3 Report

I regret that the article is still negative and I suggest reediting it completely. Not much has changed in the new version of the article. The text, in my opinion, still does not meet the standards of a scientific article. The purpose and scope of the research have not been formulated. It is not known what is the inspiration for the Aytors. What is the novelty aspect? The methodology used is not described, and should normally be described in a separate chapter. The results were not clearly presented, no discussions took place, and no final conclusions were drawn.

Verses 37, 49, 63, and others – should be Karl Braun (or Braun), not Brown.

Author Response

The authors are grateful for the comments. Keeping the order of the comments of the highly respected reviewer.

1. “The purpose and scope of the research have not been formulated. It is not known what is the inspiration for the Authors. What is the novelty aspect? The methodology used is not described, and should normally be described in a separate chapter. The results were not clearly presented, no discussions took place, and no final conclusions were drawn. The methodology used is not described, and should normally be described in a separate chapter. The results were not clearly presented, no discussions took place, and no final conclusions were drawn.”

In the opinion of the authors, the scientific novelty of the presented work consists in two main aspects:

1. A) Attempts to extend the well-known principle of shifting chemical equilibrium to systems, in the case of the initial substances or reaction products belonging to phases with large (sometimes extremely large) positive deviations from ideality. In these cases, the contribution of the excess partial thermodynamic functions of the components to the equilibrium shift may be comparable and even exceed the contribution of the standard thermodynamic functions of the reaction participants. This aspect, in the opinion of the authors, has not been considered before.
2. B) Attempts to extend the well-known principle of shifting chemical equilibrium to systems of several chemical reactions with common reagents, products or intermediates. In these cases, there is competition between several chemical reactions for both participants in the reaction, and the displacement of the equilibrium in one reaction affects the displacement of the equilibrium in the other reaction. And this aspect has not been considered before, as far as the authors know.

Thus, the main goal and results of this work was an attempt to extend the well-known principle of equilibrium displacement to complex interrelated chemical processes occurring in highly nonideal systems. The methodology of consideration, in the opinion of the authors, is quite traditional and corresponds to the general principles of chemical thermodynamics, the poet does not need an additional description.

Corresponding paragraph with the text is inserted in lines 64-81.

2. “Verses 37, 49, 63, and others – should be Karl Braun (or Braun), not Brown”. Authors are grateful for the comments and make corrections.

Reviewer 4 Report

Still, I am not satisfied, as there is no citation of papers published in 2020, 2021, and 2022. This showed that the authors have not performed a critical review considering the recent research.

However, I recommend adding more recent papers in Introduction and discussion section and highlighting the main research gap and novelty of the current research.

 

 

Author Response

The authors are grateful for the comments. Keeping the order of the comments of the highly respected reviewer.

1. “Still, I am not satisfied, as there is no citation of papers published in 2020, 2021, and 2022. This showed that the authors have not performed a critical review considering the recent research. However, I recommend adding more recent papers in Introduction and discussion section and highlighting the main research gap and novelty of the current research”.

We also have included links to the latest works for 2021 and 2022 in the text (see, for example articles [10, 11]). These works (as well as earlier ones) were carried out within the framework of the standard and generally accepted methodology in thermodynamics. Corresponding paragraph with the text is inserted in lines 82-84.

Reviewer 5 Report

All of my questions from the last review have been addressed. I really appreciate the authors' response. But I still have some concerns for the paper. 

1. The sentence of "3. Phrase “Let us number of common components is the 1-st” is changed on the phrase: “Let's assign the number 1 to the common component" in the conclusion should be removed. I believe the sentence was pasted by mistake.

2. I understand that the authors are not native English speaker and the English writing is challenging for them. But part of the expressions in the paper is still hard to understand due to grammatical mistake. This expressions will also retard the authors to share their idea and result among researchers. I'm wondering if the author can take use of software to improve the writing, like Grammarly, google translate, or some other software.   

Author Response

The authors are grateful for the comments. Keeping the order of the comments of the highly respected reviewer.

1. “The sentence of "3. Phrase “Let us number of common components is the 1-st” is changed on the phrase: “Let's assign the number 1 to the common component" in the conclusion should be removed. I believe the sentence was pasted by mistake.”

You are completely right. Phrase is deleted, thank You very much.

2. “I understand that the authors are not native English speaker and the English writing is challenging for them. But part of the expressions in the paper is still hard to understand due to grammatical mistake. This expressions will also retard the authors to share their idea and result among researchers. I'm wondering if the author can take use of software to improve the writing, like Grammarly, google translate, or some other software”.

We apologize again for the terrible English. We are trying to use Your kind advice to improve our language in the article. We don't know how successful, though. In any case, we are sincerely grateful to You