Effects of Anion Impurities on the Solubility and Nucleation of Borax Decahydrate Crystals in Carbonate-Type Brine
Round 1
Reviewer 1 Report
Needs significant improvement on the formatting/ language use, in particular lines 23,24,27,28,33,35,36, 100,115,176,184,185,187, 240.
Experimental set-up not well defined.
Paper very similar to 2014 paper by similar authors, not clear what is novel in this paper.
Conclusions very short and again no clear novelty recorded.
Author Response
Respond to the reviews’
Thank you for giving us a chance to revise the paper. The comments are very valuable and instructive to correct and improve our paper. We appreciate for Editors and Reviewers’ warm work earnestly and hope that the corrections will meet with approval.
1. Needs significant improvement on the formatting/ language use, in particular lines 23,24,27,28,33,35,36, 100,115,176,184,185,187, 240.
We have sought expert assistance for the correct translation of the manuscript into English. We have learned a lot through the revision process, including the writing, arrangement, and details of the experiment. The revised portions are marked in blue in the revised manuscript.
2. Experimental set-up not well defined.
We have revised the part about the experimental set-up. And marked in blue in the revised manuscript.
3. Paper very similar to the 2014 paper by similar authors, not clear what is novel in this paper.
The findings of this investigation complement those of earlier studies. Different from previous studies, this study focused on the comprehensive influence of various salts in Na2SO4-NaCl-Na2CO3-Na2B4O7-H2O system on the crystallization of borax. Compared with previous studies, the systems in this study are more complex and closer to the actual composition of brine. This study has identified that the common ion effect is the main cause of the solubility changes, the salt effect becomes more significant as the system studied becomes more complex. In addition, we also found that the effect of NaCl on MSZW was correlated with the concentration. The above conclusion can provide guidance for the development of boron resources in brine, such as the time of separation, the way of purification.
4. Conclusions very short and again no clear novelty recorded.
The conclusion has been rewritten.
Ones more thank you very much for your help.
Sincerely yours,
Prof. Yaping DONG
May 30, 2019
Reviewer 2 Report
Turbidity measurements are used for establishing crystal nucleation onset in systems containing Na2B4O7·10H2O in mixture of Na2CO3, NaCl and Na2SO4, chemical titrations and gravimetry being auxiliary methods. This is an interesting study; however, I miss the word crystals is in the Title. My recommendation is to change it as follows: Effects of anions impurities on solubility and nucleation of borax decahydrate crystals in carbonate-type brine
I noticed some mistakes:
- In the first equation (where the numbering (1) is missing): Tlim must be written in power 3. The same correction is obligatory for equations (4) and (5) as well.
- Correction is needed in line 67, eq. (2): the supersaturation ratio is S = clim/co (but not the reverse!), where clim and co are the actual and the saturation concentration of solute at a given temperature T.
I am recommending some amendments:
- Line 62: It should be added that the rate of nucleation (J) is the number of nuclei formed in a unit volume (1 cm3) for (infinitesimally short) nucleation time.
- Lines 218-219: ”Solid–liquid interfacial energy is an important thermodynamic parameter that indicates the ability of the solute to crystallize from solution.” My comment here is that because the solid–liquid interfacial energy is in power three in the exponent (nucleation energy barrier) of eq. (1), it affects tremendously the crystal nucleation rate - even interface energy variation of only 10% can alter the nucleation rate by orders of magnitude [e.g. see: Theory of nucleation. In Handbook of Crystal Growth, 2edit. Volume I, (Fundamentals: Thermodynamics and Kinetics); Nishinaga T, Ed; Elsevier: Amsterdam, 2015; p. 332].
- It should be noted that, due to its relatively low sensitivity, the XRD analysis is unable to detect trace amounts of anions.
I am not a native English speaker, but even for me, it is evident that language corrections are highly needed. I would like to point-out only some most glaring language mistakes, starting with the Abstract (as an example):
Measurements of the solubility and metastable zone width (MSZW) of borax decahydrate (disodium tetraborate decahydrate) within chloride, sulfate and carbonate solution were carried-out. The MSZW was measured by conventional polythermal method with turbidity technology. The results showed that the addition of impurities decreased the solubility, and the order of the effect was Cl-<SO42-<CO32-. The effect on the MSZW was different. The MSZW was wider at first, then decreased with the addition of NaCl; but the MSZW was widened with the addition of Na2SO4. Applying the classical three-dimensional nucleation theory approach, it was found that the addition of carbonate and hydroxide ions led to higher values of solid–liquid interfacial energy (γ) increasing, which indicated that the CO32- and OH- ions adsorb on the nuclei, thus suppress the nucleation rate.
Surprisingly, even verbs are missing in some sentences:
- Lines 23-24: … which usually is rich in lithium, …
- Line 258: move faster and increase nucleation rate, which is consistent with the changes of kinetic factor A.
Other mistakes may mislead some readers, which are not aware of all details in the crystal nucleation and growth theory (and practice):
- Line 48: MSZW is defined as the difference region between …
- Line 142: Because the supersaturation has obviously influences on nuclear determines the crystal nucleation speed rate, thus it is …
- Line 191: explained by different mechanism on the nuclear crystal nucleation process.
- Line 194: for crystal nucleation [19].
- Line 249: The presence of impurities will affect both the thermodynamics and kinetics of borax crystallization: both …
- Line 256: As the volume of these anionic groups is bigger, diffuse slowly than Cl- .
Also, some misprints must be corrected:
- Double numbering in Literature, e.g.: 3. 3.; 4. 4. ; 5. 5.; 6. 6.; etc. must be avoided.
- Line 176: Correct “Table 3” to Table 1.
My conclusion is: The paper presents novel results that may be of practical importance. Excluding some (pointed) faults, generally, authors’ conclusions are sound. So, after correction of the errors and addressing the recommendations, the paper is worth publishing.
Author Response
Respond to the reviews’
Thank you for your careful review. We have studied comments carefully and tried our best to revise the manuscript. We appreciate for Editors and Reviewers’ warm work earnestly and hope that the corrections will meet with approval.
1. About mistakes and language corrections.
We have revised the manuscript according to the comment. We also seek professional translation help, and we hope that the corrections will meet with approval.
2. It should be noted that, due to its relatively low sensitivity, the XRD analysis is unable to detect trace amounts of anions.
The purpose of XRD is to verify that the crystal precipitated from the solution is borax. As can be seen from the XRD pattern, all the precipitated crystals are consistent, which indicates that the impurity is not embedded in the crystal to change the lattice structure. Even if the separated borax contains impurities, it is caused by entrainment of the solution and has no influence on the result.
Ones more thank you very much for your help.
Sincerely yours,
Prof. Yaping DONG
May 29, 2019
Round 2
Reviewer 1 Report
Much improved paper. some minor issues:
formatting of figure 3 with title. Also could you discuss the repeatability of the results for fig. 3 and fig. 4. Reference need to be tidied up particularly, ref. 13, 16 and 18.
Author Response
Respond to the reviews’
Thank you for giving us a chance to revise the paper. The comments are very valuable and instructive to improve our paper. We have suitably addressed the comments and stated our opinions. We appreciate for Editors and Reviewers’ warm work earnestly and hope that the corrections will meet with approval. The revised portion is marked in blue in the revised manuscript.
Telephone numbers: +86-13639719919
E-mail: [email protected]
With Best Regards
Sincerely Yours,
Yaping DONG
Author Response File: 
Author Response.docx
