Mechanism and Kinetics of Interaction of FLiNaK–CeF3 Melt with Water Vapors and Oxygen in the Air Atmosphere
Round 1
Reviewer 1 Report
Overall, the authors studied the mechanism and kinetic parameters of the interaction of the FLiNaK - CeF3 melt with water vapors and oxygen in the air atmosphere by using Raman and IR spectroscopy, XRD, FTIR, and thermodynamic modeling processes. The FLiNaK - CeF3 melt with water vapors and oxygen interactions were conducted in the Raman device in situ with varied times and temperatures to see the temporal changes. Clear changes can be observed due to the newly formed CeO2. Based on the obtained spectral data, the type of the kinetic equation, order and rate constant of the chemical reaction were determined. The concentration of cerium dioxide was found to increase linearly in time and zero reaction order with respect to CeO2 was detected. By combining different characterization methods, the authors cross-verified the formation of CeO2. Followed by a thermodynamics modeling to find out the reaction pathways, the authors also studied the kinetics of CeO2 formation which can provide useful information for future metal fluoride melts study.
Comment 1: REM in line 31, page 1 should be written in the full name.
Comment 2: Can the authors put the XRD graph together for samples before air treatment and after air treatment? This will better showcase the newly formed peaks of CeO2.
Comment 3: The authors fixed the H2O and O2 content for all the experiments. What will happen if the compositions of H2O and O2 change?
Author Response
Response to Reviewer 1 Comments
Point 1: REM in line 31, page 1 should be written in the full name.
Response 1: Done
Point 2: Can the authors put the XRD graph together for samples before air treatment and after air treatment? This will better showcase the newly formed peaks of CeO2.
Response 2: XRD graph together for samples before air treatment and after air treatment was added to the manuscript
Point 3: The authors fixed the H2O and O2 content for all the experiments. What will happen if the compositions of H2O and O2 change?
Response 3: We are grateful to the reviewer for drawing our attention to this aspect. Hypothetically, with an increased content of water vapor in the atmosphere above the melt, in addition to cerium dioxide, one can expect the formation of cerium oxyfluoride CeOF in accordance with reaction 3 (Table 1 of the manuscript).
The authors thank the reviewer for an interesting idea that appeared - to carry out a separate study of the interaction of fluoride melts with water vapor.
Reviewer 2 Report
The manuscript deals with a nice study on the mechanism and kinetic parameters of interaction of the FLiNaK - CeF3 melt with water vapors and oxygen in the air atmosphere through the joint use of Raman scattering, IR absorbance, XRD analysis, and thermodynamic modeling of processes. The authors verified the presence of the reaction 4 CeF3 (solution) + 6 260 H2O(g) + O2(g) = 4 CeO2(s) + 12 HF(g) that disturbs the homogeneity of the fluoride melt.
The manuscript is well written resulting clear also for non expert readers. The spectroscopic data are well presented and discussed. The conclusions are self - consistent.
I suggest the authors to add some more detail in the conclusion paragraph that is to much "summarising".
In conclusion I believe that the manuscript deserves publication on the journal Processes after this minor revision.
Author Response
Response to Reviewer 2 Comments
Point 1: I suggest the authors to add some more detail in the conclusion paragraph that is to much "summarising".
Response 1: Details are added to the conclusion paragraph
