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abrastein

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I have received two reviews of your manuscript. One reviewer suggests relatively minor revisions. However, the other reviewer has found that the manuscript does not provide sufficient new physical insight to warrant publication in the Journal of Physical Chemistry. I¡¯m sorry, but based on the serious concerns of this reviewer, I cannot accept your manuscript for publication at this time. However, if you believe that you can adequately address the concerns of this reviewer, then you are welcome to resubmit a revised version of your manuscript at a later date, in which case your manuscript will receive a new submittal date and new manuscript number.

Thank you for considering the Journal of Physical Chemistry for the publication of your manuscript.


With sincere regards,



------------------------------------

Reviewer(s)' Comments to Author:

Reviewer: 1

Recommendation: This paper is not recommended because it does not provide new physical insights.

Comments:
The referee was interested and also intrigued by the title of this paper which claims Ni UPD on iron. In fact, it sounded rather challenging to observe Ni UPD, i.e. depositing Ni at potential more positive than the standard Nernst potential ENi = -0.5 V/SCE corrected for the solution concentration. In such condition of polaization the Fe electrode is expected to be unstable as it dissolves (EFe = -0.71 V/SCE).

Page 2, bottom: arguing that C2 is a UPD process because it is more positive than wave C1 (assigned correctly to bulk Ni deposition) is essentially wrong. A UPD process, as is specified in introduction, refers to a deposition process that occurs at potential positive of the Nernst potential (here ¨C 0.5 V/SCE for Ni). Whatever its origin, peak C2 can, by no mean, be assigned to NI UPD.

As far as the reader understands the CV iare starting n Figs. 1-2 from U = - 0.7 V/SCE. At this potential the Ni film is stable but the Fe layer is not stable because one is too close to EFe. Hence Fe slowly dissolves before starting the CV with the Fe/316ss electrode. The observation reported in Fig.1 must therefore be attributed to the re-deposition of dissolved Fe together with Ni deposition. This phenomenon has nothing to do with Ni UPD on Fe. This is rather the opposite that is occurring.

As a consequence of this confusion, the purpose of the rest of the paper must be reconsidered.

Other comments:
- Define acronym PQR. Page 2, ¡ì related to QCMB.

Conclusion:
In conclusion the paper must be rejected.

Reviewer: 2

Recommendation: This paper is publishable subject to minor revisions noted. Further review is not needed.

Comments:
The manuscript is dealing with a very intersting subject, the deposition of a metal and surface alloying on foreign substrates.
However I have some remarks before publication seen below.

In Fig. 1 and 5, what exact is the meaning of A1? Why is the dissolution charge so low in comparison to deposition? It would be helpful if the current yields are calculated.
especially in Fig. 5.
Can one assume that the Ni Dissolution is accompanied by passivation or the Ni UPD is accompanied by hydrogen evolution respectively?
Would the latter side reaction explain the more than 100 fold charge consumption during deposition in comparison to monolayer formation.
Why the presence of Iron ions reduces the Ni UPD as well if one assume an alloy formation? In a couple of cases the alloy deposition should be preferred compared to the single components?

[ Last edited by abrastein on 2010-5-16 at 08:31 ]
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