Electrochemical overpotentials (V3+/V4+ redox)

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Discussion Overview

The discussion centers around the topic of electrochemical overpotentials related to the redox reaction of vanadium species, specifically the reduction of vanadyl cation (V4+) to vanadium (V3+) at carbon or graphite electrodes. Participants seek data and methods for estimating overpotentials associated with this reaction.

Discussion Character

  • Exploratory
  • Technical explanation
  • Debate/contested

Main Points Raised

  • One participant requests sources for overpotential data on carbon/graphite electrodes for the reaction V4+ + 2H+ + e- <-> V3+ + H2O, specifically looking for overpotential values.
  • Another participant provides a potential of +0.34V vs. SHE for the reduction of the vanadyl cation to V3+, suggesting a possible connection to vanadium redox flow batteries and shares several literature references for further exploration.
  • A participant notes the limited data available for the VO2+ to V3+ transition, observing that some articles indicate a larger overpotential for this redox pair compared to other vanadium redox pairs like V3+/V2+ and V5+/V4+.
  • Another participant agrees with the observation of limited data and emphasizes the importance of using half-reactions that are well-separated in potential when dealing with common redox ions.

Areas of Agreement / Disagreement

Participants express a shared understanding of the limited data available regarding the VO2+ to V3+ redox pair and agree on the implications of overpotential differences among various vanadium redox pairs. However, there is no consensus on specific overpotential values or methods for estimation.

Contextual Notes

Participants mention the need for further literature review and the potential influence of electrode material on overpotential values, indicating that the discussion may be limited by the availability of empirical data and specific experimental conditions.

tinska.h
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Hey,

Does anyone know a good source for overpotentials on carbon / graphite electrodes? Especially looking data for V4+ + 2H+ + e- <-> V3+ + H2O (+0.34V vs. SHE) overpotential. Or are there any ways to estimate the overpotentials?

Thanks
 
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I'm going to take a stab at this, but I don't know how much help I can be with your specific question. So it looks like the reaction you're looking for is reduction of the vanadyl cation to V3+.
$$VO^{2+} +2H^+ + e^- \rightarrow V^{3+} + H_2O$$
This is the reaction that I found with a potential of +0.34V vs. SHE. This means maybe you're looking for information about cross-contamination in vanadium redox flow batteries? A quick lit search yields a few papers that may be of some interest:
http://pubs.acs.org/doi/abs/10.1021/la00009a054
http://ecst.ecsdl.org/content/35/32/11.short
This last one has kinetics info about vanadyl reduction, but nothing specifically on overpotentials.
http://onlinelibrary.wiley.com/doi/...ionid=9952D8759BBB8B5B3D01A5E8277E1316.f04t01
This one is as close as I've gotten: it's a system looking specifically at the reduction of VO(acac) to V(acac) in an acidic acetonitrile environment over glassy carbon electrodes. You might want to follow the references from this one.
Sorry I couldn't be of more help. Best of luck.
 
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Hey, Thanks for your effort!

Yeah it seems that there's very limited data regarding VO2+ -> V3+. I saw few articles where the graphs indicated much larger overpotential for the VO2+ and V3+ redox pair compared to V3+/V2+ and V5+/V4+.
 
tinska.h said:
Hey, Thanks for your effort!

Yeah it seems that there's very limited data regarding VO2+ -> V3+. I saw few articles where the graphs indicated much larger overpotential for the VO2+ and V3+ redox pair compared to V3+/V2+ and V5+/V4+.
This makes sense. You'd want to use half-reactions that are well-separated in potential if they're going to have a common redox ion.
 
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Likes   Reactions: jim mcnamara

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