Dissolved oxygen related to redox potential

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Discussion Overview

The discussion revolves around the relationship between dissolved oxygen and redox potential, particularly in the context of iron oxidation in water used in industrial boilers. Participants explore the implications of redox potential on iron chemistry and the potential for reduction reactions in anaerobic conditions.

Discussion Character

  • Exploratory
  • Technical explanation
  • Conceptual clarification
  • Debate/contested

Main Points Raised

  • One participant suggests that removing dissolved oxygen lowers the redox potential, which may prevent Fe+2 from oxidizing to Fe+3.
  • Another participant argues that redox potential may not be as significant, asserting that oxygen is a strong oxidizer and can oxidize iron even at low concentrations, referencing the Nernst equation.
  • A participant acknowledges the limiting reactant concept regarding oxygen and its role in iron oxidation.
  • Questions are raised about the potential for Fe2O3 to convert to Fe3O4 in an anaerobic solution and whether this could involve electron transfer from water, particularly under low redox potential conditions.
  • Another participant responds that the reaction is not straightforward but suggests that Fe2O3 could reach equilibrium by interacting with water, potentially converting some to Fe3O4.

Areas of Agreement / Disagreement

Participants express differing views on the significance of redox potential in the oxidation of iron and the role of dissolved oxygen, indicating that multiple competing perspectives remain without a clear consensus.

Contextual Notes

Participants note the complexity of the reactions involved and the importance of stoichiometry, as well as the need for equilibrium considerations in the proposed reactions.

Who May Find This Useful

This discussion may be of interest to those studying redox chemistry, industrial applications involving iron, or the effects of dissolved gases in aqueous solutions.

Rexmundi
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I have read a little bit about some industries deaerating water used in boilers made of iron to prevent them from becoming damaged.

I think this is because removing dissolved oxygen from the water lowers its redox potential. I think that this works because once the redox potential of the surrounding environment is lowered past a certain point it is no longer possible for Fe+2 to oxidize into Fe+3.
Am I right about any of this?

I was also wondering about the reverse reaction, I have read a little bit about using electrolysis for this. If I had some other method of lowering the redox potential of the system far enough would the Fe+3 go back to Fe+2?

I'm sure I shouldn't be I'm sort of thinking of this as a parallel to melting point/boiling point.
 
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Rexmundi said:
I think this is because removing dissolved oxygen from the water lowers its redox potential.

I don't think potential plays important role here. Oxygen is an oxidizer strong enough to work on iron even in very low concentrations. It can be easily calculated from Nernst equation, at the moment I am only referring to my intuition. Call it an educated guess.

However, if you take a look at the reaction stoichiometry, it becomes obvious that amount of iron oxidized is limited by the amount of oxygen present. Less oxygen present, less iron oxidized.

--
methods
 
Okay I see the oxygen as a limiting reactant idea now and that makes sense, it's simpler than I was making it out to be.

I'll try to restate the second part of my question.

If I had some Fe203 in an anaerobic solution could it change to Fe304?
Could it take an electron from H20 somehow?
Would it help if the redox potential of the solution was very low?

Sorry if this is nonsense, I have not taken a chemistry course in a long time and do not really know how these things work.
 
The answer is not straightforward, but simple in that it would attempt to reach equilibrium:
Yes, it could steal things from water (O, H or electrons and break up an H2O)
A solution of Fe2O3 would change some to Fe3O4 as needed to reach equilibrium

Your boiler situation is a little different, you are oxidizing zero-valent iron (Fe) to other states (both Fe2+ and Fe3+) depending on redox potential.
 

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