Sciencemadness Discussion Board

Ferric oxalate to ferrous oxalate

veerenyadav - 20-5-2014 at 01:57

how to convert ferric oxalate into ferrous oxalate

gdflp - 20-5-2014 at 11:00

Firstly you should be more specific about your question. Secondly, this belongs in Beginnings not Organic Chemistry. To convert it, dissolve the ferric oxalate in water, add an equivalent stoichometric amount of sodium hydroxide, then bubble hydrogen gas through the mixture, the ferrous oxalate will precipitate out. The balanced equation is Fe2(C2O4)3 + 2NaOH + H2 --> FeC2O4 + Na2C2O4 + 2H2O

woelen - 20-5-2014 at 11:32

Are you sure that bubbling hydrogen through the solution does the reduction? I strongly doubt it, actually I can hardly believe this. Hydrogen gas is quite inert and does not easily react with oxidizers in aqueous solution. Maybe this reaction with ferric oxalate is a rare exception, but if this indeed is the case, then I would like to see from where you have this information, or experimental evidence.

CHRIS25 - 20-5-2014 at 12:18

Ah photography knowledge here - ferric oxalate can decompose to ferrous oxalate through sunlight. Faster still use a UV lamp.

gdflp - 20-5-2014 at 13:02

This page gives a reduction potential of -0.83 for the reaction 2H2O + 2e- --> H2 + 2OH-. I would assume from this that the reaction would occur since it has a negative delta G.

woelen - 20-5-2014 at 23:05

Reduction potential only tells something about the energy needed for (or released by) a reaction. It does not tell anything about a mechanistic pathway for the reaction to occur. So, energetically, a reaction may be favorable, but it might be that in reality the reaction needs a large activation energy.

A nice example is combustion of wood. This is a highly exothermic process, but it does not occur spontaneously. First, some activation energy must be supplied. Usually this is done by heating part of the wood and the heat of the reaction then is the activation energy for other parts of the wood (activation energy is not lost, it is returned after the reaction), so the net effect is highly exothermic.

With H2 I expect the same. I do not expect it to react just by bubbling through the solution. You need some activation energy (heat, intense radiation), or you need to modify the mechanistic pathway for the reaction (suitable catalyst) such that its activation energy is lowered.

veerenyadav - 21-5-2014 at 04:15

Thanks all, but

Actually, I have ferric oxalate green solution. Addition of NaOH add one more compund in solution that is sodium oxalate. I want pure ferrous oxalte to precipitate.

I used UV or sun light but it is a bit slow and do not have any idea about its commericla scale application. So searching some reducing agnet which should not add any impurity in ferrous oxalate like H2O2 for oxidation.

So, suggest some thing which can help me.

veerenyadav - 21-5-2014 at 04:18

Thanks all, but

Actually, I have ferric oxalate green solution. Addition of NaOH add one more compund in solution that is sodium oxalate. I want pure ferrous oxalte to precipitate.

I used UV or sun light but it is a bit slow and do not have any idea about its commericla scale application. So searching some reducing agnet which should not add any impurity in ferrous oxalate like H2O2 for oxidation.

So, suggest some thing which can help me.

gdflp - 21-5-2014 at 05:27

Sodium oxalate is soluble in water and ferrous oxalate is insoluble, so the two are very easy to separate. Just filter and wash with water, there will be no measurable residual sodium oxalate left.

blogfast25 - 21-5-2014 at 09:56

Quote: Originally posted by gdflp  
This page gives a reduction potential of -0.83 for the reaction 2H2O + 2e- --> H2 + 2OH-. I would assume from this that the reaction would occur since it has a negative delta G.


I even doubt that it has a negative Delta G because I'm pretty certain you were looking at the reduction potential for Fe<sup>3+</sup> + e ===> Fe<sup>2+</sup>.

But here the iron (III) is present as trisoxalato ferrate (III), a complex. Complexes are much harder to reduce, depending on complexation (formation) constant, because it [the complexation] adds an endothermic term to the Delta G calculation.

And as woelen said: a negative Delta G still wouldn't prove the reaction would be practical. Hydrogen gas is pretty inert at RT.

[Edited on 21-5-2014 by blogfast25]