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Author: Subject: Elemental sulfur from sulfates
shannon dove
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[*] posted on 27-11-2012 at 10:35


My explanation is a rotten egg smell coming from a lead acid battery.
but this might be caused by lead sulphate getting hot with reduced lead. Usually when my car battery starts making hydrogen sulphide smell, its going bad.
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elementcollector1
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[*] posted on 27-11-2012 at 10:44


Empirical evidence is always a good start.
I couldn't find any evidence of car batteries emitting H2S, but perhaps I haven't been looking hard enough. It would be a useful method, however (although my stomach turns at using my conc. sulfuric acid, when poor chemists in other states don't have any acid).
The only related thing I could find is "sulfation", when stable, crystallized lead sulfate collects in a car battery instead of turning back to lead metal or oxides, leading to the loss of useable lead.




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shannon dove
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[*] posted on 27-11-2012 at 11:37


I can't find the book right now, but I can assure you that it said that both hydrogen sulphide and elemental sulphur can be made by electrolysis of sulphuric acid. I read it over and over again just to make sure I was understanding correctly. If my memory is right, the sulphur and hydrogen sulphide formed on the anode.
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[*] posted on 27-11-2012 at 11:44


I'll have to try that when I have the time! Incidentally, what if anything did it say about other sulfates?
Now is a great time for me to figure out a gas-capturing electrode...




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[*] posted on 28-11-2012 at 01:47


Quote: Originally posted by shannon dove  
I read in an old chemistry book that sulphuric acid can be electrolyticly reduced to elemental sulphur or hydrogen sulphide depending on acid concentration, amp density and temperature. Unfortunately, after hundreds of hours of searching, I could not find a similar electrolytic reaction to make elemental phosphorus from phosphoric acid. Can anyone explain why sulphuric acid can be electrolyticly reduced to elemental sulphur, but phosphoric acid cannot be reduced to elemental phosphorus by electrolysis. ?


Because phosphorus is a stronger reducer.
From:
http://www.webelements.com/sulfur/compounds.html
in acid solution, the electrode potential of HSO4/S is not expressly shown, but easily computes as +0,39 V. The electrode potential S/H2S is smaller but also positive at +0,14 V.
From
http://www.webelements.com/phosphorus/compounds.html
in acid solution, the electrode potential of H3PO4/P is not expressly shown either but also easily computes, as -0,412 V. The highest reduction potentials of H3PO4 are actually the expressly shown H3PO4/H3PO3 at -0,276 V and the not expressly shown but easily computed H3PO4/PH3 at -0,281 V.

So. In acid solution, cathode can reduce sulphate first to sulphur and then to hydrogen sulphide.

Under the same conditions, cathode cannot reduce phosphate because it reduces protons first, and ALL forms of phosphorus save phosphoric acid are unstable against reducing hydrogen from acids.
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[*] posted on 1-12-2012 at 18:02


Can we get it to reduce just to sulfur and not H2S? This would probably require specific conditions, but give the end-product with less reactants involved.



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AJKOER
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[*] posted on 1-12-2012 at 18:41


Note, the following reactions (see http://books.google.com/books?id=25qJbzc1wMEC&pg=PA83&am... ):

2 HI + H2SO4 --> SO2 (g) + I2 (s) + 2 H2O

6 HI(g) + SO2(g) --> H2S(g) + 3 I2(s) + 2 H2O

So heating an excess of Oxalic acid (or Tartaric or Citric acid) with an excess NaI with CaSO4, for example, may produce H2S which can be reacted aqueous NaOCl (or SO2) to produce Sulfur.

[Edited on 2-12-2012 by AJKOER]
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elementcollector1
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[*] posted on 1-12-2012 at 18:51


I liked the electrolysis of sulfuric acid because it required so few reagents, just sulfuric acid, bleach and electricity. It would have been even better to use a sulfate such as magnesium or calcium.
NaI is hard for me to procure, the closest analogue would be KI which I could probably extract from tincture of iodine.
Oxalic acid? I just ran out of that...




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shannon dove
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[*] posted on 15-12-2012 at 16:32


I have already said this before, but I will talk about it again because it pertains to this. Bacteria can reduce sulfates to hydrogen sulphide. Landfill gas contains a little hydrogen sulphide. Some of it comes from decomposing plant and animal, but some of it comes from bacteria reducing sulphates especially calcium sulphate wall board in construction debris.
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