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Author: Subject: Wierd reaction in chlorate cell
Deluxbert
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[*] posted on 24-4-2017 at 09:20
Wierd reaction in chlorate cell


So i started a chlorate cell because I now finally have the electrodes to do that.

Problem was that I really needed to clean up my psu(smelled burny) so I had to shut the whole cell down after ~6 hours of running at 5v 2.5A

Today i readded the electrodes and for some reason the MMO (Iridium Ruthetium oxide on titanium) started bubbling even though there was no connection at all (Not between the anodes or psu)

Could this be an indication that the anode is a fake? Or is this a catalyzed reaction?
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Deluxbert
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[*] posted on 24-4-2017 at 09:25


Also whats to note is that both electrodes are not magnetic and the one that should be pure titanium isnt bubbling at all.
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AJKOER
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[*] posted on 28-4-2017 at 08:27


To be honest, I do not theoretically or, in practice, advocate an electrolysis path to chlorate.

Theoretically problematic as there is some radical chemistry afoot, just as is occurring in my thread promoting a photolysis approach (see, for example, my discussion at https://www.sciencemadness.org/whisper/viewthread.php?tid=34... , which I detail and mostly understand), plus more. I have seem only one attempt to indicate the likely precise mechanics of the chlorate formation pathway via electrolysis. Also, electrolysis is inherently slow by nature, and chlorate yield may depend on solution temperature and pH control.

So, we have a not so clearly understood, or documented, slow pathway to start with, and now seemingly an unexplained reactions with your new electrodes. I, for one, am not surprised and can offer limited insight.

Also, this electrolysis method to chlorate is so popular, and expected by legal authorities, that even the main ingredient, KCl, when sold in large bags as a water softener, may be a watched/flagged purchased. With respect to equipment also, last year in Radio Shack, I was buying clips and wiring to perform an electrolysis path to CuSO4, on which I was asked about the purpose of my endeavors, that I explained to the sales representative.

Do better, use solar light or your microwave oven, in a faster, cheaper, more understood and discrete path to chlorate, which I am still aiming to improve!

So, we have a little understood or known process and a possible quality issue with respect to the electrodes, to which something strange appears to occur. But is 'unknown' + 'uncertain' + 'strange' = 'weird' ?

[Edited on 28-4-2017 by AJKOER]
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softbeard
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[*] posted on 28-4-2017 at 11:12


Quote: Originally posted by AJKOER  

Do better, use solar light or your microwave oven, in a faster, cheaper, more understood and discrete path to chlorate, which I am still aiming to improve!


I'll probably regret asking this, but just how do you make chlorates with a microwave oven?
With sunlight, at least you can have it shine on a solar cell to make DC current, then use that to electrolyze an aqueous chloride solution.

Seriously, if anyone can improve on the Chlor-Alkali industry's ~130 year-old electrolysis process, they'll be instant billionaires.

Making chlorates through chloride electolysis is slow because it takes 6 moles of electrons for each mole of chlorate formed. That requires a lot of amps or long time periods, or both. 106.4 g of NaClO3 (1 mole) at 1 amp requires 579,000 sec = 160.8 hrs = 6.7 days @ 100% efficiency.

If you could use 'sunlight'to convert chloride to chlorate, you'd still need a huge number of photons and time, unless you can circumvent conservation of energy somehow.
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AJKOER
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[*] posted on 30-4-2017 at 04:20


Read my cited thread and references, especially with respect to the path to chlorate promoted by radical formation.

A short example with aqueous dinitrogen oxide (N2O is sold in stores having some popular demand being able to infuse flavors into drinks) and any formed solvated electrons:

N2O + e-(aq) ---) N2 + .O-

.O- + H2O = .OH + OH-

where the last reaction moves to the right except at very high pH.

The solvated electrons to promote the above reaction can be formed via many paths including UV photolysis of N2O, solar light on photo active metal oxides (TiO2, ZnO, MgO, FeOOH..), radiation, irradiation via micro waves, electrolysis,....

Access to cheap NaCl, electrical power and scale considerations are why electrolysis is a commercial favorite. For today's home chemist, I would assume that discreet access to ingredients (discretion can help avoid the need for bail money, legal fees,...) utilizing a non-traditional path, relatively low costs, and time to completion would be driving factors (or, at least, should be).

I would note if there is an electric service disruption, there still may be some sunlight available (use it as you will):D.

[Edited on 30-4-2017 by AJKOER]
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