plante1999
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K2C2O6 , NaBO3 and review of chlorate based oxidation
Yesterday I read the book 'manifacture of chemicals by electrolysis''. In this book It was writen that electrolisis of potassium carbonate at -20
degree celcius was making the blue solid that was named ''Potassium percarbonate'' the name changed to Potassium peroxodicarbonate in 2000. This
compound have the formula K2C2O6 in the book it was writen that the action of HCO3- radical with a base (KOH) give the product in an electrolisis. If
we assume that the sodium salt could be made the same way it would be a realy good substitute to other oxidizer. Its acid is instable because it
decompose to H2O2 and CO2 falloing this equation:
H2C2O6 -) 2CO2 + H2O2
mixed with HCl would make an good substitute to nitric because the product of the reaction would be KCl , H2O , oxidized product and CO2.
K2C2O6 + 4HCl + Cu -) CuCl2 + 2KCl + 2H2O + 2CO2
In this book they was also saying that Sodium Perborate NaBO3.nH2O was eassier to make and by this fact was used in many application. It was made by
electrolisis of an solution of sodium tetra borate and sodium carbonate , some reference claim that the sodium carbonate is nessecery because of the
perxodicarbonate radical formation , which oxidise the tetraborate salt.
My main question is , does an mmo anode is able to make these salt?
my second question is , does perboric acid exist.
-------------------------------------------------------------------
Review of my research of the oxidation by ClO3-
I made about 100g of KClO3 and 50g of NaClO3 by electrolis and have ruine many copper wire and cm2 of mmo mesh by the corrosion. ClO3- is an realy
usefull DRY oxidiser , in the dry state it seem to decompose to oxygen radicals and K/NaCl , all my test confirm that almost all K/Na+ goes as K/NaCl
when KClO3 is mixed with C11H22O11 and ligthed with stoeichiometric amount of reactan.With some reductor , chlorine is one of the product and the K/Na
goes in the molecule of the reductor , exemple is the reaction of KClO3 and Cr2O3 which make Cl2 and K2Cr2O7 as major product. When in solution (Here
I used HClO3) it seem that when a reductor is mixed ClO2 is made and oxidise to the oxide the product (I use copper) to the oxide and chlorine is
produce , then the chlorine react with the oxide in presence of H2O to make the chloride the (copper) and small amount of oxygen. The final product
of the reaction is HCl , the chloride and oxygen. with some reductor the HClO3(aq) make ClO2 but the ClO2 is consumed to slowly and it acumulate in
the solution leading to an explosion.
Thanks!!!
[Edited on 2-1-2012 by plante1999]
[Edited on 2-1-2012 by plante1999]
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Bot0nist
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Is it potassium peroxodicarbonate
C<sub>2</sub>O<sub>6</sub><sup>2−</sup>
"Rubidium peroxodicarbonate is a light blue crystalline solid that decomposes at 424 K. Its structure was published in 2003. In both salts, each of
the two carbonate units is planar. In the rubidium salt the whole molecule is planar, whereas in the potassium salt the two units lie on different and
nearly perpendicular planes, both of which contain the O-O bond."
-wiki
U.T.F.S.E. and learn the joys of autodidacticism!
Don't judge each day only by the harvest you reap, but also by the seeds you sow.
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plante1999
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I will try to post the pdf of the book.
ok I uploaded it.
[Edited on 2-1-2012 by plante1999]
Attachment: The manufacture of chemicals by electrolysis 1919 - Hale.pdf (825kB) This file has been downloaded 425 times
I never asked for this.
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plante1999
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Quote: Originally posted by Bot0nist ![](images/xpblue/lastpost.gif) | Is it potassium peroxodicarbonate
C<sub>2</sub>O<sub>6</sub><sup>2−</sup>
"Rubidium peroxodicarbonate is a light blue crystalline solid that decomposes at 424 K. Its structure was published in 2003. In both salts, each of
the two carbonate units is planar. In the rubidium salt the whole molecule is planar, whereas in the potassium salt the two units lie on different and
nearly perpendicular planes, both of which contain the O-O bond."
-wiki | Yes it is.
Eureka!!! I find it! I think I find wath I made in this post:
http://www.sciencemadness.org/talk/viewthread.php?tid=15982#...
is sodium peroxodicarbonate.... I need to make some test to test my hypotesis...
[Edited on 2-1-2012 by plante1999]
[Edited on 2-1-2012 by plante1999]
[Edited on 2-1-2012 by plante1999]
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plante1999
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I run a cell containing a sol. of 120g Na2CO3 / 45g Sodium tetraborate and enough water to make the solution at 1000ml, the anode was normal
industrial MMO and cathode is MMO grade titanium metal (MMO anode with mmo coat removed) for 24hour , the cell was at 30 degree celcius. I tested for
perborate with TiCl3 sol. TiCl3 make a red sol with peroxide. And it did not make a red sol.... Wath can I do to make perborate? ( This cell is really
nice, it did not smell anything and can be run in the house).
Does PbO2 anode make perborate/persulfates?
Does a carbon anode in fluoride containing per-salts cell will make the wanted persalts?
Thanks!!!
[Edited on 6-1-2012 by plante1999]
[Edited on 7-1-2012 by plante1999]
[Edited on 7-1-2012 by plante1999]
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plante1999
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Sorry for making a triple post but I cannot edit my last post.
I found that for the production of H2O2 by electrolisis O2 is passed in a realy porrous cathode of carbon in electrolisis , Hydroxyl ion reduce O2 to
H2O2. H2O2 can than react with the NaBO2 in the cell to make NaBO3, sodium perborate at a sertain conssentration Perborate should precipitate. The
process should be less efficent than electrolisis with a platinum anode but it should work.
What do you think of this?
Thanks!!!
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garage chemist
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MMO anodes will not make any peroxo compounds during electrolysis.
To make peroxo compounds electrolytically, you have to use a platinum anode, or platinised titanium. No other anode material will do.
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plante1999
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I suppose there is substitute to platinum anode for making peroxo compound... PbO2 anode is able to make O3 which is more oxydising than H2O2 ...
[Edited on 9-1-2012 by plante1999]
[Edited on 9-1-2012 by plante1999]
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garage chemist
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You suppose? What does that mean? Do you have a working PbO2 anode? Not many people can claim this.
A platinum anode is a must have if you're serious about electrochemistry. I got myself a length of 0,5mm platinum wire very early, and it has made
several kilograms of sodium perchlorate over the years without measurably getting thinner. This is an investment that you won't regret.
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plante1999
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I have read a paper that cleam that a lead anode in dilute H2SO4 will make a low conssentration of ozone in the O2 from the anodic gas.As you
probably know, PbO2 is made when lead is used as an anode in dilute H2SO4. I did test it and it did make O3 gas, even a few seconds after starting
the smell of O3 was evident.
Maybe should I buy this:
http://www.ebay.ca/itm/Platinum-Iridium-80-20-002-wire-x-2-F...
Several kilograms of NaClO4, did you sell some of it?
[Edited on 9-1-2012 by plante1999]
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That wire is too thin, you won't be happy with it. Current density and ohmic resistance will be too high. Get a Pt wire that is at least 0,5mm thick.
I got some 0,3mm Pt wire first and it broke after bending a few times.
Also, while Pt/Ir is the ideal anode material for making perchlorates, it may not be the ideal anode for peroxo compounds. I have a german book on
electrochemical manufacture of hydrogen peroxide, peroxodisulfate and other peroxo compounds, and it specifies pure platinum as the only suitable
anode material. Pure platinum is the best choice for electrochemical experiments.
I still have most of my NaClO4, while some of it has been converted to other perchlorates.
To be fair, I have to add that I used pure commercial NaClO3 as the precursor. If you try to make NaClO4 directly from NaCl, the Pt anode will not
last long.
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plante1999
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Why not make NaClO3 from a mmo anode cell, purifying the Chlorate and than use it as a starting material?
Is this a better offer? How much cm should I buy?(I dont want to spand more than 35 CAD for this.
http://www.ebay.co.uk/itm/PLATINUM-metal-wire-99-999-PRICE-p...
[Edited on 10-1-2012 by plante1999]
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Pulverulescent
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Quote: | That wire is too thin, you won't be happy with it. |
Hair-thin? I near pissed myself . . .
Now just need to get some tea off the keyboard!
Even 0.5mm 70/30 Pt/Ir is a fucking pain!
Moderately conductive (easy to overheat with a couple of extra amps), brittle from the Ir content and difficult to effect a secure
connection!
Every time I handle mine, the number of 'bits' increases!
Fuck it, polished 0.5mm Pt foil is what I really need!
And lots of it? ( ) ( )
P
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plante1999
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Can I simply buy an 1.5-2 micron platinum plated titanium for making perborate? (My father said to my that if I re-made bleach odor(chlorate/bromate
cell)) I will need another place to do chemistry...
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plante1999
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I found this anode:http://www.ebay.ca/itm/Platinized-Titanium-Anode-2x3-/120724679996?pt=LH_DefaultDomain_0&hash=item1c1bc06d3c#ht_1575wt_1141
Can it work for this purpose (perborate production)?
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woelen
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This anode is exactly what I ordered and last weekend I received it. It looks well manufactured. The platinum is not shiny, but a dull grey, but it
adheres strongly to the underlying titanium substrate.
Right now I cannot use my lab (we are rebuilding part of our house and at the moment we have a big mess), but at the end of the month we hope to have
finished all the work and then I'll experiment with the anode and sure I will report on my experiences with that.
I know of someone who made a few pounds of perchlorate with this anode, so it certainly is suitable for electrochemistry.
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