Author Topic: Insitu formation of Peroxyacids  (Read 107 times)

Sedit

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Insitu formation of Peroxyacids
« on: May 04, 2009, 07:41:37 PM »
Formation insitu of the formic or acetic acid from there respective sodium salts was always something that interested me because I never felt that the formed sodium sulfate from neutralization would interfere in subsequent reactions to form the peroxyacid of acidic. I have come across this text fairly recently and it seems to support what I always believed anyway and thats these peracid species can be generated insitu from the desolved salt of the organic acid.

My original thought was that Acetic acid could be liberated by the addition of sulfuric acid and converted to the peracid without further purification. It appears from the the paper[1] that it may not even be needed to liberate the salt seeing as how it disassociates in an aq solution to the respective cation and anion anyway.

Quote
In aqueous solution dissociation of borax occurs in the following manner:
Na2B407 + H20 <--> 2Na + 2BO2 + 2HBO2
When hydrogen peroxide is added to borax solution, the borate species are
converted into their peroxy forms.

I see no reason that this would not work the same with formates and acetates as it does with a borax solution. What is every ones thoughts on this and if someone where to test this with sodium acetate the smell of peracetic acid should make it self known after its formation correct.


Reference:
[1] http://127.0.0.1//sedit/MISC/PerborateInSitu.pdf

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Enkidu

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Re: Insitu formation of Peroxyacids
« Reply #1 on: May 05, 2009, 12:44:16 AM »
I can't find much about these "boron species." Does the 'acid'  look like this: HO-B=O? What's the common name for it?

Edit: Here's the wiki page for sodium perborate. So apparently that's what they mean.

I don't see why it will work for formic or acetic acid, though. (I mean, it might.... but...)
« Last Edit: May 05, 2009, 01:06:03 AM by Enkidu »

Douchermann

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Re: Insitu formation of Peroxyacids
« Reply #2 on: May 05, 2009, 01:18:04 AM »
I'm with enkidu, I have doubts that it would work.  I don't have any sodium acetate on hand though, so I can't try.

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Re: Insitu formation of Peroxyacids
« Reply #3 on: May 05, 2009, 01:20:03 AM »
Iv been looking my self Enkidu and Im pretty sure that its just the formation of sodium perborate the way they discribe the disassociating is throwing me off though because its the only reference I can find to sodium borate disassociating like that. Ill post more I have to go do something at the moment.


edit.

I feed it would work thru the oxidation of the AcOH species to AcOOH ..........
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Re: Insitu formation of Peroxyacids
« Reply #4 on: May 05, 2009, 02:26:40 AM »
Sorry about that....

But what I was thinking was when the salt of AcOH disassociates in H2O we end with AcO- , Na+ , H+ and -OH correct? I dont find it a stretch to see AcO- getting oxidised in the presents of H2O2 to AcOO which normaly happens anyway when AcOH is put into solution with H2O2.  The only difference here is instead of the disassociation looking like this (AcO-/ +H) it looks like this (AcO-/ Na+)
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Douchermann

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Re: Insitu formation of Peroxyacids
« Reply #5 on: May 05, 2009, 04:28:15 AM »
Well, peroxyacetic acid doesn't form unless in the presence of H2SO4 (or at least a lower pH).  If you add stoicheometric quantities of H2SO4 to Na acetate, you'll be right where you started if you went with glacial acetic acid, except there will be a bunch of sodium sulfate mixed in which might make purification more difficult.  Formates might be an option though

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Re: Insitu formation of Peroxyacids
« Reply #6 on: May 05, 2009, 05:43:33 AM »
LOL

Yup were on the same exact page Doucher. I went to attempt a little bit and the second the sulfuric catalyst his and fizzed a tinybit I thought...... Aww wtf. :-[.  So just like you said I quickly came to the logic of using formates and since my recent oxidation of ethanol to acetic acid went well enough I think an ozone generator is in order to eatup some MeOH and spit out some formates so I can get on with this. Also perborates have been used to make very concentrated solutions of Peracetic acid without the waiting game and an acid catalyst so that could be an option here also that a solution of perborates+acetates= peracids.


Thing bout the sodium sulfate like you mentioned is as long as the H2O2 don't interfere when the peracid is set and forming alot of the sodium sulfate will drop right out in large crystals due to its step and strange solubility curve. Its kind of cool to watch a large amount form giant crystals out of a solution honestly. Its one of the only substances I know of whos solubility goes up with the temp until it reaches a point where it goes down for a few degrees.
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Douchermann

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Re: Insitu formation of Peroxyacids
« Reply #7 on: May 05, 2009, 04:01:36 PM »
Ozone generator or oxalaic acid/glycerin.  I never used my ozone generator on methanol... or chemistry for that matter, perhaps I should start!  Oxalic acid and glycerine works quite well, but be warned - formic acid is freakin nasty stuff. 

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Re: Insitu formation of Peroxyacids
« Reply #8 on: May 05, 2009, 05:03:39 PM »
I know Iv worked with the oxalic acid/glycerol before to it is some nasty shit. Im looking for a reason to test making formic from methanol what a better reason. ;D. If you check in my short experiment threed there is a paper that talks about the ozone oxidation a bit and the yeilds on that dont look bad at all.
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Vesp

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Re: Insitu formation of Peroxyacids
« Reply #9 on: May 06, 2009, 02:46:30 AM »
Potassium permanganate might yield formates when mixed with methanol or formaldehyde, so that might be something to consider.
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Re: Insitu formation of Peroxyacids
« Reply #10 on: May 06, 2009, 02:49:15 AM »
It will but I cant find any potassium permanganate anymore. I use to have a large jug full but that got used by my family sometime ago and when I went to get more I cant find any place that carrys it all though alot claim to. Kind of pisses me off since its a nice universial oxidiser so to speak and yet I dont have any :-[
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Re: Insitu formation of Peroxyacids
« Reply #11 on: May 06, 2009, 02:57:52 AM »
I see, well that is unfortunate. 
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Douchermann

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Re: Insitu formation of Peroxyacids
« Reply #12 on: May 06, 2009, 04:00:43 AM »
Got an ACE hardware near you?  They all sell it.

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Re: Insitu formation of Peroxyacids
« Reply #13 on: May 06, 2009, 04:16:59 AM »
What brand name am I looking for? Im a damn plumber and yet these fools cant pull up PP for me. They look at me half retarted and say uhh we dont have that ... ... Its retarted I tell you. Im sure if I rattled of a name they would have it for me in a few seconds.
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Re: Insitu formation of Peroxyacids
« Reply #14 on: May 06, 2009, 05:12:18 PM »
Look for 'filter mate' I believe it was.  It's used for regenerating water softeners and can be found in the same area as the ROOTO.  It's not a set brand name, because at one ACE hardware, it said "potassium permanganate" right on the bottle, and on another one about 7 miles away, it was pretty inconspicuous.  If it says for water softeners, read the back and it will usually give you some hits.  If it says absolutely nothing, open it up while the associates aren't looking.  You'll be able to tell PP from other popular water softener chemicals.