White Yeti
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On the peroxidation of acetone using fenton's reagent
I'd like to start out by mentioning one thing, I don't enjoy dealing with explosives, I would rather be handling poisons instead, because they don't
throw shards of glass at you without warning. I am not trying to make explosives I was just wondering if this alternate method would work. If it does
work, it would provide a cheaper way to make TCAP for anyone interested in blowing things up.
Ever since someone told me about fenton's reagent, I have constantly been trying to find uses for it (aside from the disposal of waste). I have used
it in an aluminium battery to increase performance by a factor of 10. I also believe that there are many other uses that have not yet been
investigated, but that still look promising.
So, if fenton's reagent works by ripping off a hydrogen atom from organic molecules, freeing up a space on the carbon, would the combination of
fenton's reagent and acetone yield explosive acetone peroxide?
I wasn't sure where to post this topic because it's a little bit of OC and a little bit of energetic materials chemistry.
What do you guys think?
Where's the catch?
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Bot0nist
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I don't
understand. Fentons is just a solution of peroxide with an Fe catalyst, right? Cheaper because you would not need to acidify? Anyways, TCAP really
sucks all around. It fails in storability, sensitivity, and performance. It's a crappy by product of chemistry and should be avoided, IMHO.
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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White Yeti
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It would be cheaper because you wouldn't need to buy citric acid. The price of the catalyst is negligible in the grand scheme of things. I know TCAP
is aweful, but would this reaction work?
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Bot0nist
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I don't know.
I have heard of using sulfuric. Couldn't citric or sulfuric be recovered without to much difficulty? Plus, as long as your h2o2 is of sufficient
concentration the acids are only used in catalytic amounts.
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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Nicodem
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You can not have a nucleophilic addition of the peroxide on the carbonyl group of the acetone if you add a catalyst that catalyses competing radical
reactions in which the peroxide is consumed (the oxidation of acetone). This should be obvious, I would guess. Why would you want to add something in
a reaction mixture that would promote competing reactions? Furthermore, if the desired reaction is reversible, like is the case here, then the
conversion is zero when you add a catalyst that promotes the competing reactions.
Though, I agree that adding an iron salt into a mixture of hydrogen peroxide and acetone could be an interesting pedagogic demonstration on how a
runaway reaction looks like. But I think there are safer demonstrations of runaway situations available.
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bbartlog
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Fenton's reagent tends to oxidize things to the limit (like, CO2) barring exhaustion of the oxidizer (H2O2) or removal of the substance being acted on
(by precipitation or vaporization). So one problem you would see is that your desired product would be destroyed as it was created (assuming it was
created at all). Anyway, without looking in detail into the mechanisms involved in TCAP synthesis I would think that it does not involve using the
oxidizing power of the peroxide, rather maintaining it while joining the molecule to the acetone; whereas with Fenton's reagent you are using it up,
so to speak. I don't think your idea will work.
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White Yeti
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Thanks for the info!
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Rosco Bodine
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For what would you need citric acid anyway ?
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White Yeti
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For catalysis.
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Rosco Bodine
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That's a new one on me, where are you getting this? Maybe you are thinking of EDTA instead ? EDTA reportedly can be used as a catalyst for tetrameric
acetone peroxide, as an alternative to SnCl2 or SnCl4. The only thing I recall about citric acid is for use as a byproduct ammonia neutralizer for
HMTD.
[Edited on 10-9-2011 by Rosco Bodine]
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AndersHoveland
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Fenton's regent to try to make acetone peroxide makes absolutely no sense.
Fenton's regent will attack/oxidize the rest of the acetone molecule, but will not peroxidate the ketone group.
I have also read of using tetramine copper salts to catalyze oxidation using H2O2.
Supposedly this is a much milder combination than Fenton's regent, but it still can oxidize hydrocarbons.
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AndersHoveland
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I mixed 3 parts 30% H2O2 with 1 part 70% ethanol, then added some steel wool. After several minutes no reaction was observed, only very slight
bubbling on the steel wool.
Then I added a few drops of ferric chloride solution. Note: only a few drops. The H2O2/ethanol mix was about 200mL, inside a 1L plastic bottle.
After a few seconds the solution turned brown. The bubbling became very vigorous. The reaction rate seemed to increase without bound.
The cap was loosely put on to keep the ethanol vapors from escaping, but still allowing the pressurized gas to vent off.
The plastic bottle EXPLODED! It ripped into two, and one piece was hurled ten meters away. There was a spray everywhere, and everything smelled like
vinegar, with hints of ethanol and another unidentified smell. The explosion had a deep "boom" sound, so it was certainly not the liquid detonating.
It could have been an oxygen gas- ethanol vapor explosion. Or perhaps the rate of oxygen formation got out of control and built up pressure faster
than it could escape.
I had hoped to make glyaldehyde from this, which I was going to react with NH4OH, which along with the acetic acid, would hopefully have caused
2-methylimidazole to form. But it never got that far.
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bbartlog
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A problem with threaded caps in a situation like this is that internal pressure can cause them to seal (mashing them against the threads) even if they
were loose at first. It would make more sense to use no cap and (if the anticipated exotherm is great enough to boil the ethanol) use more dilute
H2O2. What was the intended role of the steel wool in your scheme?
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PHILOU Zrealone
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FeCl3 is likely to catalyticaly decompose H2O2 into H2O and O2.
30% H2O2 is 100 volumes...what means your initial 150 ml H2O2 can blow at least 15L of gaseous O2 out of the 1L bottle... this not counting the
exothermic reaction causing dillatation of the gas...
Glyaldehyde HO-CH2-CH=O...maybe try via Cl-CH2-CH=O and Pb(OH)2.
Don't expect hydrolysis with strong bases like NaOH to work fine...you would probably end up, after multiple crotonisations, with phenolic polymers of
the trype (-C(OH)=CH-)n, maybe some 1,3,5-phloroglucidol (trihydroxybenzene).
Cl-CH2-CH=O can be produced from cheap reactants HCl/Cl2 and CH3-CH=O itself obtained from ethanol oxydation/distillation.
Or directly try to use Cl-CH2-CH=O with ammonia as an in situ source of NH2-CH2-CH=NH.
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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