Peroxalic Acid

[madscientist]

Oxalic acid is (COOH)2. Therefore peroxalic acid would be (COOOH)2. It seems that the nature of peroxalic acid would be explosive. The total strength of all the bonds in a peroxalic acid molecule is 3644 Kj. It should decompose easily, releasing 317 Kj of energy per molecule.

(COOOH)2 --> 2(CO2) + H2O + 1/2(O2)

Peroxalic acid requires an average of 364.4 Kj of energy per atom, and averages an increase in energy of 31.7 Kj per atom after decomposition. Acetone peroxide requires an average of about 366 Kj per atom, and averages an increase in energy of about 19.64 Kj per atom after decomposition. According to these calculations, a kilo of peroxalic acid would be about as thermally sensitive as a kilo of acetone peroxide, but would release about 38% more energy. Oxalic acid should be able to be converted to its peroxide easily in the presence of an acid catalyst.

(COOH)2 + 2(H2O2) ---> (COOOH)2 + 2(H20)

Does anyone have any more information on peroxalic acid? If so, please share it. I am fairly certain that peroxalic acid would be more powerful than its salts and also more stable.
Also, does anyone know the actual chemical formula for hexamin? I know that it can be produced by the reaction of ammonia and formaldehyde, so I'm guessing hexamin is CH2NH.

NH3 + CH2O --> CH2NH + H2O

Anyone know the reaction for the production of HMTD?
Another question: what is the chemical structure for charcoal? I haven't been able to find the answer to that anywhere.

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"Nine Inch Nails is the devil" -my mom

[CodeMason]

You aren't the "madscientist" from the Weirdpier forum are you? http://theforum.virtualave.net/ubb/smilies/wink.gif

Regarding peroxalic acid, I'll leave this one to someone more well versed in chemsitry. To answer your other questions, hexamine is a heterocyclic structure, C₆H₁₂N₄. It is like a molecule of -CH₂-N-CH₂-N-CH₂-N-, with an extra -CH₂ branching off from each N, all three extras connecting to a fourth N.
The reaction for HMTD involves is quite complex and intricate, but the chemical formula is: (hope this helps)<font face="fixedsys">
&nbsp;&nbsp;CH2-O-O-CH2
&nbsp;/&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;\
N-CH2-O-O-CH2-N
&nbsp;\&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;/
&nbsp;&nbsp;CH2-O-O-CH2</font>
This last question puzzles me. You seem to be quite knowledgable in the field of chemistry and yet you don't even know that charcoal is simply an amorphous form of carbon? Anyway...

[Oops, Mr_Cool was right, forgot the extra O, peroxides contain, by definition, -O-O-]

[This message has been edited by CodeMason (edited September 27, 2001).]

[Mr Cool]

Charcoal is not carbon; it is carbon and many different hydrocarbons. It has no formula, since it can vary so much.
I believe that there are two oxygens joining each pair of CH2's, but I might be wrong...
317kJ per molecule?! Oh my god, if you made a kilo of that your country would not be a safe place. Perhaps you meant per mole? Roughly 602800000000000000000000 molecules IIRC.
You might need an acid catalyst. Hang on though, you're trying to peroxidise oxalic acid... think about it. And anyway, organic peroxides tend to be unstable in acid. Some decompose gradually, thus allowing acid to be used in their synthesis, some decompose violently.
However, it is quite an interesting idea, I will see if I can find any mentions of it.

[A-BOMB]

And he is the one form Quierpier same signature! get him!

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live by the bomb
die by the bomb

[kingspaz]

hey don't kill him just yet. he may have seen the light. he registered in may and this is his first post so hes been lurking for a bit and has found something intelligent to say....he better not still be going to queerpier...

[Anthony]

Dude obviously knows his shit so let's just leave him alone. He's done nothing wrong and being a member of queerpier is not against forum rules.

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"Shit happens. Get a fucking helmet"

[madscientist]

Queerpier....lol that hilarious
Shit, it amazes me that EVERYONE knows I post there, and they even know my signature! Truly amazing. Also, I do not consider myself to be a 'member' of 'queerpier', I just post there for two reasons:

1) To try to prevent people from blowing themselves up by following instructions that include heating unstable high explosives, etc.

2) Because it was the only 'questionable' site that the gay-ass internet 'protect your kids from objectionable material program' that was installed on my internet computer would let me go to.

I just figured out how to get past it, and so I plan to be here instead. 'Queerpier' is just too stupid and filled with random flaming for me to have any interest in it when this site is available. My sermom is over.

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"Nine Inch Nails is the devil" -my mom

[This message has been edited by madscientist (edited September 26, 2001).]

[madscientist]

Oh yeah, oops...317Kj per molecule, I wish. That would be really scary if I had a kilo of something that released 317Kj per molecule during decomposition!

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"Nine Inch Nails is the devil" -my mom

[CodeMason]

Mr_Cool: Crude charcoal has a small amount of hydrocarbons in it, but according to all four of my general chem. references, it is simply amorphous carbon.

[Hex]

I guess that HMTD from hexamine is from peroxide anion attack at methylene alpha to a protonated nitrogen in hexamine, or perhaps between two protonated nitrogens to give

CH2-O-O-H
/
N-CH2-O-O-H
\
CH2-O-O-H

then similar from the above peroxy or related species on another hexamine molecule to give HMTD. Obviously, this is a summary, and there is a huge number of combinations that these steps could occur in, for instance one peroxy unit could link two (degraded) hexamine units before further peroxide anion attack, and so forth..all you need to know is that it works!!
Does anyone know why peroxides have (in contrast to most other molecules) such a tendancy to forming such large rings?

[madscientist]

This has got to be one of the longest posts ever seen on this site. (Not even close. It's rather average in length by our standards. NBK2000)

Here is my report on experiments having to do with peroxalic acid.
As for hydrogen peroxide, I have been using a 3% solution. Hopefully I can get a more concentrated solution soon, preferably 30%. Does anyone know how concentrated and how pure the hydrogen peroxide in various brands and types of hair bleach? (at least I have heard there is hydrogen peroxide in hair bleach) Anyway…here’s a chronological report of what’s happened so far. Unfortunately, I have not been able to test peroxalic acid for explosive properties as of yet.

I began by purchasing 12 ounces of oxalic acid for $7 at my local hardware store. I went home, and spent 15 minutes trying to figure out how you were supposed to open the damn thing. Eventually, I got it open, and sprinkled a few grains of oxalic acid in the bottom of a beaker, poured in a few milliliters of water, and conducted a pH test to determine if I should bother adding a stronger acid to catalyze the reaction to peroxalic acid. Turned out that oxalic acid is quite a strong acid, having a pH of about 1.5 (I’m using crappy pH paper, so that number may not be completely inaccurate). I then tried to dissolve two grams of oxalic acid in 200 ml of water. It didn’t dissolve completely. I estimate that about ¾ grams of oxalic acid dissolves in 100 grams/ml of water. I added 55 ml of 3% hydrogen peroxide solution to this incompletely dissolved beaker of oxalic acid, and let it sit for 24 hours. When I returned, the incompletely dissolved grains of oxalic acid had changed to a fine powder. I inferred that this indicated that I had a solution of peroxalic acid. I’ll explain why I came to that conclusion. The incompletely dissolved oxalic acid sat on the bottom of the beaker, in relatively large grain form. When it dissolved, it soon reacted with the hydrogen peroxide, forming peroxalic acid. And since oxalic acid should be more soluble than peroxalic acid, it displaced it, causing a fine peroxalic acid precipitate to form. This solution of peroxalic acid was unfortunately soon rendered unusable and extremely contaminated due to very stupid blunders on my part that I do not wish to share.
I had predicted that peroxalic acid would be quite unstable, and that hypothesis seems to have been confirmed. The peroxalic acid precipitate at the bottom of a beaker slowly (over several hours) formed 3 or 4 small bubbles at the bottom of the beaker, indicating that it is decomposing into carbon dioxide, oxygen and water. When I stir the contents of the beaker, the rate of the bubbles being formed accelerates. After about 48 hours, the rate of decomposition goes up a few hundred times. Taking this information into consideration, I recommend that you be cautious with any dry peroxalic acid and do not make lots over five grams until you understand how it acts when dry. Also, it is important that you store dry peroxalic acid in plastic containers for now. It should be obvious that heating peroxalic acid is exercising very poor judgement.

Useful information for making peroxalic acid:

-1 gram of oxalic acid (COOH) 2 will make about 1.26 grams of peroxalic acid (COOOH) 2

-Oxalic and peroxalic acid are poisonous and can burn your skin. If it gets on your skin or soaks through your clothing, wash it off immediately.

-For every gram of oxalic acid, you need approximately 25.19 grams of 3% hydrogen peroxide solution, or 2.52 grams of 30% hydrogen peroxide solution. This should translate into a little over a ml per gram. If anyone happens to know the exact density of concentrated hydrogen peroxide, that information would be appreciated. Here’s a simple equation to find out how much you need if you have some other concentration (x stands for grams of oxalic acid; y stands for grams of hydrogen peroxide solution; z stands for concentration of the hydrogen peroxide solution, for example, if the concentration is 1% z would be 0.01):
(34/45)x = zy

My recommended process for making peroxalic acid (the variables in parenthesis relate to the above equation):

Get a beaker. Pour (x) grams of oxalic acid into it. Pour (y) grams of hydrogen peroxide solution in the beaker, and stir the mixture for several seconds. It is a good idea to add a bit more hydrogen peroxide than is needed (10% extra should be plenty), because some of the hydrogen peroxide will break down before it reacts with the oxalic acid. Give it about 24 hours to react. Then, evaporate off the water, in a plastic container (so when the peroxalic acid dries, accidental detonation won’t injure or kill you with bits of flying glass). That’s about the most detailed instructions I can give as of yet, because of the delay caused by the destruction of the first batch by stupidity.


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"Nine Inch Nails is the devil" -my mom

[This message has been edited by nbk2000 (edited October 08, 2001).]

[EventHorizon]

From Merck.

3% -> d ~1.0
30% -> d 1.11
100% -> d⁰ 1.463

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"Chance favors a prepared mind" - Louis Pasteur
PGP ID 0x147CEF54

[madscientist]

Mixing just peroxalic acid and hydrogen peroxide didn't work. I'm trying tonight using sulfuric acid as a catalyst. I should have a report on results within a few days. The biggest problem would be that I couldn't use filtration to harvest the peroxalic acid, I would have to use evaporation, since peroxalic acid should be water soluable.

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"Nine Inch Nails is the devil" -my mom

[VX]

http://theforum.virtualave.net/ubb/smilies/redface.gif oops, didnt realise it had already been covered, didnt see it the first time i read the meassage. sorry all, VX.


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Just do it! Carefuly!!

[This message has been edited by VX (edited 11-20-2001).]

[This message has been edited by VX (edited 11-21-2001).]

[madscientist]

If you actually read the whole post you would have realized that that error has been corrected.

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"Nine Inch Nails is the devil" -my mom

[madscientist]

I'm still not done with the sulfuric acid catalyzed formation of peroxalic acid reaction, but here's something else I forgot to mention:

Chances are this explosive is going to be ridicuously sensitive and unstable. When I mixed 2 grams of peroxalic acid and 60 mL of 3% H2O2, and let it sit for several days, then evaporated off the water, I ended up with about 1.5 grams of remaining residue, which was almost entirely composed of oxalic acid, meaning that almost all of the peroxalic acid formed (not too high of a yield without a sulfuric acid catalyst) decayed from normal terrestial conditions. After about two days of the reaction, bubbles began to form on the sides of the container at an ever increasing rate.

Here's a report on my synthesis of peroxalic acid with sulfuric acid catalyst:

I placed 5 grams of oxalic acid in a beaker, then added 300 mL of 3% hydrogen peroxide solution. I then added 15 mL of concentrated sulfuric acid, and placed the beaker in an ice bath, for reasons that I will soon explain. The solution cooled down, and I kept changing the ice in the ice bath for the next four hours. No bubbles formed in the beaker at all. Then I picked up the beaker and held it in my hands for a minute or two, long enough to warm up the contents of the beaker to near room temperature. I then set the beaker back down, but not in the ice bath. An hour later maybe 50 small bubbles had formed on the sides of the beaker. This has continued since (I started the experiment 10 hours ago). This information tells me that the decomposition temperature of peroxalic acid is probably around 60 - 70 degrees Fahrenheit. That probably means that it will be extremely unstable and sensitive, and will probably be worthy of nothing more than a toy to fool around with in very small amounts. That is as far as I've gotten.

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"Nine Inch Nails is the devil" -my mom

[madscientist]

Damn. I was going to have a batch ready today but a thirsty racoon did away with it during the night.

[nbk2000]

Just don't kick any dead racoons you might run across.

;)

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"I have begun evil, I shall end evil. That is the end that awaits me."

Go here (http://briefcase.yahoo.com/nbk2ooo) to download the NBK2000 files and videos.