H2O2-free AP

[UnderConstruction]

I first started to wonder about this trying to balance the acetone and hydrogen peroxide reaction: C3H6O+H2O2--->C9H18O6+X. In that reaction a catalyst (sulphuric acid) is necessary.

I saw that the extra compound would be removed under the new formula 3C3H6O+O3--->C9H18O6, (the hydrogen peroxide being substituted for ozone), and the catalyst could theoretically be removed do to the incredible reactivity of ozone.

Ozone generators are available for therapeutic purposes (some people apparently bathe themselves in a body-encasement filled with ozone gas or ozonated water...), even in the form of "bubblers" that send the ozone into water or oil (some people like to drink/cook with it also, god knows why). If acetone was replaced for the water/oil is it even theoretically possible that such a reaction could occur? Mind you that I'm not even an amateur chemist, and not suicidal enough to attempt this hit-or-miss-or-miss-&-die experiment on a hunch (and spending several hundred dollars on the equipment necessary to do so).

Thank you for any information you can give me on this subject.

[rangegal]

I've read this idea posted by somebody here before, but if your the one to get it to work, you get credit!

I think you could safely test this on a very small scale with a remote "bubbler" or something. It would probably need to be cooled pretty well though.

[UnderConstruction]

I UTFSE it before I posted, but I didn't any resemblant topic :o
I don't see any good reason why it shouldn't work, basing that on... nothing, I guess. But the logic is there, so that's what I'm counting on. Sadly, I don't have $300 to dish out on an ozone source, but even that could theoretically change at any time.
I'm convinced that it will work though, if the resources are available

[megalomania]

The mechanisms for the formation of acetone peroxides (TATP and DADP) goes through several intermediate compounds, and in fact can continue to create higher ring structures. It is not a simple 1 + 1 reaction with a direct combination of the reactants to the final products. Ozone reacts in a completly different way than hydrogen peroxide, and I strongly doubt it could form the necessary peroxide structure. It would make something, but that does not mean it will make acetone peroxide.

I applaud your forward thinking, but what science are you basing your hypothesis on? I recommend brushing up on a little peroxide chemistry. I read about the complex formation of acetone peroxides in a book about peroxide chemistry some years ago, but I can't remember the title.

Don't take my word for it though, the proof is in the pudding, that is to say experimentation is the ONLY way to proceed because all the theorizing in the world is utterly useless until someone does an experiment.

[rangegal]

Maybe you should look up how to make your own ozone generator from a salvaged high voltage source (microwave transformer, neon sign transformer, etc...). I know nothing about it, but apparently passing air through a high voltage arc creates ozone.

I'm planning on making a Marx generator sometime in the near future, so maybe I'll do it.

[Beamier Scarab]

One of the possible generators to make your ozone is the corona discharge ozone generator; it can be made using the following methodGet a glass tube that is about 1/4 inch in diameter.
Put aluminum foil on the outside of the tube, for the middle half of its length.
Put a very thin metal wire, no insulation, inside the tube.
One end of the wire is inside the part of the tube with the foil.
The other end of the wire comes out the back end of tube.
Get a fish-tank air-pump, and connect it with a rubber hose to the glass tube to push air through the tube.
The wire will need to be poked through the wall of the rubber hose to get outside where you can connect to it.
Get an AC high voltage supply, limited to 1 milliamp by a large resistor inside.
Connect one high voltage lead to the wire inside and the other to the foil outside.
We want a very small buzzing sound from the glass tube to be heard. This is high-voltage corona discharge in air.
The air being forced out of the open end of the tube should have a fair concentration of ozone in it.
It would be beneficial to dry the air before it goes into the glass tube to help eliminate the formation of nitrogen oxide. (The use of a hair dryer should be adequate)

If you wanted to just buy one, you don’t have to spend that $300, this “spa ozonator” costs just over $100.

http://www.spadepot.com/shop/Eclipse-Solid-State-CD-Ozonator-Kit-110V-P689C287.aspx

[DONMAN]

If you had an electric welding torch, you could some how encase that in a chamber and utilize the ozone, as stated above.

[UnderConstruction]

thanks for everybody's comments. The method Beamie Scarab sent me sounds pretty cool, more fun than buying it and a lot cheaper.:cool:

Also, I know that this has been discussed numerous times before, but is it possible to generate nitric acid from this method? Ozone generators supplied with elemental air (as opposed to chemically pure O2) create it as an unwanted by-product, any chance that this would occur along with the NO?:confused:

[gaussincarnate]

If you do not want to just jump into making an ozone generator,
amazing1.com has the plans for them, sometimes for free, sometimes for a small fee (<$5). I am not attempting to advertise anything; I personally do not like the company that much for their actual products, but the plans and directions are legit.

As for your fear of creating NO, I would definitely try to use pure oxygen, just in case. You are playing with what might end up being a rather sensitive explosive compound, one of the most reactive compounds in existance, a highly toxic and flammable liquid, and high-voltage electricity all at once. It is always better to be safe than sorry.

[Alexires]

gauss - I believe that the bond energy of O2 is much less than that of N2 owing to the "double" bond of Oxygen and the "triple" bond of Nitrogen. Hence, as long as you didn't exceed extremely insane voltages, you probably wouldn't have the energy to split N2 to form NO.

O2 has a bond energy of about 498kJ/mol while N2 has a bond energy of 945.33 kJ/mol. Unfortunately, I'm not sure what that translates to in actual volts.

[The_Duke]

According to PATR 2700 this will not work to form AP, just a bunch of useless gunk.

[LibertyOrDeath]

Here's something that's a bit off-topic but that's also related to non-standard(?) methods of making AP.

The Wikipedia article on AP has a reference called "Decomposition of Triacetone Triperoxide is an Entropic Explosion," but the only mention I could find of the authors (a bunch of Israeli Jews led by Ehud Keinan) or their work is on these threads:

http://www.roguesci.org/theforum/showthread.php?p=73037&highlight=Keinan#post73037 (post #6)
http://www.roguesci.org/theforum/showthread.php?t=389&highlight=Keinan&page=2 (post #20)

The PDF of the article is here: http://www.technion.ac.il/~keinanj/pub/122.pdf

What I thought was interesting was their mention that TATP (which they label "1", as opposed to DADP, "2") can be made without any catalyst at all. From p. 1148 (emphasis added):

Synthesis and Crystallization of 1 and 2. Since the first reported synthesis of 1 by Wolffenstein in 1895, various protocols for its preparation have been published, some of which are rather unsafe. Interestingly, Wolffenstein himself did not ascribe the explosiveness of 1 to the material itself but rather to traces of ether used for the workup. His uncatalyzed synthesis involved keeping a mixture of acetone (11.6 g) and hydrogen peroxide (50%, 13.6 g) for 4 weeks at room temperature and collecting the resultant precipitate (11.9 g, 26.8%) by filtration followed by recrystallization from ether. The acid-catalyzed synthesis was first described in 1959 by Millas, who slowly added acetone (0.2 mol) at 0 °C to a cold mixture of hydrogen peroxide (50%, 0.2 mol) and sulfuric acid, kept the mixture at 0 °C for 3 h, and then extracted it with pentane. This procedure, which uses large quantities of sulfuric acid, represents a fast route to 1, but it is rather unsafe, as reported by Oxley.

The authors' chosen method of making TATP not only uses concentrated sulfuric (which I understand is common in technical literature) but allows the solution to sit at room temperature:

We found that large quantities of 1 may be prepared safely with minimal amounts of sulfuric acid. For example, acetone (5.6 g, 0.1 mol) was mixed with hydrogen peroxide (30%, 0.1 mol). Concentrated sulfuric acid (5 drops) was added at 0 °C, and the mixture was kept at room temperature for 24 h. The resultant precipitate was collected by filtration with suction and air-dried to afford 1 (4.7 g, 65%) in the form of white crystals. This procedure was scaled up to produce kilogram quantities of 1 :eek:. Large single crystals of 1 for X-ray crystallographic studies were obtained by slow sublimation in a closed flask at room temperature.

Based on everything I've read, particularly about temperature issues, I would expect the above method to form a lot of the dimer form of AP. But they have a completely different synthesis for DADP:

Compound 1, which is obtained by precipitation from the above-described reaction between acetone and hydrogen peroxide, is a kinetic product, while 2 is the thermodynamic product. Accordingly, one way to prepare 2 is by acid-catalyzed isomerization of 1 in organic solvents. Thus, dissolving 1 in either chloroform or dichloromethane with a catalytic amount of p-toluenesulfonic acid and keeping the solution at room temperature for 1 week afforded pure 2, which was then collected and recrystallized from hot methanol. An alternative procedure involved slow addition of hydrogen peroxide (30%) to a cold (-5 °C) stirred mixture of acetone and catalytic amounts of methanesulfonic acid in dichloromethane. After the mixture was stirred at -5 °C for an additional 30 min, it was cooled to -20 °C, the organic layer was separated and dried over molecular sieves, the solvent was removed under reduced pressure, and the resultant crude 2 was recrystallized from hot methanol.
More on their syntheses is given on p. 1158.

I'm not particularly interested in AP as a primary myself except as a possible last resort, but I thought this article was interesting because it seems to go against the conventional wisdom about AP.

[megalomania]

The reaction likely does prepare a large quantity of DADP (~5% IIRC), but since they used sublimation to purify their crystals for the X-ray diff a contamination would not matter. They likely went with a cheap and fast route (important for some labs) rather than a tedious and lengthy preparation AFTER trying out the other routes and comparing their GC, MS, and NMR results. Well, GC probably would not work for acetone peroxide, but NMR would be fine.

[The_Duke]

His uncatalyzed synthesis involved keeping a mixture of acetone (11.6 g) and hydrogen peroxide (50%, 13.6 g) for 4 weeks at room temperature and collecting the resultant precipitate (11.9 g, 26.8%) by filtration followed by recrystallization from ether.

Wolffenstein actually did use an acid catalyst, IICR phosphoric acid. Check PATR 2700 for more info if you like.