Tetrameric!?!

[Fallout85]

I was searching on google for info about ap and found a Chinese chemical manufacturer or something like that with info on "Tin Chloride Catalysed Oxidation of Acetone with Hydrogen Peroxide to Tetrameric Acetone Peroxide". Unfortunatley you have to pay to get the information but it sounds promising and I'm sure some of the people here could figure out the details on their own. I'm guessing that the tetrameric polymer would be stronger and more stable that is why I posted it here. The website is http://www.rsc.org/is/journals/current/jcr/jc999004.htm Just scroll down to #288.
edit-removed period from url address
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"Good, bad, I'm the guy with the gun." -Bruce Campbell, Army of Darkness.

[This message has been edited by Fallout85 (edited 11-18-2001).]

[CodeMason]

Just a thought, it would probably be what HMX (this tetramer?) is to RDX (TCAP).

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Visit my website (in development): http://codemason.cjb.net

[oxyrad]

Like the website.
The part on hth/naphtha does it really work?have you tried it?how did you set it of?

[CodeMason]

Thanks, I have a friend that used to live way over in Perth. http://theforum.virtualave.net/ubb/smilies/smile.gif I'll try HTH+Naphtha when I get more calcium hypochlorite.

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Visit my website (in development): http://codemason.cjb.net

[nbk2000]

Fallout, the link you posted is 404'd.

They probably noticed all these hits on an explosive chemical procedure coming from a forum called "weapons and explosives". Wonder what that's all about. ;)

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

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[mrloud]

The link appears dead because there is a period at the end of it where there should be none.

I had no trouble downloading the full text PDF. It could have something to do with the "Free For Chemistry Week" I see mentioned. Download while you can.

I have put this particular file on the FTP site as a_bit_of_info_on_AP.pdf

[This message has been edited by mrloud (edited 11-18-2001).]

[Fallout85]

Well I gues I was right about it being stable. I have some tin chloride in my basement. Maybe I'll try a little experiment this week. http://theforum.virtualave.net/ubb/smilies/smile.gif
Tin chloride is pretty easy to make though. If you have tin (very available) and hydrochloric acid (you probably already know where to find some) then you can make tin chloride. You can also react tin sulfate (I think it's soluble) with sodium chloride.
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"Good, bad, I'm the guy with the gun." -Bruce Campbell, Army of Darkness.

[This message has been edited by Fallout85 (edited 11-18-2001).]

[rikkitikkitavi]

Tetrameric peroxide means that it has four peroxide bonds http://theforum.virtualave.net/ubb/smilies/smile.gif

What we call AP is normally trimeric peroxide, ergo three peroxide bonds.

It is probably somewhat more stable, since
it forms a larger ring-structure than trimeric AP, hence less tension leading to greater stability of the molecule.

But once a peroxide, always a peroxide.

Read the article, it is very very interesting. Good work!

/rickard

[PHILOU Zrealone]

They say they got CTeAP; but they don't mention CTriAP; maybe is it contain as impurity?
Anyway:
(-O-O-C(CH3)2)3 is quite different than
(-O-O-C(CH3)2)4; obviously the higher the polymer weight, the better the stability as I have observed and explained on alt.engr.explosive one month ago!
Often the power is increased with the density!
Typical example is trimer and tetramer of CH2=N-NO2, known as RDX and HMX!
HMX is a bit more stable (depending on its cristalline form; as expected the more ways to move a ring, the more you have cristalline forms and densities; each has different sensitivities and properties as explosives)!I can point out that only one cristalline form of HMX is less sensitive and more powerful than RDX!
Stability increase is due to more ways to dissipate heat by molecular moves (rotation arround linkages); but there can be a weak point of stress that ruins all this when the cristalline shape change (with T for example)).

I can also say tha RDX is good since it is a 6 membered ring; not too much stress; 5 rings are good too; when you go up, you never know which allotropic form you handle; you have to test all of them to properly know the stuff you play with!
A good point would be the making of a linear polymer:
(-CH(CH3)3-O-O-)n
this would be more powerful, denser and less sensitive!

PH Z

[xoo1246]

Very interesting, indeed. Maybe a good substitute to the trimeric version.

[Yi]

I will be making the tetrameric version once I get some more H2O2.. I only have the SnCl2.2H20 not the SnCl4.5H20, so I will have to see how effective it will be.

Does anyone have any idea why it is carried out at room temp? I expect the impurities will be mostly dimeric AP because of the high temperature.

The plan is to make a small quantity of the tetramere aswell as a small quantity of the trimer and compare their power and sensitivity.

Also has anyone successfully synthesised this yet? Any tips?

[PHILOU Zrealone]

I suspect the high heat is there because then more of the tetrameric form more stable at that temperature than the other forms will form and precipitate while the other forms will remain dissolved! You of course know that low temperature is needed to precipitate as cristals the CDAP and the CTriAP. The use of this temperature alows easier separation of the different multimers!
SnCl4 is better choice, I think to remeber it is done by reaction of Cl2 on Sn in the cold, generating a liquid boiling at 114°C and having a density of 2,234 at 20°C. It may form cristaline hydrates like SnCl4.5H2O!
Maybe the lack of SnCl4 can be compensated by an little more SnCl2 since they say that SnCl4 is more effective but that they have kept the concentration low to see there is a catalytic effect.
They also mention the % yield to increase with the amount of SnCl4; maybe is it the same with SnCl2?

PH Z

[Yi]

I had a dream about the method used in the pdf:

16ml Acetone (~0.27 mol)
20ml H2O2 30% (fresh)
0.5g SnCl2.2H20

The amount of catalyst was slightly different. Also the method used SnCl4.5H20. As you said i used more than 2mmol of the catalyst to make up for it (also easier to measure).

The addition of the catalyst should be done very slowly as the reaction is quite vigorous. The solution was stirred constantly for 23 hours and the solution was then filtered. The filtrate is drying right now so i'm not sure about the mass. The yield looks quite bad, only ~0.5g, but a small amount was also lost due to filtering (the filter got clogged a few times :mad: ).

I'll recrystallise from ether and then weigh.

[Yi]

Damnit... extremely low yield.
<a href="http://incoherent.topcities.com/tapyield.jpg" target="_blank">http://incoherent.topcities.com/tapyield.jpg</a>

There was quite alot of water in the clump of crystals, looked like alot more :(

[EDIT: picture link didn't work, changed to url]

<small>[ March 25, 2002, 05:14 PM: Message edited by: Yi ]</small>

[ikbendirk]

I was wondering... is it actually necessairy to wash your TeCAP with NaHCO3? Because the only contamination should be SnCl2 . H2O, which won't be seperated when washed with NaHCO3...
is this still a wise thing to do? or is washing with ethyl alcohol or DeMi-water sufficient?

[K9]

That should be CTeAP seeing as how it's a cyclo molecule. But in regards to the washing, the article in the journal only mentions washing the solid with water (and recrystallizing but that's another story).

[Desmikes]

Yi, try another reaction using the same reaction time and amounts of Acetone+H2O2, but leave out the catalyst. See how much AP forms, I think you will end up with more than .5g

[Zeitgeist]

Note how they describe it as relatively stable, yet most chemists are shit scared of organic peroxides. I wonder just how much of a stability difference there is?

[FinnBell]

This might be a stupid question, but how can a person tell how many different isomers can be formed from a certain formula? I know when nitrating AP there is usually the dimer or trimer version and now were talking about the tetra version, and I think there are like three for MEKP. Im not sure though I could be wrong. But the point is, how many different isomers can be created for any given formula, this means theoretically as well. I looked in my organic chemistry books and didnt find anything, there was stuff about the many different combinations of organic compounds in different dimmensions but nothing on isomers.
P.S. if this is a stupid question delete it or move it.

[Desmikes]

FinnBell,
I know when nitrating AP there is usually the dimer or trimer version and now were talking about the tetra version, and I think there are like three for MEKP.
WTF are you talking about? do you NITRATE AP often?
If by "Formula" you mean A+B=C, then there is only one possible outcome, in this case we get C. Isomers don't have to be produced by the same reaction, you may get one of the isomers when you react totally different reagents. You can predict geometrical structure and the number of possible isomers by 3-D modeling or drawing.

[FinnBell]

Hey you dont have to grill me, I plainly stated that if its a stupid question to either move it or delete it. I know that you can form the same isomers as well as different ones from several types of reactions. Thats no big mystery. What I wanted to know was how to predict the many possible isomers out there. Like every combination. Maybe I'm wording it wrong. I was just thinking would there be a way to predict every possible combination. Maybe it was a stupid question, maybe I just dont know how to word it. I was just curious because I read something earlier about new isomers of a medical compound being discovered and I wasnt clear on the whole subject. The way I see it, if they just "discovered it" then the same would go for explosive compounds, meaning there would be other possible isomers just waiting to be discovered.

[frogfot]

One can only predict which isomers will form if reaction mechanism is fully known, usually this can tell ammounts of formed isomers too. But it's always easier to check this experimentally...

As to actually determine which isomers there are in your product, for example check out that pdf on tetrameric AP. In the end they give names of the methods that were used to determine the composition. Though I never came in contact with that OSMO meter and elementar analysis in shool.. I assume these methods require separated isomers, well thats done with chromatography.. or?

EDIT: Oh, how about HPLC with UV detector to determine AP composition? AP should be seen by UV.. or? ...maby it's too unstable for UV though.. I dunno.

[T_Pyro]

Knowing the molecular structure of the compound, you can calculate its molecular mass. Though not a very convincing test, if the molecular mass is verified by measuring the depression in the vapour pressure of the solvent (acetone would do), at least you could make sure that you're not working with the trimer or dimer.

[megalomania]

If you have a known molecular formula you can calculate isomers, but if you are talking about an unknown number of elements then you can have an infinite number of isomers.

There is a whole branch of chemistry devoted to just finding out what moecule you have. Molecular structure ecliduation involves using multiple spectroscopy techniques and some other funky techniques nobody but a spectroscopist would be familiar with. You ever wonder how they know exactly what angle certain bonds are, or what ions exist in solution fleetlingly? I once had occasion to run a sample through a $25,000,000 NMR, it had its own room and everything. Overkill for routine determination, but not for research studies, and that's the kind of equipment you use when looking for unknown molecules. I'm just saying it's a little more involved than what most of us are used to in the lab (sticking a sample in an IR or NMR and pushing a button). People devote their careers to this stuff.

I don't think there is any room left for the discovery of explosive molecules anymore, discovery being "hey this stuff I just made is explosive." Computational chemistry is such a great thing, they know about explosive molecules before anyone even makes them. There was an excellent paper in Propellants, Explosives, and Pyrotechnics (I think, it may have been a compu chem journal) where the researchers set their supercomputers to task custom designing explosive molecules. They had very limited time with the computer, and narrowly defined only a certain range of molecules (cyclic, symmetrical, and 5 membered rings) and yet they came out with 75 molecules that theory predicts are among some of the most power explosives. (symmetrical cyclic rings have a greater density when crystallized which leads to higher explosive velocities). This was one study by one scientist... I can only imagine what they could come up with if they had more computer time, faster computers, better structure computation, and a wider search criteria. Naturally nobody knows how to make any of those explosives (yet).

[FinnBell]

Mega, I find that incredibly interesting, do you know where you read about that? Could you possibly point me in that direction. Ive been looking into the more theoretical side of chemistry. Right now Im working on my degree for Engineering physics but I have just started some O-chem and I find it so much more enticing. Our libraby has a great deal of this type of material but its mostly over medicinal applications. You said something about compu chem journal.? Well any info on this would be greatly appreciated.

[me234]

Yi's right, what a crap yield, I also tried it with Sn (II) chloride, and all I have is this pathetic little clump of gelatanous stuff, it feels crystalline between the fingers, but looks gelatanous in the mix, I used about, 0.25 cup 50% H2O2, with 0.5 cup acetone, and almost all the tin chloride I had, couldn't have been more than 40ml. Before I wasted all my stuff, however, I took a bit out and I tried to oxidize the Sn(II) to Sn(IV) with some KMnO4 solution, I alos added a tiny bit of Hcl to try and provide more Cl for the Sn(IV), but I forgot about it getting oxidized to Cl2, dumbass!

Anyway, if someone wants to try the oxidation, acidic medium helps, I think I wanna try with some H2SO4 and some chloride salt for the reaction medium. I'm pretty sure most people here know the acidic medium part, but there might be some kewlerz around who need some help.

PLEASE someone try the Sn(IV), if better yields can be gotten, it might be occasionally worthwhile to make some more stable tetrameric AP for speciality jobs where the trimer might be borderline acceptable for the job. Think how much better AP Putty could get!

[me234]

OK, wait, my mistake. I forgot a golden rule in AP manufacturing: 6 hours is not long enough to wait before passing judgement on yield. New observations were made at approx. 24 & 36 hours after SnCl2 addition, and, SO VERY COOL! My yield, previously thought to have been 'crap', is actually not so bad, in fact, it's PRETTY DAMNED DECENT

With aforementioned amounts of stuff in the dog food dispensing cup, about half full with crystals. Most had collected at the bottom of the cup, only a small amount floating (very small in fact). Crystal size appears to be larger than what is formed with well refrigerated trimeric AP. Upon addition of Tin(II) Chloride (dihydrate) solution became very warm, sitting in a freezer for half an hour did little to help this, but I read to let it react at room temp., Even almost 2 days later the mixture is still noticably above room temp. I think the large crystals may have formed due to the elevated temperature at which they crystallized, sort of like when you heat a precipitated mixture to increase particle size to ease filtering (Digestion), I reckon the slightly larger size should make trying to press it more interesting.

I'm going to let it sit until the weekend, then I'm going to filter, I'm also going to try save the reaction mixture to keep the SnCl2 as I don't have any more lying around, gonna have to go shopping some time soon.

APPN & APAN should get really cool with the tetrameric form hopefully. With these kinds of yields, manufacturing the tetrameric form instead of the trimeric form is more than likely economically viable, which is nice. Plus, no more occasional burning my hands while filtering the acidic medium.

Does anyone have some suitable tests for power comparison and shit like that I can try? Nothing too fancy, I don't really want to go out and buy a bunch of identical witness plates, but if I find something lying around the house... I'm thinking of stuff like comparing rates of dissolution between the dimer, trimer and tetramer in different solvents etc. Heh heh, now I have the 3 different types of AP sitting at home.

Anybody have any results to back mine up so I know it's not a fluke?

[Bert]

Moderators:
Perhaps this whole thread should be moved to the "other explosives" section?

[FUTI]

Well I don't think that I can really help you with this one! I think the main catalyst for a reaction of this type trimeric or tetrameric AP is acid...or reaction is chemicaly said acid catalysed ( to people that are not chemist warning do not jump to conclusion not to much acid) that is the reason the SnCl4 give better result that SnCl2 (because its stronger acid), but maybe you can change that...if you use SnCl2 and enough hydrochloric acid to make H2(SnCl4) than maybe on conntact with peroxide it can somehow make SnCl4 that is used originally :confused: or this molecule can itself substitute SnCl4 as acid :o .
As for the temperature conditions don't know...solubility issue mentioned can be true, but I always conduct reaction with peroxide as cool as posible...to much heat decomposes it, and if it is reactive who can say what is to much heat? :cool:
Let me know if you try this experiment.

[Jacob Kell]

So just acetone, H2O2 and SnCl4? well that's great, I think.I made Ap many , many times and always waited for one week to filter it, and wash it. Every time i experimented with small amounts by hitting with hammer, and it never exploded on impact or friction. So it just strikes me that so many pyro postings on net claim it is sensitive more than everything. Actually, I find this explosive very safe. If even more stable isomer could be made, it's great. So, questions. Could anyone tell me the exact synth of SnCl4 (tin + hydrochloric acid) and how much of it to use in AP synthesis? Is the tertamer more powerful than trimer? Or more endurable?

[ProdigyChild]

I've tried this a week ago. At the moment I'm analizing the result. I've got a strange observation: the cristals I've recristallized have a LOWER density than those created with HCl alone. However, there may be gas bubbles inside them, that falsify my density test. Need some more time to create perfect crystals...
In the worst case I could conclude that SnCl2+HCl yields more dimeric AP - really not what I intended :confused:

My idea was slightly different: I thought, the H2O2 would oxidize Sn2+ to Sn4+ somehow, and the additional HCl should form (Sn-) Clorides instead of Oxide/Hydroxide.

[nuclearattack]

I'm trying to make tin cloride but i have some doubts about the results.
I have putted some soldering wire (should be pure Sn) in 30% HCl and i let it react for some hours. At the end of the reaction the solution is perfectly clear but at the bottom of the jar i have a black solid powder. What is this?
SnCl2 or SnCl4?
In a previous post i read that SnCl2 is a pink liquid and SnCl4 is a solid...maybe i obtained SnCl4?

[FUTI]

to nuclearattack: I think you are on wrong path, look for MSDS on the JTBaker site or elsewhere...SnCl2*2H20 is a white crystal solid as I remember, and I think that SnCl4 is liquid, both should be miscible with water (Sn2+ much more than Sn4+). I guess that the use of alloy is wrong or at least troublesome since you don't know what is that black powder maybe it is the other metal (like Sb) or maybe that is Sn that is reduced by the other metal and that kept him undissolved. Check composition.
to ProdigyChild: I post a similar idea but I don't know does it work. Use 2mole of HCl per mole of SnCl2. My guess is that they use a complex formation by Sn and ligands are acetone and peroxide, so this promote reaction, or it is slow HCl release by SnCl4. Try this and try to monitor the pH during the course of it. Let as know what come of it. I hope that will work. If the comlex formation is the key...then some chemist must do the rest of refinement in the reaction conditions since then order and speed of mixing is very important (temperature is already a parameter I hope:)). If it goes trough complex formation I guess it must use two centered complex (two Sn) bridged with peroxo group, and that is the key step for making tetrameric from dimeric form.
Edit: I forgot to add SnCl4 is as I remember made through Sn and Cl2 so it is not easy procedure...if I need that I would buy it! But if you guys succeed to make it in situ as described above before you add acetone fantastic...let me know about it!

[ProdigyChild]

If you use the same alloy as me (96%Sn, 4%Cu) then the black residue is super fine copper. I have the same observation. This wire is used for drinking water tubes soldering. Lead free ;)

If you used 'normal' soldering wire, like for electronics, you have lots of lead (Sn 60% Pb 38% Cu 2%). Toxic PbCl2 :eek: be careful!

Pure Sn wire isn't sold, I'm pretty sure. Doesn't Sn have some very strange properties around 13 &deg; ??

I had a bad experience last night. I was so stupid to melt some (supposed to be tetrameric) AP.
The cristals I made are not perfect, so my idea was to cast a solid piecelet of AP to determine its density.
To my surprise the firt result was a opaque solid drop. The measured density was below 1.1g/cm3. Another sign of it beeing dimeric rather than tetrameric. I have other crystals of higher density (supposed to be trimeric).
Maybe because it was shock freezed by dropping into a PE mould.
The I wanted to cool it down more slowly. It got molten, then I wanted to turn the metal plate a bit around to let the drop reach the edge and....
KABAAMMMMM!!!
Fucking shit! ears ringing for a while and no interest in casting AP any more :(
When liquid this stuff detonates in smallest quantities (assuming a drop is small quantity for most members here :D )
I stick to time-consuming cristallization now.

[nuclearattack]

Yes Prodigy i'm using normal soldering wire!
What can i do? Can i use this black powder without taking care of the impurities? I don't think so but i can try.
I'm not able to get Sn because i don't know where to search it. Cola cans are made with alluminium or a kind of Sn/Al alloy so i'm not sure that it will works.
Where do you take Sn? Is it possible to buy SnCl2 or SnCl4? I made a search in my city but i didn't find it.

[sevin]

I looked in my Alfa Aesar catalog (www.alfa.com). They have it listed at around $15 for 500g of SnCl4. They obviously have shit prices for most of their stuff, but they do have everything.

[kingspaz]

Tin oxides can be bought from pottery supply places for use in glazes. Tin oxides could also be reacted with something like Al powder in a thermite type composition to liberate metallic tin. The resulting mix of Al2O3 and tin could be purified by melting the mix and pouring off the liquid tin (since tin melts at about 180 IIRC) leaving behind the Al2O3 slag.

[ProdigyChild]

There's nothing wrong with that Cu powder. Filter or decant and you're fine!

The lead cloride has low solubility at low temperature. As said, I would not work with lead salts. I've done nearly a decade ago and not anymore since then.
Pb is a bit more noble than Sn, so if you stop the reaction before all (gray) metal has dissolved, you should get rid of the Pb:

Pb2+ + Sn ==> Pb + Sn2+ (1)

Or else add a bit of aluminium powder or foil to reduce some random kations

3 Sn2+ + 2 Al ==> 3Sn + 2 Al3+ (2)
3 Pb2+ + 2 Al ==> 3Pb + 2 Al3+ (3)

Sn of reaction (2) goes on like (1).
That way you HAVE A CHANCE to get rid of the Pb salt by filtering or decanting.
Your solution then contains only unpoisonous Al and Sn salts.

[nuclearattack]

This morning i had a look to my HCl/soldering wire batch and i seen a small quantity of a white solid just on top of the black powder. The white solid has a filament shape just like the soldering wire shape. I had no time to extract it but i think that it is crystalline, maybe this is SnCl2 2H20?

[kingspaz]

Solder is typically a Pb/Sn alloy (50/40 IIRC). The white powder is probably a mixture of both lead and tin chloride.

[K9]

Well I just found an old box of tin/lead solder in the garage. I emailed the compnay to ask about an MSDS but I haven't recieved a reply yet. Is it even worth attempting to use, or just scratch that idea because of the lead impurities?

[hinz]

I think, it's crap to catalyse the tetrameric AP reaction with SnCl4.
I also wanted to make tetrameric AP with the SnCL4 catalyst,but i didn't know how to make it. Therefore i googled for it and found it's MSDS.

http://www.jtbaker.com/msds/englishhtml/s6386.htm

There it's written thats SnCl4 reacts violently with water, which is always in your H2O2 acetone mixture. It will react to HCl in contact with H2O, which is the standard catalyst for TATP


SnCl4 + 2 H2O ==> SnO2 + 4 HCl

The same thing will happen with SnCl2, but only slower and less violent.

SnCl2 + H2O ==> Sn(OH)Cl + HCl

I think those scientists decomposed their SnCl4 to SnO2 and 4 HCl and made TATP or DADP

[K9]

Care to explain "SnCl4·5H2O and SnCl2·2H2O are efficient catalysts for the oxidation of acetone with 30% hydrogen peroxide at room temperature and produce tetrameric acetone peroxide which is identified by molecular weight determination, elemental analysis, FTIR, NMR and MS." ?

Besides, doesn't that reaction only happen with anhydrous tin chloride?

[FUTI]

to K9: Honestly this is the first time I heard about SnCl4*5H2O....though I'm little sceptical about it since I saw and heard about weirder things I can't count this as hoax at start, the other salt is OK. The only form of SnCl4 that I cross by so far is anhydrous.

to hinz: This posibility you mentioned is disscused before in the thread...did you checked pH change during the reaction and come to some conclusion? If you did share it with us. Sn-oxides aren't water soluble so they could precipitate with AP, then precrystalization of product is necesary. Maybe the crude product can be checked for residue on burning (now that is a tricky one)?

[K9]

If you look at the msds - http://www.jtbaker.com/msds/englishhtml/s6386.htm
anhydrous is listed as having a CAS number of 7646-78-8, and the pentahydrate form having a number of 10026-06-9