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FLchem10
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[*] posted on 22-9-2010 at 05:52
Someone PLEASE tell me what happend....


Here's the scenario....
I was in my garage lab.....working on the synthesis of HTMD...everything went fine....I used the instructions I got off of google it called for

90ml H2O2 20%
50ml Citric acid
20g of hexamine

Now I've seen this synthesis on this site before and some are a little different but this one had me add the Hexamine to the H2O2 and chill it for an hour at 5 degrees C and then slowly, such as the nitric step in picric , until mixed then filter with 15g of sodium bicarbonate in 400ml of distilled water, then re-chill for 24 hours.....Then filter and dry.....Which I did with all pure grade chemicals

HERE'S MY ISSUE

I set the filtrate in a glass 2000ml Beaker and it was fine looking good and drying ( IN MY FUME HOOD )....The next day after I got back in my lab, not but 13 hours later I came to check on it and it was dry enough to slightly clump up so I stirred it with a glass rod out of the beaker on a watch glass and walked over to my sink to rinse and wash the beaker and BOOM it blew on the watch glass, SCARING THE SHIT OUT OF ME......

Why would this of happened!!!!!! Not to mention I dont see any glass or residue in of around my fume hood.....AND its a damn good lab fume hood I got from my dad's college lab.....

SOMEONE PLEASE HELP ME I just dont understand how this happened in a 75 degree home air conditioned environment??
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Chainhit222
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wink.gif posted on 22-9-2010 at 05:58


organic peroxides are not your friends. Did long crystals form? If you break up a large crystal of primary explosive it is much more likely to fuck you up.


You should seriously keep your organic peroxide synths < 3 grams. I remember on totse this one kid blew his hand up with 10 grams of acetone peroxide crystals he was cutting up with a playing card.

Why were you using such a large quantity of hexamine? Secondaries were invented for a reason. Put that hexamine to better use nigga!

Just be glad you don't have a chunk of glass in your eye or missing fingers. The only "safe" organic peroxide in my opinion is MEKP.... but I would not use any of these explosives for anything other then a burn test, MAYBE a paper tube salute. I would personally not press caps with them, alot of people do, but I would recommend against it.


But I must say, a spontaneous detonation is interesting. Usually I hear about accidents involving someone breaking a crystal, never it exploding by itself.

[Edited on 22-9-2010 by Chainhit222]




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-Vogels Textbook of Practical Organic Chemistry
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madscientist
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[*] posted on 22-9-2010 at 06:35


Spontaneous detonation of peroxides is a notorious problem. They are never safe.

I've even heard of them detonating on submersion in water.




I weep at the sight of flaming acetic anhydride.
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hissingnoise
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[*] posted on 22-9-2010 at 07:12


HMTD is one of the safer peroxides and the pure compound shouldn't go off without reason.
I've used the synthesis given in COPAE many times without problems and have about 15g in my fridge for months.
The precipitated HMTD doesn't need neutralisation with NaHCO3 but washing several times with cold water is highly recommended.
I wash it thoroughly while it's still on the paper and leave it to dry at RT.
I remove it from the paper by carefully scraping it off with an improvised soft plastic spatula.
If the experience hasn't put you off for life you could try the synth in COPAE (in the site library), using say half the stated reactants.
It uses 30% H2O2 so if your H2O2 is 20% you'll need to do some calculation.
Its worth remembering BTW, that HMTD is unstable above normal temperatures.
It's possible that traces of NaHCO3 remaining in your HMTD could have caused it to become so unstable that it detonated spontaneously.


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[*] posted on 22-9-2010 at 14:16


One of the "safer" peroxides huh... Let me tell you, safety and organic peroxides really shouldn't be used in the same sentence. Amazing you have to tell someone with almost 1400 posts.

Impact sensitivity is SLIGHTLY lower compared to TCAP and it is LESS volatile. However, chemical stability in combination with possible impurities make HMTD just as dangerous IMO. There is ALWAYS a reason why accidents happen, with most primary explosives however, the exact reason why it exploded "spontaneously" is not always directly apparent. As said earlier by others, make small batches, not 15 grams or so. Organic peroxides have a long and bloody history of accidents, not exclusively to amateur experimenters, but to experienced chemists as well...

Do you have any idea why plastic tools are never used in pyrotechnics btw?
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stygian
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[*] posted on 22-9-2010 at 17:26


static?
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Bismuth
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[*] posted on 23-9-2010 at 01:23


Yes, static would be correct. Plastic generates a lot of static electricity and has been the cause of many accidents in the hobby of pyrotechnics. Don’t forget, that the substances that are used in pyrotechnics are a lot safer than HMTD.

I agree strongly with nitro-genes, the organic peroxides are dangerous as heck. You shouldn’t deal with them, and if the synthesis interests you; for god sake make very small quantities of it. FLchem10’s post is nothing new, I’ve read at least a few times about samples of HMTD just detonating for no ‘apparent reason’. The organic peroxides are notorious for being very unpredictable.

The amount you were making was frankly ridiculous too. You shouldn’t have any intentions to store it and it doesn’t take much to use as a detonator. As well as it having a lot of chemical incompatibilities, HMTD is also quite sensitive to friction. It’s much more sensitive than AP towards mechanical stimuli by contamination, to the point of auto-detonation on a shelf.
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[*] posted on 23-9-2010 at 03:47


As has been said several times above, peroxides just aren't safe. Those that experiment with it (and I did so myself for several years) usually get away with it a number of times, but if you regularly synthesize peroxides for an extended period of time, you will experience premature explosions.

For this reason the amateur experimenter should consider:

A) Moving on to secondaries along with less sensitive primaries. The key to practically all good primaries (azides. tetrazoles, diazo-compounds, etc.) is nitrite, so if you can buy or make nitrite you're set.

B) Reducing your scale. One of the great things about high explosives is that practically all of the effects that HEs deliver (metal cutting, shaped charges, fragmentation, etc.), can be had even with tiny amounts (less than a gram).
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FLchem10
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[*] posted on 23-9-2010 at 09:32


I really dont think I actually used that much Hexamine, but anyways, I have made it before and yes I regret not making a lower amount......

What I had was just filtered, Then from the filter pour onto the glass and the crystals weren't long IDK I did something wrong with this particular one.....but Ive made (small) amounts of this once in a while and never stored for 24hours dry......I keep it in 2g amounts in a explosive proof ( I shouldnt be saying proof its just think metal. If I had to describe it...I would say its like putting it in a "Firesafe Brand" safe and thats in a metal rifle same ) SOOO

I know the deal with peroxides like this and usually dont make them but I had just enough of those particular chemicals left to make a batch but that will be the last time....

I do how ever dont quite see how people are getting so hurt by it unless its really getto synthesis chemistry.....I just am say this because there didnt seem to be much damage....then again I did have it in a pretty nice fume/reaction/hood/cabinet

I am surprised to see everyone shooting all these different opinions on HMTD!?!

Thanks for the replies guy I knew that's what everyone was gonna say just my first time with a spontaneous SCREW UP!!
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[*] posted on 23-9-2010 at 11:07


It is an interesting question how some spontaneous decomposition could produce enough heat to detonate
the damp material. You would think that the moisture would
limit the temperature to 100C (although portions could
have dried out)

The original poster was really lucky! The friction of a
glass rod against the bottom of glass beaker could
easily set off HMTD, and fragments from a 2L beaker
propelled by 10+ grams could easily be lethal.

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hissingnoise
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[*] posted on 23-9-2010 at 12:33


Quote:
It is an interesting question how some spontaneous decomposition could produce enough heat to detonate

The other interesting question is what caused such decomposition?
HMTD reacts with most metals even when dry and moisture speeds the process.
A tiny, unnoticed metal fragment on the watchglass could quite possibly account for what happened.


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FLchem10
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[*] posted on 26-9-2010 at 16:43


I am pretty good about using very clean glassware but I didnt know that mixing up or even moving the filtered product onto the watch glass with a glass rod can make friction of that magnitude. I didnt even know that smooth glass agains smooth glass made any friction of that sort....

The theroy of the watch glass having something on it is the closest thing I can think of to make that sort of result.... Plus it being so recently washed and pretty wet....Thats why Im guessing it didnt explode in a much more dangerous manner....
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hissingnoise
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[*] posted on 27-9-2010 at 03:06


Quote:
Thats why Im guessing it didnt explode in a much more dangerous manner....

I was kind of guessing that you didn't have a full detonation. . .
But it's difficult to know the exact cause of the deflagration - metal contamination on the glass or perhaps the use of bicarbonate in washing.
As I said, properly washed HMTD,, shouldn't go off without good reason.
The contaminents in precipitated HMTD would likely be ammonium citrate, citric acid, H2O2 and fragments of the original hexamine.
These are so soluble that plain water removes them well.
But to ensure good stability, several washings are required.

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[*] posted on 28-9-2010 at 08:33


Quote: Originally posted by FLchem10  
Here's the scenario....
I was in my garage lab.....working on the synthesis of HTMD...everything went fine....I used the instructions I got off of google it called for

(snip the "recipe")



Now I've seen this synthesis on this site before and some are a little different but this one had me add the Hexamine to the H2O2 and chill it for an hour at 5 degrees C and then slowly, such as the nitric step in picric , until mixed then filter with 15g of sodium bicarbonate in 400ml of distilled water, then re-chill for 24 hours.....Then filter and dry.....Which I did with all pure grade chemicals

HERE'S MY ISSUE

I set the filtrate in a glass 2000ml Beaker and it was fine looking good and drying ( IN MY FUME HOOD )....The next day after I got back in my lab, not but 13 hours later I came to check on it and it was dry enough to slightly clump up so I stirred it with a glass rod out of the beaker on a watch glass and walked over to my sink to rinse and wash the beaker and BOOM it blew on the watch glass, SCARING THE SHIT OUT OF ME......

Why would this of happened!!!!!! Not to mention I dont see any glass or residue in of around my fume hood.....AND its a damn good lab fume hood I got from my dad's college lab.....

SOMEONE PLEASE HELP ME I just dont understand how this happened in a 75 degree home air conditioned environment??




STOP!

You just got your 1st and most likely final "God shot". You had better start reading and studying a HELL of LOT MORE rather that asking questions like "help me".

NO ONE will help get your hands to work properly again let alone plastic pulled from corneas.

Pretty much this is a 1st and final. Don't push it any more.

You've heard it all before: static - unknown origin plus collection point of static, possible magnification of refracted light, lack of proper temp control (what happens when a peroxide is synthesized and why is it mandatory to keep it in a lower temp? (you had it in possible 30 C & all the real facts of the synth are unk).

When this thing occurs in the wrong setting suddenly confirmed Atheists are heard to mutter, "Please God allow me to see again; help the doctor get the plastic out of my cornea".
Or the MOST common "Oh God, oh God, oh God.....can they get my fingers that are left on my hand to work?"

STOP. This sort of query is a very old story. It's a wonderfully lucky warning sign & IF you heed it you will be much happier. BELIEVE ME!



[Edited on 28-9-2010 by quicksilver]




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Rosco Bodine
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[*] posted on 28-9-2010 at 11:38


Wise men talk because they have something to say; fools, because they have to say something.

Plato

Greek author & philosopher in Athens (427 BC - 347 BC)

Am I the only one who is growing weary of such discussions as is this thread where replies further strain credulity by indulging such unworthy and /or implausible topics as are represented by the original post ?
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franklyn
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[*] posted on 29-9-2010 at 15:35


Just my observation not the most relevant or informative regarding your primary query.
You did not do anything obviously wrong or it would have been immediately critiqued.
You were not observing the material or had instruments recording it when it underwent
this event so your guess is as good as anyone else's who might venture a hypothesis.
Sensitive primary explosives are unpredictable , particularly peroxides. HMTD although
more reliably made than TATP is more sensitive to initiation 3 cm as compared to 10 cm.
in the 2 Kilogram drop test See =>
4 Discussion - Decomposition of Mult-peroxidic Compounds Part II Hexamethylene Triperoxide Diamine (HMTD).pdf
Additional impact test data also in the following
The friction shoe test value is below the threshold of measurement See =>
4 Sensitivity - Attachment: Sensitivities & Performance of non-regular Explosives.pdf (1.3MB)
This file has been downloaded 2354 times

Take measures to minimize your exposure to injury
http://www.sciencemadness.org/talk/viewthread.php?tid=13791#...
http://www.sciencemadness.org/talk/viewthread.php?tid=13791#...

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Rosco Bodine
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[*] posted on 30-9-2010 at 12:26


Perhaps call the rubber police department and ask they immediately dispatch a rubber policeman to the OP's address ;) .....he may have been almost skewered for not having on hand a bamboo skewer or a PTFE rod or a wash bottle and the full circumstances ought to be investigated. This thread could devolve into one of those tiresome dozen page marathon "war and peace" chronicles of peroxide threads like some refugee topic from a checkered past at a more kewlish board.

Let's all evolve , try to rise a little higher :cool:

http://www.youtube.com/watch?v=1KK6J9CN4kM Inner Changes

http://www.youtube.com/watch?v=P95NWAHWLrc

http://www.youtube.com/watch?v=CiXR-pUrldw

http://www.youtube.com/watch?v=anKEzWO-i24

http://www.youtube.com/watch?v=k5HOBFpZRUE&fmt-18

http://www.youtube.com/watch?v=KShGGElRsxU

That monolith is an interesting thing huh

[Edited on 30-9-2010 by Rosco Bodine]
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franklyn
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[*] posted on 30-9-2010 at 19:06


The value of this thread is in elaboration of safe preparation and handling
of primary explosives which applies generally. Forensic examination of an
anecdote without physical evidence is a guessing exercise. Had explosion
occured as it was being handled then by definition something must have
been done to provoke it and arguably wrong. This did not occur and while
improbable these things sometimes occur for no apparent reason and one
cannot ascribe blame to no discernible cause.

The association of unintended explosion with peroxide compounds is the
result of it's simple synthesis facilitating many more instances of it's being
made relative to other compounds. Also made more by individuals that are
not rigorous in controling the circumstances in which it is made leading to
conditions that can foster unintended results. So there are more of these
instances occuring and reported out of proportion to other primary compounds.

.
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quicksilver
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[*] posted on 1-10-2010 at 08:24


Realistically, we don't have the facts to do a serious "post-mortum". The OP would have to have been prepared to outline step by step and almost second by second what transpired.
We would all be guessing. My gut tells me a hardened surface sliding on a primary but if we were to put that aside we don't know the circumstances of the static phenomenon.

1.) Was he working on a surface with shoes which could have produced enough Joules of energy upon contact? Or for that matter shirt / clothing of a static holding nature. (Synthetic materials)
2.) Did the glass rod lean up against a pile of materiel enough to start a slide within the container?
3.) Was there any angle to the container that could have produced that "slide effect"?
4.) Was ANY moisture present?
5.) Did any build-up of material occur on the glass rod?
6.) Then we have the weight-level of the synthesis which is problematic in itself as a gram would have surprised the OP but likely not harmed him, had he his protective garments and distance in his favor.

It seems that to really do justice to analysis of the incident we would need facts from the OP that he would have [had to be prepared for] to document. I don't know if that can really be done....unless an experiment were actually set up to imperil the experimenter.

Yes: my issue is the glass rod and the static but it could have even been more sub-rosa! {By that I would consider the possibility of magnification of light building a heat source; however unlikely that could be.} *
It has often been presented in pyro lectures on class-B displays that the operator / manufacturer should always be asking themselves "if the thing shot right now what would be the causal agenda, outcome, circumstances?" Apparently the simple existence of a harden surface as a mixing or manipulating tool obscured that thinking pattern to begin with.
My point being is that we really can't know. However since the presented facts indicate the gentleman was not prepared for that eventuality he didn't project the possibilities of occurrence within his synthesis. Therefore my strongest perception is that the OP simply STOP synthesis of primaries until such time as he is totally imbued with a series of techniques to "cover his butt" in such an eventuality.


Quite honestly, I don't disagree with the concept that "elaboration of safe preparation and handling" would be damn valuable; not at all...... But do we really have deeper facts other than hardened surface and static?

* I know I was really "reaching" there, I was simply attempting a really obtrusive example.






[Edited on 1-10-2010 by quicksilver]




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Rosco Bodine
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cool.gif posted on 1-10-2010 at 09:34
black and white


The answer has come to me :cool:
If there's a rock and roll heaven ......
you know they got to have a hell of a band ! :D

http://www.youtube.com/watch?v=5WpRnjxuBys&fmt=18

http://www.youtube.com/watch?v=UjieZpfsCsc&fmt=18

http://www.youtube.com/watch?v=jMdWzIITwoM&fmt=18

Live long and prosper :cool:

You will have a better chance of accomplishing that if you
read some interesting information at the following pages and pay particular attention to what that cranky old grandpa aka Rosco Bodine has written because it tends to be generally reliable.

http://www.sciencemadness.org/talk/viewthread.php?tid=6317#p...

http://www.sciencemadness.org/talk/viewthread.php?tid=6567#p...

http://ysatel.net/ftp/roguesci/www.roguesci.org/theforum/arc...

http://ysatel.net/ftp/roguesci/www.roguesci.org/theforum/arc...

http://ysatel.net/ftp/roguesci/www.roguesci.org/theforum/arc...

http://www.youtube.com/watch?v=ApvYngDxta8&fmt=18 Look To The Future

[Edited on 1-10-2010 by Rosco Bodine]
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madscientist
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[*] posted on 2-10-2010 at 12:34


To further emphasize how dangerous organic peroxides are, and that ALL of them can explode for no apparent reason:

The peroxide bond in organic peroxides requires somewhere around 30kcal/mol to break.

25kcal/mol is generally considered the upper limit of available energy at room temperature.

...not a lot of headroom.




I weep at the sight of flaming acetic anhydride.
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nitro-genes
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[*] posted on 2-10-2010 at 14:43


Regarding the Callery patents....

Someone posted an interesting patent on a Dutch pyro-related board recently: (Bedankt Leander! :))

--> http://www.freepatentsonline.com/y2008/0190525.html?query=am...

Maybe we shouldn't think in terms of HMTD-AN double salts, but adducts of H2O2 and ammoniumnitrate/methylaminenitrate/hexamine dinitrate/etc. Nevertheless interesting though...

[Edited on 2-10-2010 by nitro-genes]
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[*] posted on 2-10-2010 at 23:54


Regarding HMTD structure and stability, I came across a neat journal publication. The reason I think it's neat is because I know of these professors ;)

Structure of hexamethylene triperoxide diamine
William P. Schaefer, John T. Fourkas, Bruce G. Tiemann
J. Am. Chem. Soc., 1985, 107 (8), pp 2461–2463
DOI: 10.1021/ja00294a043
Publication Date: April 1985
Quote:
Abstract: The structure of 1,6-diaza-3,4,8,9,12,13-hexaoxabicyclo[4.4t.e4t]ra decane (hexamethylene triperoxide diamine or HMTD) has been determined. The compound has a most unusual, exactly planar 3-fold coordination about the two bridgehead nitrogen atoms, with N-C distances of 1.421 (8) A. It crystallizes in the trigonal space group R3m: a = 10.417 (5) A, c= 6.975 ( 3 ) A, z = 3. The structure was refined by least squares to an R index of 0.034.


I think that's cool. Explosions are for tools. Analyze crystal structures if you want to hang out with the cool kids.

[Edited on 10-3-10 by DDTea]




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[*] posted on 3-10-2010 at 13:49


Quote: Originally posted by nitro-genes  
Someone posted an interesting patent on a Dutch pyro-related board recently: (Bedankt Leander! :))

--> http://www.freepatentsonline.com/y2008/0190525.html?query=am...

Maybe we shouldn't think in terms of HMTD-AN double salts, but adducts of H2O2 and ammoniumnitrate/methylaminenitrate/hexamine dinitrate/etc.

Hmm wonder where they got that one from
http://www.sciencemadness.org/talk/viewthread.php?tid=14308&...

H2O2 adducts have not proved to be energetic either in practice for me nor is
there evidence that they may exibit such property in literature.
http://www.sciencemadness.org/talk/viewthread.php?tid=7553&a...

.
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[*] posted on 6-10-2010 at 15:44


Everybody who makes organic peroxides to use in caps should be told that there is a very easy and safe way to det secondaries. Heat 1,5 gr ETN wrapped in multiple pieces of aluminium foil and use a minibooster 20 gr AN/ETN 10%. (ANNM might work too) This works all the times and dets every explosive that doesn't require a serious booster. I got the idea from a topic here, and it's my standard way of detting now. It's a shame why I heard of this method so late. It's ideal for the beginning HE-hobbyist.
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