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Author: Subject: erythritol tetranitrate recrystallization
prometheus1970
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[*] posted on 7-12-2010 at 20:29
erythritol tetranitrate recrystallization


I know most etn syntheses call for recrystallization in ethanol, but I'm pretty sure I've seen methanol also listed as a viable solvent for these purposes. I know I've seen that acetone will dissolve etn, but it's a bee-yatch to get the etn to precipitate back out of solution. Does anybody know if methanol will work?



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crazedguy
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[*] posted on 7-12-2010 at 20:43


well ive tried but i dont know if i didnt have the meOH hot enough or what the problem was i think it would work if you got it relatively warm hotter than i could get with hot water



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[*] posted on 8-12-2010 at 04:45


Methanol worked fine for me.

@crazedguy: You should read this thread http://www.sciencemadness.org/talk/viewthread.php?tid=14999
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prometheus1970
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[*] posted on 8-12-2010 at 06:33
routes to neutrality


I generally use baking soda (bicarb) solution for neutrallization, but the bicarb usually precipitates back out at some point making things messy, plus water is not miscible with alcohol. I know ammonium hydroxide works well too. My question is do I need reagent grade NH4OH, or will grocery store ammonia work fine?

[Edited on 12-8-2010 by prometheus1970]




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[*] posted on 8-12-2010 at 06:50


Depends on the "brand" of NH4OH: there IS some 10% that is really, totally free from soap or any adulterants that will be fine. In fact you could make a ammonia generator bottle of a sealed container with a flexible feed-line and some ammonium sulfate (fertilizer grade) and some Lye; drop in a small amount of water and feed the tube through the existing 10% NH4OH and drive that up beyond expectation. I've used both ammonia and sodium carbonate ( or bicarb)and I found that the solid did a better job but left some material on occasion while the ammonia left a very pure product but wasn't as neutral in the final analysis.

My suggestion is to mix your bicarb with very hot water so as to really bring it into solution prior to use so you don't get any real weight changes. or use a very strong ammonia solution.
I have done very distinctive side by side experiments of methanol and ethanol ad both are fine. Acetone is to be avoided! Methanol appears to produce a more uniform crystal: a bit more granular than platelet: ethanol gives the clearest, thinnest platelets, the crystals shaving much more rapidly.

[Edited on 8-12-2010 by quicksilver]




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[*] posted on 8-12-2010 at 07:08


Quote: Originally posted by prometheus1970  
plus water is not miscible with alcohol.


If that were true, than those yellow HEET bottles wouldn't be methanol.

[Edited on 8-12-2010 by gnitseretni]
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prometheus1970
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[*] posted on 8-12-2010 at 09:12


My bad, I was thinking back to my high school days when we made "trash can punch" and the etoh would rise to the top. I ws temporarily confusing solubility with density differences.



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[*] posted on 10-12-2010 at 09:04


Has anyone tried recrystallization by melting and slowly cooling? It's probably not the best way to do it but it's certainly feasible.



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quicksilver
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[*] posted on 10-12-2010 at 09:13


The whole idea is to have the solvent carry away the impurities. Re-constitution would not accomplish the separation of adulterants.



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[*] posted on 10-12-2010 at 09:31


Quote: Originally posted by DougTheMapper  
It's probably not the best way to do it but it's certainly feasible.

Forget probably, it's definitely not the best way!
Melted ETN is fine when left to itself but the liquid is more sensitive than the solid!
Agitating melted ETN would be courting disaster!



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shocked.gif posted on 15-12-2010 at 18:50
Recrystallization in Methanol and Sensitivity


In my experience, methanol is the most attainable and economic recrystallizing agent- 20L @ $40. Quicksilver mentioned in his legendary ETN lab diary that methanol is as viable of a recrystallizing/deacidifying agent as ethanol.

I have used it myself, and was certain that methanol has to be warmed up to about 50C. However, I noticed time and time again ETN gained a much different structure, crystals being much finer and the unshaven flakes being extra "fluffy" and light. This always resulted in more sensitivity in impact tests......15-20cm hammer fall would always provide a report. :o Usually, it requires more acceleration, but it went off from a rather regular fall, if I recall correctly. As a result, I have been recrystallizing ETN in regular temperature methanol, just using excess of it where ETN dissolves without much effort and generously adding sodium bicarbonate to the mix. Am I cheating my ETN of being acid-free by doing that? So far, ETN has been stored for 2 months without any change in color or sensitivity.

I've also had an experienced friend tell me that long recrystallization in methanol produces long ETN needles, with similar properties to primary explosives.


Disclaimer: Roscoe, if you think this belongs in ETN recrystallization, please, merge them, but I think this needs its own thread at least to get the discussion started.



[Edited on 16-12-2010 by holmes1880]
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[*] posted on 15-12-2010 at 18:55


As long as it is recrystallized it should have no problem being stored for a very long time.



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[*] posted on 15-12-2010 at 19:01


I would think so, sure. But I am questioning the difference in structure b/w warm/hot recrystallization methods. There is certainly quite a difference. I once did a newb mistake of warming the pitcher with methanol to 55C as advised, using pot with hot water, but didn't realize the bottom of the pitcher will be hotter than the rest of the methanol mix. Surely enough, quite a bit of ETN melted.....maybe that's what cause the change in structure. Cast ETN to recrystallization, and we have a type of very low density fine crystals.
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[*] posted on 15-12-2010 at 19:08


"Much like PETN, ETN is known for having a very long shelf life. Studies that directly observed the crystalline structure saw no signs of decomposition after four years of storage at room temperature." Wiki
For the melting of ETN it melts at 61C witch I think would be no big deal to be at 55C for recrystallization, it decomposes at 160C so it wouldn't change the structure to be at 61C although it would be much more sensitize.




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15-12-2010 at 19:53
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[*] posted on 15-12-2010 at 20:35


I really don't know. Quicksilver maybe can shine some light on the warm recrystallization.


[Edited on 16-12-2010 by holmes1880]
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[*] posted on 15-12-2010 at 21:37


When you precipitate and acidify those fumes are nasty are know what you mean you should filter and wash your or rinse your ETN before recrystallization which should prevent those fumes, unless you get a headache from just MeOH



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[*] posted on 16-12-2010 at 07:36


Quote: Originally posted by crazedguy  
"Much like PETN, ETN is known for having a very long shelf life. Studies that directly observed the crystalline structure saw no signs of decomposition after four years of storage at room temperature." Wiki


Be very careful with Wiki and energetic materials.
Wikipedia (The "Encyclopedia the Public Writes Itself") has been so wrong at times it has cost people money who thought they were getting some reviewed source & it was OK to bet on it.*

Find out what "studies" the writer was quoting. I'll not be surprised if there is nothing in notes other than the usual "Federoff, Urbanski" - - if that.
There is VERY little background material on ETN. It simply fell by the wayside due to the expense of the original source materiel for nitration. In that period in history; it simply cost too much to be little more than a lab curiosity & a bone of contention between Nobel and DuPont: it really was not used commercially. It's the commercial use energetics or the deeper research destined to a commercial (or military application) that actually have some serious science behind them.

Many people who can run a good synthesis have found that ETN will have damn good shelf life IF re--crystallized; neutralized of all acid, etc, etc. but that's personal experience for individual to individual; not a peer-reviewed stone-real post Doctoral paper.


edit:
My experience with methanol & ETN is similar to that holmes1880 described. Ethanol & methanol are appropriate to re-crystallize ETN. Acetone actually is too strong a solvent.
There is a "family similarity" in some aspects of MHN and ETN. The deepest most people dig is the NOV 20th patent but supposedly Naoum wrote more about it than what he published in his book (pp 237, etc)


* The reason I am commenting on this issue is that THERE REALLY IS VERY LITTLE ON ETN Especially in-depth post-Doc studies & similar MODERN material. There are some folks who are very good at hunting down written, quality background on their hobbies. ETN is basically a "lab explosive" & it did not get near the attention MHN did at any time in the past (at least that was ever public).
ETN is in many aspects, an unknown. Be VERY careful with it. There are areas that chemists have gone with "family" oriented materials that one could extrapolate with some reasonable bit of likelihood however.....explosives blind and mutilate in botched experiments & careless handling. Some of the BEST pyrotechnic and special effects engineers and lost most of their hand(s) or been blinded. Some of the most knowledgeable chemists have had serious tragedies as well.

[Edited on 16-12-2010 by quicksilver]




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[*] posted on 16-12-2010 at 08:09


What really annoys me is the volume of pretenders and/or outright idiots who have some sort of compulsion to participate in discussions in science forums as shuck and jivers about all the authoritative "tests", observations and "experiments" which they have done only in their "dreams", and it becomes evident that they have less knowledge than they pretend. It is like some kind of unattainable descent to an apprentice status for them to admit they are a novice and simply to ask about what they do not know, honestly seeking knowledge, and it can make for a lot of confusion and misinformation being exchanged.
I never mind anyone wanting to pick my brain a little about what I may know that they don't know.....but I don't like it when the guy doing the brain pickin' is a plumber who is pretending to be a brain surgeon engaged in fixing inside my head what isn't broken in the first place.

Exhibit A: hot solvent recrystallizations involve a vapor pressure ....so just maybe some sort of pressurization to a controllable and releasable extent might be a plan there.
They put these nifty threaded lids on bottles and jars which can contain a degree of pressure according to how tightly the closure is torqued, and when the pressure exceeds the sealing ability provided by a given torque ....wouldn't you know it ....like magic they leak.

What is just mind boggling to me is how somebody who
has allegedly done so many "tests" with their drop test apparatus ? would be so technically proficient and advanced in that scientific methodology and yet not understand how threaded closures on containers are useful for things like keeping nasty hot methanol vapors inside.

Am I missing something here or is it more like I am getting everything just fine.
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[*] posted on 16-12-2010 at 08:27


Quicksilver is correct in concluding there is a lack of information on ETN. Thank you, quick.



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[*] posted on 16-12-2010 at 08:53


On that we can agree. Some charted ETN solubility data for specific solvents and cosolvent systems would be great to have. Maybe some of the pharmaceutical literature would have something listed under one of the medicinal names.

I was looking at a video showing a methanol recrystallization of ETN being done
and the methanol was being heated in a flask on a ringstand on a kitchen stove
over an open gas burner .....indoors of course.....and this video is of a Darwin award contender at work. If you want a dismaying look at reckless stupidity,
here it is in full glory:
http://wn.com/erythritol_tetranitrate_15g

Would you want to be the insurer for this *idiot* or for the property there ?

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[*] posted on 16-12-2010 at 09:47


I think, I know the ETN/methanol video you're talking about. http://www.youtube.com/watch?v=EEYtr1tU66E There is really only one, by "tooelitetodetermine". I think he just came up with that method on his own, although my first googbook search gave me a simple recrystallization method I use today. As dangerous as it might seem, I think he was rather safe.

Well, give me the worst case scenario of ETN getting past 70C.....it goes liquid and it's mixed with methanol, reducing its sensitivity. Or do you mean like the flask cracking and all that ETN going on the hot stove......;)
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[*] posted on 16-12-2010 at 09:51


Explosive vapors from hot methanol are bad enough and there you have a choice of what is worse the inhalation toxicity which is certain, or that being compounded by the ignition and explosion hazard of heating over an open flame.
This is worse than cooking rocket fuel on a hibachi....it is just off the scale dumb.

A hot water bath is the proper tool for heating the solvent container, along with some provision for carrying away the
fumes, and that should be controlled too.

[Edited on 16-12-2010 by Rosco Bodine]
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[*] posted on 16-12-2010 at 09:58


*chuckles* Hot methanol vapors is the worst part about that process. Now, if all those 50ml of methanol and ETN went on the stove, I predict deflagration. However, having that thin-glassed flask around in case of DDT is just spooky. Hundreds of tiny glass shards all over you.
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[*] posted on 17-12-2010 at 06:07


Another (|possibly dumb) question: isn't the 'synthesis' of ETN really just the nitration of erythritol?



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[*] posted on 17-12-2010 at 06:32


Yes. It's not a "dumb" question: as it (terminology) has utility.
However there are really specific reasons why some people widen their descriptors.

Syn·the·sis (snth-ss)
n. pl. syn·the·ses (-sz)
1. Within chemistry;
a. The combining of separate elements or substances to form a coherent whole.
b. The complex whole so formed.
2. Chemistry Formation of a compound from simpler compounds or elements.
3. Philosophy
a. Reasoning from the general to the particular; logical deduction.
b. The combination of thesis and antithesis in the Hegelian dialectical process whereby a new and higher level of truth is produced.

Not all explosive materials are nitrated, nor are they nitric esters. The use of the term imply a "coming into being" "a making". While nitration is common it is by NO means the sum of all methods to produce explosive (or energetic) materials. Often times a simple combination at a given temp (binary) will yield an energetic..... And thus -
"Why use terms such as "synthesis" or "energetic" when terms such as nitration and explosive may describe the same thing?"
Often by widening the methodology the usage standard can fit the application. One "energetic materiel" may be used as both an explosive and as a propellant - so by the usage of the term "energetic" we envelope the whole of it's possible applications. This is done for the reader's sake as he may be reading about the material in a contextual format. The same exists with a synthesis. Remember we don't stop at a nitration to make an energetic materiel. We neutralize, test, re-crystallize, etc. So by utilizing a wider encompassing description we describe what is really taking place. Think about a double base smokeless powder.



Edit: @ Roscoe: yes, I know what your talking about. I have thought that as well.
Often times shit like that makes me fly off the handle. When I was a kid we used to call that "Butt-fuck stupid" because generally the young wastrel couldn't find the correct hole with a compass, road-map, and written directions.
The absolute abominations on uTube with idiots doing things like heating flammable solvents in flame have made my blood pressure rise.






[Edited on 17-12-2010 by quicksilver]




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