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Author: Subject: erythritol tetranitrate recrystallization
prometheus1970
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[*] posted on 17-12-2010 at 14:33


I see, I was thinking of a nitration as being more like repainting a car rather than redesigning and rebuilding it, quite possibly the result of my limited knowledge of chemistry. I have degrees in psychology and philosophy.. I'm not wholly ignorant, nor unintelligent (not that I felt anyone was implying such) I've learned quite a bit about chemistry in the last couple of years (since I took up an interest in energetics), but I'm learning chemistry from the top down. I'm completely unaware of what your backgrounds are, I don't know if you just aced chemistry in high school, have bachelor's degrees or phd's in chemistry. I'm trying to compensate for my awkward approach to learning chemistry by taking very small steps and doing all the background research I can. I've always been very forthcoming in admitting that by using this forum I'm appealing to those in the know while admitting I'm not (in the know)



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[*] posted on 18-12-2010 at 08:06


Don't give it a second thought.

An excellent example is that long discussions go on about the use of acronyms, etc in communications clarity. I'm not sure if it's even important to many others. I had been average / mediocre in everything I did academically & it rarely bothered me that most everyone I've interacted with were brighter, more studious, or generally more successful than I was. Frankly I believe that intellectually, I have less going for me than the majority. But I have a large penis and THAT is important. :P




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prometheus1970
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[*] posted on 18-12-2010 at 11:30


most important is to speak softly and carry a BIG DICK!(as long as it's your own)



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[*] posted on 18-12-2010 at 12:34


It would seem discussion here is wandering off topic ....

so.....

Now that we are on the subject of bluegrass ....

http://www.youtube.com/watch?v=JjnV-KkUr_w&feature=relat...

http://www.youtube.com/watch?v=5zQmVgvHVvw&feature=relat...

http://www.youtube.com/watch?v=6pUPIVHifrM&feature=relat...

http://www.youtube.com/watch?v=n10GGxocZt4&fmt=18

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prometheus1970
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[*] posted on 18-12-2010 at 13:09


Back to a question that pertains to realty. Is there any problem with using NaOH solution for neutralizing other than the possibility of over-neutralizing (making basic)? If that is the only problem, wouldn't using a very weak solution solve that problem?



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[*] posted on 18-12-2010 at 22:17


NaOH, from the basic google research results, seems like a bad idea to mix into an ETN solution.....it makes lots of heat with water. Better to just overdo it with NaHCO3.......worst case scenario your nitrate will have a bit of baking soda in it.

[Edited on 19-12-2010 by holmes1880]
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SB15
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[*] posted on 23-12-2010 at 13:17


NaOH can work if added dropwise as a very weak solution - 0.1M is fine. The neutralization reaction with NaOH has the advantage of producing no gaseous products, so it won't foam your product into the sink if there's a good deal of acid left in the wash water. You'll need litmus to determine when the solution is neutral, as there won't be any clear visual indicator.
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shocked.gif posted on 14-4-2011 at 01:47
Yellow liquid precipitation


First time nitration of 7.5 g erythritol with 50ml H2SO4 (96%) and 30 g KNO3.
SA and KNO mixed till clear liquid, chilled in icewater bath to <10°C, sugar added while stirring over 30' period. Continued stirring for 20', then left overnight in same water bath.

Mixture was solid next day, adding dH2O produced red nitric fumes, possibly from stuff stuck to the sides and on stirring rod, stopped after swirling. poured in coffee filter, 2 more washes.

Didn't have as much dH2O as I would have liked, and next actions were not so smart.
First step was neutralising the acid; Added dH2O, than NaOH, 4 mol/l :( while stirring. Mix got warmer and got foam on top. Fourth addition went passed neutral straight to pH 13 or 14... :o
Best option I could think of was adding some of the previous water wash. That got it acid again, then added small amounts of NaOH till pH around 6.

Filtered, left on stack of coffee filters to absorp most of the water, then put in beaker and added methanol.
Without quantitative solubility data to go on, and having added a considerable amount of methanol, I turned to acetone. When that didn't have any effect I of course realised I was trying to dissolve salts, not ETN. :(

Cooled the solution, fitered out the salts, then let evaporate for a night to reduce the volume.

Added icecold dH2O, filtered, got a bunch of white semi-transparent flakes. However, on the bottom of the flask was a yellowy mass with crystals in, as if the crystals had half melted.
Dissolved the contents of the flask in a little methanol, then slowly added cold water while swirling contents. When the water turned white from the crystals precipitating, a yellow liquid formed at the bottom.
First thought was Ooow shit, NG! :o

Separated yellow liquid whith eye-dropper.

A tiny amount of the fluid was absorbed in a strip of filter paper. Burnt with yellow flame and some crackles...

put it in a test tube and added water, white crystals formed at the contact surface, separating the two liquids. at the bottom there are some tiny solids floating around.

First theory was: impurities in chemicals, glassware, tools or solvents. Did I spill some glycerin somewhere? Maybe reaction mixture warmed up and developed hotspots after I left it.

Been doing some serious reading last few hours. Flunked chemistry 20 years ago, so it's a steep learning curve.
Came across a pdf:
"The alkaline hydrolysis of nitrate esters" by R.T.M. Fraser

Given the rapid hydrolysis of NG in alkaline medium (k = 0.24 /(M.s) ), and the similarity between NG and ETN a plausible scenario?
That leaves the question of what the liquid is. I know it didn't solidify after a few minutes in ice water, it's soluble in methanol and aceton, not soluble in water.

Don't want to take the risk of examining it further, will dispose of it in a safe way. A lot more learning to do before I experiment with HE again.
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[*] posted on 14-4-2011 at 06:59


Yes, you swam way out to sea on your neutralizing procedure. One method to keep it simple and effective is the use of standard commercial ethanol of 95%. The 5 [remaining percentage] will contain enough water to dissolve sodium carbonate (or bicarbonate) and a simple re-crystallization therein will allow the base to enter the crystal as it re-forms. A few washes with a anti-acid before hand and that type of re-crystallization should bring you to a comfortable 7 without going overboard.
Too many variables exist to take a good guess as to the liquid.




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[*] posted on 14-4-2011 at 09:19


I imagine the yellow liquid was a mixture of lower nitrated forms of Erythritol, resulting from a significant amount of partial esterification.

Your entire process seems really quite absurd, and you should probably do a lot more research before attempting another HE synthesis.




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[*] posted on 14-4-2011 at 11:15


@quicksilver:
Thanx for the tip. :)

@SB15: I know, I had some written notes on the reaction itself but couldn't find the ones about neutralizing and recrystallizing. So I improvised, based on experience with some other reactions. Should have gone back to check. (don't have a pc there).
With less sensitive chemicals one can overshoot neutral with few consequences, and simply boil off excess solvent. Realised a bit late that that wasn't an option ...

Lot's of mistakes, I know. But no point in posting if I embellish the truth. :)

For those interested: The pdf I mentioned: The Alkaline Hydrolysis of Nitrate Esters
http://www.dtic.mil/cgi-bin/GetTRDoc?AD=AD675917&Locatio...
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[*] posted on 20-4-2011 at 23:22


Hi,
i have few experiences with ETN.
Recrystalization is made from methanol - on magnetic stirrer, quick cooling => nice crystals, but is little bit more sensitive, than i want. So i was thinking abaut flegmatisation. Other explosives, like PETN or RDX can be flegmatized with some wax (parafine, or even with DNT), pressing is easier and safer. But, what can we use for ETN? DNT is impossible because of low melting point of ETN, wax maybe better...
Do you have any experiences?
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[*] posted on 21-4-2011 at 06:11


I certainly agree that ETN is extremely sensitive & has some similarities to MHN: it IS potentially extremely dangerous. Made correctly, it possesses some of the highest levels of sensitivity of any solid secondary. To desensitize (from an industrial perspective) you are on the right track with wax. That could work provided you used a very refined Bee's wax that had a very low MP. The major challenge would be to use the appropriate amount (not too much or too little) & to coat the material as completely as possible.
Castor Oil has been used as a phemitizer (Cheddites) with success but the "run off" is not desirable. Perhaps the best overall method would be to develop a plastique as it provides a degree of container development in addition to protection from many stimuli. The wax ratio that had been used in RDX was a 1:7 level - I believe that may be a good place to start for ETN as well.
With commercial MHN the agenda was to avoid and "snap cap" or pressure top (cork) friction containers, static electrical discharge, etc. If you use a screw top, coat the threads with Teflon tape and don't put the lid on tight.
I would add that you could reduce crystal size by using a temperature swing (from hot to cold) when re-crystallizing: smaller crystals are easier to work with for this agenda. Methanol works very well but there is often some product lost in the alcohol itself, so drowning as a re-crystallization procedure will get your full yield back. I believe you're on the right track w/ wax. That is what I would start with if I wanted to maintain a particulate material. A solid (as in PBX or plastique) would certainly affect this issue in a positive direction however.


Please see patents on "PBX" via a search. There is a great deal of valuable information on this issue as a whole.

[Edited on 21-4-2011 by quicksilver]




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[*] posted on 21-5-2011 at 06:39
Recrystallisation with Ethanol


Hi there.

When i did my last ETN experiment, I was not satisfied with the products apperance. I had dissolved it in denatured ethanol and then crashed it into cold water.
The product had a very low density, like little snowflakes, and got airborne anytime I worked with it, contaminating erverything.
Have you ever used Eckart bright flake aluminium? Just like that.


Now I recrystalised a batch of ETN by slowly cooling down a saturated solution in denatured ethanol.
Because I didn't have enough ethanol ready and a small amount of ETN had not dissolved I added about 5% Acetone.

Upon cooling it developed small needles... When you touch it, it feels like hair, even stings a little.
I haven't compared sensitivity yet.
Density is MUCH bigger.


I whould prefer some sqared crystals over the long needles, who are still annoying to work with. I want table sugar!
Using Methanol is out of question, it's hard to get here for private people due to it's toxicity.


I thought about stirring the solution while cooling down, keeping the stuff in motion.

Do you have any idea how to prevent needles forming?

[Edited on 21-5-2011 by mabuse_]

[Edited on 21-5-2011 by mabuse_]
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[*] posted on 21-5-2011 at 08:09


Like quicksilver said, do not warm up your methanol/ethanol, but simply use larger quantity of it. I wouldn't shy using 300-400ml per 20grams of product, it dissolves fast and the result are small ETN scale-like plates that are easy to shave. There won't be any needles- those needles start coming up with hot recrystallization that you're doing.

[Edited on 21-5-2011 by holmes1880]
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[*] posted on 18-6-2013 at 18:37


Alright ... I got impatient and having a tough time now.
I was all out of MeOH and wanted to re-crystallize some ETN.
So I tried some Acetone. Well to my surprise I had about 70+ grams of ETN dissolved in about 150 ml of Acetone. Wow.
So I proceed to add some 500 ml warm carb and urea solution to the ETN solution after filtering..
And the mix turns milky. Great it's ppting out ... I thought.
Well ... When I stopped stirring I noticed a separate phase on the bottom.
I am assuming this I a saturated solution of Acetone and ETN since it appears to be close to the original volume of Acetone used.

I do have the flask sitting in a 50*C bath with stirring hoping to evaporate the Acetone off and form crystals in the carb urea solution.

How do I separate it out ?

Well driving off the Acetone seems to work .... I see crystals again.
However .... They are not needles or plates. They seem to be cubic and dense clusters.
Won't know for sure till I dry them.

[Edited on 19-6-2013 by Motherload]

Ok ... The crystals are somewhat dry. They resemble NaCl crystals .... They are not fluffy at all.
Anyone know about this crystal structure ?


[Edited on 19-6-2013 by Motherload]




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[*] posted on 21-6-2013 at 09:42


ETN vs Mannitol Hexanitrate
Which one have better stabilty than other ? ( which one is more sensitive impack and friction ? ) I guess M.Hexanitrate is more sensivitiy than ETN but I read it is more stable than etn :S

[Edited on 21-6-2013 by gamez34]
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[*] posted on 11-7-2013 at 23:22


I took a pic of acetone only recrystalised ETN at 10X


[Edited on 12-7-2013 by Motherload]

image.jpg - 160kB




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[*] posted on 12-7-2013 at 11:38


Hi

considering the neutralisation issue, is it necessary to use NaHCO3 ect. ?

Ethanol is not a very good solvent, hence you have very much of it to dissolve the acid (enough?).



Also when first crashing the acid/ETN slurry in water, why not just use a very large vessel for the procedure, so that the acid gets dilluted to a large extent?

I dont advertise the waste of precious drinking water, but considering that this is an expensive hobby tap water is dirt cheap.
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[*] posted on 12-7-2013 at 11:43


Wait, there's difference in tap water and drinking water? For final recrystalizations, I'd suggest only distilled water. For organic peroxides only distilled, or if it's not available, deionized water.
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[*] posted on 12-7-2013 at 13:38



Quote:

Wait, there's difference in tap water and drinking water?

Where I live there is no difference;)

But i had nothing in mind to use two different words for it.
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[*] posted on 12-7-2013 at 17:54


Neutralization and stabilization are huge issues with nitric esters. The great thing about using commercial "drinking" EtOH (95%) for a recrystallization is that the 5% or so of water allows a bit of carbonate to go into solution with the dissolved ETN, and thus is crystallized into the ETN, allowing more assured stability over time. I believe Quicksilver mentioned this up thread. Golden Grain, or Everclear (brands of 95% EtOH for consumption) are very common here in the states, and very convenient for this, in my opinion.



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[*] posted on 10-11-2013 at 12:50


I've been experimenting a bit (had some free time today) with a different way of making ETN using anhydrous Nitric acid so as to hopefully make the procedure a bit more scaleable. I tried dissolving 35g of Erythritol in 100ml of Sulfuric acid not letting the temp rise above 40*C, then cooling this back down to 25*C, while slowly adding 70ml RFNA over about 15 minutes with stirring, not letting the mixture go above 35*C, after this is all added, stirred for 10 minutes and then slowly cooled down to 10*C then poured into 600ml Cold water. Theoretical yield is around 85g, I haven't weighed it yet but it looks to be about 30-40g. Next time I will try this with adding the sulfuric acid/E mixture to Nitric acid and taking more time, I also am wondering if the Erythritol not being finely powdered had anything to do with it, using stoichiometric amounts of HNO3 for Eryrhtiol, I think excess of HNO3 would give much better yield, but that would defeat the purpose.

As for recrystalization, one thing I have been seeing is while trying to dissolve all ETN in ethanol, it looks like ETN melts and settles out in the bottom as a milky/waxy liquid in the solvent, but the thermometer reads 55*C? (MP of ETN is 61*C)
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[*] posted on 21-1-2014 at 13:58


i just wonder what the specific solubility would be for ETN

also for ETN dissolved in acetone then evaporated off.. adding abit of NH4OH should do the trick..? then let it evaporate off and if desire for more pure product rather than just ETN with great density water could be poured over it then be re-evaporated from acetone
H2SO4 + NH4OH > (NH4)2SO4
which will obviously be safer to dissolve away rather than attempt to thermally decompose

if anyone really cares about it, (NH4)2SO4 shouldnt be the worst of all impurities as it is capable of being part of a detonation, not yielding much if any real power, but its one of the good impurities out there




~25 drops = 1mL @dH2O viscocity - STP
Truth is ever growing - but without context theres barely any such.

https://en.wikipedia.org/wiki/Solubility_table
http://www.trimen.pl/witek/calculators/stezenia.html
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[*] posted on 21-1-2014 at 14:22


I'm not sure if the acidity of the sulphate is desirable. It may give tiny amounts of bisulphate and nitrite, and some nitric esters don't stay too stable in water and acidity(nitrite will give off water). I've been neutralising with dilute ammonia and had no problems whatsoever so far. Not sure how is magnesium carbonate for a stabilizer. Looks very gentle compound.
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