Sciencemadness Discussion Board

methyl nitrate

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vulture - 5-6-2003 at 12:48

Methylnitrate, CH3NO3, is the nitric acid ester of methanol.

Volatile liquid, D 1,2075, boiling point: 64,6C.
Deflagrates at 150C.

I was wondering if anybody ever prepared this compound and/or knew a good synthesis.

Safety warnings and more data are also welcome as usual.

a_bab - 5-6-2003 at 13:01

I never tried it although I may sometime. I know that the headache you can get from it is like a flash (almost instant pain if smelled). It's very sensitive (much more that NG) and very volatile also. I colected some info during the past years about it in a single text file. I don't have the references, but the info seems to be reliable.

Attachment: myrol.txt (17kB)
This file has been downloaded 3984 times


vulture - 5-6-2003 at 13:09

I doubt the information about it exploding at the boiling point. My chemistry encyclopedia says 150C as the decomposition point and this: http://www.orgsyn.org/orgsyn/prep.asp?prep=cv2p0412 states it can be distilled when properly neutralized.

a_bab, your text was very helpful.
8000m/s aint nothing to sneeze at...

Madog - 5-6-2003 at 16:56

i want to make it but i need to get some methanol, ugh.

i do have a kinda cool file that has some info, itsn ot too scientific, its one of those improvised explosive PDF things, you know what i mean, its of that sort.

PHILOU Zrealone - 6-6-2003 at 11:28

Distillation is really a hell and could cause severe explosions.
The fact they say it can explode at boiling point is that it often occure while distillating...aside with HNO3 and NOx fumes.

The use of urea nitrate is advised like in isopropanol nitrate from IP and 70% dillution HNO3.

I personnally would avoid as much as possible distillation (even under vaccuum)...it would be too bad to loose distillator, glassware and vaccuum pump.
50g to make 65g primary HE? Crazy....never more than a few grams at the time.

A friend of mine did CH3-NO3 by simply allowing CH3-OH to get dropwise into excess Urea nitrate + HNO3 (98%) at 0°C and mild magnetic stirrer agitation.Then with caution and by portions he dropped all the batch in iced water saturated with Na2CO3 and agitated faster with its magnetic stirer well in the center of the beacker for 1/4 h...the tiny droplets of CH3-NO3 and CO2 bubbles made the neutralisation flask cloudy.
There is very little friction that way and neutralisation is very efficient.Water is then tested for mild basicity.After standing for an hour an oily phase should float on top.It is collected with an eyedropper and placed in neutral distillated water where it is mildly agitated and washed a second time.After standing an oily layer in the bottom is the desired product; collected and put in a wel closed PE plastic vessel with CaCl2 dehydratant.Methanol might be added to reduce sensitivity to shock.
The plain product doesn't detonate easily when hit by a hammer, but readily when absorbed in tiny piece of paper.AN/MN mix is very sensitive and powerfull.

Better use the old NG preparation that distillate such a devil.:)

Iv4 - 7-6-2003 at 06:01

I was thinking about the making of formaline when I came across this.My idea(for formaline)was to add methanol to ammoniam nirtrate(don't know how I got that idea).After a few minutes I realized how it could'nt work so I'm thinking this be more aplicable here.

Madog - 15-7-2003 at 09:54

i just made some methyyl nitrate, here is goes...

11ml of H2SO4 and 7.5ml 70% HNO3 were cooled in an ice bath and 6.5ml methanol added to it in small parts keeping the temprature below 20C. the mix grew cloudy. after the addition was done it was swirled for another minute and then let sit at room temprature for about 5 minutes, a nice clean clear oil was observed floating on the spent acids. the mix was drowned with some ice cold water and a clear oil sat on the bottom. it was sucked outwith a pipet, a little was absorbed in paper and struck with a hammer, it made a satisfying crack.

the yield looked great, but i took a 1000ml beaker, and added about 200ml of water with sodium bicarb and then i squited some of the methl nitrate in there and it fizzed, but disapeared! how water soluble is it? i could still smell it good though, i think some disolved, alot formed a really thin layer ontop(couldnt see it really, not to mention get it off) and some stuck to the sides. but anyways, i couldnt see any of it.

im going to have ot do this again.

also, despite me takeing several good wifs of it, and actualy getting some of the wash water on myself, i have no headache. but then again, i have never gottten a headache from NG, even though i havegotten it directly on my skin, i did actualy get NG headaches 2 times, from tasteing it.

im going to try it again and try useinga small amount of water, putting the product in there, then add NaHCO3 solution into that and swirlingnad letting it sit.

Madog - 15-7-2003 at 12:00

:o:):D:D:cool:

i just did another nitration, this time i didnt bother to really neutralise and wash, i just detonated some immediately. the yield was bad this time, i dont know why,porobaly because the nitration itself was faster, i should have given it more time.

i detonated about a ml, i took a think straw, put some PETN in it, pressed, then some HMTD, pressed that down lightly, fused it, then i wraped a little paper towel around it and taped it in place(idea from brainfever, my standard "charge" for liquid explosives) i added about .8ml of it to the paper and whent outside, put it in a sand pile a few inches down. it whentoff with a, hmmm, not like NG, not a boom, it was a loud pfft, the sand shot strait up, the high VoD is evident here. unfortunately there was some kids in the pool next door and they started screaming after it whent off, just like the barking dog effect. luckily it was quite a strange sound, didnt sound like it was definately an explosion.

very nice.

edit:

it doesnt have that ummf NG has. NG is alot louder and definately more powerful

its more sensitive, but i say not terribly so.

[Edited on 7/15/03 by Madog]

Theoretic - 30-9-2004 at 13:59

Maybe MN hydrolysed in the alkaline solution to NaNO3 and CH3OH?

garage chemist - 30-9-2004 at 15:21

This sounds very interesting.

Theoretic, I'm sure you're right about the ester hydrolizing in the alkaline media.
This is also the reason why you must never wash nitrocellulose with dilute NaOH.

I tried out what happens with NC in warm NaOH, and the NC totally dissolved and the reaction mix had a very good smell, exactly like fresh bread! :o Some kind of maillard reaction must have happened.

I have absolutely no acess to methanol though, so I won't be able to make methyl nitrate.

I once tried to make ethyl nitrate. I mixed a few drops of >90% orange fuming nitric acid with a few drops of ethanol, there was a VILOENT reaction at the moment as the liquids touched. Most of the reaction mix was vaporized and there were lots of red NO2 fumes.
Ethanol + red fuming nitric acid seem to make a rather good liquid rocket propellant! :)

But this is not what I want. I want ethyl nitrate.
I will try to nitrate ethanol with a standard nitration mix ( 2 volumes conc. H2SO4, 1 volume 65% HNO3).
Has anyone tried this out before?

vulture - 1-10-2004 at 04:47

Ethanol with HNO3 must be carried out at very low ( I would say subzero) temperatures because HNO3 has an oxidizing effect on higher alcohols like ethanol. You were very likely producing glyoxal, acetaldehyde and acetic acid.

Polverone - 1-10-2004 at 09:33

In Muspratt (and later texts too I think) it is stated that oxidation takes place because of nitrous acid contamination/production from the nitric acid, and can be suppressed by the addition of urea.

"When two ounces of absolute alcohol and one ounce of strong nitric acid are mixed, and twenty grains of urea are added, the reaction is very moderate; and after some time a very heavy oily liquid begins to separate, and is increased in quantity by the addition of water."

RIPPER - 2-10-2004 at 04:40

Are this not methylnitrol about you talk ?

:mad:

-----------------------------------------------

Could you PLEASE post clear and in english? 90% of your posts don't make any sense to me, including this one.

[Edited on 2-10-2004 by vulture]

[Edited on 2-10-2004 by vulture]

sylla - 2-10-2004 at 14:27

I've done some theoretical expectations about methyl nitrate (CH3ONO2) and a few calculus lead me to :

Methyl Nitrate (CH3ONO2), Enthalpy about -171 kJ/mol, Temperature of Explosion 2736°C, VOD at density = 1 is only 4986m/s. It has a fucking gaz volume of 1.102 l/g at 0°C 1atm and energy of 3180 J/g which gives it a index power of 129.7% (Picric Acid %).

It's not really helpful and remain theoretical expectations so nothing sure at all but I guess it should be close to that :cool:


EDIT: Damn, I misencoded some data here are the good results : 6369m/s at d=1.2, 4464°C, 5882 J/g, 0.873 l/g, Power Index 190.1%.

I'm pretty close to the real enthalpy, -171kJ/mol is 2200kJ/kg ! :cool:

[Edited on 3-10-2004 by sylla]

And here some empirical data

Mephisto - 2-10-2004 at 15:00

Methyl Nitrate
colorless volatile liquid
empirical formula: CH3NO3
molecular weight: 77.0
energy of formation: – 456.7 kcal/kg = –1911 kJ/kg
enthalpy of formation:
– 483.6 kcal/kg = –2023.6 kJ/kg
oxygen balance: –10.4%
nitrogen content: 18.19%
volume of explosion gases: 873 l/kg
heat of explosion
(H2O liq.): 1613 kcal/kg = 6748 kJ/kg
(H2O gas): 1446 kcal/kg = 6051 kJ/kg
specific energy: 123 mt/kg = 1210 kJ/kg
density: 1.217 g/cm3
boiling point: 65 °C = 149 °F
lead block test: 610 cm3
detonation velocity, confined:
6300 m/s = 20 700 ft/s at r = 1.217 g/cm3
deflagration: evaporation, no deflagration
impact sensitivity: 0.02 kp m = 0.2 N m
friction sensitivity:
up to 36 kp = 353 pistil load no reaction
critical diameter of steel sleeve test: 18 mm

Methyl nitrate is a highly volatile liquid, and its brisance is about equal to that of nitroglycerine. Its vapors are both flammable and explosive and produce headaches. Methyl nitrate dissolves nitrocellulose, yielding a gel, from which it rapidly evaporates. It can be prepared by introducing methyl alcohol into a nitrating mixture at a low temperature or by distilling methanol with mediumconcentrated nitric acid.


Taken from "Explosives" by R. Meyer (2002)

Chris The Great - 13-3-2005 at 08:58

Yay, my first nitration :)

I gathered the materials, all of which were fairly easy for me to obtain, methanol (99.9%), H2SO4 (boiled battery acid) and NH4NO3 (instant cold pack).

100mL of H2SO4 was cooled in an ice bath, while I measured out 65 grams of NH4NO3. This was mixed into the H2SO4 with lots of stirring, and let sit for 10 minutes until the mixture had achieved an even consistancy and had time to cool down.
29mL of methanol was slowly added with a syringe over a peroid of 30 minutes with constant rapid stirring. Occasionally I stopped and checked on the temperature.
Before addition 3.0*C
2.5mL 8.0*C
10 min (10mL) 11.5*C
15 min (15mL) 11.5*C
20 min (20mL) 10.0*C
27 min (29mL) 12.0*C
After this there was a ~1cm thick oily layer floating on the surface, that vibrated rapdily for several seconds when the jar was lightly tapped, indicating a very low viscosity.

http://img81.exs.cx/my.php?loc=img81&image=after0pm.jpg

I did a little dance at this point, as it meant I was probably successful.

I extracted the top layer of methyl nitrate with a syringe, squirting it into ice water to rinse it. I then removed the ice cubes and sucked it out again with a syringe and squirted into sodium bicarbonate solution, and then from there I transferred it to a small jar. About 20mL was obatined.

Another layer was forming on top, so I extracted it and got another 4 to 5mL.

http://img81.exs.cx/my.php?loc=img81&image=product0ou.jp...

The warning is for my dad, who has the other half of the workshop, and often moves things because he likes them to be clean. I would rather him not be moving my myrol around.

More myrol was floating to the top of the mix, so I capped it with a blue PVC pipe endcap and left it for the night.
I went back about 16 hours later, to find the inside of the blue plastic had turned a nice purple colour, the acid mix had cleared up and there was more myrol floating on top. Another 3 to 4mL was obtained.

Total yield is about 28mL (34 grams), or alot less than theorectical.
However, there are some little beads of water (maybe 0.25mL total) of water floating on top, and it isn't clear, it is slightly murky. I think I need to get rid of it quickly before it gets rid of itself.
It smells very nice however, much like chloroform. I haven't got a headache from inhaling it deeply however, though apparently some people don't get them.

Joeychemist - 13-3-2005 at 13:59

“It isn't clear, it is slightly murky. I think I need to get rid of it quickly before it gets rid of itself.”

That is more than likely the water in the Methyl Nitrate that is making it “milky” and “cloudy”. This turbidity should disappear after letting the Methyl Nitrate sit in the open for a day or so.

Putting it in a desiccator will speed up the process greatly.


Btw, Congratulations Chris, everyone remembers they’re first nitration. It’s like loosing your virginity.:D;)

The_Davster - 13-3-2005 at 14:08

I do not think that you can leave methyl nitrate in the open to allow the water to evaporate off like you can with NG. Methyl nitrate is too volatile for this to work, you would loose a great deal of it, the only way to remove the water is in a desicator.

Chris The Great - 13-3-2005 at 17:19

Ok, I'll put it in a dessicator later today. I was worried about explosions, but I still want to get rid of it as soon as possible.

And yes, it is very volatile, more so than water, so leaving in the open will not work, unless I want water and not methyl nitrate!

garage chemist - 14-3-2005 at 10:01

Add a few pieces of anhydrous CaCl2 and swirl it around.
This worked wonders with turbid ethyl acetate, methyl benzoate and chloroform. The liquids were crystal clear after about half an hour.
Perhaps this also works with NG.

The_Davster - 14-3-2005 at 15:22

I do not think adding any solid dessicant to NG or methyl nitrate is a good idea... Same reason as why semi frozen NG is so sensitive, the 'grinding' of the liquid between the crystals.

[Edited on 14-3-2005 by rogue chemist]

chemoleo - 14-3-2005 at 16:21

Ok, how about a saturated solution of NaCl (or whatever)? That should remove the water, if you mix the two liquids and stir for several hours with a teflon magnetic stirrer.

Joeychemist - 14-3-2005 at 18:04

That should work!

It will also raise the density of the water in the solution and insure a cleaner separation of the two liquids.;)

Myrol - 19-3-2005 at 06:34

I made Myrol three times, moderate succes and also no headache after breathing it. My biggest problem was the good solubility of it in Water...40g Myrol per Liter Water...thats a lot! So thats why I washed it with 22% NaCl sol.

The results in Explosion tests were great. 18,5ml Myrol produced a 30cm wide shallow crater with a nearly white flash at night and a little louder BOOM than NG.

8,5ml Myrol (my second) batch were just burned down. I was to lazy to make a Blasting Cap so I thought I can prime Myrol like I've primed always my NG earlier. With a sparkler:P.....stupid Idea....The Myrol burnt very fast down with a around 50cm high bright white flame!

My third batch were 22ml wich I fired under Water. Blast was quite massive, I felt a shock at the edge of the pit and the water moved fairly high (around 30cm hemispherical shape). The Charge was 40cm deep placed.

And don't forget: Because of Myrol's very faint viscosity, it can detonate even with 8000m/s if you use a strong Cap (1g HMTD) and not to small amounts.

Myrol burn-out.JPG - 22kB

Myrol - 21-3-2005 at 08:08

I can't edit my previous post, but I've forgotten somethin' so I make it short:

For everybody (like me) who have a Vacuum pump etc. can make Myrol also with GREAT yields if you prepare the Myrol with AN /H2SO4 mix in an ordinary way and then just Distill the Myrol out of the mix at such a Vacuum that he boils at less than 35°C.

Myrol is so volatile and enough chemically stable that you can heat that mix without problems to around 45°C without getting serious problems:cool:. I think I will try this method, because I have all the necessary Glassware etc. The distilled Myrol must be neutralized before you store him, if you don't do so, H+ won't be with you:P

Chris The Great - 31-3-2005 at 23:29

Some tests today :)
My methyl nitrate has now turned yellow, and the small amounts of sodium bicarbonate left after dehydrating it has stuck to the sides and soaked up all remaining water.

At first, I tried hitting a drop with a hammer, which resulted in nothing, as I can't put much force into a hammer swing or I miss all the time. But it reassured me that it won't suddenly explode anytime soon.

I then tried (after firing a new detonater design, which worked great and was also used in this test) detonating a mL of methyl nitrate in a thin metal casing, crimped at the end and taped to the detonater. I made a small cut in the ground with a garden shovel, and dropped it in, and then closed the gap by stomping (carefully!), in order to keep the roots etc as undisturbed as possible (I tried digging, then packing the dirt over an explosive once, with the result of the dirt flying up and that was pretty much it). It gave me a half foot crater and according to my brother the farthest flung piece of grass went up over fifty feet and landed nearly forty feet away. I couldn't see this as I was inside the door of my lab, as it was raining and I didn't want to get my switch wet. I did find the piece forty feet away however.
Also, the noise was not extreme, nothing to cause the nieghbours to come after me or even look outside.

I am thoroughly impressed.
:D :D :D :D :D

I'll do it again tommorrow and take some pictures and maybe a video, as I like to document my experiments with a camera, makes them fun to look back on.

Chris The Great - 7-2-2006 at 12:58

450ml of the same brand drain cleaner was added to a jar in a salt-ice bath (made from crushed ice I chipped out of my freezer, since I ran out of other ice) and was allowed to cool while I weighed out 300g of ammonium nitrate. The ammonium nitrate was added at first one tablespoon at a time with heavy stirring (this time with a glass rod, so my stirstick wasn't being dissolved by the nitric acid fumes that come off the mixture). It turned black, and then an orange colour acid the acid (slowly this time) oxydized the dye. I added the rest much faster since it wasn't fuming too much and the oxidation was complete. I put a plastic lid on top of the jar to keep the nitric fumes from escaping and let it set for about 15 minutes to cool down while I measured out some methanol and sat down since my back was sore.

The methanol was added in little squirts from a syringe over 15 minutes. No trouble was had with the temperature and there was no NOx fumes coming off. The nitration is very tolerant of higher temperatures and rapid addition times. It was stirred for another few minutes after all the methanol had been added, and then was allowed to sit for 15 minutes or so to finish up.

As can be seen, there is still some dye that colours the mixture a bright orange. Oh well, the coloured acid is much cheaper than the higher quality clear drain cleaner.

Water was poured in slowly with stirring. The bottom layer was very thick and was a precipitate, most likely ammonium acid sulfate. It dissolved with a bit of vigorous stirring. The methyl nitrate then slowly floated to the top.


I stuck a length of aquarium tubing to the very bottom, and then sucked a bit on the other end to pull up the liquid (it was about 4 feet of tubing so there was no danger of me accidently drinking some of the spent nitrating mix). I then let the bottom layer drain out into a 5 gallon bucket half full of water (it was there in case of runaway, and then to dump the spent acid into after the nitration). It came out fairly quickly, with a fair amount of pressure. I stopped when the bottom layer was a little more thick then the top layer of methyl nitrate.


More water was poured in, and the methyl nitrate then sunk to the bottom of the jar.


I carefully cleaned the tubing used for the diluted acid, and now used it to drain out the bottom layer of the methly nitrate into a jar. However, there was too much pressure so I couldn't stop it in time and a fair amount of water also came through. Next time, I'll use pliers to close the tube and stop the flow.


The top layer was suctioned off carefully using a plastic syringe, leaving behind a large amount of (yellow/orange) methyl nitrate. Some chunks of anhydrous magnesium sulfate were added to soak up the remaining small amount of water floating on the top, and whatever water is dissolved in the methyl nitrate. The jar was then closed and some tape wrapped around the lid edges to prevent any methyl nitrate from evaporating out.


Normally, the methyl nitrate would be clear, but it still has dye in it from the acid. Normally I would have washed it, but it is going to be used within the next two days so I didn't bother. My next batch will be washed, and I suspect it would remove a large amount of the dye from the product as well.
Finally yield is approximately 130ml, which is a huge improvement over last time. This corresponds to 60% of the theoretical yield.

It burns with a very large, non-luminous gray flame, which looks really cool. It leaves behind some water and the dye, so there is a fair amount of water dissolved in it. I will probably add some more magnesium sulfate chunks to it to speed up the drying process. The burnt dye hurt my nose when I sniffed it, probably decomposed to give some toxic products. Shouldn't effect explosive performance too much though.
It is planned on being used in some high power shaped charges :D


EDIT: I noticed the links to the pics of my first attempt at broken, and I can't edit the original post. So here are the pics with thumbnails on this thread instead (if I mod wants to edit them back to replace the broken links in my original post, that would be nice :) )



[Edited on 7-2-2006 by Chris The Great]

Dream of the iris - 17-2-2006 at 18:54

:D Lol! "Ultra Super Mega Explosive! Don't touch".

Good job. I've been meaning to try this explosive.

BTW, Methanol OTC is sold as "HEET Gas tank Anti-freeze". It's the yellow bottle and it says on the back "Warning contains methanol" :p

Dream of the iris - 12-3-2006 at 16:51

What's the shelf-life of methyl nitrate dynamite?

Boomer - 14-3-2006 at 03:23

One week to one decade, depending on how well it is washed and whether the other stuff is compatible.
Adding 1% chalk helps too. Don't add too strong a base as it DE-creases stability! And the colder the better, every ten degrees C will double the life, meaning freezer vs. room gets you a 1600% shelf life increase. :)

PS: The horror stories about frozen NG (no concern here) come from either big amounts of partially frozen stuff, with chunks banging around in the liquid on transport, or from thawing big amounts without supervision. Does 'Tc' ring a bell? Even for the much more thermally stable PETN, you WILL get an explosion if you bring a 1m-radius sphere to 88C. Even lower if the packaging is insulating. Small amounts stand that temp for a long time, and worst case will eventually start to smell .... ;)

Chris The Great - 14-3-2006 at 16:32

I found that even poorly washed methyl nitrate stores well. However, that was in very small amounts so....

You are more likely to lose it to evaporation than decomposition IMO.

Zinc - 4-7-2006 at 04:21

Quote:
Originally posted by Madog
i did actualy get NG headaches 2 times, from tasteing it.



Does it taste good?

hinz - 5-7-2006 at 05:08

I've also made some of it. Later, when I cleaned my glassware, I had the involuntary pleasure to taste some of it as I cleaned my pipettes by sucking water in it with my mouth. (Sorry I do not have any big pipette nipples)
It tasted spicy sweet, with an burning in the mouth like if you get accidentally acetone or conc. ethanol on your tongue. I didn't get any headaches, maybe it's because I flushed my mouth with water afterwards, later I used my aspirator to suck the water through it.

I didn't use any given methanol/nitrating acid ratios, I just added as much methanol as the nitrating acid could nitrate.
I used:
400ml 96%H2SO4
250ml 53% HNO3
appr. 150ml more or less absolute methanol, which I destilled once from modell aircraft fuel

In the beginning I used twice Maddog's ratios (22ml H2SO4,14ml 53%HNO3 and 10ml methanol, a bit less than him, it's due my crappy 53% HNO3). I found out that it's important that all MeOH gets nitrated, only methyl nitrate is insoluble in nitrating acid. If one use to much MeOH, the excess of MeOH will disolve some methyl nitrate. The disolved MeONO2 is prone to hydrolysis by the nitrating acid. I found this out in the first two more or less small scale nitrations.
In my third nitration I used appr. 250 ml nitrating acid. I did it in an ice bath and added appr. 20ml MeOH slow enought to keep the temperature down. As I saw a layer of MeONO2 on the top of the mixture, I decanted the top layer in a graduated cylinder and pipeted the lower layer(nitrating acid) back into the nitrating baker. I repeated this till no MeONO2 layer formed on top, then I stopped and waited half an hour and took the layer on top that had formed slowly. It's important that you stop there, because of the hydrolysis. At my first attemps I added to much MeOH so it dissolved the MeONO2, the solution hydrolysed, forming lots of small bubbles of an undefined gas (maybe CO2) and little NOx.
The power of the first charge (15g), which demolished an old Mac CD-R drive and cutted the herbage in a circle of 20cm:cool: was so amazing that I nitrated more (last big scale synthesis) that gave me 130 ml MeONO2, used with some old stuff to make a charge of 150ml. This charge blew up an old lawn-mower engine with that much power that no parts of it left at the place, where it detonated:D.

This was my first nitration and I loved it;).

[Edited on 5-7-2006 by hinz]

Chris The Great - 5-7-2006 at 14:36

It really is amazing stuff isn't it?

I fired a film canister a while ago, from a hundred feet away the blast gave a strong thump across mine and the spectators chest, and set off some guys car alarm a block away (the neighbours actually, since this was a rural area).

Today I set of 45g of 90% methyl nitrate/10% nitrocellulose gell with 30% added aluminum powder :D


I didn't know about the excess methanol problem, thanks for bringing it up. It might explain why a slight reduction in nitrating acid relative to the methanol caused a big drop in yield (65% -> 45%) for me...
You will probably end up with methanol dissolved in the methyl nitrate as well as lossing methyl nitrate, giving not only a lower yeild, but an impure product.

I've done this procedure a few more times, and have gotten it nearly figured out for a completely improvised synthesis...

I get best results with a 10% molar excess of ammonium nitrate realative to methanol, ie 1.1mol AN for every mol methanol. Then, I have 2 moles of sulfuric acid per mole AN, or 2.2mol H2SO4 per mol methanol. This is using undried AN and sulfuric acid, and I get about 65% yeild.
The reaction only needs very poor cooling. I added all the methanol over 20 minutes using a cold water bath, which was a bucket with cold water in it with a couple ice packs dropped in. Maybe 10*C or so, not cold at all. The reaction was a little warmer than usual and gave off a lot of fumes, so an ice bath would be best, but a salt ice bath is not necessary at all and is not worth the trouble mixing it and then disposing off a bunch of wet caked salt the next day.
I honestly think that this reaction would be impossible to get a runaway, in fact I may try to get one by adding all the methanol to the hot acids without cooling, on a small scale and outside of course. But I think that the methanol and methyl nitrate will just boil away and prevent a runaway from occuring even in the absolute worst case scenario.

For washing, I tried making a basic saltwater solution with salt and bicarbonate, didn't work. The stupid bicarbonate doesn't dissolve at all. So don't bother. You cannot use NaOH, it will destroy your product. However, just saltwater works fine. I use pop bottles to wash it, and about triple the volume of methyl nitrate in saltwater. I start shaking slowly but the two layers mix quickly, after which I give it a very good shake for a few minutes. Then I seperate the layers and repeat. I did this two times, but I think three might be better.
Whatever you do, don't wash with a only bicarbonate solution, not only is it useless, it dissolves a large portion of the methyl nitrate!

Whatever the hell makes the orange colour in the drain cleaner does not come in the washing. I might try steam distilling the methyl nitrate (I don't want to try straight distillation) and see if that helps. Once distilled, I will add salt to the receiver containing the methyl nitrate and water, which will cause any dissolved methyl nitrate to precipitate. Hopefully that will give a batch of pure (and clear) methyl nitrate.

I mentioned earlier in this post that I suspect some methanol is in the methyl nitrate product, I should point out this will not be removed completely by washing nor by steam distillation should you choose to do that as well, since the boiling points are almost exactly the same. However, I started another thread about forming complexes with methanol. Calcium chloride will do so, as well as complex water. If used as a drying agent, not only will it remove all the water from the methyl nitrate, it will also complex and remove any methanol in the product! See this thread:
http://sciencemadness.org/talk/viewthread.php?tid=6063



I'm thinking for my next batch, I'll make a cheap seperatory funnel from a 2L pop bottle. A plastic tube will go into the bottom (but not the very bottom, on the side, so it can stand upright) and allow the liquid to flow out, and can be stopped using a pair of pliers to close it off. A small hole is drilling into the lid.
To operate, the methyl nitrate and diluted spent acid are poured in the top hole with the tube held up high and the lid is screwed on. Then the tube is crushed with a pair of pliers, and the bottle inverted. You need to close the tube so the mixture can form two layers after being diluted. Some will squirt out the bottom, but it won't be that bad. Then, open it up and seperate.
It should take a few bucks to make this for this procedure, and beats a $50 seperatory funnel any day. I make a lot of nitric esters so a special seperatory funnel for them is definateyl worth it.

Sort of off topic, but such a funnel will make this procedure vastly easier for those who don't have access to standard lab equipment.

hinz - 19-7-2006 at 14:57

I've just tried the destillation-nitration method. I borrowed my sister's camera to make some pictures of a synthesis that should give a nice HNO3 to HE-ratio.
So I set up my destillation apparatus:

http://pic20.picturetrail.com/VOL1206/4241286/11641500/16900...

I heated the mixture of appr. 400ml 53% HNO3 together with appr. 70ml MeOH in a water bath to 65°C. At the beginning no NOx was produced. The mixture went yellow and began to destill over. I switched the hotplate off, since the water bath temperature was around 70°C and the first vapour bubbles were forming in the nitration mixture.

http://pic20.picturetrail.com/VOL1206/4241286/11641500/16901...

I took this picture and looked how the first drops condensed inside the liebig, when the mixture began to produce lots of “brown fumes”.
I took the flask immediately out of the water bath, but the NOx production didn’t stop. The production of it was quite scary as you can see in this picture: (look at the NOx that comes out of the vacuum destillation adapter:o)

http://pic20.picturetrail.com/VOL1206/4241286/11641500/16901...

http://pic20.picturetrail.com/VOL1206/4241286/11641500/16901...

I grabbed my gas mask and poured some cold water in the pot to stop the NOx generation. After a while this helped to cool down the flask so that the NOx generation stopped.
Due the heat of the runaway nitration, some more liquid came over. First I poured the stuff into a graduated cylinder and saw those stupid bubbles again, those which I saw also at the classic H2SO4/HNO3 method. Later I realised that it might be dimethyl ether according to this equation.

CH3-O-NO2 + CH3-OH [CH3+…+…NO3-+...CH3-OH (SN1) ==> H3C-OH+-CH3 + NO3-].==> H3C-O--CH3 + HNO3

This gas was also produced inside of the destillation setup, I know this because some pressure build up at the vacuum destillation adapter (I put my finger on it and recognised the small pressure, but the gas was not brown). I was able to lead some of it into a test tube and it burned with a methanol like flame and smelled afterward like some kind of aldehyde (formaldehyde, I suppose). For me this reaction is plausible since:

-MeONO2 is a strong methylation agent (less strong than DMS, but the NO3- group should be a nice leaving group due it’s thermodynamic resonance stability)
-Dimethyl ether is a gas.
-The gas burns.
-The gas produces a adlehydic smell after burning and doesn’t smell unburnt.

Who is gonna pay me a GC/MS that I can identify this gas for sure:)

In the end I poured the destillate into a sepeatory funnel and added a saturated, aqueous NaCl solution, but it didn’t form two layers.

http://pic20.picturetrail.com/VOL1206/4241286/11641500/16901...

Does anyone has also some experience with those kind of nitrations and does She/He know what I’ve done wrong? I might add some urea nitrate to get rid of a bit of NOx but with those amounts I produced, I think the urea nitrate is overstrained and I doen’t have any (but I might produce some with my own piss:P). I might try to destillate the stuff under vacuum, but I think that the liebig condensor will get some problems to condense liquids that boil below 30°C.
Btw I’m glad that the shit didn’t explode, although I don’t suppose that much MeONO2 formed.

[Edited on 19-7-2006 by hinz]

nitro-genes - 19-7-2006 at 15:54

Quote:
Originally posted by hinz
In the end I poured the destillate into a sepeatory funnel and added a saturated, aqueous NaCl solution, but it didn’t form two layers.


Most likely you just collected some methanol and water, no esterification has taken place...:)

I hope you are aware btw that distillation of methylnitrate, especially without any vacuum, may result in unexpected explosions?
With this setup and destillation temperature it is likely you collect a mixture of methylnitrate, NOx and small amounts of nitric acid all together, which may sponteanously ignite/detonate. :o

hinz - 19-7-2006 at 16:33

The only liquid that should come over at 50-70°C is methanol or methyl nitrate, water has a far to low vapour pressure at this temp, for this purpose I've added a vigreux column. I think it was mostly methanol. Acording to Fedorff IIX p M110, it was first prepared in a small yield by destilling 63% HNO3 with methanol, not too much different to my reaction conditions. What wonders me why I got that much NOx, if other people prepared it also by destilling and I don't believe that these people feed their condensors with salt/ice, dry-ice/acetone etc. to destill MeONO2 with a boiling point of 25°C under vacuum. With other methods you can't destill a liquid with bp. of 25°C. The equilibium is also shifted to MeOH/MeONO2, (because it destills first and water remains). The ratio of 1:3 of MeOH to pure HNO3 should be able to nitrate most of MeOH before it comes over.
Maybe I'm wrong and those people really used vacuum with exotic cooling

nitro-genes - 19-7-2006 at 16:45

Also, wouldn't the use of 53% nitric acid alone make oxidation of the methanol much more favorable? I've no idea how susceptable methanol is to oxidation though, but at 65 deg...

[Edited on 20-7-2006 by nitro-genes]

hinz - 20-7-2006 at 14:13

After my extremly nice results with the conventional method I came to the conclusion that the destillation method is the biggest crap, at least in the home lab, because I’m pretty sure, even with conc. nitric that would end up again with lots of brown fumes or I’ll suck half my destillate through the aspirator if I would use vacuum. Now I used 400ml H2SO4, 400ml fresh destilled fuming nitric acid:cool: ( 500ml H2SO4 + 750g KNO3) and a lot of methanol I’ve destilled over CaSO4 to get it completely anhydrous. This is the yield I’ve got::D
http://pic20.picturetrail.com/VOL1206/4241286/11641500/16939...
(not exactly, it would be 20-40ml more if I wouldn’t get a runaway in the end, the last separatory funnel hydrolysed and the mixture boiled out of it)

One of those numerous fractions I’ve searatd:
http://pic20.picturetrail.com/VOL1206/4241286/11641500/16939...
I’ve only nitrated 50-100ml MeOH at once, this should prevent that too much methanol dissolves into the MeONO2, furthermore it will decrase the mess at a runaway and the detonation risk due the stirring.

The yield is:
400ml HNO3 x1.5g/cm3 = 600g
600g/m(HNO3/63g/mol)=9.5 mol HNO3

530ml MeONO2 x 1.2 g/cm3 = 636g
636g/m(MeONO2/77g/mol) = 8.25mol MeONO2

This gives a yield of 8.25mol MeONO2 /9.5mol HNO3 =86% product in relation to the used nitric.
This is quite nice, isn’t it?! :cool:

Tomorrow I’ll nitrate some cotton and gelatinise the methyl nitrate till it’s nice kneadable and keeps it’s form. Then I’ll put it into a PE plastic bag to prevent evaporation and knead it over in a 70° bend 0,5mm thick brass sheet. This should give a nice, very improvised linear sharped charge without any casing, only the liner.I think I’ll lay the blasting cap just on the plastic bag, held by some cardboard strips. After I’ve detonated it I’ll post my results in the “sharped charges threat”

[Edited on 20-7-2006 by hinz]

Chris The Great - 20-7-2006 at 14:19

You'll need a lot of nitrated cotton. I did a 10% solution and it's still pretty runny stuff. Then again, I could just have made "short" nitrocellulose which doesn't gell as well... but just keep in mind that the gelatines are very runny compared to nitroglycerin, which is supposably very thick.

Anyway, sounds like an interesting idea, don't see any reason for it not to work. Good luck!

gregxy - 20-7-2006 at 14:38

Many years ago I made methyl nitrate by distilling methanol with 70% HNO3. I added some urea to the HNO3. This was
supposed to remove any nitrious acid. There were no problems with oxidation. I know that what I got was methyl nitrate since I used to store it under water. Maybe you need
to add the urea to prevent the oxidation?

I also remember trying to nitrate ethanol and propylene glycol by distilation, but they just oxidize and give brown fumes.

hinz - 24-7-2006 at 13:34

Sorry guys, the sharped charge project wasn't realised, the guncotton didn't really gelatinise my methyl nitrate, so I couldn't knead it on the brass liner. I first added some chalk to neutralise the excess acid, later I filtered the chalk off aggain (the vapors still colored pH paper, but not as strong as in the begining) and begann to dissolve NC (appr. 70g). In the beginning the MN got gelatinsed quite well, I found that the MN gets well gelatinised as long as the NC isn't fully dissolved and the fibres bind the MN between them, so its the best to gel it right before use, but a few hours later it went syrup-like so I begann to build a case for my sharped charge and coated the brass with epoxy resin so that it won't form any nitrate together with MN. I wanted to dry it overnight, but in the evening I went bach to my lab and saw that the MN was decomposing together with the NC, there were only 420ml of the 500ml left. The NC decomposed to a foarmy chuck inside my erlenmayer and nitrous gases were released, maybe I should have really washed my MN.

So I grabbed a detcap and went together with my erlenmayer outside of the village and detonated it. The erlenmayer had to die:( the decoposed NC chuck didn't get out of it, so I just sticked the cap at the wall of the erlenmayer. The crater had an diameter of 30-40cm and was about 25cm deep, I really felt the shockwave going trough me (interresting feeling), I was arroud 30m away.

[Edited on 24-7-2006 by hinz]

Chris The Great - 24-7-2006 at 16:42

Interesting you got it to decompose... probably dissolved NO2 if it happened that fast. I found my main problems where that the mix isn't thick enough once fully dissolved, and also that the methyl nitrate loves to evaporate out while I mix it. Not really the best to gell unless you have some very high viscosity NC.

Bert - 24-7-2006 at 20:41

Hinz, it is more likely that your nitrocellulose was the culprit than your methyl nitrate. It is VERY difficult to properly neutralize home made nitrocellulose.

hinz - 25-7-2006 at 01:19

Dissolved NO2 might be a reason, my MN was always a bit reddish/brown/yellow, pure MN sould be colourless.
I let my NC stand for one hour in a baker filled with dest. water and then I washed it with ethanol to get it dry faster, I think that the MN was the culprit of the decomposition because it wasn't pure, but you're right, it's quite difficult to get the acid out of the NC fibres, in water insolube liquids are easier to wash.

agent_entropy - 25-7-2006 at 08:30

Is there any reason why store bought smokeless powder (double base) couldn't be used for gelatinizing MN? Or might the other ingredients just foul up the works? IIRC The powder I have (Alliant, Red Dot) is composed of nitrocellulose, nitroglycerin, nitroguanidine, diphenylamine, polystyrene, and some other ingredients that weren't specifically identified.

Also, just how stable is MN (well neutralized/washed) for storage? Would it maybe be more stable in a solution of methanol?

Chris The Great - 25-7-2006 at 08:53

It's very hard to gell the processed powder AFAIK. It gets pretty hard and takes a long time for solvents to soak in.

I have never had a problem with homemade NC, but I did boil the stuff for many hours...

agent_entropy - 25-7-2006 at 08:56

When you boiled your NC did you use NaHCO3 solution? Because that's what I did, and I think it partially destroyed the nitroesters because it was pitiful when I burnt it.

Later in the day... no one else has posted since I did so I'll just edit this post.

Anyway, I just made some MN using the method outlined above by Madog (page one) and I washed it once with water, then once with saltwater. This yielded several ml of perfectly clear, colorless product. Chris, this leads me to believe that perhaps the cloudiness of your MN might be the result of more than just water diffused (dissolved?) in the mixture. Perhaps something leftover from the drain cleaner or AN instead of or in addition to water.

I tried putting a drop of the MN on a piece of paper and hitting it with a hammer but it didn't detonate, only deflagrated. So next I tried putting a few drops on a small piece of fluffy NC, it gelled as expected, and when I hit that with a hammer it sure as heck did detonate (my ears are still ringing).

So, how stable is methyl nitrate for storage? Is it one of those compounds that just detonates for no reason and without warning? What is the best/safest way to store it? (if it is indeed storable)
[Edited on 26-7-2006 by agent_entropy]

[Edited on 26-7-2006 by agent_entropy]

agent_entropy - 26-7-2006 at 09:03

I just noticed something, apparently "methyl nitrate"and "nitromethane" are two different things. I've seen the two names used interchangeably in a couple of places, which is rather confusing.

methyl nitrate > CH3ONO2
nitromethane > CH3NO2

Are we sure that these procedures produces methyl nitrate and not nitromethane? As I understand it, nitromethane is the one used as a racing fuel additive, and I found an MSDS on it. However, I can't seem to locate a satisfyingly complete MSDS on methyl nitrate. Any help would be appreciated.

not_important - 26-7-2006 at 09:28

yeah, kind of weak
http://physchem.ox.ac.uk/MSDS/ME/methyl_nitrate.html

http://www.chemlaw.co.jp/Result_Eng_M/MethylNitr.htm

methyl nitrate is the ester of nitric acid and methanol, similar in general concept to methyl acetate or whatever.


nitromethane is a nitro-alkane, with the nitrogen directly bonded to the carbon; industrially made by the vapour phase nitration of methane by nitric acid.

Chris The Great - 26-7-2006 at 09:28

Yes, we are completely sure. We're making an ester from an alcohol.

My colour is from the drain cleaner, I believe I established that. It's yellow/orange, not just cloudy. That cleared up in a short while with drying.


For the NC, I boiled in plain old water.


When storing methyl nitrate, I had my first (clear) batch turn yellow over a two week period, but this never caused any stability problems (still could not detonate with a hammer).
The bloody stuff evaporates away every time you open the container though which is a real pain in the ass.

hinz - 26-7-2006 at 11:09

The storage problem is because methyl nitrate is a good methylating agent, other esthers like NG and MHN etc. don't have this problem due steristic reasons (the possitive charged organic rest, CH3+ for MN, can't attach to other molecules because the possitive carbon can't form a bond, because other nitrate groups are shielding the C-atom). The other reason why MN and theoretically especially ethyl nitrate and other secondary or tert. alcohol esters are unstable is that these mono-esters don't have another nitrate group (like EGDN) which prevents that the electrons gets into the ONO2 group, forming a ONO2- leaving group. The stronger the organic rest (CH3<CH2CH3<CH(CH3)2<C(CH3)3 for those who don't know:)) pushes the electrons into the ONO2 group, the more unstable the explosive should be.

This effect is nicely seen in HC(NO2)3 (no ester but nitro-groups have the same effect), as its a strong acid, because each NO2 pulls electrons so that the C can't form a bond with H and has to leave the H as a proton.

The methylating effect of MN has maybe also formed dimethyl ether in some of my synthesis, but I'm not sure about it, if anyone has some MN around, can he/she mix it with methanol and look if it bubbles please, I fogot it and all my MN has formed CO2 and CO:P, it would be interesting for me, as it might prove or disprove my theories.

agent_entropy - 27-7-2006 at 09:07

Oh, I see, sorry Chris, I knew that you had gotten rid of the dye but I was under the impression that you still had some cloudiness.

Anyway, thanks to all for the information.

I tried the synthesis using drain cleaner for sulfuric acid and in situ nitric acid from NH4NO3, according to the procedure outlined above by Chris The Great. I was able to dry the product (no cloudiness) but I can't seem to get rid of the dye from the drain cleaner. Also, it still smells like ammonia (washing with water/saltwater didn't help).

Edit:
Tried a third time and took some pictures of products:



From Left to Right...
1. Using reagent grade nitric and technical grade sulfuric acid, then washing with water and saltwater yielded a clear, colorless product, which posessed a semi-stinging smell.
2. Using undried NH4NO3 (from a cold pack) and drain opener grade sulfuric acid, then washing with water and saltwater yielded a clear but yellow looking product which posessed a stinging smell.
3. Using undried NH4NO3 (from a cold pack) and technical grade sulfuric acid, then washing with water and saltwater yielded a clear, but faintly yellowish product which did not seem to posess a stinging smell (although this one was the most fresh).

All three products detonated when a drop on a paper was struck with a hammer.

[Edited on 28-7-2006 by agent_entropy]

Chris The Great - 27-7-2006 at 22:26

No, I was unable to get rid of the dye. So I think the only way will be steam distillation, which I have not had the time to make an improvised setup for, nor have I had time to make more methyl nitrate.
My product does not have the ammonia smell, as you describe it, until I burn it, in which case there is a very slight residue which smells fairly strongly of ammonia (but then again, ammonia smells pretty strong anyway). In fact, my product always smells wonderful, just like chloroform.

What kind of yields did you get with the different procedures?

agent_entropy - 28-7-2006 at 04:06

Rough estimates of % yield:
1: 60%
2: 20%
3: 20%

These are probably much lower than actual yield since I was trying to isolate very pure product (more losses); and I didn't wait for second fractions of product to phase separate from the reaction mixture as I don't like to let nitrating mixtures sit too long.

hinz: I tried putting a few drops of methyl nitrate into some methanol but it produced no bubbling, so probably no diethyl ether was produced. This is likely due to OH being such a lousy leaving group.

Chris The Great - 28-7-2006 at 07:49

Methyl nitrate does not react with methanol. A 75/25 MeN/MeOH mixture is used as rocket fuel since it is insensitive, and will not evaporate to give pure methyl nitrate. The mixture does still detonate, but with a fair bit of difficulty, and is nearly completely insensitive to friction and shock. The mixture, of course, is quite stable if it is to be used as rocket fuel, since having it change over time would be a big no-no. It was used by the Germans under the name myrol, although now sometimes pure methyl nitrate is refered to as myrol as well.

Should have mentioned that in my last post.

agent_entropy - 29-7-2006 at 16:48

Seeing that cellulose nitrate is soluble in methyl nitrate made me wonder what other polymers it might dissolve. Knowing which polymers it has an effect on might be important in deciding what containers are suitable for using with methyl nitrate (designing the device... can't have it dissolve its container). So, I investigated the effect of methyl nitrate on various common polymers.

The experimental method was to place a few drops of methyl nitrate on the surface of the polymer in question. Then wait about 30 seconds (short time due to the volatility of methyl nitrate). Then record visual and tactile observations of the effect of the methyl nitrate on the polymer. (Sorry, I couldn't figure out how to post this as a table)

KEY:
Polymer (effect of methyl nitrate) [source of polymer sample]

THERMOPLASTICS:

Polyethylene Terepthalate (No effect) [Soda Bottle]
High Density Polyethylene (No effect) [Water jug]
Polyvinyl Chloride (Surface softened) [Pipe]
Low Density Polyethylene (No effect) [Shopping bag]
Polypropylene (No effect) [Food container]
Polystyrene (Soluble) [Styrofoam packing]
Chlorinated Polyvinyl Chloride (Surface de-glossed) [Pipe]
Cellulose Nitrate/Guncotton (Soluble) [Nitrated cotton ball]
Polycarbonate (Soluble)[CD]
Polymethylpentene (No effect) [Plastic labware]

THERMOSET ELASTOMERS (all are crosslinked):

Natural rubber aka. polyisoprene (No effect) [Glove]
Nitrile rubber (Rubber swelled) [Glove]
Polychloroprene aka. Neoprene (No effect) [Glove]
Ethylene Propylene Diene (No effect) [Roofing membrane]

Sensitivity?

agent_entropy - 10-8-2006 at 05:51

The article "The Chemistry of Powders and Explosives" (by Tenney L. Davis, 1943), from the Sciencemadness Library, states, on page 192 :

"Methyl nitrate is very much more sensitive to initiation than nitroglycerin, a fact which, like its higher velocity of detonation, is probably associated with its lower viscosity. It is less sensitive than nitroglycerin to the mechanical shock of the drop test."

I find this somewhat confusing, since the two statements seem to be contradictory. Is there some difference between "sensitivity to initiation" and "sensitivity to mechanical shock"? If so, what is the difference?

Chris The Great - 10-8-2006 at 12:13

Yes, there is indeed a large difference.

"Sensitivity to mechanical shock" is to impact, for example how hard you need to hit it with a hammer to make it explode. Methyl nitrate needs a harder hit than nitroglycerin to get an explosion.

"Sensitivity to initiation" is refering to how well it detonates from a detonation shock, from a blasting cap. In this case, methyl nitrate easily detonates from very small caps, while nitroglycerin needs a fairly powerful cap in order to get a full detonation.

agent_entropy - 11-8-2006 at 05:41

So, a "detonation shock" is not a mechanical shock?

pyromainiac420 - 14-4-2007 at 10:56

What temperature should you keep it under during the nitration?

Zinc - 22-4-2007 at 07:08

A little off topic but did anyone try to make ethyl nitrate?

Boomer - 27-4-2007 at 05:00

Yes there is a thread by me on APC about it.

To put it short: The distillation method is dangerous, direct esterification needs very low temps but is staightforward.

I succeeded with both 96% sulfuric/AN and 96% sulfuric/fuming nitric (at least 95%, nearly colourless). The latter yield was higher of course, not as high as NG but above 80% IIRC. The key is to use freezer-cold precursors in a salted icebath. It can run away as low as 0C. Once sucked off and washed it is stable.

Properties: Bad OB and low density makes it less powerfull and less brisant than MeNO3 or NG/NGc, also not as good for gelling NC, makes a good AN fuel though. The smell is nice, but too much and instant headache (unless you like poppers that is).

UnintentionalChaos - 27-4-2007 at 08:46

Poppers are amyl nitrite, I imagine ethyl nitrate is just quite toxic.

Zinc - 27-4-2007 at 11:48

Quote:
Originally posted by Boomer
Yes there is a thread by me on APC about it.


What is APC?

Joeychemist - 27-4-2007 at 12:50

http://www.apcforum.net/forums/index.php

nitro-genes - 27-4-2007 at 16:17

The HE section is restricted to members only and access is not easiliy given. When I wanted to sign up for APC, I contacted the admin, (forgot his name) who told me that I hadn't got enough experience for their HE section. Lol, after 12 years of experience and having produced almost any conventional HE, flashpowder and other pyrotechnical composition. Anyway, the old accessable forum contained some interesting topics but I think APC is more pyro related than for discussing HE's...

Btw, some types of the ethylene glycol anti-freezes are replaced by the less toxic propylene glycol (PG types). The dinitrate makes a much easier produced sensitizer for AN, which is quite stable (for a nitric ester), and less senstive than EGDN or NG.

Ethanol oxidizes pretty fast resulting in a runaway with even slightly increased temperatures of nitration. For this reason I found that adding some urea during nitrationwith NA, like for the nitrolysis of HDN to RDX, helps keeping oxidation to a minimum by controlling the amount of NO2 formed.

[Edited on by nitro-genes]

Zinc - 28-4-2007 at 03:56

Here is a method for ethyl nitrate from http://www.sciencemadness.org/talk/viewthread.php?tid=253&am...

Ethyl Nitrate without distillation
Author: Fly
Procedure: Prepare a nitrating mix using 260 ml 65% HNO3 and 300 ml 96% H2SO4. Slowly add the H2SO4 to the HNO3 with cooling and constant stirring. Let the nitrating mix cool down to 0°C in a refrigerator. In another container place 160 ml of pure ethyl alcohol and slowly add 16 ml 96% H2SO4 with cooling and stirring. Let this mix cool down to 0°C as well. Prepare a salted ice bath and place a 1L or larger beaker in it. Pour the cold nitrating mix into the beaker, place a thermometer in it and begin the addition of the cold ethanol mix. Keep stirring the mixture, adjust the rate of addition so that the temperature stays around 5°C, do not allow the temperature to rise above 10°C. When the addition is complete, continue stirring the mixture for another 5 mins. Transfer the mixture into a separatory funnel and let it stand for 15 mins. The crude ethyl nitrate should separate out, drain the acid portion. The separation should not be carried out for more than 15 mins., after that the product might start oxidizing. The crude ethyl nitrate is washed by 300 ml of cold water (shake the mixture thoroughly in a plastic bottle). Repeat the separation and wash the product again with 300 ml water, then add a small amount of NH3 solution to the mixture and shake it again. Repeat the NH3 addition until the solution is pH neutral. Repeat the separation and washing steps, check that the product is clear and colorless. Now the product can be finally separated, dried over CaCl2 and filtered. The product obtained in this way should not be stored.


It says that it shouldn't be stored if made that way. Does anyone know how long can it be stored safely?

quicksilver - 28-4-2007 at 05:10

Quote:
Originally posted by nitro-genes
The HE section is restricted to members only and access is not easiliy given. When I wanted to sign up for APC, I contacted the admin, (forgot his name) who told me that I hadn't got enough experience for their HE section. Lol, after 12 years of experience and having produced almost any conventional HE, flashpowder and other pyrotechnical composition. Anyway, the old accessable forum contained some interesting topics but I think APC is more pyro related than for discussing HE's...


How would that person KNOW how much "experience" an individual has in any given field?

nitro-genes - 28-4-2007 at 06:46

He wanted to look through my posts on this board, though I think he never really did. Some people even gave me a vote of confidence with no effect, so I think APC has just a strong emphasis on pyrotechnics instead of HE's.

Boomer - 7-5-2007 at 03:34

I know what poppers are, it's just that both work by vasodilation. With EtNO3 it will be more of a headache and less a dizziness experience I guess.

And yes HE discussion on APC has more or less died. My thread was back when it was more active, and because it is a challanging thing to directly nitrate. Now that you mentioned, I probably had urea nitrate in the acid the times it did *not* go yello-plumes-oh-not-again.

The storage thing is BS, if neutral, cool and regularly checked it will be fine. Storing badly washed NG or Myrol is equally non-advisable. I only made a few batches of some milliliters out of interest, exactly *because* you hardly see it mentioned on k3wl bombz sites.

Anyone try it as an ethylating agent? ;)

separation of methyl nitrate

sarika - 9-12-2007 at 09:57

can methyl nitrate be detected and separated from a mixture of volatile organic compounds?if so how?

Mason_Grand_ANNdrews - 11-12-2007 at 05:05

What you mean whith methyl nitrate ? Methyl nitrate is alknown as CH3ONO2.
How can you prepaare CH3-NO2 ?
When you will prepare methyl nitrate, it`s easy when you a chilled mix of H2SO4 is stirred and under a condition of below 5 degrees centigrade some drops of MeOH is stirred in and a calculated amount of (easy calculated by wight) around >80% HNO3 is dropped and stirred in and the mix is hold under the same conditions for around for one hour. Let sit the mix for some hours and a slight milky tough liquid of "MeNO2" is
sucked of. I hope it will explode easy ;) .
My time is restricted todeliberate for a useful way to make CH(NO3)3 trimethylnitrate or something more. A little hint will help to the trinitromethanolnitratrate manufactrure.

Exuse my guys but i`ve nothing much more time to thinking
now. It`s sometimes to expensive.

I mean a useful suggestion is surely when a little amount of glacial acetic acid is refluxed for some hours in >98% HNO3
(ratio 1:10) to make some CH(NO2)3. I don`t know how it
separate. Maybe the crystals will precipitate in a to 0 degrees celsius water pulluted chilled mixture. ;)

[Edited on 11-12-2007 by Mason_Grand_ANNdrews]

Mason_Grand_ANNdrews - 13-12-2007 at 17:32

Excuse for some complements to the topic. I found always
some more then strange contrasts in the chemical
nomenclatura of some chemicals.
F.i benzy alcohol is C6H5-CH2-OH but what is methyl
nitrate ? Is is a derivate of CH3-NO2 or CH3-CH2-NO2 ? I
mean methyl nitrate should be easy nitroethane and i think
methylnitrate can be prepared from galcial acetic acid and
>98% HNO3. I`ve thinked somehwat in the last few days
and a small amount of tetranitroethane should precipitate.

In my opinion it should work like that:
Prepare a solution of 0,5 mol of > 98% HNO3 in a salt ice
bad in a large beaker, set the beaker to a stirrer and over
one hour drop 0,1 mol of glacial acetic acid in the HNO3.
Stirr the mixture for some time and take care that the
solution will not destroy the stuff when the hydrogen iones
will replaced with an -NO2 ion. Much more heat will destroy
the synthesis. (see metanol nitrate)

But how do it precipitate ?
Maybe it work when the solution is diluted with 5 mol of
distilled H2O, the mix is standing for a half day in a fridge
and the crystals are filtered out. The result shoud be
minimum tetranitroethane. (methyltetranitrate) Maigth it
works better to get a small amount of hexanitroethane
when the you use 1 mol of concentrated HNO3.

Maigth it is correct when the mix is strong chilled and 1 mol
AAA or TFAAA is stirred rapidly into the mix, the temperature
is hold below 5 degrees centigrade and crystals of
(NO2)2-CH-CH-(NO2)2, (NO2)3-C-CH-(NO2)2 or
(NO2)3-C-C-(NO2)3 should form.

I don`t know H2SO4 will destroy the material and the crystals will
precipitate when over some hours around 0,5
mol of concentrated H2SO4 will dropped into the chilled mix.

Excuse me to post this in this topic. I mean trinitromethane
(TNM) and tetranitromethane (TeNM) can be manufactured
with the same procedure but formic acid is used instead
acetic acid. Maybe someone can test it out if the quantities
work and how much is the yield.

I have a little incursion to nitrate MeOH. I mean when the
synth. is very careful is handled you can get NO2-CH2-ONO2.
(NO2)2-CH-ONO2 and (NO2)3-C-ONO2 needs higher
temperatures.

Prepare a solution of 0,4 mol of > 98% HNO3, set the mix in
a salt ice-bad and over a few hours 0,1 mol of MeOH is
stirred with a glass rod into the mixture, continue stirring
and over one or two hours 2 mol of 99% H2SO4 is dropped
and stirred in. When the mix became to much heat dump the
mix into an small amount of crushed ice. The result shoult be
nitromethanenitroxide. Maybe the result is a liquid and di-
and trinitromethanenitroxide is prepared careful over an
longer period when the HNO3 mix is diluted with AAA or
TFAAA when it slowly heated to room temperature.
Complete works should be washed and cleaned from
remainders of acid when not water soluble.

Excuse me when not all is correct but this are only some
suggestions of me.

Intergalactic_Captain - 14-12-2007 at 10:09

Just thought I'd chime in here for any amateurs looking to add MeNO3 to their "I made this collection." Although the synth is rather straight forward (I've had good success with H2SO4/NH4NO3, ~80%+ every time), you absolutely MUST keep the temp below 5degC. The shit is rediculously volatile, and very easy to runaway. I usually set up a beaker in a icebath w/ stirring, then drip the MeOH in drop by drop over an hour or so depending on the batch size. Dropwise addition is essential - a .5mL addition to a ~300mL acid volume at the proper temp once gave me a runaway. Isolation is hit or miss- sometimes it crashes out when diluted, others I've needed to use DCM to pull it.

As for EtNO3, don't do it unless you have a great deal of experience...It's an outrageously temperature sensitive synth...The only time I've come close was the first time I tried it - Took 45 minutes to add 5mL EtOH, got impatient and doubled the rate...Needless to say the icebath could only handle it for about 5 minutes before I had to evacuate. After about 5 more tries, I've since given up. I'm sure I can find another ethylating agent...Methyl nitrate makes a decent methylator, but ethyl nitrate is just too much of a bitch to make to actually use it for that purpose.


All in all, in my experience NG and EGDN are much more forgiving synths, with less volatile, less sensitive (I believe - though as someone pointed out before, friction and drop are 2 very different things) substances...If you just wanna blow something up, stay the hell away from the alkyl nitrates...Though they do have some utility in the lab if you'd rather store an explosive than a carcinogen.

Boomer - 19-12-2007 at 09:31

Ethyl nitrate *is* a bitch, it tends to oxidize rather than nitrate. But if you use fuming nitric free of NOx and work in a freezing mix instead of a simple ice bath, it works like a charm. Crushed ice with the right salt added goes to -30C, the nitration is easily held below -10C.
Rock salt is barely sufficient, but doable with enough patience. Just never let it get above -5C. Once isolated, the ethyl variety is tamer both due to higher bp (less headache) and lower sensitivity.

Oh I almost forgot, adding urea nitrate to the nitric helps too. Not urea for purging of the acid, but the nitrate added to the nitration. Also recommended for RDX, but we're far enough OT.
Just my two cent.

Bromine - 27-12-2007 at 15:18

I heard that methyl nitrate is carciogenic.
I was thinking that this could be true because it is methylating reagent. But on the other side i didn't found that information nowhere alse. So what do you think about it ?

Oh and how safe is to use 2 days old methyl nitrate?

[Izmenjeno 28-12-2007 Bromine]

[Izmenjeno 28-12-2007 Bromine]

Mason_Grand_ANNdrews - 3-1-2008 at 08:55

TNX -- Intergalactic_Captain. I don`t understand what you commenting to my "small" incursions. I don`t wan`t
give a commentary to the Me-NO2 synthesis. When you nitrate a strong chilled Me-OH, i will tell you the synthesis
will come like a opended flask of mineral-water after a short time. Every hydrogen ion is replaced wiht an (NO2)-ion and
this produces "somewhat" heat with the concentrated H2SO4 they will convert it to dilute H2SO4 and H2O/NO2. The
Et-ONO2 or more than CH2(NO2)-ONO2 will chauses a lot of heat what block the reacion into dilute H2SO4/HNO3
and evaporated "Oil" of CH3-NO2 (CH2-(CH-OH2)2). Maybe the water is picked up with acetic acid anhydride, the yield is
much more better because the converting of -H into H2SO4 causes not so much heat and something more.

:(

View User's Profile View All Posts By User U2U Member

[Edited on 3-1-2008 by Mason_Grand_ANNdrews]

SecretSquirrel - 3-1-2008 at 11:27

Quote:
Originally posted by Bromine
I heard that methyl nitrate is carciogenic.
I was thinking that this could be true because it is methylating reagent. But on the other side i didn't found that information nowhere alse. So what do you think about it ?


Here is some toxicity info on methyl nitrate
http://physchem.ox.ac.uk/MSDS/ME/methyl_nitrate.html


And the fact that it can be used as methylating agent has nothing to do with its toxicity. Dimethyl carbonate for example is a very good methylating agent and is not carcinogenic.

tr41414 - 4-1-2008 at 01:09

A bit offtopic... so what is it that makes a methylating agent carcinogenic? As far as i know the mutation comes from methylating dna. If so, is the resistance to hydrolysis an important factor?

Does maybe anyone have a ref (interested in procedure, not only mentioned) to using alkyl nitrates as alkylating agents?

tr41414 - 5-1-2008 at 04:28

tr41414 just made himself a few mls of EtONO2 (don't have any MeOH handy). It is a clear colorless liquid with chloroform like smell. It didn't detonate with hammer and burned with yellowish-white flame.

PS:Adding some H2SO4 to ethanol and chilling that prior to rxn helps with runaway, also mech. stirring...

Zinc - 5-1-2008 at 05:31

Can you describe the details how you made it please?

SecretSquirrel - 5-1-2008 at 06:36

I belive the adaptation of this synthesis can be used. Just use EtOH instead of MeOH and proceed with the synthesis as written.

[Edited on 5-1-2008 by SecretSquirrel]

[Edited on 5-1-2008 by SecretSquirrel]

franklyn - 7-1-2008 at 00:20

Recipe from Fownes Manual of Chemistry Theoretical & Practical
as it was done in 1878 _
Methyl nitrate is prepared by distilling 50 grams of NaNO3 with 50 grams of
Methyl alcohol and 100 grams of sulfuric acid, in a retort without external
heating.
( presumably if the heat of nitration is enought to boil it , a larger quantity
can easily run away. The Na2SO4 formed serves to keep water in the retort )
It is a colorless liquid density 1.182 at 20 ºC (68 ºF); boils at 60 ºC (140 ºF);
has a faint ethereal oder. It's vapor detonates when heated to 150 ºC (302 ºF).
Heated with alcoholic ammonia, it yields methylamine nitrate. CH3NH2.HNO3

.

tr41414 - 7-1-2008 at 03:31

The first try was using 7 ml of H2SO4, 4 ml of 60% HNO3 and 3 ml EtOH. A few granules of urea was added to the nitration mix, probably not the best idea as it didn't dissolve and seemed to give of bubbles? It went well until last drops of EtOH were added. The mixture started to give of NOx and turn black. It was dumped in ice/water, from where only a ~0.5ml blob of EtONO2 could be rescued...

Second try was using double the reagents, improvised overhead stirring and addition funnel :cool: also ~2ml of H2SO4 were premixed with ethanol and chilled (mixing 0degC reagents resulted in fairly warm mixture). Addition was done at about 1 drop per second. Product was separated using separating funnel. I got around 5ml of product which was neutralized using bicarbonate and then dried using CaCl2. Half an houf after spent nitration mixture started to give of NOx and turned completely black (after rxn it was removed from cooling bath; there was probably some EtOH/EtONO2 still in there). After a day it was again almost colorless.

In both tries 0degC water + AN bath was used...

The EtONO2 seems to be pretty damn inert...

[Edited on 7-1-2008 by tr41414]

Zinc - 7-1-2008 at 06:05

What concentration of ethanol did you use? And could a mixture of NaNO3 and H2SO4 be used?

So ethyl nitrate is not very sensitive?

tr41414 - 7-1-2008 at 09:38

Ethanol was food grade 94% i think (you can dehydrate it to get better yields)... I guess that mix should work also...
With being inert I meant i couldnt detonate it /w hammer and it also didn't react with NaOH prill... On heating a drop simply vaporised (vapor goes of with less of a woof than AP if you light it). But on the other hand i have done this with small drops of it and there are warnings about it oxidising in explosive manner on contact with nitrating mixture...

garage chemist - 8-1-2008 at 04:04

There is a synthesis of ethyl nitrate that uses no H2SO4, but ethanol and 68% nitric acid at 120- 130°C. A mixture of those two, with addition of urea nitrate, is distilled and the distillate washed with water and soda solution.
http://www.lambdasyn.org/synfiles/ethylnitrat.htm
As you can see, the nitration is much, much less sensitive to temperature when there is no H2SO4.

Boomer - 8-1-2008 at 05:21

I still dislike methods where nitric esters are heated (or their precursors, which is the same after some product has formed). Note orgsyn mentions "frequent explosions" for the distillation method if used for MeOH instead of EtOH. :o

Plus, using fuming nitric + conc. sulfuric is more satisfying to the eyes. Where else do you have the pleasure to see more product than spent reagents? I once had approx. 20ml of EtONO2 sitting on top of 18ml spent acid. :D

(OK it's less dense, and dissolves up to 10% of nitric, but still.)

Zinc - 8-1-2008 at 11:35

Did anyone had an accident while making ethyl nitrate?

Mason_Grand_ANNdrews - 11-1-2008 at 04:09

At first, i must to excuse me for the written formula (CH2-(CH-OH2)2).
I can`t find it elsewhere. I`ve written down this answer in the topic
after a nice night with some friends. I mean the somewhat incorrect
nomenclatura of something like dimethanolmethane (correct formula
CH2-(CH2-OH) is not a allday available stuff.

Some more examples of my writing errors are:

2,2-isopropanoldimethanol
1,2-isopropylalcoholdimethanol
1,3-isopropylalcoholdimethanol
and so on.


Something more what give a little diversity of the stuff.
I would mean, nitrated in a AAA(TFAA)/HNO3 solution it gives some easy nitrates
when dissolved in the water converter and the HNO3 is slowly stirred in over some
hours into the solution.
Concentated H2SO4 should work too, but i mean it`s can not easy form a -CH2-NO2
nitrate without developing of to much heat or destroying the material.

1,1-isopropyldimethanol tetranitrate (O2N-CH2)2-C(ONO2)-CH2-NO2
1,2-isopropyldimethanol trinitrate (O2N-CH2)-(CH-ONO2)-CH2-NO2
1,3-isopropyldimethanol trinitrate (O2N-CH2)-(CHONO2)2-(CH2ONO2)
and something more.

Any simple formulas to some unkown stuff, maybe for guys they know how it
can get from suppliers or prepared or have a way to prepare. Amines and more
stuff here not mentioned here.

I mean what my expieriences told, this nitrates are very insensitive and i think
they are more than good to make a insensible solvent for a high explosive in ratio 60:40. (nitorxides only !!!!)

The first procedure can be - the alcohols are stirred into concntrated H2SO4 and
treated with concentrated HNO3 to make the simple nitrate.
The nitration of the -OH ion should be finished when some little blows will heat the
mix and you dump it into a smal portion of ice water. The milky liquids which will placed
are easy cleaned when they stirred with 10% soda for an hour (ratio 1:5 )
let sit and suck off the viscous layer of the f.i ethyl nitrate.

Easy Step one:
I mean the nitration to the f.i. 1-nitromethylethanol (exuse me for my thought, 1-nitroethane-2-nitroxide)
should walk after 0,5 mol of 95 to 98 % sulfuric acid is
mixed with 0,1 mol of EtOH, the stuff is stirred and over an half hour 0,3 mol of 70 to
80% HON3 is stirred into the mix that nor fumes of nitrogen oxides will form. The mix
should be chilled with a dish of cracked ice. Stirr it until it begin to bubble, the ice will
be melt and dump it into 500 ml of ice water. Let sit, add a little soda, stirr it for
an half hour, let sit and suck the little layer of ethylnitrate inot a small dish.

Easy Step Two:
Pour around 200 ml of fresh distilled acetic acid anhydride into an beaker, let sit it in a
water bad of crisehd ice, add the ethylnitrate and slowly 3 mol of 96 to 98 % HNO3 is dropped
into the solution with rapidly srirring. Stirr the mix for two hours or mor and
add more ice when it heated to much. Let sit it until the ice is molten, suck off the
nitromethylethanol (I hope it will have still a liquid, stirr it into 500 ml water with a
dissolved soon of soda, make it free of acid while stirring and let sit it that you can
separate it from the soda water.

CH3-OH ---> methylnitrate --> CH3-ONO2
CH3-CH2-OH ---> ethylnitrate --> CH3-CH2-ONO2
CH3-CH2-CH3-OH ---> nitropropanol --> CH3-(CH2)2-ONO2
CH3-(CH-OH)-CH3 ---> isopropylnitrate --> CH3-CHONO2-CH3
isopropyl-2,2-dininitromethanol ---> CH3-(C(CH-OH)2)2-CH3 ---> isopropyl(dimethanoldinitrate :P)
or
nitrobuthanol ---> CH3-(CH2)3-CH2ONO2 (propylnitroethanol ;), CH2(NO2)-(CH2)3-CH2-ONO2, pentanitrobuthanol CH2(NO2)-(CHNO2)3-ONO2)

Exucuse me for the somewhat long description. When you will make some
methylnitrate you can buy some methanolic acid from sigma, the mix is
more than good for minimum MeONO2.


Supelco - Methanolic H2SO4
10% in methanol, pkg of 6 × 5 mL
Sulfuric acid solution
CAS Number 7664-93-9

I`ve locked around at roguesci at the last two days but the forum is down.
Someone can told me why ? :mad:
The forum gives some "little " motivations to make a good stuff in the explosives section.

[Edited on 11-1-2008 by Mason_Grand_ANNdrews]

quicksilver - 11-1-2008 at 12:14

Quote:
Originally posted by Zinc
Did anyone had an accident while making ethyl nitrate?


During the latter part of the 2nd World War the Nazis were running short on just about everything. Slave labour was routed to the production of explosives for uniquely inexpensive land mines. Due to production techniques utilizing slave labour and economics of nitric esters instead of nitro benzenes, the common light alcohols were used. Methyl nitrate was perhaps the least expensive production ester to manufacture a "dynamite" filler. The loss of life and limb were so extensive that often the production facilities were cordoned off and many escaped due to the isolated facilities needed....

The problems in production with methyl or ethyl nitrate is that temp control is tough as the material is thin. If you study the "run-a-way" reaction mechanism in nitric esters, the thinner the material the more controls are needed to stabilize & maintain consistency in the estrification, bla, bla, bla... temp, addition speed, whatever, ...becomes a headache (pun intended)!

gnitseretni - 30-8-2008 at 17:05

Could Nitromethane in ANNM mixtures be substituted with Methyl Nitrate or would it be too dangerous,as in the AN pellets 'grinding' the liquid?

AndersHoveland - 12-1-2012 at 22:07

Interestingly, ethyl nitrate can be prepared with only moderately concentrated nitric acid, without the need for concentrated sulfuric acid.

Quote:

Ethyl alcohol is nitrated continuously by adding a mixture of 61% nitric acid with 95% ethyl alcohol, saturated with urea (as much as can dissolve), into a flask set up for distillation containing boiling 50% nitric acid. The nitrate ester and water formed are continuously distilled off at about 98 °C from the reaction mixture. The volume of the reaction mixture is held constant by drainage of nitric acid and unstable by-products from it as the reactants are added. Unless you have a special flask with a stopcock on the bottom, you will have to periodically disconnect the flask from the condenser and dump out some of the used nitric acid. You will also have to momentarily disconnect the flask to add more acid/alcohol mix if you do not have an addition funnel. Be very careful doing this as you will subject yourself to a blast of acid fumes. A small quantity of gas, such as air, nitrogen, or carbon dioxide is blown through the reaction mixture to improve mixing and to facilitate the elimination of the volatile byproducts. The optimum ratio of nitric acid to ethanol is about 2:1. The yield is 78%.

Pulverulescent - 13-1-2012 at 01:43

Quote:
Interestingly, ethyl nitrate can be prepared with only moderately concentrated nitric acid

Quote:

Many moons ago, I had a runaway distilling methyl nitrate from 70% HNO3 ─ 2litre RBF ~half full . . .
The NO2 was like some crazy, fucking live thing, writhing, and uncoiling itself out the flask!
I mean, this stuff looked like it was solid!!!

The trick is to get the adapter out of the flask real fucking quick!

P

franklyn - 28-7-2012 at 09:19

Can the electrolysis of ammonium nitrate in acetic acid yield methyl nitrate ?
There is some evidence to suggest this might work.

Some New Anode Reactions Involving Nitrate Ions & Aromatic Compounds
http://actachemscand.org/pdf/acta_vol_25_p3246-3254.pdf


On the electrolysis of ammonium nitrate in acetic acid.

Kolbe electrolysis of acetic acid yields hydrogen , carbon dioxide and ethane.
The half cell reaction of the carboxyl anion is decomposed thus :
2 CH3COOH => 2 CH3COO => 2 CO2 + 2 CH3• => ( 2 CH3• => CH3CH3 )

Electrolysis of ammonium nitrate yields hydrogen , ammonia ,
and oxygen with nitrogen dioxide.
The half cell reaction of the nitrate anion is decomposed thus :
2 NH4NO3 => 2 NO3 => 2 •NO3 => O2 + 2 •NO2 => N2O4

The nitrogen trioxide radical has a fleeting existence only.

The mol weight of acetic acid is 60 , the mol weight of ammonium nitrate 80
a stoichiometric proportion of 3 to 4 , CH3COOH + NH4NO3.

The cathode would expel hydrogen and ammonia. The anode would expel
CO2 with the recombination of CH3• and •NO3 into CH3NO3

Ammonium nitrate and acetic acid ignites when warmed , it's an explosive.
This should serve to caution any intrepid investigator.
Addition of a non participating non aqeous cosolvent will provide safe operation.
Question is what ?

.

497 - 28-7-2012 at 19:55

Very interesting concept!
It was already brought up in this thread http://www.sciencemadness.org/talk/viewthread.php?tid=1716
They say nitroglycol is produced from ethylene, so it seems possible to combine with a kolbe reaction. No mention of yields unfortunately.

If other options failed, you could always just hook two cells in series, so that the ethylene produced from acetate ran directly in to the next cell where it is nitrated. Nitroglycol is good stuff too, and then you'd have less oxidizer+fuel mixture risks...

AJKOER - 8-9-2012 at 12:07

I have an interesting idea to somewhat safely prepare and promptly detonate a small amount of Methyl nitrate. Place Cl2 and CH4 gas (the latter in excess) in a plastic (or glass) container (that is not dissolved by chloromethane as is ordinary rubber) . Some KNO3 (or NaNO3) has been placed on the bottom (with possibly some H2SO4). The vessel is surrounded by Aluminum foil to create a solar heat source and/or initiate a photo-chemical reaction (see http://www.youtube.com/watch?v=ukxOtG7d3OA ). Intended reactions, first:

CH4 (g) + Cl2 (g) --> HCl (g) + CH3Cl (g)

Source: Wikipedia ( http://en.wikipedia.org/wiki/CH3Cl ) which states that chloromethane is produced by heating a mixture of methane and chlorine to over 400 °C. This, however, may be a tough for a solar setup, and hopefully the photo-chemical induced chain reaction will create an effective yield. Wiki describes this reaction as moderate to fast (see: http://en.wikipedia.org/wiki/Free-radical_halogenation and also http://www.stanford.edu/group/Zarelab/publinks/zarepub525.pd... ). Otherwise, a metal container and a more conventional heating source can be employed.

Final required reaction, the nitration of the chloromethane:

KNO3 + CH3Cl --> KCl + CH3NO3 or

HNO3 + CH3Cl --> HCl + CH3NO3

Note, Gmelin, vol. 8, p. 468, for example, notes the historic use of Sulphuric acid, alcohol and saltpeter in the preparation of related Ethyl salts, although I would prefer to avoid the use of H2SO4 as the reaction vessel is intended for immediate ignition.

The amount of CH3NO3 formed (via the suggested gaseous reaction synthesis) would be small, but given the reputation of Methyl nitrate, this may be a good thing.

[EDIT] Note, the MSDS for CH3Cl (see http://www.airgas.com/documents/pdf/001036.pdf or http://www.mesagas.com/_Specialty%20Gas%20MSDS/Methyl%20Chlo... ) warns that chloromethane is extremely flammable in the presence of strong oxidizers (KNO3/HNO3 in this case) even without or before the formation of any CH3NO3, which per Wiki, explodes at 64.6 C. Both compounds are toxic.


[Edited on 9-9-2012 by AJKOER]

AJKOER - 9-9-2012 at 19:48

OK, I may be a day early on a similar concept that was recently presented by AndersHoveland. My idea is the creation of Methyl nitrate from CH3Cl and a nitrate, and AndersHoveland's is proposing the formation of RDX from CH2Cl2 + NH4NO3 (link: http://www.sciencemadness.org/talk/viewthread.php?tid=19106 ).

Note, the related formation of these two methyl chlorides:

CH4 (g) + Cl2 (g) --> HCl (g) + CH3Cl (g)

and with added chlorine:

CH3Cl (g) + Cl2 (g) --> HCl (g) + CH2Cl (g)

Some comments by AndersHoveland that may be applicable to my suggested methyl nitrate synthesis:

Quote: Originally posted by AndersHoveland  
.....
NH4NO3 and CH2Cl2 might be able to react using DMSO as the solvent, with some CuCl2 and ZnO as the catalysts. The reaction would probably take about 24 hours.

Under these conditions, the ammonium ions should be able to act as a nucleophile toward the CH2Cl2, and the resulting HCl should be able to act as the dehydrating agent.


However, in the presence of Methyl chloride, CH3Cl, one MSDS notes an explosion hazard (see http://www.mesagas.com/_Specialty%20Gas%20MSDS/Methyl%20Chlo... ) in the presence of Zn (or ZnO?) and AlCl3 (or CuCl2?, may react similarly). I believe I have also seem mention of Iron (forming FeCl3) as a catalyst, but these catalysts may be unnecessary or inappropriate (precipitating a possible detonation, so exercise extreme caution).

[Edited on 10-9-2012 by AJKOER]

AJKOER - 22-9-2012 at 15:25

Quote: Originally posted by AJKOER  
.....
Final required reaction, the nitration of the chloromethane:

KNO3 + CH3Cl --> KCl + CH3NO3 or

HNO3 + CH3Cl --> HCl + CH3NO3


Some have implied a preference for an Ammonium salt (NH4NO3) in place of KNO3/HNO3 to accomplish the nitration of chloromethane. There is seemingly some support by the fact that CH3Cl is readily attacked by Ammonia. For example, the ammonolysis reaction, per one source (http://www.docstoc.com/docs/68188299/CHAPTER13 ) is given as:

CH3Cl + NH3 --> CH3NH2.HCl --> CH3NH2.HCl + NH3 --> CH3NH2 + NH4Cl

and combine this with the thermal decomposition of NH4NO3 which proceeds in two stages, with the 1st stage, at temperatures below 200 C, characterized by an endothermic dissociation into NH3 and HNO3. The second stages, at 200 C to 290 C, creating the ionic NO2(+), which leads to the formation of N2O (see http://energetics.chm.uri.edu/system/files/1989%20Thermal%20... ).

Clearly, limiting the thermal decomposition of the NH4NO3 to the 1st stage only might produce a successful reaction if:

CH3NH2 + HNO3 --?--> CH3NO3 + NH3

recycling some of the NH3 to react with more CH3Cl. However, research suggests the following reaction instead (see top of last page at: http://math-wizard.com/netionic.pdf )

H(+) (aq) + CH3NH2 (aq) --> CH3NH3(+) (aq)

implying the formation of Methylammoniun nitrate and not Methyl nitrate. In fact, per Wiki (http://en.wikipedia.org/wiki/Methylammonium_nitrate ) "Methylammonium nitrate is an explosive chemical with the molecular formula CH6N2O3, alternately CH3NH3+NO3-. It is the salt formed by the neutralization of methylamine with nitric acid. This substance is also known as methylamine nitrate and monomethylamine nitrate, not to be confused with methyl nitramine or monomethyl nitramine." And further, unlike Methyl nitrate which has no military applications, apparently methylamine nitrate was first used as an explosive ingredient by the Germans during World War II. It more recently as been combined with AN to form PR-M which is considered a low cost blasting agent (water gel explosives) to replace explosives based on nitroglycerin (dynamites).

A major assumption of this possible synthesis of methylamine nitrate is, however, that a low temperature heating of the dry NH4NO3 salt in an atmosphere of CH3Cl does not immediately precipitate an explosion.

[Edited on 23-9-2012 by AJKOER]

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