methyl nitrate

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.

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]

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! 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?

Are this not methylnitrol about you talk ?



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

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]

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


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 !

[Edited on 3-10-2004 by sylla]

And here some empirical data

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.

“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.

That should work!

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

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.....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.

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. 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

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.


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.

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


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]

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

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 ....

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 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.

This was my first nitration and I loved it.

[Edited on 5-7-2006 by hinz]

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


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.

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)

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). 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]

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.

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 ( 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:
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?!

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]

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]

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, it would be interesting for me, as it might prove or disprove my theories.

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]

Sensitivity?

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

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]

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]

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 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]

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.

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.

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

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 )
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 ?
The forum gives some "little " motivations to make a good stuff in the explosives section.

[Edited on 11-1-2008 by Mason_Grand_ANNdrews]

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.

Quote: Originally posted by AJKOER

..... Final required reaction, the nitration of the chloromethane: KNO3 + CH3Cl --> KCl + CH3NO3 or HNO3 + CH3Cl --> HCl + CH3NO3