Sciencemadness Discussion Board

MeNO3 (Methyl Nitrate) Synthesis

freedompyro - 23-2-2012 at 23:00

Curious if anyone has any thoughts on this synthesis below with mixed acids. Be careful attempting this... MeNO3 synthesis is literally more dangerous than MEKP. Have NG and EGDN experience under your belt before you mess with MeNO3. Don't mean to scare anyone off. :D This nitration can be done completely safely on the small scale with a half inch of plexiglass between you and the nitration with holes drilled to control it.

I'm interested in mixtures of MN/Me that are somewhat self oxidizing but do not detonate for hobby use. I do buy gallons of pure NM but MN/Me is so so interesting... Also, it's not practical to synthesize NM for those in certain countries that cannot buy it.


"Methyl Nitrate (8000m/s) - Optimal Yeild: ?x +

Nitric Acid Synthesis (NOT OPTIMIZED FOR YIELD YET!!!)
25g Methanol + (10g H2SO4 + 0.5g Dissolved Urea) (Not sure if the urea here is necessary...)
50g Nitric Acid (93% Concentration) + 1-10g H20 With Dissolved Urea
110g Sulfuric Acid (98% Concentration)

1. Add H20/Urea solution to HNO3 drop by drop with steady stirring until solution is free of nitric oxides(clear). This will lower the risk of a dangerous Methyl Nitrate runaway... Those can go very badly!!!
Skip this step if you have perfectly pure WFNA.
2. Mix sulfuric acid and nitric acid in ice bath keeping temperature below 40C.
3. Cool to 20C. Keep temperature below 25C for the entire nitration.
4. Add Methanol/H2SO4 solution slowly drop by drop with automatic steady stirring (Required) at 20-22C and do not exceed 25C.
5. Methyl Nitrate will seperate out into it's own clear layer after a while. Remove this layer with either separation glassware or a plastic syringe. Waste acids can be recovered if you know how to do it safely. It's likely that the MN will just evaporate off after a while and all of the H2S04 can be recovered.
6. MN is washed with a small amount of cold water with maximum dissolved salt and sodium bicarbonate to prevent the MeNO3 from absorbing water.
7. It is dried if needed by placing it inside a sealed container with a desiccant like CaCl2 suspended above it.

Note: Methyl Nitrate can be desensitized from shock as needed by adding upto 20% methanol. Evaporation rate of Methanol and Methyl Nitrate is the same so the composition will not change over time."

[Edited on 24-2-2012 by freedompyro]

Ral123 - 24-2-2012 at 03:19

Few milligrams in a thin tube exploded on me(with out main mass being heated, only ignition). I think the vapours deflagrate so fast that they detonate the MN.

Pulverulescent - 24-2-2012 at 05:40

The fairly extreme volatility of methyl nitrate make it of little use for serious experimentation, though!
A novelty sure, but not much else . . .

P

killswitch - 24-2-2012 at 13:46

Interestingly, though, it would seem that a sealed container of methyl nitrate with some air inside it could be initiated via a battery (heated wire ignites fuel/air mixture which sets off the bulk of the MeNO3). This would be a very simple NPED that doesn't rely on acquiring finely-milled pyrotechnic metal/oxidizer mixtures.

freedompyro - 24-2-2012 at 15:14

The vapors do detonate easily. What synthesis did you use Ral? Vacuum distillation or mixed acids?

killswitch, design a detonator that works reliably inside commercial 6mm OD Al tubing that uses methyl nitrate then well see if it's practical. Perhaps a mix of large ETN needle crystals at medium density with 5-10 drops MN sealed in a detonator could be initiated high order via 70/30 flash powder. How you would seal in the ETN/MN I am not sure... A 0.25mm layer of Al foil then a 1.5mm layer of some type of plastic glue that is not solved by MN may work. Ugh... This is getting complicated.

If it doesn't work with both fuse and electrical ignition scratch it...

Heck... 5mm of hot toaster wire inside 6mm OD(0.45mm wall) Al tubing with a hobby battery will initiate a gram of ETN, MHN, or NG high order so it sure better initiate MN... LoL!!!

[Edited on 24-2-2012 by freedompyro]

freedompyro - 24-2-2012 at 15:21

Quote: Originally posted by Pulverulescent  
The fairly extreme volatility of methyl nitrate make it of little use for serious experimentation, though!
A novelty sure, but not much else . . .

P


The volatility isn't too bad. Mixed with Me for use as a fuel it's hardly worse than plain Me.

Ral123 - 24-2-2012 at 20:31

I don't distil offcourse. I'm intrigued of the idea of MeNO3 initiated by its own vapours. Now some modifications-the gases need to travel long enough to have like 3000m/s vel. Second-it's better if the gases are oxy/propane under some pressure (more powerfull and cold proof). Igniting oxygen enriched gases is unbelievably comfortable. A tiny spark from piezo ignition from a lighter. A broken lamp or hot wire. Another advantage is that with piezo ignition there'll be absolutely no delay. Absolute instant detonation :D If you can see what's in the device, you'll be confident if there'll be a problem.

NitricSynth - 25-2-2012 at 00:44

Oxygen enriched gasses are lots of fun... Got a scar on one of my fingers from a piece of a soda can when experimenting with oxygen/ethylene when I was 13. Needless to say I moved to remote ignition with a fence shocker and piped the gas in through small ID 10' tubes from then on.

quicksilver - 25-2-2012 at 07:35

Methyl nitrate was used in WWII by the Nazi's in an attempt to find a cheap replacement for more more difficult to obtain materials & they used slave labor to work with it due to high casualty rates (see, Brassey's Hist) Methyl Nitrate is an extremely dangerous material as well as being difficult to maintain. It's high viscosity level makes for difficulty in most useful arenas.
Ethyl Nitrate is found in the re-routing of fumes during mercury fulminate synthesis and had been problematic during the plant-level synthesis of of that product.
As a "not so subtle hint" - I'd like to see the thread get back to a modicum of science as it appears to have lost most potential in that direction.

killswitch - 25-2-2012 at 12:43

Has any research been done on a gas-phase synthesis of this molecule under inert atmosphere and reduced pressure?

497 - 26-2-2012 at 10:31

Why not just run the nitration with enough DCM to keep it from becoming sensitive?

killswitch - 26-2-2012 at 12:43

Because DCM is harder to get for the amateur than some vacuum pump equipment and tanks of nitrogen.

Bot0nist - 26-2-2012 at 14:13

Really? Buy gooey paint stripper, dilute, distil with warm water bath, dry. Easy and OTC, IMO.

killswitch - 29-2-2012 at 10:26

Quote: Originally posted by Bot0nist  
Really? Buy gooey paint stripper, dilute, distil with warm water bath, dry. Easy and OTC, IMO.


Wait, seriously? How have I never heard about this?

I know sharing direct brand names is against policy on these boards, so what characteristics should I look for in paint strippers to tell if they likely contain DCM? What kinds of coatings require DCM strippers?

Bot0nist - 29-2-2012 at 10:52

The ones that list "methylene chloride" as their ingredient. It's all over the site, multiple threads. Use The Forum Search Engine, when in doubt...

There is one on the "todays posts" right now!

http://www.sciencemadness.org/talk/viewthread.php?tid=18824

[Edited on 29-2-2012 by Bot0nist]

SB15 - 29-2-2012 at 10:53

Quote: Originally posted by killswitch  
...so what characteristics should I look for in paint strippers to tell if they likely contain DCM?


An MSDS sheet that lists DCM/methylene chloride as a principle component of said paint stripper...

I haven't been able to locate a source in my country, but I've been told it's quite readily available in the USA.

Ral123 - 29-2-2012 at 12:42

And is there a possibility that something can be made from chloroform and sodium nitrite/nitrate?

killswitch - 14-3-2012 at 11:21

I've been trying to model the gas-phase behavior and liquid-vapor equilibrium of methyl nitrate, but I can't find any sources, nor can I find the lower flammability limit or upper flammability limit for the vapors (for calculating optimum fuel-air mix for spark-initiated DDT). If I knew the intermolecular attractive forces I could use the van der Waals equation with Maxwell's correction, but that data doesn't seem to show up anywhere on the internet (that I can find, at least).

Ral123 - 14-3-2012 at 13:32

For practical reasons I'd say you don't need to calculate fuel to air ratios. Fill all volume with cold oxygen, add cold MeNO3. Expect reliability only when it's warm. I don't know if you have experience with this stuff but for me upper flammability limit is a silly concept :D

quicksilver - 14-3-2012 at 13:49

Quote: Originally posted by killswitch  
I've been trying to model the gas-phase behavior and liquid-vapor equilibrium of methyl nitrate, but I can't find any sources, nor can I find the lower flammability limit or upper flammability limit for the vapors (for calculating optimum fuel-air mix for spark-initiated DDT). If I knew the intermolecular attractive forces I could use the van der Waals equation with Maxwell's correction, but that data doesn't seem to show up anywhere on the internet (that I can find, at least).


Some of this may have been discussed back in '03. You could check back then. And the Organic synthesis search:

http://www.orgsyn.org/orgsyn/prep.asp?prep=cv2p0412

http://www.sciencemadness.org/talk/viewthread.php?action=pri...

[Edited on 14-3-2012 by quicksilver]

killswitch - 16-3-2012 at 08:58

Quote: Originally posted by quicksilver  
Quote: Originally posted by killswitch  
I've been trying to model the gas-phase behavior and liquid-vapor equilibrium of methyl nitrate, but I can't find any sources, nor can I find the lower flammability limit or upper flammability limit for the vapors (for calculating optimum fuel-air mix for spark-initiated DDT). If I knew the intermolecular attractive forces I could use the van der Waals equation with Maxwell's correction, but that data doesn't seem to show up anywhere on the internet (that I can find, at least).


Some of this may have been discussed back in '03. You could check back then. And the Organic synthesis search:

http://www.orgsyn.org/orgsyn/prep.asp?prep=cv2p0412

http://www.sciencemadness.org/talk/viewthread.php?action=pri...

[Edited on 14-3-2012 by quicksilver]


I wish the older Org Syn articles would show up on Google... I feel like a dumbass.

Edit: actually, they don't have the exact information I'm looking for.

Quote:
The van der Waals equation can be cast into the better known form



where



is a measure of the attraction between the particles,



is the volume excluded by a mole of particles.

The parameter b' is proportional to the proper volume of a single particle - the volume bounded by the atomic radius. This is the volume to be subtracted from V because of the space taken up by one particle. In Van der Waals' original derivation, b' is four times the proper volume of the particle.

The equal area rule can be expressed as:




where PV is the vapor pressure (flat portion of the curve), VL is the volume of the pure liquid phase at point a on the diagram, and VG is the volume of the pure gas phase at point c on the diagram. The sum of these two volumes will equal the total volume V.

/end quote.

What I'm looking for is exact values for a' and b' for methyl nitrate.

[Edited on 16-3-2012 by killswitch]

[Edited on 16-3-2012 by killswitch]

quicksilver - 16-3-2012 at 09:01

No sweat: I'll look for the whole deal and post it if I find it. It may be on the machine I'm using now.

killswitch - 19-3-2012 at 19:05

Quote: Originally posted by quicksilver  
No sweat: I'll look for the whole deal and post it if I find it. It may be on the machine I'm using now.


Thank you! I haven't been around as long, so I didn't get the chance to stock up on books and papers before a few guys flew planes into stuff and ruined everything.

SB15 - 24-3-2012 at 11:47

Quote: Originally posted by killswitch  
I've been trying to model the gas-phase behavior


At which temperature/pressure range? STP or close to it? If so, the vapour is going to behave very similar to an ideal gas, so the ideal gas law should be a sufficiently accurate model. No need for the van der Waals equation unless the conditions are non-standard.
Quote:
and liquid-vapor equilibrium


A brief search didn't turn up any data on the vapour pressure of methyl nitrate, but the value for methanol is approximately 100mmHg (~1.9PSI) at room temperature. These two compounds are said to have similar volatility, so that figure may have some limited usefulness.
Quote:
nor can I find the lower flammability limit or upper flammability limit for the vapors (for calculating optimum fuel-air mix for spark-initiated DDT).


You don't need the upper and lower flammability limits to calculate the optimum (stoichiometric) air/fuel mixture.

4CH<sub>3</sub>NO<sub>3</sub> + O<sub>2</sub> -> 4CO<sub>2</sub> + 6H<sub>2</sub>O + 2N<sub>2</sub>

This gives you a ratio of 4 moles of methyl nitrate to 1 mole of oxygen gas. Air is approximately 21% oxygen, so you need 21/(1/4) = 84% of the volume of air in CH<sub>3</sub>NO<sub>3</sub>. The stoichiometric fuel percentage is then 84/(100+84) = 45.7%.

killswitch - 25-3-2012 at 13:07

Quote: Originally posted by SB15  
Quote: Originally posted by killswitch  
I've been trying to model the gas-phase behavior


At which temperature/pressure range? STP or close to it? If so, the vapour is going to behave very similar to an ideal gas, so the ideal gas law should be a sufficiently accurate model. No need for the van der Waals equation unless the conditions are non-standard.
Quote:
and liquid-vapor equilibrium


A brief search didn't turn up any data on the vapour pressure of methyl nitrate, but the value for methanol is approximately 100mmHg (~1.9PSI) at room temperature. These two compounds are said to have similar volatility, so that figure may have some limited usefulness.
Quote:
nor can I find the lower flammability limit or upper flammability limit for the vapors (for calculating optimum fuel-air mix for spark-initiated DDT).


You don't need the upper and lower flammability limits to calculate the optimum (stoichiometric) air/fuel mixture.

4CH<sub>3</sub>NO<sub>3</sub> + O<sub>2</sub> -> 4CO<sub>2</sub> + 6H<sub>2</sub>O + 2N<sub>2</sub>

This gives you a ratio of 4 moles of methyl nitrate to 1 mole of oxygen gas. Air is approximately 21% oxygen, so you need 21/(1/4) = 84% of the volume of air in CH<sub>3</sub>NO<sub>3</sub>. The stoichiometric fuel percentage is then 84/(100+84) = 45.7%.


So, then, is the next step to calculate volumes at STP for methyl nitrate vapor and air wherein both the ratio of air and methyl nitrate are at ideal stoichiometry and the partial pressure of air and the vapor pressure of methyl nitrate are equal? Or did I forget how to do physical chemistry again?

niertap - 26-3-2012 at 14:12

Does anyone know how it would react with nitrocellulose, ammonium nitrate, or nitro ethane?


Just speculation, but acetone seems like something that could be used to temporarily desensitize it, then let it evaporate off to reconstitute it.

killswitch - 26-3-2012 at 16:27

Quote: Originally posted by niertap  
Does anyone know how it would react with nitrocellulose, ammonium nitrate, or nitro ethane?


Just speculation, but acetone seems like something that could be used to temporarily desensitize it, then let it evaporate off to reconstitute it.


With nitrocellulose, it would form a goo as the nitrocellulose molecules and methyl nitrate interpenetrate.

With powdered ammonium nitrate, it would also form a paste, and help protect the ammonium nitrate from atmospheric moisture. However, this might pose a danger from friction of the ammonium nitrate particles rubbing against each other. A very fine mesh size would help mitigate this.

With nitroethane it would be completely miscible.

Nevertheless, it will slowly evaporate out of any mixture it is added to, unless the mixture is in a sealed container.

niertap - 26-3-2012 at 19:04

Have you ever heard of anyone mixing it with a sawdust, an oxidizer and nitrocellulose to thicken it a little? I believe that was one of the formulations of dynamite. wrapping it in foil would probably keep it from evaporating, if that works for things like diethylether.





For some reason the word interpenetrate makes me slightly confused and oddly curious.


in·ter·pen·e·trate (ntr-pn-trt)
v. in·ter·pen·e·trat·ed, in·ter·pen·e·trat·ing, in·ter·pen·e·trates
v.intr.
To become mixed or united by penetration:
v.tr.
1. To penetrate reciprocally:
2. To penetrate thoroughly; permeate or pervade.

The American Heritage® Dictionary of the English Language, Fourth Edition copyright ©2000 by Houghton Mifflin Company. Updated in 2009. Published by Houghton Mifflin Company. All rights reserved.
interpenetrate [ˌɪntəˈpɛnɪˌtreɪt]
vb
1. to penetrate (something) thoroughly; pervade
2. to penetrate each other or one another mutually

killswitch - 7-4-2012 at 21:18

Quote: Originally posted by niertap  

Just speculation, but acetone seems like something that could be used to temporarily desensitize it, then let it evaporate off to reconstitute it.


Acetone would desensitize it, but evaporating it would result in a substantial loss of product.

497 - 7-4-2012 at 21:48

Butane might be a good desensitizer.