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megalomania
June 9th, 2003, 05:58 PM
Jumala
Frequent Poster
Posts: 200
From: Germany
Registered: OCT 2000
posted 05-30-2001 12:10 AM
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Hallo,
I have scanned receipes and propertys of some nitric esters from an old book (Phokion Naoum 1923)and I would like to post it here.
But to prevent the mods from a nervous breakdown I ask for o.k. because they are some bookpages long. Then I´ll add the text.

Methyl Nitrate
Of the nitric esters of the primary alcohols of the fatty series, methyl nitrate is theoretically the most important on account of its high explosive properties and high energy content, which is on a par with nitroglycerine, to which it is stochiometrically related very closely, as can be seen from table 12. Practically, it has had no importalice äs an explosive up to the present time on account of its great volatility, as well as on account of the danger from fire or explosion of the liquid or vapors in increasing the risk in commercial manufacture or use.
According to Meyer-Jakobsen it has been made commercially for some time for use in the dye industry for methylation, but on account of several disastrous explosions its manufacture was given up.
Preparation.1 Methyl nitrate, like ethyl nitrate, can be obtained by careful distillation of the proper alcohol with moderately strong nitric acid, e.g., of a specific gravity of 1.4. It can also be obtained, like nitroglycerine and nitroglycol, by putting the alcohol into a mixture of concentrated nitric and sulphuric acids, with good yields, while ethyl alcohol and other mono- and polyvalent alcohols con-taining methyl or methylene groups readily undergo oxidation in such a case.
Example. One hundred grams of pure, anhydrous methyl alcohol was added gradually to 630 grams of a mixed acid containing 40 per cent HNO3 and 60 per cent H2SO4, contained in a spherical glass vessel having three openings for a stirrer, thermometer and inlet, the mixture being well cooled, mechanically stirred and maintained at 0 to 10°C., the Operation taking twenty-five minutes. Agitation by compressed air is out of the question on account of the volatility of the ester. The ester separated rapidly in a funnel. It was digested with cold water and then neutralized with a soda solution. There was obtained 196 grams of neutral methyl nitrate, or 81.5 per cent of theory (240.6 grams).
Properties. Methyl nitrate is a colorless, very mobile liquid of a high volatility and strongly aromatic odor, somewhat resembling chloroform. The vapors cause headache when inhaled. It is some-what less viscous than water, and has a specific gravity of 1.21 at 15°C. At ordinary pressures it distils at 65°C. without decomposi-tion. Water dissolves it only slightly at room temperatures. One hundred cubic centimeters of water at 20°C. dissolve 3.85 grams of methyl nitrate. Collodion nitrocotton is dissolved, forming a gelatine, from which the methyl nitrate evaporates very easily.
TABLE 12
Relation of methyl nitrate to nitroglycerine
METHYL NITRATE NITR0G LYCE RIN E
Molecular weight........................... 77 227

Composition: C....................................... •per cent 15.6 'per cent 15.86
H,...................................... 3.9 2.20
0....................................... 62.3 63.44
N....................................... 18.2 18.50
100.0 100.0
Explosive character. The thermo chemical relations of methyl nitrate have already been determined by Berthelot.2 The explosive decomposition is possibly along the line of the following equations:
1. 2(CH3ON02) = CO2 + CO + 3H2O + N2
2. 2(CH3ONO2) = 2CO2 + 2H2O + H2 + N2
The molecule lacks one atom of oxygen for complete combustion. The oxygen balance is therefore —10.39 per cent.
Based on a molecular heat of formation of 39.6 Calories for methyl nitrate Berthelot calculated for 1 kg. of this material at constant volume and with water liquid a heat of explosion of 1609 Calories according to Formula l, and 1616 Calories according to Formula 2. Methyl nitrate has therefore a somcwhat higher energy contcnt than nitroglycerine (1595 Calories), and this makes itself evident also by a slightly higher explosive action. When shot in the lead block with water tamping:
10 grams methyl nitrate gives.................... 615 cc. expansion
10 grams nitroglycerine gives..................... 600 cc. expansion

The expansions are as 102.0:100. The heats of explosion are as 101.0:100, or a satisfactory agreement,
When mixed with kieselguhr or gelatinized with collodion nitro-cotton it shows about the same explosive effect on the lead block as nitroglycerine, namely 320 and 565 cc.
Sensitiveness. Methyl nitrate is extremely sensitive to an initiating Impulse, and when shot with a No. l cap under water tamping, ifc gives approximately the same effecfc äs with a No. 8 cap, in contrast to nitroglycerine, which is more difficult to detonate.

Methyl Nitrate Nitroglycerine
Blasting cap No. l.. 520 cc. (84.5 per cent) 190 cc. (32 per cent)
Blasting cap No. 8.. 615 cc. (100 per cent) 590 cc. (100 per cent)
or after deducting 30 cc. for the No. 8, and 5 cc. for the No. l cap:
Blasting cap No. l... 515 cc. (88 per cent) 185 cc. (33 per cent)
Blasting cap No. 8... 585 cc. (100 per cent) 560 cc. (100 per cent)

The crusher fest also shows similar rclations, which were obtained with 100 grams of the liquid in a sheet lead shell with walls l mm, thick, tamped by thin cork plates, i.e., under slight confinement:
Methyl Nitrate Nilroglycol Nitroglycerine
Compression.............. 24.5 mm. 30 mm. 18.5 mm.

The lower viscosities of methyl nitrate and nitroglycol as compared to nitroglycerine give higher velocities of detonation with the first two, even with a weak confinement.
The sensitiveness also is evidenced by a flame causing detonation Given in a narrow space, a small amount of methyl nitrate in a beaker, when ignited by fuse containing a black powder core, sometimes gives a puff and destruction of the glass into large pieces, Bometimes a brisant detonation and pulverizing of the glass to a fine powder.
In an open dish methyl nitrate ignites immediately when in contact with a flame, and burns quietly with a large, non-luminous flame. The vapors puff readily on ignition, and on heating them to 150°C. they explode. Methyl nitrate is also sensitive to shock, although less so than nitroglycerine and nitroglycol. Under a 2 kg. weight it explodes at a drop of 40 cm. Even when mixed with kieselguhr it is appreciably less sensitive than nitroglycerine.
Velocity of detonation. The velocity of detonation was determined by Berthelot3 at very small diameters. In glass tubes 3 mm. in diameter and 1 mm, wall thickness he found 1890 meters per second, and with 4.5 mm. wall thickness 2480 meters. Nitroglycerine gives only about 1500 meters per second at such small diameters- It is indeed probable that methyl nitrate at larger diameters such as 30 to 40 mm. would give velocities of detonation of far higher magnitudes, such as 6000 to 8000 m/s.

rooster
June 10th, 2003, 05:24 AM
This sure sounds like one hell of a good explosive.
Greater lead block expansion than nitroglycerin and easy to make. Somewhere I rad that the VoD was higher than 8000m/s. The only actual problem is its volatility.

Though, it says that it one molecule of methyl nitrate lacks one molecule of oxygen for complete combustion.

2(CH3ON02) = CO2 + CO + 3H2O + N2

Actually TWO molecules of methyl nitrate lacks ONE molecule of oxygen.

Why do some people mean this explosive is so dangerous?

vulture
June 10th, 2003, 06:45 AM
Very sensitive and extremely toxic.

Arthis
June 10th, 2003, 08:55 AM
The method proposed using a nitric/sulfuric mix should be quite difficult to make (needs really pure acids).

What would be the ratios for the distillation method (though I'm not sure I want to try it, distilling HE is pretty scaring, especially when more sensitive than NG).

( btw, what alcohol/fuel can't you nitrate to HE ? ;) )

knowledgehungry
July 18th, 2003, 06:02 PM
I was thinking of using a solvent maybe such as DCM as opposed to distillation, or maybe a sries of solvents. Anyone know what it is soluble in?

Arthis
July 19th, 2003, 05:49 AM
DCM will dissolve nitric acid.

I've heard of another method of making methyl nitrate, by reacting methanol with NO2. I need to search a bit more about the possibilities of the method, but as both compounds are easy to make it could be a new easy way.

knowledgehungry
July 19th, 2003, 11:19 AM
Is methyl nitrate water soluble?If its not what you could use the DCM to get out the HNO3 and methyl nitrate than allow DCM to evaporate pour lots of cold water into solution to precipitate out the Methyl nitrate.

Madog555
July 21st, 2003, 07:45 PM
i prepared methyl nitrate from 70% HNO3/H2SO4

4ml yielded 2.5ml of the explosive, i think, i didnt do this long ago but for some reason i cant remeber the other numbers, damnit, if i find my paper i wrte it on i'll come back

Madog555
July 23rd, 2003, 06:59 PM
i can only edit a message some minutes after ive posted it... thats queer, anyways.

im prtetty sure it was

4ml methanol
7ml HNO3
12ml H2SO4

Dr_Pind
May 23rd, 2006, 10:49 AM
Is it just me, or has it's been very quiet in the forum for quite a while :confused:

To the point of my post... Since this thread is supposed to be about methyl and ethyl nitrates, I thought I might bring the ETHYL-nitrate up. Methyl nitrate has been discussed quite a bit, but I haven't seen much (if any) on ethyl nitrate.

I have found a german synthesis on it. By distilling a mix of 96% ethyl alcohol, and 65% nitric acid, with the addition of urea nitrate to remove nitrous acid, which could lead to explosive decomposition of the bach, it should be possible to obtain a yield of 44% of ethyl nitrate. The synthesis appeals to me, since I have the necesary equipment, and the chemicals, but the very lov yield isn't really a fact that comes to my liking. Also, a lot of urea nitrate is used in the process, I thought that only a few gr. would be necesary to destroy the traces of nitrous acid.

I thought, since the explosive has been considered (used?) as a rocket propelant, there must be a synthesis for it with better yields than 44%.

The explosive itself looks quite promising:
High brisance. Low sensitivity; can't be detonated in a pure liquid form without a booster. Relatively high VOD; around 6200-7000 mps, if i remember correctly. Can be mixed with AN or other crystaline materials, to yield dynamites and other cap sensitive mixes). Maby not the same thing as other nitric esters, but quite enough for most everyday purposes :rolleyes:

I also thought about raising the VOD and brisance of urea nitrate, by mixing it with ethyl nitrate. I know that urea nitrate is acidic, byt it is also used to stabilize the formation of the ethyl nitrate in the synthesis. Do you think it would be safe to mix the two explosives?

The procedure I found is in german, but i can post it if someone is interested.

If anyone has any information on synthesis, properties, yield or personal experience with this explosive, feel free to post.

Maniak
May 26th, 2006, 05:07 PM
I've never tried synthesis of ethylnitrate yet. But it's quite interesting stuff so I plan to do it as well as IPN.

Distilling of alcohole + NA can be quite dangerous even with urea nitrate and as you wrote it produce lower yields. The right way should be the continuous process - addition of EtOH into the flask with boiling 65%NA with urea nitrate. The product continually leaves the flask through the condenser and then it is washed and dried. There is just some unimportant amount of EtN in the flask during the procedure so it should be safe.
Of course, urea nitrate is recovered after the syntesis in nearly quantitative yield and can be used next time.

Mixture of urea nitrate with EtN can be quite dangerous idea. The urea nitrate couldn't stabilize EtN itself - it serves just as a destroyer of NO2 which can be formed during the syntesis. EtN must be neutral and when it's mixed with any acidic substance it can start gassing and decompossing after few days.

The_Duke
May 26th, 2006, 05:38 PM
There has been some discussion about EtN at the old APC forum, mostly by wedge, Boomer and myself.

http://www.xsorbit2.com/users/apcforum/index.cgi?board=High_Explosives&action=display&num=1136985466

The distilling process is shit.

jarynth
August 7th, 2008, 12:43 PM
A long time ago, when I first acquired conc. nitric acid, I mixed it pretty carelessly with 94% ethanol, which predictably resulted in a run-off reaction. After allowing the nitric oxide production to subside, I noticed the flask contained a pale green residue. I cannot recall whether this was divided into two layers or not. The odor was pleasant, sweet, almost fruity at low concentrations, but strong ad somewhat obnoxious from close by. After cooling, the addition of NaOH prills turned the content of the flask into a bright reddish-orange liquid. The solution was bottled, and after several days a pale yellow precipitate started to form, while the color of the solution gradually faded.

Does anyone have any experience with this kind of reaction? Was the green liquid ethyl nitrate, or rather nitrite? There was probably some aldehyde present due to the oxidation of the EtOH, but this certainly cannot account for the color. And then, why did the solution turn red upon addition of NaOH?