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Chris The Great
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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.
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hinz
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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.
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agent_entropy
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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]
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Chris The Great
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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?
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agent_entropy
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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.
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Chris The Great
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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.
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agent_entropy
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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]
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agent_entropy
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Sensitivity?
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?
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Chris The Great
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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.
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agent_entropy
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So, a "detonation shock" is not a mechanical shock?
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pyromainiac420
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What temperature should you keep it under during the nitration?
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Zinc
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A little off topic but did anyone try to make ethyl nitrate?
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Boomer
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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).
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UnintentionalChaos
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Poppers are amyl nitrite, I imagine ethyl nitrate is just quite toxic.
Department of Redundancy Department - Now with paperwork!
'In organic synthesis, we call decomposition products "crap", however this is not a IUPAC approved nomenclature.' -Nicodem
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Zinc
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| Quote: | Originally posted by Boomer
Yes there is a thread by me on APC about it.
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What is APC?
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Joeychemist
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http://www.apcforum.net/forums/index.php
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nitro-genes
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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]
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Zinc
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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?
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quicksilver
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| 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...
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How would that person KNOW how much "experience" an individual has in any given field?
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nitro-genes
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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.
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Boomer
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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? 
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sarika
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separation of methyl nitrate
can methyl nitrate be detected and separated from a mixture of volatile organic compounds?if so how?
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Mason_Grand_ANNdrews
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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]
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Mason_Grand_ANNdrews
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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.
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Intergalactic_Captain
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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.
If you see me running, try to keep up.
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