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Author: Subject: methyl nitrate
Ral123
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[*] posted on 27-9-2012 at 09:11


I just found my old 2.5cc model aircraft engine. First I discovered that it can run with methanol and car oil :D Then of course I nitrated some methanol... That thing greatly increased power, above like 30% there are spectacular deflagrations in the engine with flames from both the intake and the exhaust when I apply current to the hot wire(platinum coated of some kind). It also tends to not need current at all. I'll see what happens with more if I gather courage. Damn I can sell it like super powerful diesel engine :D I never thought one day I'd wish my rdx and tetryl were also liquid :D
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[*] posted on 12-10-2012 at 11:35


Quote: Originally posted by Ral123  
I just found my old 2.5cc model aircraft engine. First I discovered that it can run with methanol and car oil :D Then of course I nitrated some methanol... That thing greatly increased power, above like 30% there are spectacular deflagrations in the engine with flames from both the intake and the exhaust when I apply current to the hot wire(platinum coated of some kind). It also tends to not need current at all. I'll see what happens with more if I gather courage. Damn I can sell it like super powerful diesel engine :D I never thought one day I'd wish my rdx and tetryl were also liquid :D


You're gonna get someone killed. Irrespective of its energetic properties, MeNO3 vapor is an incredibly potent vasodilator. Its volatility is so great that it could easily reach levels that knock someone out. Use a heavier ester and wear gloves, long pants, close-toed shoes, a jacket, and eye protection at all times.

In addition, MeNO3 is the only nitric ester in the polyol series (EGDN, NG, ETN, XPN, MHN) with a negative oxygen balance. It's only marginally better than nitromethane as a fuel additive.

It would probably be safer to use nitroglycerin as an additive than methyl nitrate. EGDN is preferable, however.
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[*] posted on 16-10-2012 at 23:45


@ AJKOER

What a farrago of misconceived notions.

Boiling KNO3 in HCl will not displace HNO3 , so why should you suppose
that the covalently bound Cl of CH3Cl will.
The only scheme of this type that works is with , N I T R I T E since it
forms a weaker acid than Chlorine and so can be displaced.
http://www.sciencemadness.org/talk/viewthread.php?tid=3901&a...

U P D A T E
As always exceptions exist as shown here below _

Substitution of a Halogen by -NO3.gif - 10kB

I still remain skeptical that the proposed synthesis of CH3ONO2
in this manner is realistic. By your own reference in this other post
http://www.sciencemadness.org/talk/viewthread.php?tid=21529#...
at the bottom of the indicated page 279
http://books.google.com/books?id=aBAFAAAAQAAJ&pg=279

" It's alchoholic solution precipitates Silver Nitrate rapidly. "
In other words the reaction is reversable , and that's with
Iodine , it is also shown above for a secondary alcohol
with Bromine. Chlorine is dubious.

__________________________________________


With regard to this cited reference
http://www.docstoc.com/docs/68188299/CHAPTER13
for this _
CH3Cl + NH3 --> CH3NH2.HCl --> CH3NH2.HCl + NH3 --> CH3NH2 + NH4Cl
the first part is correct , . . . . . . . . . . . . . . . . .this next part is very wrong

Ammonia is a weaker base than Methylamine so it cannot displace it to
form NH4Cl with HCl. See _
http://www.chemguide.co.uk/basicorg/acidbase/bases.html
Comparing the strengths of weak bases


From above here _
http://www.sciencemadness.org/talk/viewthread.php?tid=744&am...
Methyl nitrate is prepared by distilling 50 grams of NaNO3 with 50 grams of
Methyl alcohol and 100 grams of sulfuric acid, in a retort without external
heating. It is a colorless liquid density 1.182 at 20 ºC (68 ºF); boils at 60 ºC
(140 ºF); has a faint ethereal oder. It's vapor detonates when heated to
150 ºC (302 ºF).
Heated with alcoholic ammonia , it yields methylamine nitrate , CH3NH2 • HNO3

It follows that CH3Cl heated with ammonia will result in CH3NH2 • HCl

bio2 posted this
http://www.sciencemadness.org/talk/viewthread.php?tid=3901&a...

Other ways to get there
http://en.wikipedia.org/wiki/Methylamine
http://www.orgsyn.org/orgsyn/prep.asp?prep=cv1p0347
http://www.erowid.org/archive/rhodium/clandestine/methylamin...

Methylamine threads
http://www.sciencemadness.org/talk/viewthread.php?tid=1261
http://www.sciencemadness.org/talk/viewthread.php?tid=7410


[Edited on 18-10-2012 by franklyn]
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[*] posted on 17-10-2012 at 03:04


Quote:
Methyl nitrate is prepared by distilling 50 grams of NaNO3 with 50 grams of Methyl alcohol and 100 grams of sulfuric acid, in a retort without external heating.

<i>"Without external heating"?</i> WTF!

The distillation is extremely sensitive ─ a couple of degrees above the ~66°C B.P. will produce a spectacular runaway (great eruption of NO2 vapour) as I found, distilling methyl nitrate from a mixture of the alcohol and concentrated (~68%) HNO3!
Also, small quantities only to ensure a runaway doesn't progress to deflagration ─ or worse . . .


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[*] posted on 17-10-2012 at 03:31


Quote:

"Without external heating"

Is an exotherm produced on mixing the reactants, perhaps?

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[*] posted on 17-10-2012 at 19:09


Quote: Originally posted by killswitch  

In addition, MeNO3 is the only nitric ester in the polyol series (EGDN, NG, ETN, XPN, MHN) with a negative oxygen balance.

Perhaps with the exception of PETN.
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[*] posted on 19-10-2012 at 07:59


Quote: Originally posted by Kalium  
Quote: Originally posted by killswitch  

In addition, MeNO3 is the only nitric ester in the polyol series (EGDN, NG, ETN, XPN, MHN) with a negative oxygen balance.

Perhaps with the exception of PETN.


Fist CH3-ONO2 is derived from a mono-alcohol and can't be member of the polyol family.

Secondly propandiol, butandiol dinitrate and many other polyols polynitrate esters also display negative OB.

[Edited on 19-10-2012 by PHILOU Zrealone]




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[*] posted on 24-10-2012 at 14:27


Quote: Originally posted by franklyn  
.......
With regard to this cited reference
http://www.docstoc.com/docs/68188299/CHAPTER13
for this _
CH3Cl + NH3 --> CH3NH2.HCl --> CH3NH2.HCl + NH3 --> CH3NH2 + NH4Cl
the first part is correct , . . . . . . . . . . . . . . . . .this next part is very wrong

Ammonia is a weaker base than Methylamine so it cannot displace it to
form NH4Cl with HCl. See _
http://www.chemguide.co.uk/basicorg/acidbase/bases.html
Comparing the strengths of weak bases
......


Franklyn, per one of your supplied references, in particular [5] cited below (http://www.orgsyn.org/orgsyn/prep.asp?prep=cv1p0347 ):

"3. Discussion
Methylamine can be prepared by the action of ammonia on methyl iodide [4], methyl chloride [5], dimethyl sulfate [6], methyl p-toluenesulfonate [7] and methyl alcohol with a catalyst and at elevated temperatures [8] by the action of bromine and alkali [9] and of bleaching powder [10] on acetamide; by the action of sodamide on methyl iodide [11] by the reduction of chloropicrin [12], hydrocyanic or ferrocyanic acid [13], hexamethylenetetramine [14], nitromethane [15], methyl nitrite [16], or formaldoxime [17] from acetyl chloride and sodium azide [18] and by the action of formaldehyde on ammonium chloride [19].

References and Notes

1. Sharp and Solomon, J. Chem. Soc. 1477 (1931).
2. Werner, J. Chem. Soc. 111, 850 (1917).
3. Sommelet, Compt. rend. 178, 217 (1924).
4. Hofmann, Ann. 79, 16 (1851).
5. Vincent and Chappuis, Bull. soc. chim. 45, 499 (1886).
6. Ephrian and Gurewitsch, Ber. 43, 139 (1910); Denham and Knapp, J. Chem. Soc. 117, 236 (1920).
7. Rodionov, Bull. soc. chim. (4) 45, 109 (1929).
8. Davis and Elderfield, J. Am. Chem. Soc. 50, 1786 (1928); E. I. du Pont de Nemours and Co., U. S. pat. 2,017,051 [C. A. 29, 8001 (1935)].
9. Hofmann, Ber. 15, 765 (1882); François, Compt. rend. 147, 430, 680, 983 (1908).
10. Bader and Nightingale, U. S. pat. 1,489,380 [C. A. 18, 1836 (1924)].
11. Chablay, Compt. rend. 156, 328 (1913).
12. Geisse, Ann. 109, 282 (1859); Wallach and Boehringer, Ann. 184, 51 (1877); Frankland, Challenger, and Nicholls, J. Chem. Soc. 115, 159 (1919).
13. Mendius, Ann. 121, 139 (1862); Debus, Ann. 128, 201 (1863); Denham, Z. physik. Chem. 72, 674 (1910); Riedel, Ger. pat. 264,528 [Frdl. 11, 110 (1912–14)]; Dreyfus, U. S. pat. 2,072,247 [C. A. 31, 2619 (1937)].
14. Meister, Lucius, and Brüning, Ger. pat. 73,812 [Frdl. 3, 15 (1890–4)]; Trillat and Fayollat, Bull. soc. chim. (3) 11, 23 (1894); Kundsen, Ger. pat. 143,197 [Frdl. 7, 24 (1902–4)]; Meister, Lucius, and Brüning, Ger. pat. 148,054 [Frdl. 7, 26 (1902–4)]; Isono, J. Pharm. Soc. Japan No. 397, 209 (1915) [C. A. 9, 2232 (1915)].
15. Pierron, Bull. soc. chim. (3) 21, 783 (1899); Mailhe and Murat, ibid. (4) 7, 954 (1910); Zerewitinov and Ostromisslensky, Ber. 44, 2403 (1911).
16. Gaudion, Bull. soc. chim. (4) 7, 824 (1910); Ann. chim. phys. (8) 25, 136 (1912).
17. Takaki and Ueda, J. Pharm. Soc. Japan 58, 276 (1938) [C. A. 32, 5376 (1938)].
18. Naegeli, Grüntuch and Lendorff, Helv. Chim. Acta 12, 227 (1929).
19. Brochet and Cambier, Bull. soc. chim. (3) 13, 534 (1895); François, Compt. rend. 147, 429 (1908); Werner, J. Chem. Soc. 111, 848 (1917); Jones and Wheatley, J. Am. Chem. Soc. 40, 1411 (1918); Wietzel and Köhler, Ger. pat. 468,895 [C. A. 23, 846 (1929)]. "

However, in defense of your opinion, I suspect an important detail (like a strong base acting as a catalyst,..) is missing from the discussion, but perhaps mentioned in the cited reference [5].


[Edited on 24-10-2012 by AJKOER]
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[*] posted on 24-10-2012 at 15:37


@ AJKOER

My initial warning is based on elementary first principles.
Now I'm not so sure , in fact I've solicited a review.

http://www.sciencemadness.org/talk/viewthread.php?tid=18006#...

.
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[*] posted on 25-10-2012 at 02:13


Quote: Originally posted by franklyn  
@ AJKOER

My initial warning is based on elementary first principles.
Now I'm not so sure , in fact I've solicited a review.

http://www.sciencemadness.org/talk/viewthread.php?tid=18006#...

.

Reply posted in the tread:

Le Chatelier's rule/principle for reactions in equilibrium...
A reaction system in equilibrium placed in a closed reactor with stable parameters (P,V,T) tends to a stable proportion of reactants (concentration)... A static equilibrium.

But if the system is open... V tends to be infinite and if a compound is volatile (gaseous) the reaction /equilibrium will be shifted to that side of the reaction and go to near completeness. The same kind of theory applies to precipitation reaction where the precipitate goes to a concentration of "zero" and is considered as dropped out of the system.

Here N2H4 is much less volatile than NH3...
So in an open system despite NH3 is more basic...N2H4 will remain because NH3 will escape faster and continuously from the reactor.
In a closed reactor:
N2H4(l) + NH4Cl(s) <==--> N2H5Cl(s) + NH3(g)
In an open reactor:
N2H4(l) + NH4Cl(s) <--====> N2H5Cl(s) + NH3(g)

In the case of NH3 and CH3-NH2... CH3-NH2 is more basic than NH3 but both are very volatile... so the question is more delicate.
In a closed reactor:
NH3(g) + CH3-NH3Cl(s) <==--> NH4Cl(s) + CH3-NH2(g)
In an open reactor:
NH3(g) + CH3-NH3Cl(s) <==?==> NH4Cl(s) + CH3-NH2(g)




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[*] posted on 25-10-2012 at 16:36


Per this questionable source (http://www.hoboes.com/pub/Prohibition/Drug%20Information/Mis... ), "Methyl Chloride + Ammonia in an ether solution (CH3NH2 + NH4Cl)"

However, the use of a different medium was, in fact, suggested by the review thread as a plausible explanation ( http://www.sciencemadness.org/talk/viewthread.php?tid=744&am... ). Extract:

Quote: Originally posted by Nicodem  
Quote: Originally posted by franklyn  
My query relates to another post in which I assert that Ammonia is a weaker
base than Methylamine so it cannot displace it to form NH4Cl with HCl.
According to this _

CH3NH2 •HCl + NH3 => CH3NH2 + NH4Cl

Which appears analogous to the displacement of the weaker base Hydrazine
N2H4 •HCl + NH3 => N2H4 + NH4Cl

Those are just equations which essentially just define the reactants and the products, but say nothing about the synthesis. Several times I already tried to explain that bare chemical equations like those do not describe the chemical system. The problem is that it is the whole system (solvent, temperature, reagent ratios, rate and order of addition, catalyst, stirring...) that defines the reaction results. For example, if you add methylamine hydrochloride to aqueous ammonia, no product will form. But if you add methylamine hydrochloride to ethanolic ammonia, I believe it is quite likely that you will obtain a precipitate of NH4Cl. All the parameters are the same, only the solvent changes and the change can be as dramatic as that.

Also, you say ammonia is a weaker base than methylamine. That is true for aqueous solutions where ammonia is about 10-times weaker base, but this is not necessarily true for other solvents. Compare the pKa values of NH4+ and RNH3+ ions in DMSO and you will see how things can change. Besides the proton transfer reactions are just one of the many possible driving forces for a product to form - they are not necessarily the determinative force.


Now, I would humbly add to Nicodem's comment "The problem is that it is the whole system (solvent, temperature, reagent ratios, rate and order of addition, catalyst, stirring...) ", citing a recent example involving the decomposition of Chloric acid. Frequently unreactive chloride ions are present in commercial chlorine products (for example, Chlorine Bleach, active ingredient NaOCl, also contains NaCl) and, in the case of the discussion of HClO3, its decomposition proceeds differently in the presence of chloride ions. In effect, the once spectator chloride ions are promoted to a full reactant. Also, a previously inert energy source (for example, light) may initiate a reaction. The unexpected reaction is probably a significant factor for many garage chemists starting with impure ingredients, and I would add it to Nicodem's list. More damaging result occurs for those experimenting with energetic materials which, at times, can be made unexpectedly more hypersensitive in the presence of certain metallic impurities. On a larger scale, I have (in a prior thread) noted an event involving the loss of an entire cargo vessel. The suspected cause relates to a Mg impurity in a Calcium ore, which could have added a touch of Magnesium hypochlorite (perhaps chlorate also), to a shipment of Ca(ClO)2 made from that ore.

I would also give an illustration of how the reactant ratios can change the reaction products. In the case of the action of Oxalic acid on say NaClO3, for example, initially the H2C2O4 liberates HClO3 from the chlorate salt, but in excess, the Oxalic acid decomposes the newly formed HClO3 into ClO2.


[Edited on 26-10-2012 by AJKOER]
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[*] posted on 27-10-2012 at 15:56


Quote: Originally posted by PHILOU Zrealone  
Quote: Originally posted by Kalium  
Quote: Originally posted by killswitch  

In addition, MeNO3 is the only nitric ester in the polyol series (EGDN, NG, ETN, XPN, MHN) with a negative oxygen balance.

Perhaps with the exception of PETN.


Fist CH3-ONO2 is derived from a mono-alcohol and can't be member of the polyol family.

Secondly propandiol, butandiol dinitrate and many other polyols polynitrate esters also display negative OB.

[Edited on 19-10-2012 by PHILOU Zrealone]


I was talking about alcohols with a number of hydroxyl groups equal to the number of carbon atoms. Technically, yes, those are polyols, but hardly anyone uses their nitrates as energetic materials. And yes, methanol is not a polyol, just as 1 is not a prime number.
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[*] posted on 28-10-2012 at 03:50


Quote: Originally posted by killswitch  
Quote: Originally posted by PHILOU Zrealone  
Quote: Originally posted by Kalium  
Quote: Originally posted by killswitch  

In addition, MeNO3 is the only nitric ester in the polyol series (EGDN, NG, ETN, XPN, MHN) with a negative oxygen balance.

Perhaps with the exception of PETN.


Fist CH3-ONO2 is derived from a mono-alcohol and can't be member of the polyol family.

Secondly propandiol, butandiol dinitrate and many other polyols polynitrate esters also display negative OB.

[Edited on 19-10-2012 by PHILOU Zrealone]


I was talking about alcohols with a number of hydroxyl groups equal to the number of carbon atoms. Technically, yes, those are polyols, but hardly anyone uses their nitrates as energetic materials. And yes, methanol is not a polyol, just as 1 is not a prime number.

I know Killswitch ;) the familly H-(CHONO2)n-H (with n from 1 to infinite).
From my study of famillies of HE and explosives substances, I can tell that negative OB is not a real problem to get very usefull explosives.
PETN or polyvinyl nitrate are good examples.




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[*] posted on 24-11-2012 at 13:08


i tried to make Metyl nitrate with 10 ml %50 HNO3 and 10ml %99 H2SO4 solution.
After mixing the acids i cooled down it in a ice bath than ad slowly drops of CH3OH. After a few mins a thin layer is showed up just as i waited. I collect it and test it
I burned it with a lighter. there was a white-gray colored flame but it was not fast . It burned slowly . That means ıt is not pure.
I tried different way like changing the amount of acids but result was same.
What is the problem in my way ?!
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[*] posted on 29-11-2012 at 20:52


Question for the familiar:

Has there ever been an application of methyl nitrate dynamite? When I think "volatile liquid explosive" the next thought that always comes to mind is keiselguhr. Or perhaps something like starch / guar gum?

Just seems this stuff could be a fun toy if you could deal with it in a less sensitive, nonliquid state.
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[*] posted on 10-12-2012 at 05:13


Hello all. I have been trying to make methyl nitrate using 40ml sulfuric acid(Rooto drain opener) 26g ammonium nitrate (instant cold packs from Rite-Aid) and 11ml methanol(Heet). I cool the acid, mix in the NH4NO3, and put it in a salt water bath. I then add the methanol drop by drop. The trouble is that when I am done, no layer forms on top. I can smell the methyl nitrate(smells really good BTW), but when I crash it into water it still doesn't separate . I am totally bumfuzzled.
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[*] posted on 16-12-2012 at 10:53


So yesterday I decided to test the purity of my methanol. I burned about 30ml of it. After it went out there was still about 15ml of liquid left that would not burn! I checked the Heet msds but all it lists is 99% methanol and 1% "proprietary ingredient". Any idea as to what I have? I bought it at Wal- mart. Is there a possibility that it is diluted?
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[*] posted on 14-3-2013 at 10:24


Today I tested 100ml methyl nitrate. I did not expect that the damage would be so small. Iron on which the tested methyl nitrate was placed on the mud and buried in the ground in the explosion.











[Edited on 15-3-2013 by SherlockHolmes]




Sorry for my english. I am not from England. Thank you!
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[*] posted on 14-3-2013 at 11:04


Like the syringe detonator ─ adds a whole new dimension to the phrase "shooting-up" . . .
Which primary, BTW?

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[*] posted on 14-3-2013 at 11:26


Detonator is 0.20 grams of lead azide and 1.5g pyroxylin pressed into the syringe. My idiot friend accidentally deleted a video explosion. I'll do a video pictures with detailed descriptions of the test and show video.



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[*] posted on 14-3-2013 at 12:26


Here is the video: http://www.youtube.com/watch?v=ZT_PCuGMR68



Sorry for my english. I am not from England. Thank you!
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[*] posted on 14-3-2013 at 12:27


Douh, you're still not as failo like that brisanse54 guy. You've reached the capabilities of MN. The hole, that thing dug is impressive :D MN today, HN tomorrow, that target wont survive.
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[*] posted on 14-3-2013 at 12:54


Detonate as hard as he can. Brisantse54 failed to detonate any high explosive with high detonation velocity. With 300 grams ETN / NG only 2 mm sheet metal bent. His explosives detonates with no more than 2500 m / s Methyl nitrate density 1.15. and do much damage.



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[*] posted on 14-3-2013 at 13:50


Some people should get into propellants or something :D
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[*] posted on 15-3-2013 at 02:06


A colleague pointed out to me a big mistake. Detonator has directed most of the energy away than the iron plate. You can see how the blast wave struck the ground side.



Sorry for my english. I am not from England. Thank you!
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