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Author: Subject: Tetranitromethane
Microtek
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[*] posted on 21-1-2007 at 07:45


I have prepared a small amount of TeNM via the Ac2O/HNO3 method. I tried mixing a small amount of it with the calculated amount of toluene for oxygen balance, then absorbed a drop of it in tissue paper and hit it with a hammer. It detonated much like NG from this treatment.

I wore a gas mask which didn't cover my eyes and the vapours from the TeNM stung quite a lot. I quickly determined the evaporation rate to find out how much could be hanging around the lab ( which was very little; much less than the permitted concentration level when diluted to lab volume ). In the end I got so paranoid about poisoning hazards that I took all of it outside and let it evaporate on its own.
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[*] posted on 20-3-2009 at 20:23


Quote:
Originally posted by Microtek
I have prepared a small amount of TeNM via the Ac2O/HNO3 method. I tried mixing a small amount of it with the calculated amount of toluene for oxygen balance, then absorbed a drop of it in tissue paper and hit it with a hammer. It detonated much like NG from this treatment.

I wore a gas mask which didn't cover my eyes and the vapours from the TeNM stung quite a lot. I quickly determined the evaporation rate to find out how much could be hanging around the lab ( which was very little; much less than the permitted concentration level when diluted to lab volume ). In the end I got so paranoid about poisoning hazards that I took all of it outside and let it evaporate on its own.


How much of TNM did you made, and what is found evaporation rate? Today i've prepared HNO3/Ac2O mixture witch will produce TNM on standing, but i'm seriously worried about high toxicity, so actual evaporation rate digits can help me to make it more safe.




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[*] posted on 23-3-2009 at 08:16


I made maybe 20 ml. I can't remember what the actual numbers were, but I had removed a sample and kept it in a small vial for testing. When it started stinging, I placed the vial with contents on my laboratory scale and monitored weight loss over 60 seconds, then computed possible concentration levels based on the period I had it open. IIRC just a few milligrams evaporated over the course of one minute, but obviously that will vary depending on temp and surface area, etc. I would estimate (I'm working from memory here) that the vial I used was about 1.5-2 cm in diameter.

Incidentally, I didn't suffer any ill effects at all (except the stinging eyes), but I have such an active imagination that the suspicion of poisoning is enough to make me physically ill. That's why I discarded the rest without doing anything with it, even though I was going to convert it to trinitromethane and then experiment with all sorts of nitroform condensates.
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[*] posted on 27-3-2009 at 09:04


Preparation of tetranitromethane from acetic anhydride & nitric acid



Procedure:

Flat bottom flask with 500 ml capacity is filled with 63g (1 mol) of 99% nitric acid and placed on ice bath, then 102g (1 mol) of acetic anhydride is added by small portions with efficient stirring, not allowing temperature to rise above 10C (#1). After all nitric acid is added, neck of the flask is thoroughly dried with bath towel and flask is capped with small glass turned upside down. Mixture is allowed to stand in ice bath until it will heat up to room temperature, then reaction flask is removed from water bath and allowed to stand at room temperature for 7 days (#2). Mixture is poured to 600 ml of cold water, carefully stirred and heavy oily layer of tetranitromethane is separated in separation funnel. Crude product is washed with pure water until acid-free, with 15 ml of 40% sulfuric acid and then dried by careful washing with 10 ml of concentrated H2SO4 (#3), to get about 18 ml (29g) of pure tetranitromethane with melting point at 13.9C. Yield is ~60% from theory (#4).


Notes:

1. Temperature of reaction mixture must be kept below 10C at all times (above this temperature reaction speed up greatly). Reaction at the beginning of addition is strongly exothermic and acetic anhydride must be added by small portions (0.5 ml). Then about 10 ml of acetic anhydride is added, exotherm is reduced and portions can be slowly increased from 1 to 10 ml. After addition is complete mixture must be allowed to sit in ice/water bath, slowly heating up to room temperature. If cooling during first several hours is removed, violent exothermic process can start and at 30-35C mixture must be immediately poured to emergency drain with large amount of cold water.

2. On mixture aging slow reactions takes place, at first trinitroacetic acid is formed and is decarboxylated to nitroform evolving carbon dioxide, then nitroform is slowly nitrated to form tetranitromethane. Contamination by nitroform can be clearly evidented by intense yellow coloration of water layer, then tetranitromethane is separated from reacted mixture. Different sources mention different aging periods, but 7 days at room temperature found to be most common in references.

3. Occasional batches of tetranitromethane were found to evolve considerable heat and turn black if allowed to stand over concentrated sulfuric acid for longer then 10-15 minutes. So actual contact time must be minimized, and tetranitromethane must be separated on separation funnel as soon as possible.

4. Some literature sources mention higher yields on other aging time and temperatures. Some sources mention use of catalysts and chipped glass to improve yield of this reaction, however those statements are unconfirmed in later publications.


Photos:





[Edited on 27-3-2009 by Engager]




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Anders Hoveland
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[*] posted on 20-6-2010 at 00:21


Quote: Originally posted by photoguy  
I know that Isopropanone vapour in direct contact with Nitric Acid fumes can create trinitromethane - so I wonder if trinitromethane can be further nitrated to be Tetranitromethane?? I don't know if this is even remotely possiable...

Trinitromethane is acidic, and forms powerful, but very stable nitroformate salts with NH4OH or amines. I am unsure what "Isopropanone" is. Do you mean acetone?
Could someone characterize hydroxylamine nitroformate? It should be better than NH4ClO4 for solid rocket oxidizer.
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[*] posted on 20-6-2010 at 09:20


Quote: Originally posted by BromicAcid  
I've read that it forms quite explosive mixtures with toluene as this quote illustrates "When mixed with hydrocarbons in approximately stoicheiometric proportion a sensitive highly explosive mixture is formed.... Explosion of only 10 g of a mixture with toluene caused 10 deaths and severe injuries..." (Stettbacher, A., Tech. Ind, Schwetz. Chem.) "



In 1920 at the University of Münster a massive iron gas
burner containing a residue of 10 grams of tetranitromethane
and toluene mixture decomposed suddenly. The detonation
splintered the container, and of 300 students in the area,
10 were killed and 20 injured!

Several secondary references. Primary reference not seen
by me:

Zeitschrift für das Gesamte Schiess- und Sprengstoffwesen
25:439 1930


Weird - this discussion has gone of for 7-years, yet — no one
noted that Urban'ski has all that you need to know 'bout TNM.

For more recent methods of synthesis see Köhler and Meyer.

Chattaway's method (Patented by Farbenfabriken vorm. F. Bayer
and Company), J. Chem Soc. CCXX 2101 (1910) is described in detail
in good old —Capt. E. de W. S. Colver, High Explosives, Crosby
Lockwood and Son. London 1918. A somewhat hard to find book,
I do not remember where I purchased my copy. It maybe easier
to look up the J Chem. Soc. And ... if I was working on energetic
materials I would want to read the original reference, and check
following volumes for additions/corrections!



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[*] posted on 20-6-2010 at 09:25


Trinitromethane thread is here _
http://www.sciencemadness.org/talk/viewthread.php?tid=3061

attached references for both


Attachment: Nitroform Tetranitromethane & derivitive compounds .txt (11kB)
This file has been downloaded 1416 times
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AndersHoveland
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[*] posted on 24-5-2011 at 13:37


Tetranitromethane has been obtained from iodopicrin I3CNO2 and silver nitrite AgNO2.
Hantzsh, Chemische Berichte, 39, p2478, (year 1906)
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[*] posted on 24-5-2011 at 15:32
From Köhler and Meyer


Tetranitromethane
Tetranitromethan; t´ etranitrom´ethane; TNM
colorless liquid with a pungent smell
empirical formula: CN4O8
molecular weight: 196.0
energy of formation: +65.0 kcal/kg = +272.1 kJ/kg
enthalpy of formation: +46.9 kcal/kg = +196.4 kJ/kg
oxygen balance: +49.0%
nitrogen content: 28.59%
volume of explosion gases: 685 l/kg
heat of explosion*): 526 kcal/kg = 2200 kJ/kg
specific energy: 69.1 mt/kg = 677 kJ/kg
density: 1.6377 g/cm3
solidification point: 13.75 °C = 56.75 °F
boiling point: 126 °C = 259 °F vapor pressure
Pressure Temperature
millibar °C °F
12 20 68
57 50 122
420 100 212
1010 126 259 (boiling
point)
detonation velocity, confined:
6360 m/s = 20 900 ft/s at r = 1.637 g/cm3

* The presence of small amounts of impurities may easily increase the experimental value to above 1000 kcal/kg.

Tetranitromethane is insoluble in water, but soluble in alcohol and ether. The volatile compound strongly attacks the lungs. The oxygen rich derivative is not explosive by itself, but forms highly brisant mixtures with hydrocarbons such as toluene. Tetranitromethane is formed as a by-product during nitration of aromatic hydrocarbons with concentrated acids at high temperatures, following opening of the ring. It can also be prepared by reacting acetylene with nitric acid in the presence of mercury nitrate as a catalyst. According to a more recent method, tetranitromethane is prepared by introducing a slow stream of ketene into cooled 100% nitric acid. When the reaction mixture is poured into ice water, tetranitromethane separates out.

Mixtures of tetranitromethane with organic fuels are very sensitive to impact and friction and may react spontaneously by detonation or fast deflagration.

R. Meyer
J. Köhler
A. Homburg

Explosives
6th Ed

----------
Patented Oct. 13, 1936
2,057,076
UNITED STATES PATENT OFFICE
2,057,076
PREPARATION OF TETRANITROMETHANE

Joseph A. Wyler, Allentown, Pa., assignor to Trojan Powder Company.
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AndersHoveland
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[*] posted on 19-9-2011 at 17:10


some non-scientific sources on the internet claim that nitromethane transforms into dinitromethane from exposure to UV light, but this could just be a perpetuated myth among the non-scientific community of racers and hobbyists.
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[*] posted on 26-9-2011 at 06:36


Some people have suggested that tetranitromethane might be easily made through halogen substition. For example,
CCl4 + 4 NaNO2 --> C(NO2)4 + 4 NaCl

Unfortunately, it is not that easy. The above reaction would not work for three reasons.

First, chlorine does not substitute off carbon atoms very readily. Such reactions are very slow, and typically require nearly a whole 30 days to go to completion. (there do however exist certain complexed copper catalysts that can speed up the reaction to only a few hours)
Bromine and iodine substitute off much more easily.

Second, especially in light of the fact that the reaction is so slow, the two reactants would need to be mixed together. That is going to be problematic, because NaNO2 is water soluble, whereas CCl4 is oil soluble. There are not many solvents that can dissolve both. One of the few that can is propylene carbonate, which you would have to prepare yourself. Another idea would be to make lithium nitrite, which is soluble in ethyl ether, and simply mix with CBr4. Yet another idea would be to mix NaNO2 with carbon tetraiodide, CI4, using acetone as a solvent. Unusually, NaI is actually soluble in acetone. So the solid NaNO2 (which would not dissolve) could react with the CI4 dissolved in acetone to form NaI, which would also dissolve in the acetone. It is important that the NaI dissolves, otherwise it would form a protective layer over the solid particles of NaNO2, which would prevent the reaction from happening.

Third, forming nitro groups by substituting nitrites is problematic. It gives low yields, especially when you are trying to put more than one nitro group on a molecule. Such yields would be expected to be low, less than 11%, since nitrite substitution on secondary and tertiary haloalkanes gives successively lower yields than a primary haloalkane because a small proportion of nitrite gets substituted instead of nitro groups, which in this case would lead to degradation of the molecules with such undesirable substitutions. When subsituting only one halogen group, such as iodomethane, a small portion of methyl nitrite results as an undesirable byproduct, but when three or more halogens are being substituted, accidental addition of even one nitrite group will lead to hydrolysis of the unstable molecule, even if the other two halogens have successfully been replaced with nitro groups. Formic acid, or carbon dioxide , will form.

Furthermore, tetranitromethane is somewhat thermally unstable, especially in hydrocarbon solvents. It is also extremely dangerous to heat tetranitromethane, since it forms sensitive explosive mixtures with hydrocarbons. Therefore it is unlikely that tetranitromethane could be directly prepared from any reaction that involves refluxing or heating.


Here is a summary of possible ways to make tetranitromethane through halogen substitution.

CBr4 (or CI4) with AgNO2, using benzene solvent.
AgBr will solidify out.

CBr4 (or CI4) with NaNO2, using propylene carbonate solvent

CBr4 (or CI4) with LiNO2, using ethyl ether solvent

CI4 with NaNO2, using acetone as a solvent.
The solid NaNO2 will slowly react into the solvent, the NaI that forms is soluble.

In the above reactions, yields will likely be less than 8 percent, the remaining CBr4 will be oxidized to CO2.

Bromoform CHBr3 (or CHI3) could be used instead in the above reactions, this would give improved yields (since only 3 nitro groups are being substituted on instead of 4). The trinitromethane that then forms could be dissolved in excess methylene chloride (for safety), and nitrated to tetranitromethane.

Carbon tetrachloride (or chloroform CHCl3) can alternatively be used to prepare carbon tetraiodide (or to prepare iodoform) by reaction with sodium iodide. This requires a special catalyst. This catalyst is basically copper(I) iodide complexed to ethylene diamine, or more preferably CH3NHCH2CH2NHCH3. 1,2-diaminobenzene can also be used instead. The reaction needs to be refluxed at 110degC for 8 hours. Butanol, dioxane, or DMF can be used as the solvent.

Bromoform CHBr3 can be prepared similar to chloroform. Either ethanol or acetone is mixed with NaOH, then bromine is slowly added. Unlike with the chloroform reaction, it is better to minimize the percentage of water in the reaction, because bromoform gradually hydrolyses with water (actually chloroform slowly does also but the reaction takes many days)

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VladimirLem
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[*] posted on 26-9-2011 at 08:07


Hi guys

I've got a question

Pure Tetranitromethane is said to have a VoD of around 6400m/s (at ~1.6g/cm3)

But some sources say that the mixture of TeNM+Toluene got up to 9300m/s (and that with a lower desnity - sure, cause of the Toluene - 0.86g/ml)

Is it "similar" to anfo - where pure Ammoniumnitrate just got a VoD of around 1800m/s and mixed with oil, up to 3500?

How the hell can that be?

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[*] posted on 26-9-2011 at 08:35


Tetranitromethane mixed with some toluene is more energetic, because the toluene can be burned off by the extra oxygen in the tetranitromethane.

When tetranitromethane explodes, it produces extra oxygen.

C(NO2)4 --> CO2 + (2)N2 + (3)O2

More energy can be produced if the oxygen can be used to burn some other fuel.
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[*] posted on 26-9-2011 at 08:44


Quote: Originally posted by AndersHoveland  
Tetranitromethane mixed with some toluene is more energetic, because the toluene can be burned off by the extra oxygen in the tetranitromethane.

When tetranitromethane explodes, it produces extra oxygen.

C(NO2)4 --> CO2 + (2)N2 + (3)O2

More energy can be produced if the oxygen can be used to burn some other fuel.


interesting stuff...

- I know, TNM got an awsome OB of +72 but does that theoretical work at every (solid) explosive (with +OB) mixed with fuels (like toluene/ethanol/oil) ?

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[*] posted on 26-9-2011 at 08:55


Tetranitromethane gives off extremely poisonous vapors. It is so poisonous, it was one time considered for use as a chemical weapon. At least trinitromethane is much less poisonous.

Trinitromethane toxicity: 800 mg/m3/2 hour Inhalation Mouse LC50,

Tetranitromethane toxicity: 1230ppm (for 36min, LC50)


Mixtures of tetranitromethane and fuel are very sensitive explosives, and the mixtures are not thermally stable, which means that the tetranitromethane slowly decomposes at room temperature, giving off nitrogen dioxide.

For trinitromethane with hydrocarbon fuels, the mixtures quickly decompose above 100degC, and the decomposition can lead to detonation. No doubt tetranitromethane mixtures are even less stable.

Tetranitromethane REACTS with toluene at room temperature
Tetranitromethane actually reacts with phenol, to form nitrophenol and trinitromethane in 100% yield. (at 30degC in water). At higher pH, nitrite is also results.
"Reaction of Tetranitromethane. I. Kinetics and Mechanism of Nitration of Phenols by Tetranitromethane."
Thomas C. Bruice, Maurics J. Gregory, Saundra L. Walters


So tetranitromethane likely reacts with toluene in similar way also. Therefore, it may likely be somewhat pointless to mix tetranitromethane into toluene. Perhaps better just to mix mononitrotoluene with trinitromethane, because that is what the resulting mix will contain either way.

[Edited on 26-9-2011 by AndersHoveland]
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[*] posted on 26-9-2011 at 09:43


Quote: Originally posted by AndersHoveland  

So tetranitromethane likely reacts with toluene in similar way also. Therefore, it may likely be somewhat pointless to mix tetranitromethane into toluene. Perhaps better just to mix mononitrotoluene with trinitromethane, because that is what the resulting mix will contain either way.

[Edited on 26-9-2011 by AndersHoveland]


hm...ok...

"In actual practice a mixture of 80% ammonium nitrate and 20% TNT by weight yields an oxygen balance of +1%, the best properties of all mixtures, and an increase in strength of 30% over TNT."

Source

No way ! The 80/20 compound will bei 30% more powerfull than pure TNT (at same weight) ?


And dont worry, i'm not going to make T(e/r)NM ;)

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