Sciencemadness Discussion Board » Special topics » Energetic Materials » Trinitrotoluene preparation Select A Forum Fundamentals   » Chemistry in General   » Organic Chemistry   » Reagents and Apparatus Acquisition   » Beginnings   » Responsible Practices   » Miscellaneous   » The Wiki Special topics   » Technochemistry   » Energetic Materials   » Biochemistry   » Radiochemistry   » Computational Models and Techniques   » Prepublication Non-chemistry   » Forum Matters   » Legal and Societal Issues

Pages:  1  2    4    6  ..  11
Author: Subject: Trinitrotoluene preparation
CD-ROM-LAUFWERK
Harmless

Posts: 30
Registered: 23-4-2005
Member Is Offline

Mood: No Mood

i cant open both of it...
quicksilver
International Hazard

Posts: 1820
Registered: 7-9-2005
Location: Inches from the keyboard....
Member Is Offline

Mood: ~-=SWINGS=-~

I was very curious about something related to TNT and didn't want to start another thread so I thought I would reserect this one. I have two questions that I was wondering about :

1.) TNT appears to crystalize in needles and in platlets. What contributing factors allow TNT to crystalize in needle form?

2.) Has anyone developed a solid nitrate synth for TNT? It appears that those who have attempted same have not had success. I have put together what looks like a good experiment for a solid nitrate / nitrafication of toluene but wanted to know if there are circumstances that inhibit the synth of TNT using soolid nitrates. Superficially it appears to solve the higher nitration issue in the "German" single pot
nitration.

nitro-genes
International Hazard

Posts: 1029
Registered: 5-4-2005
Member Is Offline

IIRC, higher concentration solutions of TNT favor plattlets while lower concentrations favor needles...
YT2095
International Hazard

Posts: 1091
Registered: 31-5-2003
Location: Just left of Europe and down a bit.
Member Is Offline

Mood: within Nominal Parameters

I made a few milligrams of TNT many moons ago following an A level text book, my Nitric acid wasnt all that strong though and so my crystalisation took place in the fridge to leave waxy needle like crystals growing off the walls in the test tube under the soln.
they were an off white color and washed up very nicely.

so a Not so strong nitrating mix and fridge cooling over a few days seemed to work for me.
other than quantity of the reaction mix being less that outlined thats the only deviation I made from the text book.

\"In a world full of wonders mankind has managed to invent boredom\" - Death
Twinkies don\'t have a shelf life. They have a half-life! -Caine (a friend of mine)
quicksilver
International Hazard

Posts: 1820
Registered: 7-9-2005
Location: Inches from the keyboard....
Member Is Offline

Mood: ~-=SWINGS=-~

From what I had seen temp and nitration concentration had direct effects on crystal structure but I would not quantify the results. I had two observations of two nitrations; both equal. One went to needles (nice ones) the other platlets... it was infuriating.
I am convinced that TNT is one of the easiest energetic materials to synth aside from NG and I love crystal structue in general so it has been a favorite of mine for many years to study. However there seems no reason not to be able to utilize a solid nitrate to this end and that would put it in the realm of hobbiest material. There was someone who attempted it awhile back and said that it appeared that the nitration went too fast! -That the high concentation of acids didn't allow for the control needed to maintain temp, etc. This seemed too much for me. Higher concentrations have always been just as easy to control if the temp was controlable. This is the same issue as tetryl. Dimethylaniline (also a benzene) nitrates much too vigorously in streight HNO3 so the use of sulfonation (via H2SO4 in a prior solution) controls that issue. But most of the original material calls for a higher concentration than 70% HN03. So why not use a mixed acid in addition to the sulfonated solution? It works with no problem so long as the original H2SO4 is accounted for in the nitration (no by products). -Extrapolating this and attempting it with toluene would seem even easier. Toluene is easy to nitrate. But the original material calls for 75% HNO3 and indeed, if the level IS higher the yield should be better and product purer. With 68-70 % it's easy to get an 80% yield. I believe that with using a solid nitrate the yield should be vastly higher and the product purer due to lack of water in the nitration. But I have not heard of it being done. This is something that if successful, would produce a workable secondary of consistent quality.
TNT may be a gateway to a heck of a lot of fun stuff.

Found some answers. (Friends at the local university are great)

Notes on trinitrotoluene 1/14/07
TNT has isomers in its production as a crude product. These produce differing crystal: needles palettes, rhomboids, etc. The isomers are alpha, beta, gamma, delta, epsilon, & zeta. Alpha produces needles. Beta –thin platelet’s, gamma –rhomboids & zeta possibly plates of a differing type.
The MP of the differing isomers are : alpha – 80C beta- 112, gamma 104, delta-137, epsilon- 97, & zeta-79.5
Gamma isomer crystallizes first from recrystalized material dissolved in hot (boil level) ethanol. This is a crude separation from fractional crystallization.
Alpha isomer is separated by fractional precipitation from warm etoh: Alpha being slightly more soluble than the others.
Alpha, beta, & gamma will react with aniline (or dimethylanaline but it will or course be a dimethyl isomer) and this gives distinctive products – nice crystals.
Alpha crystallizes in long glinting VIOLET needles! (the same as trinitrobenzene – mp 83C)
Beta – deep red plates, Gamma – reacts w/ hot alcoholic aniline to give orange rhomboids.
Super Sensitizing Idea;
Beta & Gamma Isomers react w/ NaOH to sensitize powerfully. But NaOH is not the only salt that will sensitize TNT thus the care in which anti acid wash should be chosen. Even carbonates of the alkali metals will sensitize (barium carbonate used in Japan?) Sodium carbonate (alcoholic solution – 1% in reaction) precipitates a dark blue substance in the solution being treated w/ acid. – Turns out this substance is dinitrocresol! However 1% sodium carbonate in alcoholic solution also produces dinitrotolyloxides. When they are formed salts of this complex are very explosive (primaries?)
Ammonium sulfide in reaction w/ TNT isomers yield interesting color variations.
Alpha – deep red. Beta –greenish yellow Gamma – blue! Epsilon –rose red (light). Zeta – orange
TNT dets from heat! There is something called “Goettig’s Mixture”. Heat from platinum wire causes explosion! Actual detonation as in primary is yet to be proven. Data from German text book (1907).
TNT - 22.22%
Barium Nitrate - 9.83%
Nitro Cellulous (smokeless powder nitrate level - 67.96%
Intimate mixture via whetting, etc.

So why does a batch have one isomer greater or another?? Well I have a collection of isomers in each batch. So the primacy of one, let's say alpha is more determined by getting rid of the rest via either recrystalization or happenstance when a batch is finished. Since hobbiest lab conditioons vary no matter what due to small batch size and lack of automation I don't think I can do much about it other than "weed-out" the unwanted isomers rather than the other way....

[Edited on 15-2-2007 by quicksilver]

quicksilver
International Hazard

Posts: 1820
Registered: 7-9-2005
Location: Inches from the keyboard....
Member Is Offline

Mood: ~-=SWINGS=-~

Interesting crystal growth pictures utilizing differing re-crystalization methods....
Using acetone and ethanol differing crystals may be obtained. Rhomboids (acetone) are unusually dense while needles (ethanol) can be grown up to one inch in size. MP on both 80 C.

[Edited on 25-2-2007 by quicksilver]

Attachment: pics.rar (806kB)

Rosco Bodine
Banned

Posts: 6370
Registered: 29-9-2004
Member Is Offline

Mood: analytical

Hey quicksilver . Could you please edit that image size
downward to about half what it is .....so that it doesn't
mess up the text page width formatting ?
quicksilver
International Hazard

Posts: 1820
Registered: 7-9-2005
Location: Inches from the keyboard....
Member Is Offline

Mood: ~-=SWINGS=-~

Sorry about that. I thought it was a querk of FireFox and would be compensated for in a relaod of the page.

Rosco Bodine
Banned

Posts: 6370
Registered: 29-9-2004
Member Is Offline

Mood: analytical

optimum nitrating acid composition

This short article provides some insight concerning the
optimum yield nitrating acid composition for nitration of
a mononitrotoluene precursor to the trinitrated TNT .

As the article states , this data is not pertinent to the
disclosure of the most economical proportions or stepwise
process , but only studies the composition and quantity
of acid in order to identify the optimum conditions in terms
of yield for the complete nitration of a mononitrotoluene
precursor , to develop good data which is relevant to
further process modeling . The most pertinent data is
the perhaps surprising result concerning the beginning and final water content of the nitration acids , where the result is that some water content actually provides a higher yield than
anhydrous nitration acid mixtures which are attained by
use of fuming sulfuric acid , as oleum .

This result has also been reported for nitration mixtures for nitroesters , where some small water content in the nitrating acids also results in a higher yield than absolutely anhydrous
nitrating acids .

Anyway , the charted nitrating acid data should be useful in projecting and calculating what may also be a useful acid composition for a more typical nitration which is applied to a dinitrotoluene precursor . For example something a bit over half the quantity and composition of acid reported optimum
for the conversion of mononitrotoluene to TNT should be
applicable for conversion of dinitrotoluene to TNT , resulting in a similar spent acid composition .

I believe this is also good news with respect to the possible usefulness of dehydrating salts which might be an included part of nitrating acid mixtures , as an alternative strategy to the use of oleum to reduce the water content of nitration acids for TNT . I have long had the idea that a respectably efficient nitration mixture for TNT could be attained by use
of dehydrating salts , and perhaps added nitration catalysts also , if indeed the dehydrating salt did not serve that function also , without the need for nitration mixtures made up from oleum .

Attachment: Nitration of Toluene to TNT.pdf (308kB)

tito-o-mac
Hazard to Others

Posts: 117
Registered: 30-6-2007
Member Is Offline

Mood: No Mood

You can find TNT preparation here with many other explosives: http://www.roguesci.org/megalomania/explo/trinitrotoluene.ht...
Zinc
National Hazard

Posts: 472
Registered: 10-5-2006
Member Is Offline

Mood: No Mood

When I make MNT I will not convert it to DNT right after I make it. I will store it for around 1 week. Can I just remove it from the spent acid or do I also have to neutralize and wash it?

quicksilver
International Hazard

Posts: 1820
Registered: 7-9-2005
Location: Inches from the keyboard....
Member Is Offline

Mood: ~-=SWINGS=-~

In order to complete a synthesis you should do your best to clean the product from it's lab components and clean your equipment as well. Things should not be haphazard in any of your work. YES, clean the product; that way you'll know that you have that material, not many others in that container. Additionally it will keep better and be less reactive.

Just like doing homework for school, you wouldn't do a half-job there / so why do that in your lab? Be thorough and complete; reach for exacting standards.
Zinc
National Hazard

Posts: 472
Registered: 10-5-2006
Member Is Offline

Mood: No Mood

To 60 ml of conc. H2SO4 (made by boiling down the acid extracted from a old car battery) I added 45 g of NaNO3. When the NaNO3 dissolved I added 30 ml of toluene in 4 portions). The toluene first turned in a red liquid, then orange and then again to red. After around 45 min it looked like this:

Then I added it to water, then to a sodium bicarbonate solution and then in a saturated salt solution. Final yield is around 26 ml of non-clear orange MNT (it has a very nice smell)

Zinc
National Hazard

Posts: 472
Registered: 10-5-2006
Member Is Offline

Mood: No Mood

Does anyone know in what ratio should I add MNT to a H2SO4/NaNO3 mixture to nitrate it to DNT?

You know there is an edit button for your previous post, so you should have edited and added this to that post as opposed to making a new post. Next time it gets deleted.
-Davster

[Edited on 3-2-2008 by The_Davster]

quicksilver
International Hazard

Posts: 1820
Registered: 7-9-2005
Location: Inches from the keyboard....
Member Is Offline

Mood: ~-=SWINGS=-~

How do you know you did something "wrong" or "right"? What mechanism are you using for verification of success?
Zinc
National Hazard

Posts: 472
Registered: 10-5-2006
Member Is Offline

Mood: No Mood

 Quote: Originally posted by quicksilver How do you know you did something "wrong" or "right"?

If I did something right the product is what it must be. If I did something wrong the product is not what it must be.

 Quote: Originally posted by quicksilver What mechanism are you using for verification of success?

By the color, smell, and does it float or sink in water.

Sobrero
Harmless

Posts: 21
Registered: 20-5-2006
Location: Belgium
Member Is Offline

Mood: Lifting my skinny fists like antennas to heaven

I've made TNT a few times, by first nitrating toluene to DNT and then to TNT.
I like this path a lot since it contains only two steps and proceeds just as fine!
Toluene can be easily nitrated to dinitrotoluene by adding , for example, 10ml of toluene to a cooled nitrating mixture comprising 18g of ammonium nitrate (130% of theory) and 32ml sulfuric acid, and heating this for 2 hours at 60Â°C, with stirring. Then, after drowning, washing and neutralising, DNT is obtained in 95% yield, as a light yellow, slightly waxy solid .

So, @ Zinc, for the preparation of DNT from MNT, a nitrating mixture containing a slight (~5-10% excess) molar excess of (in your case) sodium nitrate and sulfuric acid should be entirely adequate (with reaction conditions mentioned above).

"There exists a world. In terms of probability, this borders on the impossible." (Jostein Gaarder)
Fashist
Hazard to Self

Posts: 73
Registered: 19-7-2007
Member Is Offline

Mood: Powerful

I made tnt very easy by reflux system(see below picture)
First i made Dnt and then made tnt in the reflux system(100-105c, 2hour)

Zinc
National Hazard

Posts: 472
Registered: 10-5-2006
Member Is Offline

Mood: No Mood

I have tried the method that Sobrero posted only a little upscaled and used sodium nitrate instead ammonium nitrate. I heated the mix for two hours (sometimes even hotter than 60 C). At the begging I had a runaway but I cooled it fast and then again put it on a hotplate to heat it. After two hours there is an orange oil on top of the acid. As DNT is solid I think that the reaction failed. What did I do wrong? At least I got some MNT

Fascist what ratios of chemicals did you use to make your DNT and how long did you heat it?

Sobrero
Harmless

Posts: 21
Registered: 20-5-2006
Location: Belgium
Member Is Offline

Mood: Lifting my skinny fists like antennas to heaven

You mean liquid at elevated (60-70Â°C) or at room temperature (after 'drowning')? Dinitrotouene melts quite easily (around 50-60Â°C IIRC, for a mixture of isomers).

[Edite le 8-2-2008 par Sobrero]

"There exists a world. In terms of probability, this borders on the impossible." (Jostein Gaarder)
Zinc
National Hazard

Posts: 472
Registered: 10-5-2006
Member Is Offline

Mood: No Mood

It was liquid at the elevated temperature.

Fashist
Hazard to Self

Posts: 73
Registered: 19-7-2007
Member Is Offline

Mood: Powerful

I used this book Ratio
http://rapidshare.com/files/90231545/fmx.zip.html
Zinc
National Hazard

Posts: 472
Registered: 10-5-2006
Member Is Offline

Mood: No Mood

Thank you!

Very interesting book.

Zinc
National Hazard

Posts: 472
Registered: 10-5-2006
Member Is Offline

Mood: No Mood

Today I made more MNT. Now i have 132 g I want to make DNT from it using a mixture of sodium or ammonium nitrate and H2SO4. So how much of NO3/AN should I use? As far as I know I need one mol of NO2 anions per one mol of MNT to make DNT. 132 g of MNT is around one mol. So for that I need one mol of NH4NO3 (or NaNO3) and that is around 80 g (or 85 g of NaNO3) as one mol of NaNO3 or NH4NO3 gives one mol of NO2 anions. So how much of H2SO4 should I add to the nitrate (I think one mol as the nitrates turn to bisulfates and how much more to absorb the water?)? And how much excess of nitrate and sulfuric acid should I use? And under what conditions should the reactants to be to react (heat how long and that things)? And are the things I wrote above correct?

Sorry for too much questions but I don't know a lot of theoretical chemistry.

Fashist
Hazard to Self

Posts: 73
Registered: 19-7-2007
Member Is Offline

Mood: Powerful

My Suggestion is Using Con.Nitric Acid
I Made it Using Dry Mg(NO3)2 + HNO3(57%) and then Distil.
Pages:  1  2    4    6  ..  11

 Sciencemadness Discussion Board » Special topics » Energetic Materials » Trinitrotoluene preparation Select A Forum Fundamentals   » Chemistry in General   » Organic Chemistry   » Reagents and Apparatus Acquisition   » Beginnings   » Responsible Practices   » Miscellaneous   » The Wiki Special topics   » Technochemistry   » Energetic Materials   » Biochemistry   » Radiochemistry   » Computational Models and Techniques   » Prepublication Non-chemistry   » Forum Matters   » Legal and Societal Issues