Trinitrotoluene preparation

TNT

I also have another method from one of those links thats connected to meglomainia's site.Its a more easyior method and can be made form more readly avaliable chemicals.

Despite What Some Preceding Documents May have stated, Crude 2,4,6 TrinitroToluene Can be prepared from less concentrated, more commonly available, easily produced acids. The Process is a Modified Three Step Nitration, Whereby Toluene is converted into MonoNitroToluene, Dinitro, And Finally Trinitro by the addition of fresh portions of Mixed Nitric/Sulfuric Acid. An External Source of heat is neccesary

Purification is accomplished through the usage of a boiling water liquidation, Whereby impurities float to the surface, which are easily decanted.. It can be scaled up or down depending upon materiel availability.

Materiels

Sulfuric Acid 99~%

This can be Found in Home Depot, In White Plastic Containers, Marked "Instant Power Drain Opener" Marketed By Scotch Corporation Of Dallas, Texas - 64Oz Containers of Concentrated Sulfuric Acid Found in the plumbing section. It is of 93% Purity - It must be concentrated via heating at 100C+ For 10 minutes. Water will boil off yielding Theoretically pure H2SO4 - This should be done OUTSIDE, As all Experiments should be.

Nitric Acid 70~99 % Concentration

The ~70% Materiel is available commercially, 99~ materiel is available via 88~C Distillation of Potassium Or Sodium Nitrate With Sulfuric Acid. The 70 % materiel will work, although yields will be less.

Toluene

This is found in the Solvent section of Home Depot in Gallon cans

It is used as a specialty solvent. ACE May carry it if it is unavailable in Home Depot

3 Glass, Heat Resistant Container(Pyrex, Kimax Beaker or Flask Preferably)

Acid Resistant Volume Measurement device( Graduated Cylinder Or Etched Beaker)

Glass Stirring Rod

Plastic Spaluta

Plastic Baster

Heat Source

Thermometer(Optional)

This Item would greatly increase reproducibility - But TNT Will still form without careful temperature control and based on subjective sensory perception. Celsius Has been included for those who do have the luxury of a thermometer. TNT is not a sensitive HE and thus there is no danger of temperature based runaway reactions leading to detonation.

Procedure

Measure Out 300 Milliliters Of ~99% Sulfuric Acid into the heat resistant glass container. It should be able to hold at 1000 ML. Add To This 100 Ml Of Nitric Acid 70%. If One is using 99~ Distillation Acid then 75 ML Of That should be used. Or .75

This is the standard ratio 3/1 Or .75 If 99~ Acid is used. Heat will be generated upon the Nitric acid mixing with the Sulfuric acid and a cloud of barely visible white N0x should be seen wafting over the vessel. Now One adds 100 Milliliters of Toluene. Upon The Toluene contacting the mixed acid, it will convert to a yellowish/Red oil which will float on the surface of the acids - Large Amounts of heat will be generated - This is Good. Just let the vessel sit alone untouched reacting for 2 hours. A very noticeable odor shall appear - This is due to MNT. Do NOT confuse this with the odor of Reddish/Brown N02 which may begin to bubble off the beaker when the reaction temperature reaches a climax. Some reckon it smells like "shoe polish", While others relate to it smelling "Almondish". Personally, it has a completely distinct smell that i do not feel is adequately characterized by any particular description. Let it react for 2 hours

The MNT will be a Aromatic oil on the surface of the acids. It should now have turned cold - Temperature must now be maintained externally. With a bunsen burner, alcohol lamp, or other heating device, heat the beaker to 80C~. If you lack a thermometer, It should be heated to the temperature of the beaker during the vigorous reaction. By this i do not imply one wait around while it is reacting, as Volumes of Nitrogen Dioxide, a reddish Brown gas, is produced, which is quite toxic and will produce pulmonary edema which may go unnoticed for a week, at which point one may die. This does not mean you will die if you take a little whiff, No, But common sense dictates that one should distance themselves from the vessel while it is reacting and avoid inhaling any fumes. It is heated externally for 30 minutes. Now using the Plastic Baster, suck up as much of the now dilute acid from the container and transfer to another suitable container for recycling(See Below) Or should be disposed of properly. Try not to get any of the MNT in with the acid, this will take practice. Now In another container mix another batch of 3/1 acid and add this to the MNT. Repeat above steps involving 2 hour wait and 30 minute external heating. Remove spent acid and add to portion of spent acid recovered form MNT nitration. The DNT will be a Yellow oily liquid, or a waxy yellow solid. Now Comes the final nitration. To The DNT is added a fresh portion of 3/1 acid.

The vessel will get hot and when it cools after 2 hours yellow needles may be visible in addition to some DNT. After allowing the vessel to react for 2 hours, external heating should be applied for 1 hour. When heating is removed the insoluble oil floating on the surface will solidify as it cools, forming a yellow crystalline cake, with many yellow needles embedded into it - This is TNT. Earlier methods involved filtration, but due to economic reasons good filter paper is not used, instead coffee filters - Since corrosion of the cellulose based filters has been shown, a spatula is used to "Fish out" The cake from the surface of the acid and into a separate plastic container like a cream cheese container. This can be done by tilting the container gently and sliding the cake along the side of the vessel and into the empty plastic container.

Purification

The empty cup with the fragments of cake, acid, is covered in about 150 ML Of boiling water - This will melt the TNT into a puddle under the water and cause insoluble droplets of DNT impurity to float onto the surface as an oil. Any Acid Will dissolve in the water. Let this cool, drain off the water and remove the "Wet Cast" TNT from the container, preferably plastic "I Can't Believe Its Not Butter" container, which bends easily allowing the TNT to loosen and fallout without cracking it. Place it on Layers of Paper towel to dry, as TNT will exude a yellow oil. Puddles of such exudate can be found in munitions dumps across the country. You will notice the Paper towels colored yellow. Allow the TNT to lay undisturbed on the towels, and if neccesary fresh portions of towel should be used to dry it. Later Castings should be done dry using a bath of boiling water surrounding a dry container with the TNT in it.

One should not worry too much about possible safety dangers, as TNT is fairly difficult to initiate accidentally. Although it is better to be cautious around explosives paraphernalia.

Acid Recycling

For higher efficiency, Or for 99~ Nitric acid production, a distillation apparatus should be obtained or set up. A decent one can be made with two Flasks and appropriate rubber stoppers and glass tubing, With a bunsen burner or other heating instrument providing the means for distillation and ice water the means for condensation. The efficiency of the above mentioned reaction can be greatly improved if one uses the large amount of still usable acid present in the spent acid. Spent acid can be recycled by adding to it additional sulfuric acid , 2 parts spent acid to 1 part fresh sulfuric acid. Distillation is

effected at 80~C To obtain 99~% nitric acid, which can be reused in above reaction, or for PETN, RDX, NitroCellulose, etc... After Half An Hour of 80C careful distillation, All the Nitric Acid has been driven off, the condensation apparatus is removed and the spent acid vessel is heated to a higher temperature to drive off ALL water from the sulfuric acid. Quite Ingenious

Suggestions

If PETN is available, a Pentolite Booster can be made easily from the powdered, sieved PETN, mixed into the molten TNT, 50/50. If Cost is an issue, an AMATOL should be made. DRY Ammonium Nitrate should be mixed into the molten TNT, 50/50. There is a stichiometric fuel/oxygen balance that makes this explosive more powerful than Either components seperatly. I suggest Gentle heating in an oven on the TOP RACK to drive off any moisture. Also a Tritonal Is an interesting Explosive, If Only for its impressive Night-Time Flash. 20 Parts powdered Aluminum, available form various Mail-Order Pyrotechnics Companies, is sieved into a beaker full of molten TNT, 80 Parts.

-325 Or Better Should be used, German Black Flake 3 micron is Optimal. Care must be taken to avoid Moisture when using this in a sealed casing, as H2 gas will be generated by Aluminum Oxidation, and it may crack a casing before it is given a chance to be employed.

abbreviation of explosives/chemistry

more abbreviations

/UHE/ - Ultra High Explosive - explosives with vod > 10k/s

My list

What do these acronyms have to do with preparing trinitrotoluene?

A little runaway occurs

SHIT I Made Trinitrotoluene

Trinitrotoluene,
TNT is soluble in conc H2SO4 and HNO3; the yield of the reaction is very high from DNT to TNT you should at least get 25g of TNT (and max 27)!
Of course you have to put all the batch in iced water to allow the big % of TNT dissolved in the acid mix and then neutralise the solution with Na2CO3! You will have much more than 6g then!
If you have trowed away your acid mix, you have wasted at least 19g TNT!!!

I think I am going to attempt to make TNT. I was thinking that I could pass H2SO4 over anhydrous MgSO4 to produce SO3, which could then be dissolved in another batch of H2SO4 to produce oleum. The setup would be something like this:

If I understand that post you think that simply mixing nitric acid and toluene will give you TNT. You are mistaking this with RDX synthesis: nitration requires the nitronium ion (NO₂⁺, which doesn’t exist in straight nitric acid but does in a nitric-sulfuric mix.

I will also post some other preparations of TNT derivatives. I will put all but this one in one file and attach it to a post I will make later. But I will post this one now.
Triperchloroaminobenzotridiazonium triazide. Souns scary, eh? Well, basically it's a benzene ring with three perchloratoamino (a perchlorate group attached to a nitrogen atom with a hydrogen attached to it also, the nitrogen is attached to the benzene ring) groups and three diazonium ion groups attached. The negative charge is compensated by three azide ions.
The preparation is as follows. TNT is oxidized to trinitrobenzoic acid, this is decarboxylated by boiling with alkali, the resulting trinitrobenzene is reduced in neutral solution (i.e., with zinc and ammonium chloride) to trihydroxylaminobenzene. That is reacted with perchloric acid to give triperchloroaminobenzene. That is reacted with chloramine to give triaminotriperchloroaminobenzene. This is diazotized with nitrous acid, sulfuric acid as well to give you triperchloroaminobenzotridiazonium sulfate. That is reacted with calcium azide, which precipitates CaSO4 and leaves you with triperchloroaminobenzotridiazonium triazide (TPABDA). This explosive has perfect oxygen balance, I expect it to be a crystalline solid, be quite sensitive and probably more powerful than HMX.

enter

I know this is a VERY old thread but I wanted to add that both TNT and PETN may be produced by lower concentrations of acid than what one would normally expect (distilled HNO3, etc). I guess I have seen time and again that 70% HNO3 could not be used or that mixed solid nitrates could not be used for both benzene ring nitrations and nitric estors, that I wanted to post an example or two.

**************
for TNT synth:
**************
Trinitrotoluene - single batch method.
Yield is approx. 85% of theory, crude product.
Patent supports the only singe batch method in current usage.

NOTE: alkaline (sodium hydroxide) will sensitize TNT, Sodium Sulfite is used to bring the crude product to a technical chemical level. The product below is some rather crude stuff but MAY be brought up to higher purity level. However the end result will work.

Procedure: Place 191 grams of 70% nitric acid into a beaker, and then gradually
add over a period of 2 hours, 420 grams of 98% sulfuric acid. (Total; 611gr of
mixed acid) Then place the beaker into a cold-water bath and cool to 10 to 15
Celsius. When the acid mixture reaches a temperature of about 10 to 15 Celsius,
pour 96 milliliters of this acid mixture into a clean separate beaker, and then
cool to 10 to 15 Celsius by means of a cold water bath. When the temperature of
this 96-milliliter portion of acid mixture reaches 10 to 15 Celsius, slowly add
46 grams of toluene over a period of 4 hours while rapidly stirring the acid
mixture and maintaining its temperature at 10 to 15 Celsius. After the addition
of the toluene, continue stirring the reaction mixture for an additional 2 hours
while keeping the reaction temperature at 10 to 15 Celsius. After which, add the
remaining acid mixture obtained at the start of the procedure, to the reaction
mixture and then after the addition, raise the temperature of the reaction
mixture to 70 Celsius, and hold this temperature while rapidly stirring the
reaction mixture for 2 hours. After 2 hours, raise the temperature to 80
Celsius, and heat at 80 Celsius for 2 hours while rapidly stirring the reaction
mixture. After heating the reaction mixture to 80 Celsius for 2 hours, remove
the heat source, and allow the reaction mixture to cool to room temperature.
Then add the entire reaction mixture to 1000 milliliters of cold water, and then
filter-off the precipitated TNT product. After which, wash the TNT precipitate
with 1000 milliliters of water, and then vacuum dry or air-dry the TNT
precipitate. Then, place 400 grams of 70% sulfuric acid into a beaker, and then
add the dry TNT product. Afterwards, stir the mixture to form a slurry. Continue
to stir the slurry for 2 hours at room temperature, and then filter-off the TNT
product, wash with 1000 milliliters of cold water, and then vacuum dry or air
-dry the TNT product

Extrapolated from Legard's book and one of the FEW patents that could actually be varified IIRC it was a guy working for ISCC who developed it.


***********
for PETN synth
***********
Verified efficient method of preparing PETN from diluted HNO3

use
32,7 ml of 70% HNO3 (75% excess)
18,9 ml of 96% H2SO4
10,0 g of Pentaerythrite
------------------------

or
34,0 ml of 65% HNO3 (66% excess)
24,8 ml of 96% H2SO4
10,0 g of Pentaerythrite
------------------------

or
34,8 ml of 58% HNO3 (48% excess)
36,3 ml of 96% H2SO4
10,0 g of Pentaerythrite
------------------------


Nitration:
1. Cool nitration mixture during mixing of acids, thus minimalize even minimal decomposition of HNO3. Nitration mixture must be cooled before nitration process to temperature of 10°C.
2. While stiring, add pentaerythritee in small portions (1-2g) to nitration mixture, always after previous batch is dissolved. Nitration mixture gradually thicken as PETN forming in solution.
3. Constantly monitor reaction temperature and maintain it in 10-15°C range. Interval of adding pentaerytritol conform to reaction temperature, must not rise over 15°C, leave beaker in cold water.
4. Stir with mixture for next 5 minutes after all pentaerythrite is added and dissolved. Mixture is now thick, but stirring is going well. During nitration process must not be developed any brown fumes of NOx!
5. Now put beaker with mixture into water bath and maintain temperature at 50°C, continuously stir with mixture. During 20 minutes at this temperature, all of possible sulfoesters come into PETN for maximal yield of nitration.
6. While maintaining mixture at higher temperature, mixture must be monitored for developing of NOx fumes. Only light brown colour can be in shrouded beaker. Raised development of NOx pointing to higher temperatures used (even during previous nitration) or insufficient chmemicals purity and further heating may end up in uncontrolled reaction and oxidation of formed PETN. In this case it is better to do not heat at all and end just after nitration (if brown fumes apperas during nitration), the yield will be lower. In case of accidentally runaway reaction during heating, immedialtely pour mixture into cold water, don't try stop reaction by cooling beaker, it will not help.
7. When heating after 20 minutes pass off, pour reaction mixture into cold water and follow standart procedure of filtration, neutralization and purifying of PETN.

Yield was 22,1g of PETN from 10g of pentaerythrite, ~95% of theoretical yield (with 65% HNO3 used).

This procedure is result of research of most effective method preparing PETN from diluted HNO3. Acid ratios are precisely calculated on data from PETN nitration graph published by T. Urbanski in his book vol. IV. Look at the graph from the FTP and it makes a great deal of sense. Generaly said, PETN is forming to maximum 30% of water portion in nitration mixture. But, when also H2SO4 is contained in nitration mixture, minimum amount of water must be keep, or oxidation with small yields occur. With this acid ratios 20% of H2O is minimum. So, this nitration mixture has 20% of water on nitration start and 30% at the end, area for most effective nitration, but again only with this ratios. For other acid ratios must be all recalculated. Excess of HNO3 is used to controll amount of reaction water. Only amount of nitration mixture can be extended for lower mixture thickness, but it lower utilization of acids and overall efficiency. But it isn't necessary.


-=-=-=-=-=-
The TNT synth is somewhat scaleable - the PETN is not due to the above stated issues. (both of these have been floating around for a few years, I believe)





[Edited on 14-6-2006 by quicksilver]

Do not sneeze during the process or the entire sample
will be gone with the wind


Here is a good reaction vessel for microtek


http://cgi.ebay.com/Large-reactor_W0QQitemZ110003787509QQihZ...

Here is an old patent which relates to nitration catalysts
which may have some usefulness regarding TNT as well as other nitroaromatics . I have not done any experiments regarding the patent , but the procedure for tetranitronaphthalene is on my " experiments to do list " . Vanadium phosphate is one of the catalysts which I would look at . The TNN would likely make a good stable base charge for caps and is a bit more powerful and sensitive than TNT , about like picric acid but non-corrosive , has a good crystalline form and doesn't have the purification / separation problems of TNT . The patents mention of even higher penta and hexa nitro forms of naphthalene is also interesting , as well as the obscure primary initiating composition which may be formed from the hexanitronaphthalene in combination with an oxidizer . This is an intriguing old patent which may or may not withstand scrutiny . In fact it was the first patent which I communicated here in this forum as being " interesting " in its implications . You see if the nitration catalysts do
work as advertised , then higher nitrations of aromatics can be performed under less rigorous conditions for acid concentration and temperature which would be very helpful
for our purposes .

Attachment: GB501034 nitration catalysts.pdf (212kB)
This file has been downloaded 1484 times

OK....I F*cked up there. That was a typo and a hurried job of typing when I was running out the door for work. What I thought was a file from a collection of ISEE stuff (International Society of Explosive Engeneers) was simply another file from Legard's book, it wasn't the correct file - The typo was ISCC. I spent sometime tracking down what the existing citations in that damn book were. Some lead simply no-where - others had some interesting origins but I also have one unholy collection of files and need some way to organize them better. I didn't notice the whole thing until it had been posted quite awhile. - appologies....

What I looked for at the time was some US Gov't patents issued to a "H. William Voigt, Jr". of Wharton, NJ and a Mr. Bernard R. Banker, also from NJ. The patent number (like a WHOLE LOT OF STUFF IN LADGARD'S BOOK) was supposedly application # 104,499 12-17-79. That was a dead end. But somewhere I have a patent from 1981 that was a contractor to the gov't that looked like what it could be. That's a long convoluted story; I got that one from a guy who told me he submitted stuff he worked on via a university prof who published stuff for the ISEE.... a volume on nitrobenzenes has the same labs. However; the one-pot process can work; too many people have worked with it and it does produce a scalable, crude product. If I find the EXACT PDF file I'll append this and post it.



[Edited on 24-7-2006 by quicksilver]

Doesn't it seem strange that in a book which proposes
many procedures for syntheses of energetic materials , and given the potential dangers attendant to such business , that there would be such dismal performance in providing the references to sources which were the basis for the procedures being described ?

It doesn't exactly seem to be a trivial failing in my estimation , in fact it is a troubling departure from the accepted convention for technical writing . All the fancy graphics don't mean shit if a writer can't be bothered to cite accurate references to substantiate his proposed synthetic procedures . Such a writing style for describing chemical syntheses should be reassigned to storytelling and banned from technical writing all together

Is there even one single good patent number given as a reference in that Ledgard work ?
( which we should perhaps rename )
Energetica Ledgerdermainica Acta ....
written by Poofer the Magician

Quote:

Originally posted by Rosco Bodine Doesn't it seem strange that in a book which proposes many procedures for syntheses of energetic materials , and given the potential dangers attendant to such business , that there would be such dismal performance in providing the references to sources which were the basis for the procedures being described Is there even one single good patent number given as a reference in that Ledgard work ? ( which we should perhaps rename ) Energetica Ledgerdermainica Acta .... written by Poofer the Magician

optimum nitrating acid composition

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)

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 60°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).

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)

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?

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.