Sciencemadness Discussion Board - Trinitrotoluene preparation

https://youtu.be/uwASaAqyuAk

This thread has been a goldmine of knowledge about making TNT. It wasn't something I thought I could make, but after reading this thread and watching the above video that I linked, I am seriously considering making some. I already got pure toluene and sodium bisulfite (metabisulfite actually, but it becomes bisulfite when added to water, which is what is needed anyway).

I've seen so many methods listed that I will just ask for advise using the video as a reference. in the video they use around 200ml of H2SO4 (I will make sure the concentration is as close to 98% via boiling as possible) and 115g of ammonium nitrate for both steps, and 50g of toluene. In the video he mixes the nitrating mixture first and then cools it to room temperature before adding the toluene dropwise.

The actual process is not what I am curious about, since it seems quite straightforward. What I am concerned about are the reagents. He nitrates the toluene to DNT via ammonium nitrate and H2SO4, and then he says that a 'second' nitrating mixture is made for the DNT to TNT step. I obviously assume that he uses another 200ml of H2SO4 and another 110.5g of ammonium nitrate (I will be using a slight excess of both in my case). Would this work? because if that is the case, it would make making TNT a far more simple and economical process than other energetics that often require very concentrated HNO3, such as RDX.

Also for the nitrate salt. Is the ammonium ion preferable to using something like sodium nitrate or potassium nitrate?

With a big enough excess of acids you can make TNT straight from toluene in a single nitration. And yes, ammonium nitrate works fine.
Just be aware of the toxic and carcinogenic properties of TNT and more importantly its lower nitrates. Not something to handle carelessly in terms of skin contact, inhalation or ingestion. like you could many other compounds like ETN for example.

ManyInterests - 7-9-2023 at 17:49

I am well aware of the toxicity of TNT. I was quite cautious with a lot of other dangerous material and I plan on applying the same caution to TNT as well.

The reason why I was asking about ammonium nitrate and not a nitrate salt is because even though I can make WFNA (I need to make it a few more times to make sure that I can make it consistently. The last I did it, I made some with a specific gravity of 1.52 at 15C...), it takes a lot of nitrate salt to make that much WFNA. This is why if I wanted to make picric acid again, I would use sodium nitrate and not bother with trying to make nitric acid since I would need much more nitric acid than I would in nitrate salt.

Quote:

I never nitrated DNT with a salt, but ammonium nitrate gives a nicely stirrable mixture while KNO3 doesn't mix well with sulfuric. NaNO3 is hard to get dry, probably also doesn't mix well.

I didn't find NaNO3 to be difficult to dry. Putting it in the oven for a few hours and stirring it around at around 150C will make it dry as a bone. I don't know about its mixability in a nitrating mixture (haven't tried that) but I do agree that KNO3 forms a thick mixture and is annoying.

I can make ammonium nitrate with the sodium bisulfate, ammonia, and other nitrate salt (sodium nitrate is currently my favorite since it is much cheaper to make than other nitrate salts).

Quote:

With a big enough excess of acids you can make TNT straight from toluene in a single nitration. And yes, ammonium nitrate works fine.

How much of an excess are we talking about here? In the video the total amount of reagents he used would be 400ml of H2SO4 and 221g of ammonium nitrate. If I put in 500ml of H2SO4 and 300g of ammonium nitrate, would it be sufficient for fully nitrating 50g of toluene? I need some kind of formula or stiochiometry here if you can provide it. Please explain the science!

OneEyedPyro - 7-9-2023 at 21:37

At the warmer temperatures you run a toluene nitration ammonium nitrate is not too viscous to stir and I'd guess that's also true with sodium nitrate though I never tried it.
You really don't need fuming nitric acid and oleum to get it to full nitration or anything special. It can actually be prepared in a single nitration with 94% drain cleaner grade sulfuric acid and ammonium nitrate at the expense of wasting some potential of the reagents.
It's industrially more efficient to prepare it in multiple steps but you're making grams, not tons.

Just try a small batch with an excess of SA/AN mixture. Add toluene dropwise with good stirring, let it go for a while then bring the temperature up slowly and let it stir for an hour or so. You'll be left with TNT.

ManyInterests - 7-9-2023 at 21:52

At the warmer temperatures you run a toluene nitration ammonium nitrate is not too viscous to stir and I'd guess that's also true with sodium nitrate though I never tried it.
You really don't need fuming nitric acid and oleum to get it to full nitration or anything special. It can actually be prepared in a single nitration with 94% drain cleaner grade sulfuric acid and ammonium nitrate at the expense of wasting some potential of the reagents.
It's industrially more efficient to prepare it in multiple steps but you're making grams, not tons.

Just try a small batch with an excess of SA/AN mixture. Add toluene dropwise with good stirring, let it go for a while then bring the temperature up slowly and let it stir for an hour or so. You'll be left with TNT.

Yeah, in the video the guy used 50g of toluene, I will not be using more than 100g at a time (and even that is quite a lot). Industrial production is an entirely different beast. Those factories, even older factories during WW2 with fairly primitive equipment compared to today still churned out unfathomable tons.

So I am still wondering what an excess would be, and if I need more than a 2 stage process. I still need a bit of an idea, but the stuff I have in mind is a little over double the amount the guy used in his video. Without more information, that is all I have going in my mind. All information I have on TNT production comes from this thread. I might need to open up an Urbanski book at this point, but basically most of what they describe is industrial processes.

Edit: Now that I've learned about how much more liquid ammonium nitrate is in sulfuric acid. I might try to make ETN or PETN syntheses with it. Since one of the first attempts posted on this forum who made ETN did so with ammonium nitrate and got a fairly good yield, I might do that instead of making nitric acid, since it will be more economical that way. I don't know about how much ammonium nitrate I would need with sulfuric acid to make PETN, so I'll need more research on that.

Edit2: Actually on second thought, maybe a 2-stage process might still be better for my purposes.

[Edited on 8-9-2023 by ManyInterests]

[Edited on 8-9-2023 by ManyInterests]

DennyDevHE77 - 8-9-2023 at 03:29

Now that I've learned about how much more liquid ammonium nitrate is in sulfuric acid. I might try to make ETN or PETN syntheses with it.

PETN can indeed be obtained from mixtures of sulfuric acid and nitrate salts. But due to the ease of esterification, it is still more profitable to synthesize it using sulfur-nitrogen mixtures, since even with 56% nitric acid a yield of >90% is achieved.

But regarding production through nitrate salt.

The ATK company obtains it with a yield of 62% through ammonium nitrate (8 mol) and a certain amount of sulfuric acid within 2 hours. I'm not sure if this is beneficial...

You can first obtain pentaerythritol sulfate by dissolving it in 6-7 parts by weight of concentrated sulfuric acid, then usually (this method is called a two-stage method) add 10-12 parts of nitric fuming acid (not necessarily white). Here, in theory, you can replace it with a mixture of sulfuric acid and nitrate salt. Just recalculate the proportions. Someone even managed to get the same yield of 80-90%.

Then everything is the same, transesterification at 55-60°C, dilution with water, neutralization, boiling in a 1% soda solution and then recrystallization from acetone from a soda solution or grinding with chalk (if there is no acetone).

But in general, by the way, this is off-topic, I’m not sure that another explosive can be discussed in the topic about TNT. In general, by the way, me need to check with the administration.

[Edited on 8-9-2023 by DennyDevHE77]

[Edited on 8-9-2023 by DennyDevHE77]

ManyInterests - 8-9-2023 at 11:30

Quote:

There is another thread about PETN or close, we can bump that up if you want (I wrote about it in the RDX thread). I just do want to make this one single comment here.

OK so making PETN with nitric acid is better. But I do have one question about it: What could have made my yields go bad in the one time I tried it? I used 88g of PE (98%, it was technical grade), but I ended up with only about 122 grams of the stuff. In all videos I've seen an literature I've read I should have ended up with 166 or a bit more.

I used 290ml of 90% HNO3 (purged of all NO2 contamination by blowing dry air through it) and 170ml of H2SO4. I froze the beaker in a solid block of salt water ice (as I normally do. The ice always melts to a very large degree during the additions) and I added the PE gradually, but I did not time it. During the addition I did notice some yellowing happening. There were no major temperature spikes and temperature was below 20C during all the additions. This yellowing was concerning to me as I thought it was destroying my product and this is what wanted to try to hurry things along. After the addition, I did let the temperature rise to room temp, but I kept returning it to the ice water bath. I wasn't sure if it was gonna stay at 25C or not. After a while of doing this (not timed either) I decided to move onto the heating step. As I was heating it, I did notice the yellowing get darker and I did see some very faint brownish red fumes start to form. To me, this was the sign of a runaway and I decided not to take any chances. I cut my losses and crashed everything into a bucket of cold water.

The cleaning was done as normal. lots of water, followed by bicarbonate solution, followed by more water, then let it dry. After wish I recrystalized it in acetone. It was quite an adventure since the the liquid during recrystalization turned orange!

What could have caused all this and had such an effect on my yield?

I promise, you can bump up another thread if you don't want to continue it here.

OneEyedPyro - 8-9-2023 at 13:09

Brining up the temperature too much toward the end of nitration isn't necessary with PETN, it's rather easily brought to full nitration by bringing it up to 25-30C in warm water for the last half an hour.
In my experience PETN is fairly tame and not prone to runaway IF constantly/thoroughly stirred in a cold water bath and the PE additions are done in a few steps with a couple minutes in between to make sure the temp isn't climbing which for me it never has.
I would guess the NO2 evolving when you heated it was likely decomposition of your PETN, that's probably where your yields went.

ManyInterests - 8-9-2023 at 17:54

Brining up the temperature too much toward the end of nitration isn't necessary with PETN, it's rather easily brought to full nitration by bringing it up to 25-30C in warm water for the last half an hour.
In my experience PETN is fairly tame and not prone to runaway IF constantly/thoroughly stirred in a cold water bath and the PE additions are done in a few steps with a couple minutes in between to make sure the temp isn't climbing which for me it never has.
I would guess the NO2 evolving when you heated it was likely decomposition of your PETN, that's probably where your yields went.

Duly noted. Next time I will simply allow the PETN to stay at room temperature for a while before simply crashing it in a large amount of ice cold water.

I will also use an excess of around 75% nitric acid and go as strong as 90%. I am hoping to have the yield that others have had (2.2g PETN per 1g PE) than the poor yield I got.

I will also time it and try to not to worry too much about the yellowing. It is probably not as bad as I made it out to be.

OneEyedPyro - 8-9-2023 at 20:34

A lot of procedures involve heating to around 40-45C for 20 minutes or so before crashing it out, I've tried it and found that 30C works about the same with less fumes to deal with. The yellowing may be indicative of impurities due to dehydration/ooxidation.
If you run a small batch at just above room temp you'll find decent yields, maybe not mid 90% but still acceptable.

DennyDevHE77 - 8-9-2023 at 22:24

I used 290ml of 90% HNO3 (purged of all NO2 contamination by blowing dry air through it) and 170ml of H2SO4.

So, as I understand it you used the sulfur-nitrogen method of nitration in one stage, but you used the proportions for 70% nitric acid. You should realize that too strong sulfur-nitrogen nitro mixtures oxidize PETN much easier than nitrates.

Correct nitration should be carried out as follows: Pentaerythritol is added to the prepared nitro mixture cooled to 10°C, the temperature is not allowed to rise above 15°C. If this limit is exceeded, thermally unstable compounds are formed, which will show themselves on further heating. After the addition of all pentaerythritol, give a rest of 5 min, continuing stirring.

Then the beaker with PETN is placed in a water bath with warm water. It is necessary to gradually raise its temperature to 25-30°C. The water in the water bath is then replaced by very hot water and the main heating to 50°C is started. When the temperature of PETN reaches 50-52°C feel free to take the beaker out of the water bath, and return it when the temperature drops below 50°C again. At this stage, the sulfo groups in PETN are replaced by nitro groups, this is called the transesterification reaction. It starts at +35°C but reaches an acceptable rate at +50-60°C.

full nitration by bringing it up to 25-30C in warm water for the last half an hour.

So no 25-30°C, it is not enough and therefore useless, or heat normally, at least to 50°C or pour into a bucket of water without heating at all, after a 5-minute soaking time. For PETN by this method, 20 min at 50°C is sufficient. From personal experience I can say that this is the most calm temperature, during all 20 min light yellow vapors are emitted, and no more. I not infrequently increased the temperature to 55-60°C, then more vapors are released and the reaction mass begins to bubble in 15 min. OneEyedPyro is right above, saying that PETN is not prone to escape. If you are concerned about nitrous oxide vapors and yellowing of the mixture, you can just blow into the beaker and blow out the nitrous oxide and the mixture will be white)))

The real sign of escape is a strongly bubbling, almost boiling mixture, that's when you can safely pour it into a glass of water. And I'll tell you right away that I had a few runaways a long time ago, when I chickened out and just did not dare to take a glass and pour it into the water. It began with a bright red fire in the center of the boiling mixture, after which the whole mass caught fire, with the release of large quantities of NO2, and since I did not use in my school days heat-resistant utensils, then when burning nitro-mixture glass burst in the water bath, the mixture was diluted with water, and the burning stopped. it remained only to ventilate the apartment from nitrogen dioxide. There was never an explosion in 3 runs.

However, with your mixture with 90% nitric acid I am almost sure that oxidation could start abruptly at 50°C.

And you really can not heat your PETN (but this will require longer cleaning), the yield will be on average 70-80%, or it is possible to heat for a short time, as at 50°C for 7-10 min of heating the yield already becomes about 90%, at full transesterification the yield is 92%. I often produce PETN, with 100g of pentaerythritol I consistently get ~220g.

In general, if you have 90%, you would be better off immediately nitrating with pure nitric acid, getting the same yield of 90%, but saving yourself from lengthy cleaning. Just in case, I will point out that nitration is carried out with 90-99% nitric acid at the rate of 100 g of acid per 20 g of pentaerythritol at a temperature of 20°C. This method is convenient for cleaning.

You see, PETN obtained by a two-stage or one-stage method through a nitro mixture is contaminated with mixed sulfoesters, which reduce its power and stability, since previously PETN was produced in two stages industrially, this issue is generally well studied. So, especially if you did not heat the mixture, you need to pour 9-10 parts of a 1% aqueous solution of sodium bicarbonate, and boil your PETN until it stops foaming. Instead of baking soda, you can use, for example, magnesium oxide or sodium carbonate, but here it is better to keep the temperature at 90°C, which is less convenient; at 100°C there will be slight decomposition.

It was quite an adventure since the the liquid during recrystalization turned orange!

Then recrystallization from boiling acetone with soda. And yes, the neutral solution of PETN in acetone, in principle, has a yellowish color, and even more so with traces of sulfoesters, at this stage they are completely destroyed. In the photo below I dropped what my PETN looks like in acetone, usually by the way it is even more yellow, here there is simply an excess of acetone.

I’ll also post a photo of what PETN looks like at 51°C after 10 minutes of heating; in this photo, the glass was removed from the water bath to prevent further heating. As you can see there are only small yellow vapors present here.

And the same advice) do not try to immediately filter PETN after pouring the nitro mixture into water, PETN obtained using the sulfur-nitrogen method is very fine and without vacuum filtration, its filtration takes a lot of time, it is better to let it settle to the bottom, and only then filter.

So the next time you make it, select the right mixture (or use pure nitric acid, if there are nitrogen oxides, you can add a little urea to it, it does not interfere with nitration), maintain a temperature of 10-15°C, gradually heat the mixture, and organize intensive mixing, especially at the heating stage.

Well, the last photo is the finished product)) there is exactly 1 kg, but in two different jars. The red one contains fine-crystalline PETN (you can see from the walls how much it stains the surfaces). in a transparent jar it is coarse-crystalline

[Edited on 9-9-2023 by DennyDevHE77]

Etanol - 9-9-2023 at 01:01

On the contrary, strong nitros mixtures usually form nitroesters very well.
I think it's not about the stiffness of the nitro mixture.

I used 88g of PE (98%, it was technical grade),
I used 290ml of 90% HNO3 (purged of all NO2 contamination by blowing dry air through it) and 170ml of H2SO4

Have you checked the concentration of your sulfuric acid?

A salt-ice mixture is not required. A ice-water mixture is enough.

Do not hurry. Pentaritritole is poorly dissolved in HNO3-H2SO4 mix.
Add should take at least 15 minutes. After that, let the temperature very slowly rise to 20C. Wait 15 minutes. Never stop stirring!

Only if everything is fine, smoothly raise the temperature to 50C.
You may not heat the reaction mixture. Then, after stabilization in an aqueous solution of soda and recrystallization, the output of the product will decrease by 5-10%.

[Edited on 9-9-2023 by Etanol]

DennyDevHE77 - 9-9-2023 at 01:26

On the contrary, strong nitros mixtures usually form nitroesters very well.

PETN appears to be a small exception to this pattern. Once I tried to nitrate it with a mixture of 95% nitric acid and 98% sulfuric acid, I almost got a fountain, the temperature rose very sharply. A friend who used distilled nitric acid with phosphoric anhydride 99.7% with 98% sulfuric acid had a problem and it ended in failure. Maybe for 90% the difference is not so significant, but the reaction proceeds much worse than with 70% and especially 58% nitric acid, perhaps due to a very thick mixture and poor heat removal. Therefore, in the presence of fuming nitric acid, the best option would be to obtain PETN directly, without sulfuric acid.

And finally, I don’t remember a single method for producing PETN using highly concentrated nitro mixtures. In the books of Naum, Stettbacher and Solonina for 1920-1930, PETN was obtained by esterification of pentaerythritol in >90% nitric acid, and straining with sulfuric acid (which now sounds like a waste of sulfuric acid), there was a two-stage method, when sulfate was obtained and then nitrated > 90% nitric acid. Then they switched to a one-stage process, without using sulfuric acid at all. And the method through dilute nitric acid and concentrated sulfuric acid seems to have been invented by the Czechs in 2002, and it seems that this method was then spread to home hobbyists.

Well, it is obvious that for 90% of nitric acid and sulfuric acid a lot was taken, it is necessary to recalculate how much is needed according to the schedule from Urbansky. But here I am no longer a helper((

A salt-ice mixture is not required. A ice-water mixture is enough.

It’s not for nothing that Ethanol mentioned this, nitration of pentaerythritol at too low a temperature 0-5°C leads to the formation of a certain amount of PETRIN, this is pentaerythritol trinitrate, a liquid explosive at room temperature. It was previously used in the USA for all sorts of plastisol explosives. On the other hand you can just add your pentaerythritol faster, it is important that the temperature is kept at 10-15°C

[Edited on 9-9-2023 by DennyDevHE77]

DennyDevHE77 - 9-9-2023 at 01:39

Ethanol, since the administration will still transfer all the latest messages to another topic (and rightly so), let me ask, do you know how to calculate the proportions from the diagram? This would be very useful to know.

I thought so, you need to select such a value of acid concentration so that it is on the lower border of region 1. After that, find out the final concentration of acids, this point will be somewhere higher and to the left. Then you need to calculate how much nitric acid has decreased (or water has been added) and create a proportion to this mixture. And here I’m already slowing down... Or maybe my logic is completely wrong.

If you know this, could you write down at your leisure how to count correctly. (Or maybe back in 2002 this was already covered here)

[Edited on 9-9-2023 by DennyDevHE77]

Etanol - 9-9-2023 at 02:04

do you know how to calculate the proportions from the diagram?

You can’t count anything according to this diagram. It is not even known it refers to the initial acid or to the spent acid. There are no nitration conditions, an excess of nitric acid to pentaritrite, no nitration time.
If you can find and show the source that Urbansky refers to, then we can do something.

There are reasons not to trust this diagram.

[Edited on 9-9-2023 by Etanol]

ManyInterests - 9-9-2023 at 18:26

Quote:

Then the beaker with PETN is placed in a water bath with warm water. It is necessary to gradually raise its temperature to 25-30°C. The water in the water bath is then replaced by very hot water and the main heating to 50°C is started. When the temperature of PETN reaches 50-52°C feel free to take the beaker out of the water bath, and return it when the temperature drops below 50°C again. At this stage, the sulfo groups in PETN are replaced by nitro groups, this is called the transesterification reaction. It starts at +35°C but reaches an acceptable rate at +50-60°C.

Ahh, so THAT'S why I got my yield so low. I guess if I am going to use the H2SO4 + HNO3 the HNO3 does need to be lower than RFNA. OK that does make sense. If I am going to use nitric acid stronger than that, I should only use WFNA if/when I have it. It's starting to click.

Quote:

And you really can not heat your PETN (but this will require longer cleaning), the yield will be on average 70-80%, or it is possible to heat for a short time, as at 50°C for 7-10 min of heating the yield already becomes about 90%, at full transesterification the yield is 92%. I often produce PETN, with 100g of pentaerythritol I consistently get ~220g.

In general, if you have 90%, you would be better off immediately nitrating with pure nitric acid, getting the same yield of 90%, but saving yourself from lengthy cleaning. Just in case, I will point out that nitration is carried out with 90-99% nitric acid at the rate of 100 g of acid per 20 g of pentaerythritol at a temperature of 20°C. This method is convenient for cleaning.

You see, PETN obtained by a two-stage or one-stage method through a nitro mixture is contaminated with mixed sulfoesters, which reduce its power and stability, since previously PETN was produced in two stages industrially, this issue is generally well studied. So, especially if you did not heat the mixture, you need to pour 9-10 parts of a 1% aqueous solution of sodium bicarbonate, and boil your PETN until it stops foaming. Instead of baking soda, you can use, for example, magnesium oxide or sodium carbonate, but here it is better to keep the temperature at 90°C, which is less convenient; at 100°C there will be slight decomposition.

I'm still not sure what you mean by two-stage or one-stage. But I will take it at this point that I should do the following for my successive PETN syntheses.

1: Either use 99% WFNA alone, or 70% HNO3 + H2SO4. If using WFNA and there is some yellowing, a touch of urea will clear it up.

2: don't let temperatures be too cold, keep at 10C and don't let it go above 15C until all the PE is added. I understand why. PETN needs that temperature otherwise a trinitrate will form. This could also be why my yield was so bad in addition to other factors.

3: Let it stay at 25-30C for a while (30 minutes) and not necessarily heat it beyond that. But it can be heated to 40 or 50C for around 10 minutes.

4: After washing with lots of water and sodium carbonate water, boiling it in carbonate solution is a good idea? I assume a lot of stirring is needed here.

I'll get to the recrystalization part later.

DennyDevHE77 - 9-9-2023 at 20:22

I'm still not sure what you mean by two-stage or one-stage.

Three methods of producing PETN are usually distinguished:
1. Production in one stage through nitric acid of 90-99% concentration (the main modern method of production of PETN in the industry).
2. Production in two stages. First, pentaerythritol sulfates are obtained by dissolving pentaerythritol in concentrated sulfuric acid. And then nitrate the sulfates with fuming nitric acid at 50-60°C (obsolete method of PETN production in the industry).
3. Production in one stage through sulfuric-nitric acid mixture.

Let it stay at 25-30C for a while (30 minutes)

No, I repeat, the transesterification reaction, that is, the substitution of sulfogroups for nitro groups begins at +35°C, and goes more or less quickly at 50-60°C. So after adding the last part of pentaerythritol to the nitro mixture, wait 5 min, and then you can immediately pour into water, well or start heating.

I assume a lot of stirring is needed here.

The boiling water causes the PETN to float on its surface and itself agitates it on its surface. But a good idea from time to time is to sink down out the PETN floating on the surface with a skimmer. Usually one hour of boiling is enough.

[Edited on 10-9-2023 by DennyDevHE77]

ManyInterests - 9-9-2023 at 21:58

OK sounds simple. So upon the final addition, either dump or start heating. I'll probably start heating since I don't want any delay.

I'm taking a bit of a break from most chemistry for now. But I will be back at it in a month or so.

Etanol - 9-9-2023 at 22:03

Boiling is an incorrect description of the procedure. Literally, stiring in a 1% aqueous solution of sodium bicarbonate at a temperature of about 90°C with pH control, not 100° C. Bicarbonate decomposes and hisses. It looks like a boil, but it is not a boil of water at 100C. When boiling at 100°C, the PETN decomposes partially.

2: don't let temperatures be too cold, keep at 10C and don't let it go above 15C until all the PE is added. I understand why. PETN needs that temperature otherwise a trinitrate will form. This could also be why my yield was so bad in addition to other factors.

The optimum temperature when adding pentaritrite is +5 ... +15°C.

There are two reactions that require exposure at elevated temperatures:
transformation of trinitrate into tetranitrate at 15...25°C.
and the transformation of sulfate into tetranitrate at 40...60°C.
These are two stages that require each control. You should not heat the mixture up to 50°C, while there are pentaeritritole and its trinitrate.

For WFNA 90%, you can increase its excess to 80 grams of WFNA to 10 grams of pentaeritritole and do without sulfuric acid and without heating,
That is, after adding, the mixture should be stirred 30...45 minutes at 20°C and pour into water with ice.

Or you can leave 50% excess of WFNA and thread by mixture:
10 g of pentaeritritole
30 g of WFNA 90%
20 g of sulfuric acid 96%
Temperature when adding PE is +5...+15°C,
then stirring at 15...20°C,
then stirring at 50...60°C,
then cool and pour into the water with ice.

Or
10 g of pentaeritritole
50 g of WFNA 90%
10 g of sulfuric acid 96%
Temperature when adding PE is +5...+15°C,
then stirring 30...45 min at 15...20°C,
without heating!
then cool and pour into the water with ice.

[Edited on 10-9-2023 by Etanol]

DennyDevHE77 - 9-9-2023 at 23:11

Literally, stiring in a 1% aqueous solution of sodium bicarbonate at a temperature of about 90°C with pH control, not 100° C. Bicarbonate decomposes and hisses.

I've read about it in some industrial chemistry books. Usually they would heat the soda solution to 90°C, then add the PETN, and stir for an hour.

But I've also seen descriptions of laboratory methods where PETN was poured into the soda solution and heated to boiling, boiled until the foam stopped forming.

Having tried both methods with baking soda and soda ash, I have come to the conclusion that when boiling with baking soda, a very small amount of PETN is lost. In fact, I may have been losing them on the filter.

That said, when boiling with sodium carbonate (soda ash), the PETN decomposes significantly, and it's really worth maintaining 90°C there.

Also PETN boiled with magnesium oxide quite calmly, but then it was necessary to separate them in acetone.

In the photo below PETN is boiled at 105°C (tap water), here a little over 100 grams.

transformation of trinitrate into tetranitrate at 15...25°C

Thanks for that info, I was getting some trinitrate from nitration at 0-5°C. And so I thought (apparently wrongly) that at nitration at 10-15°C trinitrate is no longer formed, but I always gradually heated PETN, so apparently without accidents. Then, in all likelihood, keeping PETN at 20-30°C makes sense, I must apologize to OneEyedPyro. Another thing is how justified it is, will it help to raise the output by at least 5%?

In the near future I plan to get trinitrate, but unfortunately with high yield it can be obtained only through acetic anhydride, at nitration at low temperature yield usually 40-50%. As far as I know, trinitrate can be treated with alcoholic alkali solution and bis-(nitratomethyl)oxetane can be obtained. A fusible base for explosives. But I have not found much information on the forum.

Etanol - 9-9-2023 at 23:29

But I've also seen descriptions of laboratory methods where PETN was poured into the soda solution and heated to boiling, boiled until the foam stopped forming.

I think this is a shorthand description.
Bicarbonate decomposes into carbonate when boiled.

Another thing is how justified it is, will it help to raise the output by at least 5%?

This will help by 5-10% if all other conditions are met successfully, when the yield is 85 or 95%.

[Edited on 10-9-2023 by Etanol]

ManyInterests - 19-10-2023 at 17:05

I am pushing the thread back up since I have a question to ask... two questions maybe.

The first one is since ammonium nitrate will work. I want to know if the nitrogen level of the ammonium nitrate matters all that much? Meaning if I get my hands on cold-pack grade ammonium nitrate (27%) will it work, or does it have to 32%+ for it to work better? Ditto for aiding in RDX synth and other chemical reactions.

The second question: Since I ordered a good deal of pure calcium nitrate, and that can be used to make any other nitrate I want, if I do a double displacement reaction with ammonium carbonate/bicarbonate, will the resulting ammonium nitrate be 34% or will it be a lower nitrate content? If it is a lower content, is it possible to increase the nitrogen content of that AN? What about using the sodium bisulfate + ammonia method?

I am saying this because what I thought might be ammonium nitrate from the fertilizer section of my hardware store proved to be a disappointment.

Microtek - 20-10-2023 at 02:10

Pure ammonium nitrate is 35% nitrogen. If you get something with less than that, it has some impurities. If you don't know what these impurities are, you are shooting in the dark if you use it in nitrations. Some cold packs contain urea instead of AN but this is not the issue here, since urea has a higher nitrogen content than AN. It could conceivably be water or maybe ammonium chloride, but you will have to do some actual chemical analysis if you can't find a proper list of ingredients.

Your second question makes me think you should read up on introductory inorganic chemistry. I suggest finding some high school texts as this will answer all of these questions. It might also save you some money in the future.

ManyInterests - 13-12-2023 at 15:46

Bumping this up since I saw a video on YouTube that described a one-pot process. While it is interesting (and not very complicated. It simply involved a larger amount of some reagents and a steady increase of heat to a point. Similar to picric acid actually). But he did mention in purifying the final product, he said that either sodium metabisulfite (which I have) or 91% isopropyl alcohol will work to purify it. Is this true? Because I can get any 91% or 99% IPA much more cheaply and easily than sodium metabisulfite.

Sir_Gawain - 13-12-2023 at 16:50

Was it this one?

ManyInterests - 13-12-2023 at 17:10

Quote: Originally posted by Sir_Gawain

Was it this one?

Nope that is the older one (still excellent and I intend to follow it as well to see which one gets the best yield), but I am referring to this one:

https://youtu.be/H0OI3hyjkFM

edit: He starts to talk about recrystalization and final purification around the 23:35 mark.

Edit2: While I'm at this. While I am looking up on the red water issue and how to properly dispose of it. Is there some way of safely neutralizing it so it can be poured down the drain, or does it have to be incinerated? If that is the case, will a blowtorch do? Anything I should know about burning this stuff from a safety perspective? Beyond the fumes and such?

[Edited on 14-12-2023 by ManyInterests]

[Edited on 14-12-2023 by ManyInterests]

Sir_Gawain - 14-12-2023 at 09:22

Just evaporate it down and throw it on a fire.

ManyInterests - 16-12-2023 at 05:05

Quote: Originally posted by Sir_Gawain

Just evaporate it down and throw it on a fire.

You see that's my issue. I always overcomplicate everything. That sound very simple. Finding a place to safely incinerate it will be a mild challenge (I live in a big city. I can't exactly go to a public park with people around and burn stuff) but it is dooable.

OneEyedPyro - 17-12-2023 at 16:29

Edit2: While I'm at this. While I am looking up on the red water issue and how to properly dispose of it. Is there some way of safely neutralizing it so it can be poured down the drain, or does it have to be incinerated? If that is the case, will a blowtorch do? Anything I should know about burning this stuff from a safety perspective? Beyond the fumes and such?

[Edited on 14-12-2023 by ManyInterests]

[Edited on 14-12-2023 by ManyInterests]

There's a time and place for everything. Can't you simply store it until a good opportunity arises to burn it? There's no real eco friendly way to get rid of the byproducts I'm aware of but incineration is probably your best bet. Maybe prepare a campfire as in ready to light ahead of time then come back at night with the waste, light the fire and walk away.
This is assuming it's not a fire hazard area. I'd evaporate it down in a disposable aluminum cake pan and place it on the fire.

chem101st - 17-12-2023 at 21:40

Dugan uses an overhead stirrer in that video. Is that necessary due to viscosity or something? Or is a standard stir bar fine?

ManyInterests - 7-1-2024 at 12:33

No I can store it. I've store waste products until I could safely dispose of them for a while. I know how and where to do that. If incinerating it is the only option, then that is what I will do. I will find an isolated place in a park where you can start a small camp or cook fire, but I can also go into the woods when fire alerts are at a minimum (this is usually during winter time or after it has rained, and the ground is quite wet and moist...) and get my fire extinguisher and other fire fighting gear to make sure no issues arise just in case.

Quote: Originally posted by chem101st

Dugan uses an overhead stirrer in that video. Is that necessary due to viscosity or something? Or is a standard stir bar fine?

There's another video where someone just uses a stirbar. Dugan's method is only a little different than the other guy (who uses a 2-step method of making TNT).

However I do have one question: Dugan used isopropyl alcohol in place of sodium sulfite/bisulfite to purify it. Will 99% isopropyl alcohol work because TNT does have some slight solubility in water I would rather use something it isn't soluble in to clean it... unless I am mistaken. I know that TNT is soluble in ethanol more than water, but what about IPA?

Sir_Gawain - 8-1-2024 at 08:33

Trinitrotoluene is much more soluble in isopropyl alcohol than water. Didn’t Dugan recrystallize it from IPA?

DennyDevHE77 - 8-1-2024 at 11:31

The big advantage here is that cleaning is optional. Of course, it can be recrystallized from alcohol or acetone, it can be melted in boiling water and mixed with compressed air, or it can be done with the addition of sodium sulfite, this is generally an industrial cleaning method, it can be compressed in layers of newspapers so that they absorb dinitro derivatives. You can add calcium silicate so that it absorbs TNT oil.

ManyInterests - 8-1-2024 at 14:42

Quote: Originally posted by Sir_Gawain

Trinitrotoluene is much more soluble in isopropyl alcohol than water. Didn’t Dugan recrystallize it from IPA?