Sciencemadness Discussion Board - New to energetic materials, need advice

Your acid is definitely too weak. Make conc acid- it is not a great problem. Stainless steel vessel is good for distillation. Or try to use some nitrate, dissolved in H2SO4. Or add some phosphorous pentoxide to your weak acid.

jessjabb - 28-5-2019 at 19:33

Thank you guys for the advice! ill try to keep you updated

jessjabb - 28-5-2019 at 19:54

Ok do you think I could dissolve Ammonium Nitrate into the acid? I also have potassium nitrate. When I attempted to synth PETN the first couple times the PE would dissolve completely into the NA ( I didn't use sulfuric acid) creating a crystal clear fluid that would just decompose into nitrogen dioxide and smoke up my garage with orange vapor. Do I need sulfuric or can I synth PETN without it?

Microtek - 28-5-2019 at 23:26

Using 67% nitric acid alone will not work properly, but either nitric acid of 95% or more OR 67% nitric plus a suitable amount of concentrated sulfuric acid to bind the water in the nitric will be fine.

If you have P2O5 you can use that for dehydrating your nitric acid either in situ (like you would do with sulfuric acid) or in preparation for distillation, but you could also use it for a very efficient synthesis of HMX (for this you also need a slight amount of acetic anhydride though).

caterpillar - 29-5-2019 at 02:09

There seems to be some difference of opinion on this matter around here. I think most people agree that using concentrated nitric acid is better, but I think lower concentration should also work. As for example in Urbanski nitration tables (which the PETN.XLS is based on). I have done it. My only question is whether maybe I got the di-penta version, which is also explosive.

Using weak acid, you'll definitely get not tetranitrate but di-or trinitrate. If you have P2O5 you can use it for many interesting things. In your case, you need to bind water in weak nitric acid. Make a simple calculation- how much you need add to get 98-100 percent acid. Add pentoxide in small portions and do not let temp be hi.

Regarding the phosphorous pentoxide, can you give me a reference or more detail on that. I have looked around and not able to find a method using it. I have a source for inexpensive P2O5. I would love to try that. Doesn't P2O5 have some handling issues? Sucks up water out of the air and turns into phosphoric acid, right?

caterpillar - 29-5-2019 at 02:18

Of course, I ment solution of some nitrate in sulfur acid. maybe, NH4NO3 is better due to its better solubility in sulfuric acid. And keep temp below 20 Celsius. I could recommend this: Jai_Prakash_Agrawal,_Robert_Hodgson-Organic_Chemistry_of_Explosives-Wiley(2007) The last part described nitration with N2O5- you may try some methods, dissolving P2O5 in nitric acid.

jessjabb - 29-5-2019 at 09:20

Ok Ill pick up a bit of sulfuric acid, because I have done the flask in cooling water method with just nitric acid and it does not work.

twelti - 29-5-2019 at 10:31

I thought the lower nitrates of PETN were soluble in water, thus would not survive recrystalization?

As for P2O5, I thought that was used in distillation of NA, not direct nitration. If you still have to distill it, is there any advantage of the P2O5 over other approaches?

caterpillar - 29-5-2019 at 11:54

I thought the lower nitrates of PETN were soluble in water, thus would not survive recrystalization?

As for P2O5, I thought that was used in distillation of NA, not direct nitration. If you still have to distill it, is there any advantage of the P2O5 over other approaches?

No, you do not need to perform distillation- only add P2O5 to bind excess of water. If you wanna get concentrated HNO3, use some nitrate (K or Na) and sulfur acid. You may use some simple apparatus like a coffee pot- steel doesn't react with conc HNO3. Use diluted HNO3 to make styphnic acid of hexamine dinitrate or urea nitrate. Last ones are useful precursors to something more interesting.

twelti - 29-5-2019 at 12:05

I don't mean to be dense, but can you point me to a synthesis where I can just add P2O5 to 70% HNO3 and nitrate to RDX? I would much rather do that than make WFNA, but I have not been able to find such a procedure.

Simoski - 29-5-2019 at 12:42

Make ETN, just need erythritol, nitric, sulphuric and ethanol.

I made mine with 50% nitric no problem.

caterpillar - 29-5-2019 at 14:13

Try yourself. Add P2O5 to your HNO3 and cool the mix. make hexamine dinitrate, using diluted HNO3. Normally to perform nitrolysis of hexamine one has to use a large amount of nitric acid- 1: 10. If you use dinitrate, you may calculate the equivalent amount of dinitrate. Read Agrawal and Hodgson.

twelti - 29-5-2019 at 15:37

Which method are you talking about?
From Agrawal and Hodgson:

The extreme sensitivity of (238) to
hydrolysis means that nitrolysis has to be conducted under anhydrous conditions using sulfur
trioxide or phosphorous pentoxide dissolved in fuming nitric acid.

Still fuming nitric acid.

jessjabb - 29-5-2019 at 18:02

Which method are you talking about?
From Agrawal and Hodgson:

The extreme sensitivity of (238) to
hydrolysis means that nitrolysis has to be conducted under anhydrous conditions using sulfur
trioxide or phosphorous pentoxide dissolved in fuming nitric acid.

Still fuming nitric acid.

I am doing it in this method http://www.powerlabs.org/chemlabs/petn.html
I will do smaller scale, like a half batch with only 5g or 2.5g to get to know the reaction a little better.

twelti - 29-5-2019 at 18:11

That is basically the same method I used. I'm going to just bit the bullet and make some fuming nitric acid. After the last couple of experiments, I'm not really convinced I did get PETN after all. I'm going to make it with fuming nitric acid and compare.

caterpillar - 29-5-2019 at 19:14

Not this. Or you have (238- known as White Salt)? In such a case, you may try it. But if you have not (238), use the first method- hexamine + fuming nitric acid. I only recommend to use not the pure hexamine but its dinitrate. Again- make conc nitric acid, adding P2O5 to diluted nitric acid. Add slowly hexamine dinitrate. Any problem with calculations of necessary amounts of chems?

twelti - 30-5-2019 at 08:51

I think we are going around in a circle. Regarding the use of 70% NA, you said:
"Or add some phosphorous pentoxide to your weak acid"

It sounded as if you were saying the synth could be done using the weaker acid, by adding the P2O5. From your other comments and from the source you cited, it looks like the weaker acid won't work.

caterpillar - 30-5-2019 at 12:18

I think we are going around in a circle. Regarding the use of 70% NA, you said:
"Or add some phosphorous pentoxide to your weak acid"

It sounded as if you were saying the synth could be done using the weaker acid, by adding the P2O5. From your other comments and from the source you cited, it looks like the weaker acid won't work.

??? Sorry? When the appropriate amount of P2O5 has been added to weal (63-67%) HNO3, it becomes STRONG. Excess of water is bind and you have HNO3 + H3PO4. So simple.

MineMan - 30-5-2019 at 16:26

I have two dueling pistols. The only catch is they must be filled with an energetic you made.

Catapiller. I personally would fill it with NiAGP and AP for gas generation.

jessjabb - 30-5-2019 at 19:12

Ok Ill pick up a bit of sulfuric acid, because I have done the flask in cooling water method with just nitric acid and it does not work.

Alright I synthesized something that I believe is PETN. I did a small test run and ended up with a fine powder, then I did full scale with 10g of PE, I filtered off the precipitate and dissolved the powder in acetone after it dried, I diluted the acetone and sand like crystals precipitated out. I am currently in the process of drying said crystals. How would you recommend I test it?

caterpillar - 30-5-2019 at 19:39

Ok Ill pick up a bit of sulfuric acid, because I have done the flask in cooling water method with just nitric acid and it does not work.

Wrap small amount ( 0.2-0.5 gr ) in tinfoil, put it onto a steel plate and strike with a hammer.

caterpillar - 30-5-2019 at 19:41

Quote: Originally posted by MineMan

I have two dueling pistols. The only catch is they must be filled with an energetic you made.

Catapiller. I personally would fill it with NiAGP and AP for gas generation.

I made only black powred. All but it that I made were explosives, inappropriate for guns.

twelti - 31-5-2019 at 09:00

Hi caterpillar, I'm readin more of the Agrawal/Hodgeson text. It is pretty interesting (even for a non-chemist). What I'm not sure is how the use of P2O5 would affect practical synths of RDX or HMX or anything for that matter. I get that it agressively sucks up water. i haven't been able to find where it says that dilute NA+P2O5 can be substituted for WFNA. It seems that where it is used, it is still use with highly concentrated NA. I imaging there must be some potential advantages of using it, but will it allow me to ditch the WFNA? Or, put another way, does the phosphoric acid created when the P2O5 sucks up the water interfere with subsequent reactions?

caterpillar - 31-5-2019 at 10:18

Hi caterpillar, I'm readin more of the Agrawal/Hodgeson text. It is pretty interesting (even for a non-chemist). What I'm not sure is how the use of P2O5 would affect practical synths of RDX or HMX or anything for that matter. I get that it agressively sucks up water. i haven't been able to find where it says that dilute NA+P2O5 can be substituted for WFNA. It seems that where it is used, it is still use with highly concentrated NA. I imaging there must be some potential advantages of using it, but will it allow me to ditch the WFNA? Or, put another way, does the phosphoric acid created when the P2O5 sucks up the water interfere with subsequent reactions?

This is just simple basic chemistry. Anhydrides react with water and produce the corresponding acid. Make the corresponding experiment with a small amount of acid- let's say, 20 gr. Some info hardly can be found in the literature. For example, you may read in many texts that you must use white acid- free of NOx. But when I used hexamine dinitrate I successfully made RDX, using the usual product of distillation- yellow nitric acid. That yellow acid burned pure hexamine, yeah.

twelti - 31-5-2019 at 11:48

Yes I get that, but if you already are starting with distilled ("yellow" i.e. RFNA), how is using the P2O5 any better than, say Urea and/or air to get white NA?

caterpillar - 31-5-2019 at 16:17

Yes I get that, but if you already are starting with distilled ("yellow" i.e. RFNA), how is using the P2O5 any better than, say Urea and/or air to get white NA?

I got distilled (very conc- 98-100%) nitric acid. It was yellow- obviously, there were NOxs, but not much. RFNA contents up to 30% of NOx and usually is used as an oxidizer in liquid propellants. You have 60+ percent nitric acid. I had no need in P2O5, but you do have. Again- I started to add hexamine and what I saw was NOx emission. Later I used dinitrate instead and I got RDX. Add dinitrate to a strong acid (weak plus the necessary amount of P2O5) and wait for half of one hour. Then you may drop the liquid in a large volume of cold water, but it would be better to perform so-called oxidization. Assume you have 100 gr of nitric acid with dissolved hexamine (dinitrate). Prepare 30 gr of water and a small amount of your diluted nitric acid. Drop slowly that solution and water simultaneously into the weak acid. it will boil and emit NOx. But finally, you'll get RDX of better quality without unstable linear fragments (and larger crystals).

Herr Haber - 31-5-2019 at 16:19

??? Sorry? When the appropriate amount of P2O5 has been added to weal (63-67%) HNO3, it becomes STRONG. Excess of water is bind and you have HNO3 + H3PO4. So simple.

P205 is here simply used to bind water. Same as oleum (S03 in H2SO4).

You can bind water from your "weak" acid or, as the synth mentioned above says use fuming nitric acid AND P2O5 to bind the water from the reaction. I suppose you get better yields in more anhydrous conditions.

twelti - 31-5-2019 at 18:04

OK, so there IS a route to RDX that does not involve making fuming NA. Hexamine dinitrate can be made with 70% NA and then final nitration to RDX with again 70% NA+P2O5. If I'm understanding correctly. Thanks for your patience.

Can P2O5 be used similarly for nitrating pentaerythritol? ... nitric esters?

[Edited on 1-6-2019 by twelti]

caterpillar - 31-5-2019 at 18:50

OK, so there IS a route to RDX that does not involve making fuming NA. Hexamine dinitrate can be made with 70% NA and then final nitration to RDX with again 70% NA+P2O5. If I'm understanding correctly. Thanks for your patience.

Can P2O5 be used similarly for nitrating pentaerythritol? ... nitric esters?

[Edited on 1-6-2019 by twelti]

Yes. At least, I think so. When you add P2O5 to 70% nitric acid, you get highly conc acid- even with N2O5 (depends on the amount of P2O5). Oh, you may try K-method, described by Hudgdson and Agrawal.

twelti - 31-5-2019 at 20:38

I had always heard about P2O5 being expensive but I found it at Firefox for around $21/lb.

caterpillar - 31-5-2019 at 22:43

I had always heard about P2O5 being expensive but I found it at Firefox for around $21/lb.

Oh, mate, when I was young I bought it in the special shop with chems. 800 gr cost like 2-2.5 liters of beer. Phenol was twice cheaper. And in 90th I bought 12 kg of hexamine- the price was more than ridiculous. But me brainless idiot kept it at the place where the water came from the roof just on the box. Well, I got the confirmation of hi solubility of hexamine...

Herr Haber - 1-6-2019 at 09:11

Man, I've been reading most of your posts and I can promise you that you will LOVE reading all 4 tomes of Urbanski.

All your (legitimate) questions will get their answers in the relevant chapters and more. Also, you will gain quite a lot of understanding.
Several pathways for every EM you can think of, lab settings, industrial settings, historical anecdotes, everything you need to know about sensitivity, vod etc.
I know it's not the first time I'm saying this on the forum but those books are as much about history as they are about chemistry.

Oh, and look at the dates when they were written then read Agrawal.
Quite the jump in history and the complexity of current or specialized EM's

twelti - 1-6-2019 at 10:00

Having eard so much about Urbanski, I hsve scanned it/them. So much information! For a non-chemist it can be overwhelming. Im learning though. I found Cooper (Explosives Enigineering) to be quite informative and good starting place in many respects.

I still cannot find a solid answer on whether dilute NA and P2O5 can be used to nitrate HDN. I have some P2O5 on the way...

MineMan - 1-6-2019 at 23:29

Cooper is good. Cooper has stuff most other books do not. I think the absolute best book is the chemistry of high energy materials by the prof in Germany who has like 30 grad students. His book is cheap for a textbook to. It is the best organized and most informative and up to date. Don’t get any books by the Indian author arwgal. I have one of his books too much money for too little.... it’s too generic and just to technical for no other purpose of being technical. It’s like he’s trying to show off.

There is a 2019 version of the book I mentioned. Again. I heave many textbooks on the subject. The German one is nearly all of them combined and it’s a fun read.

caterpillar - 2-6-2019 at 01:39

Having eard so much about Urbanski, I hsve scanned it/them. So much information! For a non-chemist it can be overwhelming. Im learning though. I found Cooper (Explosives Enigineering) to be quite informative and good starting place in many respects.

I still cannot find a solid answer on whether dilute NA and P2O5 can be used to nitrate HDN. I have some P2O5 on the way...

Damn, mate, are you an amateur or theologist? Make this experiment. It is very simple. Not all that is written in books is the truth either- some texts skip important details. (to say nothing about dear Jared...)

twelti - 3-6-2019 at 07:18

Quote: Originally posted by MineMan

Cooper is good. Cooper has stuff most other books do not. I think the absolute best book is the chemistry of high energy materials by the prof in Germany who has like 30 grad students. His book is cheap for a textbook to. It is the best organized and most informative and up to date. Don’t get any books by the Indian author arwgal. I have one of his books too much money for too little.... it’s too generic and just to technical for no other purpose of being technical. It’s like he’s trying to show off.

There is a 2019 version of the book I mentioned. Again. I heave many textbooks on the subject. The German one is nearly all of them combined and it’s a fun read.

Klapotke right.

twelti - 3-6-2019 at 08:01