Sciencemadness Discussion Board - Erythritol Tetranitrate

Erythritol Tetranitrate

Madog - 15-11-2003 at 11:45

For those who don't know, Erythritol is a new low cal sugar subsitute.
http://www.sciencemadness.org/scipics/erythritol.gif

i used the pcedure posted on E&W by AXT

33ml of H2SO4 were added to 20g KNO3, they were blended, set in a salt ice bath and allowed to cool to about 10C. 5 grams of Erythritol were added in portions, the temp didn't rise above 15C. It was stirred alot and let sit in the ice bath for 30 minutes. the product was filtered and recrystalized from acetone. Final yield was a very embarassing 0.8g!

argh! longer nitration time, i thought. So i did the same thing again but let it go overnight. next morning i filtered, purified, etc. yield was 8.5g from 5g Erythritol. now thats wht im talkin' about! thats 1.7g ETN per g Erythritol.

.5g was pressed into a straw and taped to a block of wood, set to be initiated with .2g HMTD.

The block was placed on the ground, fuse lit, and a large rusty metal bucket placed on it to cover it, a chunk of cinder block was placed on the bottom of the bucket.

the bucket was knocked over, the bottom was 40% ton off, and there was an indent in the shape f the cinder block on it.

the piece of wood, fairly hard stuff i say, dented in around 7mm or so

i plan to do more experimention, perhaps some power comparisons, fueling, etc. i'll be sure to let you guys know about anything worthy.

the pics:
http://www.sciencemadness.org/scipics/etn1.jpg
http://www.sciencemadness.org/scipics/etn2.jpg
http://www.sciencemadness.org/scipics/etn3.jpg

Etn syntesys

rolfiboy - 16-12-2003 at 02:45

Hi Ive tryet the same metod as axt and found out that the temperature around 20 - max 25 celsius would give much larger yeilds.

Im sorry for my langue

AngelEyes - 16-12-2003 at 05:59

All well and good, but has Erythritol been approved for use here in the UK? I have searched the net, and online health stores like GNC etc, but cannot find it at all. Some have xylitol / sorbitol, but no one carries Erythritol. Are sorbitol or xylitol potential candidates for nitration?

Nevermore - 16-12-2003 at 09:19

erythritol is not available yet as sugar substitute in old europe, should be approved in this year, then will take some time till it will be distributed, so all the other sources are non OTC at now.
Sorbitol and Xylitol are good nitration candidates, as well as mannitol, dulcitol, lactose..
each one of them has its problems and is good points but most of them are easy to nitrate!

flashpoint - 16-12-2003 at 22:40

I hear from E&W, this is a powerful explosive, does it have to be detonated?....or is there another way of setting a charge off...I'm guessing this is a secondary explosive...therefore I suppose it needs to be det to be set off...

Nevermore - 17-12-2003 at 12:27

you want to set it off?
you can hammer it, warm it very fast up to 200°C, grind it, or stuffs like that..

Madog - 17-12-2003 at 14:08

its very powerful. see here.

http://www.sciencemadness.org/scipics/PETNvsETN1.jpg
http://www.sciencemadness.org/scipics/PETNvsETN2.jpg

sorry, i kept forgettingto post these. the target was a thin steel AOL CD tin that came in the mail. .5g of each explosive initiated by .2gHMTD, all pressed in astaw in configurations as close to identical as i could do.

PETN's higher bristance is clear, the hole is cleaner, less deformation in the plate and the hole is close but apears a little bigger. there is also 9 sections of metal protrudeing from the exit side. there are only 7 on the ETN one.

the other day i found a can of silly string in my house and i decidedto blow it up, i used an unmeasuredamount of ETN in a straw, musta been about .3g or so. it blew a nice hole in the can, which was unused. and there was huge chunks of green silly crap all over.

flashpoint - 17-12-2003 at 19:06

damn! You should've blown the CD's up too

Anyhow...do you use electrical ignition for the straw det's?

[Edited on 18-12-2003 by flashpoint]

hey flashpoint

Polverone - 17-12-2003 at 21:14

Your one-line response didn't add much. If you want to chat, contact members through U2U messages, instant messaging, or e-mail.

flashpoint - 18-12-2003 at 09:19

Sorry Polverone, I was just curious it he was using fuse or electrical det. I was trying to figure out what U2 was, guess that's the messenger

Thanks.

Bob - 28-6-2004 at 12:39

So I made a batch of white powder that SHOULD be ETN. It had condensed drops of liquid in the flask of ETN after a day storage. When I dried it, it melted earlier than the 60 degrees I expected. Is there water in it?

[Edited on 28-6-2004 by Bob]

DiPentaErythrit - 29-10-2004 at 11:14

So I made a batch of me !!!!!

The_Davster - 29-10-2004 at 13:43

Was that really worth bringing up a 4 month old thread? :mad:

Vikascoder - 19-11-2012 at 08:41

Can anyone post the procedure of making ETN since I have no access to E&W forms please post .

virgilius1979 - 19-11-2012 at 11:39

I successfully produced ETN using drain cleaner sulfuric acid (92%) - in excess and NaNO3 (NH4NO3 dissolves even better) and keeping the temperature at about 20-22C when adding the erythritol, with careful stirring. It is than precipitated with cold water, neutralised with NaHCO3, washed again, and recrystallized with ethanol-acetone mix (I choosed 4:1 ratio).

Swede - 19-11-2012 at 12:39

http://www.sciencemadness.org/talk/viewthread.php?tid=20638

ManyInterests - 10-11-2021 at 20:17

I've decided to necro this thread since as of writing this I have my first ETN nitration in process. I used a mixture of 22ml 68% nitric acid, 33 ml of 96 or 98% sulfuric acid that was cooled to sub-zero temperatures and in a salt-water ice bath (it was VERY cold) and I added roughly 5.4 grams of erythritol. I stirred it with my glass thermometer until I saw nothing but a white slurry with little to no granulation left in the solution. The temperature never rose above 0 degrees Celsius. I believe it was still sub-zero the whole time.

I used Darian Ballard's video as a reference. He said to keep it nitrating for just 30 minutes at 10 degrees celsius, but I don't think I can get to that level, so I will play it safe and let it continue to nitrate overnight (or a few hours at least).

But I have one question: I've seen many nitrations call for 68% or 70% nitric acid while others show that the same thing can be accomplished by adding a nitrate salt directly to sulfuric acid works all the same, as OP did. Why is this so? I am asking because it took me quite of experimenting to finally make a workable bit of HNO3, and probably a bit more to make good WFNA. If the nitrations that call for 68% nitric acid can be accomplished just by adding a nitrate salt to sulfuric acid it will make things a whole lot easier.

fredsci93 - 11-11-2021 at 01:54

Quote: Originally posted by ManyInterests

But I have one question: I've seen many nitrations call for 68% or 70% nitric acid while others show that the same thing can be accomplished by adding a nitrate salt directly to sulfuric acid works all the same, as OP did. Why is this so? I am asking because it took me quite of experimenting to finally make a workable bit of HNO3, and probably a bit more to make good WFNA. If the nitrations that call for 68% nitric acid can be accomplished just by adding a nitrate salt to sulfuric acid it will make things a whole lot easier.

Not all reactions requiring nitric acid can be substituted with a nitrate salt, ETN's synth is very viable in many conditions as it's a simple formation of a nitrate ester, these types of reaction in general are very forgiving and either a nitrate salt or nitric acid can be used. (nitrocellulose, Methyl nitrate, EGDN etc) However, for more complex reactions nitric acid is a must for the reaction to proceeded, I would imagine this is either due to the sulfate salt generated reacting or hindering good mixing or in the case of AN reactive intermediates being generated (a more complex reaction would be RDX, HMX etc). There are of course exceptions though, this is just a rough explanation/guide. There's no great way of predicting whether a reaction will work with a nitrate salt, just experimentation.

Also, this reaction in particular gives near quantitative yields with the use of ammonium nitrate and not (azeotropic) nitric acid at room temp (the reaction starts at -18C however it warms to 10C-15C and is kept there for 90minutes, don't leave it overnight, it fucks the yield and is totally unnecessary), just as an aside.

ManyInterests - 11-11-2021 at 09:47

Quote:

Duly noted. I didn't stop to think about the sulfate formation, which is something I had to learn to deal with when making nitric acid. At any rate, the only nitrate salt I have access to is KNO3, which I got from turning calcium ammonium nitrate cold packs into potassium nitrate using potassium chloride.

Quote:

Also, this reaction in particular gives near quantitative yields with the use of ammonium nitrate and not (azeotropic) nitric acid at room temp (the reaction starts at -18C however it warms to 10C-15C and is kept there for 90minutes, don't leave it overnight, it fucks the yield and is totally unnecessary), just as an aside.

Well it's a bit too late since I did keep it out overnight. I was a bit too tired last night to clean it up. It does not appear to have reduced my yield that much. But then again, I am still filtering the stuff and neutralizing the acids (you can NEVER have enough sodium carbonate/bicarbonate in this hobby!) and washing the stuff out. Once I let it air dry for a day or so I'll see what my final yield is.

For my next attempt I will definitely try to bring the temperature up to 10C or so and not let it sit for more than 90 minutes.

karolus28 - 11-11-2021 at 11:16

I have saved a method Improvised Chaos(yt) used to make etn, he said it's very high yielding. If anyone's curious they can look it up

Attachment: etn improved chaos.txt (3kB)
This file has been downloaded 798 times

ManyInterests - 11-11-2021 at 11:37

I'll definitely give it a look.

It seems like my final yield appears to be granular (crystals) instead of a fine powder. This is probably due to the fact that I used granular erythritol instead of powder because I heard it here that it was better to use that. But then again, my product isn't dry yet, I could be mistaken.

How safe is it to crush small quantities of the stuff with a rubber spatula?

If it isn't safe, I think for my next synthesis I will grind up the granular erythritol into a fine powder before adding it to the nitrating mixture.

katyushaslab - 11-11-2021 at 11:51

Recrystallize your ETN instead of crushing it to get a different particle size. Fast recryst = small particles, slow recryst = large particles.

Saturated solution of ETN in the minimum amount of hot acetone dumped into ice water (better with stirring) will give you very, very small particles of ETN.

This also has the benefit of being a mandatory purification step anyway.

Fulmen - 11-11-2021 at 12:03

No, granular erythritol is the right choice as fine powders tend to contain anti-caking agents.
The final grain size will be determined by the crystallization process. This should be covered in detail if you dig a bit through the forum, but IIRC adding cold water slowly to a hot acetone-solution works well.

ManyInterests - 11-11-2021 at 15:44

Quote:

No, granular erythritol is the right choice as fine powders tend to contain anti-caking agents.
The final grain size will be determined by the crystallization process. This should be covered in detail if you dig a bit through the forum, but IIRC adding cold water slowly to a hot acetone-solution works well.

Good thing I downloaded the video from Darian Ballard where he showed the process in great detail. As soon as my product is 100% dry I'll do a recrystalization with acetone.

ManyInterests - 13-11-2021 at 20:01

OK I just learned a VERY important lesson here.

I'm not going to bother increasing the temperature to 10 while waiting for the ETN to finish nitrating. I had a runaway nitration today (my first and I swear it will be my last) the room was filled with red NO2 gasses but I smelled nothing. It was very light, but the stuff in the beaker was BOILING. I remembering the thread 'Life after detonation' that described something similar. I had no idea what happened or why there was a runaway. I wanted to leave the whole thing for 90 minutes. For most of the nitration time it remained close to 10 c. But it just shot up without warning.

I heard a boiling sound like I was boiling water for coffee. But then I went to see what was going on and I saw that my solution turned black and it was boiling.

I was afraid to touch it. I left my thermometer in it and it was above 100 c. I remembered that dumping it in water was the necessary solution to this problem, but I didn't want to touch the beaker. Not with my hands or with a tong. What I did was walk past it, opened my balcony door to ventilate it. Turned on all fans in my apartment, opened all the windows I could, then I dressed up and left. Just didn't want to be there if something happened. When I returned the temperature had dropped to around 40 or 50 c and the boiling stopped. I put on a pair of vinyl gloves and I picked up the beaker with a pair of tongs and I removed the plastic wrap I put on top, then I dumped it all in a glass pan full of water. Then I added more water and started putting in sodium carbonate in order to neutralize everything. I washed out the beaker (it is intact. No sign of cracking or anything). I am out of carbonate, but I got lots of bicarbonate, so that'll need to do for now.

I am so damn lucky. I need to make more nitric acid and I will be trying for a 3rd ETN synthesis. But this time I will do what I did the first time and keep everything in sub-zero temperatures and as cold as humanly possible,

The only other difference between this time and the previous was that I used my magnetic stirbar for the ETN, while the last time I mixed everything by hand with my thermometer. I stirred it for a bit over 10 minutes. I am not sure if that is enough mixing, but next time I will try for more. By hand if need be.

B(a)P - 13-11-2021 at 21:03

The story you reference was about melt casting ETN not the nitration. Moral of the story is, never turn your back on a nitration. Also don't assume it will be your last runaway, if fact always assume your reaction might runaway and be prepared. I am not sure an apartment is the place for this reaction, but I have no idea of the layout and ventilation.....
If you haven't already read them, checkout the numerous threads on ETN, you will find a wealth of information on reaction conditions.

ManyInterests - 13-11-2021 at 21:51

Quote:

The story you reference was about melt casting ETN not the nitration. Moral of the story is, never turn your back on a nitration

It still cost him his hand. I got away without a hitch. I would like it to stay that way. Also definitely. I won't ever just think that it will go without a hitch ever again. Keep it cold, keep it under watch. Also keep it outside. It's cold this time of year and the ambient temperature will definitely assist whatever bath I keep it in.

Quote:

I am not sure an apartment is the place for this reaction, but I have no idea of the layout and ventilation.....

It's a small cramp apartment. The ventillation is not very good, which is why the advice I got on degassifying after something like that proved quite useful. I won't ever be letting any nitrating compounds in my apartment until the nitration is complete and I just need to wash the stuff out.

Vomaturge - 13-11-2021 at 22:19

Quote: Originally posted by B(a)P

The story you reference was about melt casting ETN not the nitration.

I've never nitrated anything, and ought to stay TF out of this but I think it's worth mentioning that Yamato71 wasn't trying to melt it. He was trying to dissolve it in methanol at a high temperature. It had already spilled (no fault of his own, glassware failure) and been engulfed in flames for a while before the actual bang.

I agree it's pertinent, just because it shows how easily you could go from "normal everyday chemistry procedures" to "pieces of body parts embedded in the ceiling" if you're processing these things.

B(a)P - 13-11-2021 at 22:49

Thanks Vomaturge, I should have checked before making that statement particularly out of respect for Yamato71 given what he went through/is still going through and the value of the post he shared. My point was meant to be that apples were not being compared with apples. Apologies to Yamato71 for misrepresenting your post.

ManyInterests - 13-11-2021 at 23:08

Quote:

Yes. I did go through it again. The glass he bought wasn't real borosilicate glass. It was a cheap Chinese knock-off of Pyrex purposefully misspelled as Pryox. It wasn't suitable for heat shock at all. I'm glad that all my glassware, while Chinese, is actual lab glass, otherwise this incident would have landed me in deep s**t with the glass shattering and spilling burning hot acid all over the place.

Right now I'm facing another challenge in making nitric acid again. I am doing it again with 1.5 portions from my last time, and I am getting nothing happening. That's another challenge I need to get around I guess. I might have to increase the temperature.

edit: Just to keep notes (and I am using this forum as a public lab note taking). The problem I had with making nitric acid in the past attempts was temperature control. My mantel's temperature is dependent on the reading it gets from its own thermometer. This meant having to put it through the top part of my distillation joint, which didn't go all the way through before, but falls right in because the seal is broken due to corrosion. While the flask's heat goes up, it doesn't carry all the way to the joints, which means it probably isn't going over through the condenser. I'm probably going to have to jack up the heat or find a way to now keep the joint up top. Normally the distillation would have been done, but after 2 hours it hasn't even really started yet...

[Edited on 14-11-2021 by ManyInterests]

katyushaslab - 14-11-2021 at 04:25

> While the flask's heat goes up, it doesn't carry all the way to the joints, which means it probably isn't going over through the condenser

The solution most people use is to wrap in aluminium foil to trap the heat inside. Make sure your joints are well greased with sulphuric acid, of course, so no nitric oxides/nitric spews out and reacts with the aluminium foil.

The heavy duty kitchen stuff is fine, its what I use.

ManyInterests - 14-11-2021 at 08:19

I did that. But I have a feeling that all my nitric acid has escaped somehow. I looked over my mantle right now (left it out overnight) While there is a sulfate cake forming, it is not totally dry. My attempts at sealing the topmost thing with aluminum foil and it didn't close up the topmost joint.

katyushaslab - 14-11-2021 at 08:57

What do you mean by "sealing the topmost thing with aluminium foil" here? Are you using Al foil to plug gaps in the actual glassware itself? Cos that is a recipe for disaster.

ManyInterests - 14-11-2021 at 09:36

OK I should clarify what I meant.

https://www.amazon.com/Distilling-Thermometer-Adapter-Distil...

I am using one of those things to connect my boiling flask to the condenser. You the cap at the top? It is for a thermometer. Once you put a glass thermometer in there, it breaks the seal that was there. It doesn't fit my mantle's thermometer without forcing it in. I did force it in and there is a hole there now. It cannot put either thermometer back in there without the thermometer falling right through. This means there is a hole for the nitric acid gasses to escape.

I need to seal that hole somehow.

karolus28 - 14-11-2021 at 09:38

shit load of teflon tape maybe?

Microtek - 14-11-2021 at 09:48

A couple of points:

- As Katyusha said, the Al-foil should be used as insulation by wrapping it loosely around the glassware, not for sealing openings. Maybe you could post a photo of your setup?

- Nitric esters are generally formed quite rapidly, and most of the waiting is to allow the nitrating species to penetrate the grains. For this reason, you should grind your substrate (the erythritol in this case) to a very fine powder, otherwise you risk only exposing some of it to nitration.

- You must babysit nitrations at all times! I know that some people like to put their nitrations in the fridge overnight. It often works, but every once in a while it will run away. I also saw that this was mentioned earlier, but it can't be stressed enough.

- If you are unable to stop a nitration from doing a thermal run away, just tip it into the cooling bath. That will quench it quite effectively and can be done in a heart beat.

ManyInterests - 14-11-2021 at 10:13

I disassembled my setup for cleaning (but left the boiling flask as is because there is still some liquid in it).

But here are the pictures of the main joint in question. If you notice, there is now a hole at the top that I need to seal, since any thermometer I put in will fall right through. This is where I believe most of the nitric acid is just escaping from.

Microtek - 15-11-2021 at 02:12

Ok, I see now. If you can find a glass rod of suitable diameter, you can use that for plugging the thermometer adapter hole. You could use the stem of a wine glas for instance. Another option is to wind PTFE tape (plumbers) around the thermometer (or other glass rod) to bring it to the required thickness.

Also, note that there usually is a flexible fluoropolymer gasket under the cap, so when you insert the thermometer and then tighten the cap, the gasket constricts around it.

[Edited on 15-11-2021 by Microtek]

ManyInterests - 15-11-2021 at 20:05

Quote:

Ok, I see now. If you can find a glass rod of suitable diameter, you can use that for plugging the thermometer adapter hole. You could use the stem of a wine glas for instance. Another option is to wind PTFE tape (plumbers) around the thermometer (or other glass rod) to bring it to the required thickness.

Also, note that there usually is a flexible fluoropolymer gasket under the cap, so when you insert the thermometer and then tighten the cap, the gasket constricts around it.

Yeah I just popped it in and didn't remove the cap, so the gasket is gone.

However in another thread I opened they did tell me about the PTFE/teflon tape. So what I got some (they're really cheap!) and I wrapped the threads of the joint nice and tight, with the hole sealed with multiple layers. I put the cap back on and off to see if anything broke. The covering on the hole remained intact. I hope I created a fairly tight gas seal to stop any gasses from escaping. I will also use the teflon tape to wrap the joints up. I won't need sulfuric acid for that anymore, which will make thing easier.

I hope my future attempts will not result in any more problems. I really want to consistently make nitric acid of any concentration. The problem now is still heat control, but I hope to manage.

In the meantime, I think I'll try to make some ETN by doing what the OP did. Just add KNO3 to H2SO4.

[Edited on 16-11-2021 by ManyInterests]

Microtek - 15-11-2021 at 23:33

Yes, that works too. Be aware, however, that the viscosity of such a nitrating mixture is much higher than one based on HNO3/H2SO4. This means than stirring is harder, and it is difficult to avoid inhomogenous regions. I recommend stirring by hand.

ManyInterests - 16-11-2021 at 07:46

Quote:

Yes, that works too. Be aware, however, that the viscosity of such a nitrating mixture is much higher than one based on HNO3/H2SO4. This means than stirring is harder, and it is difficult to avoid inhomogenous regions. I recommend stirring by hand.

Yep, it'll be like making nitrocellulose. I've seen people do it with either the HNO3/H2SO4 but I saw more people do it with the KNO3/H2SO4, I've nitrated nitrocellulose many times and I don't see any problems arising. I will definitely be doing it by hand. I will just make the nitrating mixture first, wait for the fumes to subside (adding pure H2SO4 to KNO3 makes a disgusting amount of fumes) before covering it and putting it in the freezer to cool down for several hours. I will put the beaker it in a bowl full of saltwater and keep it until the saltwater is frozen solid... and keep it there while mixing the whole time. That's what I did with my first batch and I also kept it outside. It's November and quiet chilly outside. My apartment's temperature is well beyond the ideal nitration temperature even with the heater turned off, so I must do this outside.

I've also ground up my granular erythritol into a fine powder. I think I'll make any ETN in the future this way, with just KNO3 and H2SO4. Until I get good at making nitric acid (and with the teflon tape, I hope things will come out better) it's far better to save any of the precious HNO3 for more complex nitrations, like making NHN. I will always be recrystalizing my ETN anyway.

I also want to mention after recrystalizing my first batch of ETN, I did notice that it was in large crunchy flakes. I decided to be brave and crush the bits (piece by piece away from the main batch) into as fine of a powder as I could. It worked quite fine. No detonations or anything.

But your statement that the nitration may have been partial because I didn't grind up the erythritol at the start. I'm going to weigh out tiny bits and see if I can set them off with a hammer or a bit of flame.

katyushaslab - 16-11-2021 at 10:42

If you are getting a bunch of fumes while preparing the nitrating mix, you probably are doing something horrendously wrong with regards temperature control.

Pre chill your sulphuric acid for a while, and add the potassium nitrate to it in portions with stirring, in an ice bath. Then let it cool for some time longer and swap the ice bath before you go on to doing the additions of the erythritol.

Ideally, you don't want to be evolving any appreciable amounts of fumes whatsoever.

ManyInterests - 16-11-2021 at 13:17

I always put my sulfuric acid in the freezer until it is as cold as it can get. I dried my KNO3 also in the oven before letting it cool. I spent about 30 minutes mixing this and not much gasses were generated. But I did obviously do this outside and with a fan on to vent any of the fumes that do come out.

After mixing I let my nitrating mixture settle for a bit. There was still a bit of grainy bits in the mixture. Though this always happened with my mixture when I made it to make nitrocellulose. Currently it's in my freezer in the saltwater bath. I'll add the powdered erythritol once the saltwater is frozen solid.

[Edited on 16-11-2021 by ManyInterests]

B(a)P - 16-11-2021 at 14:11

Quote: Originally posted by ManyInterests

After mixing I let my nitrating mixture settle for a bit. There was still a bit of grainy bits in the mixture. Though this always happened with my mixture when I made it to make nitrocellulose. Currently it's in my freezer in the saltwater bath. I'll add the powdered erythritol once the saltwater is frozen solid.

This time, make sure your erythritol is finely powdered and perfectly dry. Add it in small portions and watch for the slight increase in temperature with each addition then wait for the temperature spike to subside before your next addition.

ManyInterests - 16-11-2021 at 15:40

I will add them in bit by bit.

Also those grainy bits appear to be undissolved KNO3. Most of the stuff was powdered when I put it in, but I was expecting the pebble bits to be dissolved by stirring, apparently this is not the case. I hope it does not affect my yield later on.

edit: Urg! No wonder why so many prefer using nitric acid to adding a nitrate salt. My nitrating solution has frozen solid in the freezer. I can't add anything to it. :\ I'll need to wait for it to warm up. I really need to get a handle on nitric acid production!

[Edited on 16-11-2021 by ManyInterests]

[Edited on 17-11-2021 by ManyInterests]

ManyInterests - 16-11-2021 at 17:34

OK I am not going to ever freeze nitrate salt nitrating mixtures. it not only turned into a very, very hard jelly-like substance, but even after the temperature rose up (it went to almost 20C or 20C during adding the erythritol addition. I know tha twas too high a temp and either my nitration will fail or I will get a very low yield.

It was so hard to mix that I was afraid that my thermometer and glass stir rod were going to snap while working it. That being said, the temperature did drop to 10C or below, and probably going to drop lower since I'm leaving it in a salt-water bath and outside, where it is very chilly. The ambient temperature should keep everything nice and cold.

It was a nice experiment, but I think I'd rather save the salts for the nitric acid. I will need to make more batches of the stuff soon.

Edit: I'm filtering it, the level of foaming is insane. Is the foam ETN or is it something else? I'm going to be doing this for quite a while!

[Edited on 17-11-2021 by ManyInterests]

ManyInterests - 17-11-2021 at 11:32

Wow. That was the hardest synthesis I ever did. I am never making ETN through KNO3/H2SO4 again, it was just too much of a hassle. Getting the leftover bits of ETN (or what I think is ETN) away was difficult. I ran out of distilled water and needed to use tap water to continue rinsing. I'll measure my final result. I don't think I'll need any more ETN after this.

Brightthermite - 17-11-2021 at 17:36

Would love to hear your yield. Sulfuric acid and ammonium nitrate is a much easer bath to handle btw. I still need to get around to trying KN03. Apparently the yield is pretty good and its much cheaper for me then AN.

ManyInterests - 17-11-2021 at 21:44

Yeah. It was horrible. I measured my yield at just 7.08 grams starting from 60 grams of KNO3, 110 ml of H2SO4, and 15 grams of powdered erythrithol (granulated erythritol powdered with a normal coffee grinder). This is before recrystalizing with acetone and water. I had no sodium carbonate to neutralize my acids before pouring them down the drain/flushing them in the toilet, so I used regular sodium bicarbonate, which thankfully worked to neutralize nitrating mixtures.

I haven't recrystallized them yet, so I don't know what my final yield is after recrystalization. I do believe it adds to stability and storage life, so it doesn't hurt to do that.

I really, REALLY need to get a handle on making nitric acid. Making ETN with nitric acid was so simple that I could do it in my sleep. ETN with potassium nitrate added directly to sulfuric acid was so needlessly difficult. Perhaps it could have been made easier if I powderized my potassium nitrate/KNO3 as finely as possible before adding it to my acid could have avoided the grains left in the nitrating mixture AND did not freeze the mixture, which never returned to liquid no matter what temperature it reached, would have resulted in a better yield, but at rate. I'm going to further wash what I got left to make sure I have anything water soluble out of my result, as well as recrystallize them in acetone before crashing them in water again.

Either way, my yield would be tiny. But I will post what I have here once I got it. I will test it with trying to subject it to thermal shock on aluminum foil. I tried to hammer ETN, but I realize that what people told me about it's stability was true. Nothing happened. I will try to hammer what I have again, but it seems this is one stable energetic even if it is stated to be more sensitive than PETN... which I would love to try to make, but I have no way of getting formaldehyde.

Laboratory of Liptakov - 18-11-2021 at 15:14

You can use column process. Arise better mixture for nitration erythritol (polyol) . But caution. Is it work with hot acids uder pressure. I recommend use better glassware equipment than in video. But base of 3 hours process is same. Changing all NH4NO3 on NH4SO4 and create maximal content HNO3 in situ. Before nitration.
https://www.youtube.com/watch?v=UGGaC0YA2yM

Brightthermite - 18-11-2021 at 18:27

I see in the video you are getting around 50 percent yields with this method. Is that the best you are able to obtain using "The Column"?

ManyInterests - 18-11-2021 at 19:39

I'll watch the video in a bit. Right now I recrystalized my yield and I am astonished to see the dirt that got into my ETN. It is much more powdered than my previous attempt probably because I powdered the stuff before adding it to the mixture.

It will probably be equal to my first yield, but absolutely terrible overall since my first attempt (which went very, very smoothly) ended up with a final yield of 6.5 grams from 5 grams of Erythritol. I will probably end up with 6 grams starting from 15 grams.

I hope with my teflon seals, and the hole I created in my thermometer adapter now sealed again, I hope to get half-decent yields of nitric acid. Even if I need to let them temperature run up very high.

Edit: final yield after recrystalization is 4 grams. There is some mild discoloration as well, which is why I am not going to mix it with my first yield. I think there is something up with it since when I tried to pop some by burning it on aluminum foil and a lighter what happened is some of the stuff dissolved and let off a tiny bit of red fumes. Others popped fine. It isn't 100% worthless, but it's mostly worthless. I'll need to dispose of this batch ultimately.

[Edited on 19-11-2021 by ManyInterests]

[Edited on 19-11-2021 by ManyInterests]

Laboratory of Liptakov - 19-11-2021 at 12:27

It was only attempt. Maybe is possible obtain 60% from Column device. But 90% sure not.

ManyInterests - 19-11-2021 at 18:55

Well I think my nitric acid situation should be fixed. With the teflon seals my latest attempt yielded 77ml or so of very, very clean acid with a specific gravity of around 1.425. So around 70%. I want to make a few more batches before making maybe one more batch of ETN before I do NHN and RDX. Then I'll consider my chemistry hobby good and solved and move onto another interest...

Quote:

It was only attempt. Maybe is possible obtain 60% from Column device. But 90% sure not.

I am not sure if I want to make that specific column, it is an interesting experiment, but I will pass.

Also while writing this comment, I made two batches of nitric acid, one before I quoted you and now this one. I hope it 70%. If it is, then I have enough 68-70% for everything I need. I'll need to get started on WFNA.

Laboratory of Liptakov - 20-11-2021 at 03:29

HNO3/H2SO4 give always better yields than H2SO4 / nitrate salts for ETN.

ManyInterests - 20-11-2021 at 04:47

Quote:

HNO3/H2SO4 give always better yields than H2SO4 / nitrate salts for ETN.

And much easier and much more efficient. I should have enough HNO3 for my NHN, HDN, and one more ETN synthesis. I will dispose of my last batch since I don't like it. My first batch is still excellent but I will need to pulverize it as It is still a touch grainy. But I am gaining confidence in ETN's stability, so I will powder tiny bits at a time with a rubber spatula.

Edit: my second batch of HNO3 made yesterday appears to have dropped in concentration to around 65%. It's still useable for ETN, I'll need to use a bit more. One thing I learned is that you always must put an excess of sulfuric acid. That's probably why my first batch of that day was much better.

[Edited on 20-11-2021 by ManyInterests]

[Edited on 20-11-2021 by ManyInterests]

ManyInterests - 28-11-2021 at 19:57

As a final note on my latest ETN synthesis. The yield I got was 13 grams after recrystalization and drying. Starting from around 9.9 grams of erythritol. Seems like the slightly less HNO3 concentration didn't affect it that much.

If I have to put a note in, never add any sodium bicarbonate/carbonate into the water when extracting the ETN, it will form a bit of a foam that will make the extraction a bit harder to pull off. I originally thought I did not need to recrystalize this time, but I think it is always a good idea. My yield after the initial extraction was 16.5 grams, but after recrystalizing I got the 13 of very pure ETN.

BlackPowderBoy - 10-11-2022 at 04:26

Quote: Originally posted by Brightthermite

Would love to hear your yield. Sulfuric acid and ammonium nitrate is a much easer bath to handle btw. I still need to get around to trying KN03. Apparently the yield is pretty good and its much cheaper for me then AN.

Does anyone know why this is? I've only ever used AN/H2SO4 and using KNO3 that I recrystallized would be much cheaper per pound. I would assume since they're both nitrate salts it wouldn't be much of a difference but I'm not sure.

Sir_Gawain - 10-11-2022 at 05:46

Using KNO3 will probably not be cheaper as you need about 2x the sulfuric acid to render the mix thin enough to stir.

ManyInterests - 10-11-2022 at 23:02

In all honesty I found that using nitric acid is much easier than using any nitrate salt. Like I want to make picric acid, and while I could use potassium or sodium nitrate (which I have plenty) I would rather make nitric acid and use that instead. The end product is easier.

When I made ETN using KNO3 the result was barely usable and the yield abysmal. Speaking of which, I did improve my ETN synthesis by recrystallizing it not in acetone, but in methanol. Methanol will give you a fine, powder-like result while acetone will make it crunchy and chunky. This might still trap some of the acid within it.

The ones I made in 2021 (described here) were actually still quite acidic since I didn't wash my ETN with enough water. This resulted in it becoming highly degraded when I placed it in blasting caps. I solved it simply by continuously washing the ETN in the filters until the water passing through no longer contained any acid (either using pH paper to test, or simply using bicarbonate on the water to see if it reacts).

Also I will say it again, recrystalize with methanol and add a pinch of urea in both the methanol and the water you will dump it into. This will scrub out any and all acids and will leave you with a very decent product that you can store for years without issue.

BlackPowderBoy - 12-11-2022 at 19:25

How do you get your methanol? I don't have access to lab grade methanol. Would I have to distill something like HEET or could I just recrystallize using HEET since it has such a high conc of methanol? I don't think they use any additives.

[Edited on 13-11-2022 by BlackPowderBoy]

ManyInterests - 13-11-2022 at 00:10

I buy my methanol as methyl hydrate from hardware stores. It is 99.9% pure.

Where do you live? Is methanol restricted where you live?

Edit:

About my previous comment for picric acid with nitric acid... I think it would be much easier (and cheaper) to use the nitrate salt with that one, and even more efficient. I made my first successful picric acid synth today with sodium nitrate. I will need to recrystalize everything however.

[Edited on 13-11-2022 by ManyInterests]

BlackPowderBoy - 13-11-2022 at 00:44

No it's not restricted near me, it's sold in hardware stores as well. I just wanted to make sure I didn't have to purify it first even if it appeared pure and clear. I bought HEET antifreeze and the msds says it is 100% methanol. It's crystal clear and appears to have no additives except in the msds it says something about 2 other chemical names..."proprietary, 0.0006% TO 0.00120" not sure what that means but hopefully those aren't some sort of colorless chemicals they add that would ruin the ETN during recrystallization.

[Edited on 13-11-2022 by BlackPowderBoy]

Herr Haber - 13-11-2022 at 12:52

Quote: Originally posted by ManyInterests

Speaking of which, I did improve my ETN synthesis by recrystallizing it not in acetone, but in methanol. Methanol will give you a fine, powder-like result while acetone will make it crunchy and chunky. This might still trap some of the acid within it.

This can happen both with methanol and acetone.
There are reasons to favor acetone over methanol: less toxic, usually more available and if you compare solubility in methanol and acetone the latter is much much better. It's therefore easier to pour into a large volume of water with stirring and avoid creating two layers. With both solvents, in room temperature water you are going to get a crunchy crust and a mess if you pour slowly without stirring.
Urea scavenges NOx, it doesnt neutralize the acids but improves stability. You still have to use a base to do that.

BlackPowderBoy - 13-11-2022 at 16:06

That's what I'm trying to avoid, that crunchy mess. You're saying I should pour quickly with swift stirring? I've heard adding sodium bicarbonate to the water is a good neutralizer, is that true? Also I've read that heating up the acetone beforehand gives finer crystals but I'm very hesitant to do that after The Yamato71 story. Even though he used methanol.

Sir_Gawain - 13-11-2022 at 16:33

I've always used ethanol; I've never gotten acetone to work properly. When I poured the acetone/ETN into cold water, no matter how strong the stirring, the acetone layer settled out. After a few minutes the ETN precipitated out as soggy chunks.

ManyInterests - 13-11-2022 at 19:00

Quote: Originally posted by Herr Haber

Quote: Originally posted by ManyInterests

I think a double recrystalization would not be out of the question then. One with acetone, the other with methanol. Methanol isn't dangerous as long as you don't get it on your skin (and if you do, wash it off right away) or drink it.

I did notice that it did get me the recrystalized product in a nice powdery form. For the acid I did not use a base. All I did was wash it again and again and again with water until no more acids were left over. When I recrystalized I also washed it excessively. I did not use any bases, but it still works.

Quote: Originally posted by BlackPowderBoy

That's what I'm trying to avoid, that crunchy mess. You're saying I should pour quickly with swift stirring? I've heard adding sodium bicarbonate to the water is a good neutralizer, is that true? Also I've read that heating up the acetone beforehand gives finer crystals but I'm very hesitant to do that after The Yamato71 story. Even though he used methanol.

I never had a case where acetone gave me a powdery result. But then again, I only worked with small quantities of acetone and it was room temperature acetone. Maybe if I was working with hot acetone it would give me something else.

[Edited on 14-11-2022 by ManyInterests]

Herr Haber - 14-11-2022 at 18:54

No matter how well you wash the product if you dont neutralize the acids at some point in your process you are inviting trouble.
It can be done with crude and still wet ETN. The idea is that the water will be enough to dissolve NaHCO3 and that this minimum amount of water will not hinder too much your solvent.
Then you can also add NaHCO3 to the water you are going to use to crash the solvent / ETN mixture. Note that an excessive amount of base will affect crystal shape and the properties of the product will suffer.
Doing both is probably not necessary if you do one or the other properly.
I have no opinion on what would be the best stabilizer (such as urea) but Rosco Bodine pointed out on one occasion that what is a good stabilizer (diphenylamine in the case of NC) for a product might not be good in other cases.

Double recrystallization from different solvents is definitely the way to go. First one for purity and the second one to get the shape or density you are after.
If it works for the industry with a boatload of compounds you can probably make it work for you

ManyInterests - 14-11-2022 at 22:03

I'm probably going to make another ETN batch in a few months. When I do that, I will add an additional step after washing my ETN like I normally do, but I will add the step of washing it with dilute sodium bicarbonate water after I do that step.

I will also recrystalize it along with my other batch twice (during it's second recrystalization) and in addition to having the urea scavanger, I will also wash everything again with bicarbonate water. So it'll be the 2nd recrystalization for the last batch and the third for the stuff I already have. If that doesn't remove all acids then I don't know what will.

Right now I am working with picric acid synth and recrystalization. I ran into my first real complication. I used too much water so I still have most of my picric acid in the filtered water (very little actually were caught in the filter paper) so I just added everything back to the water, and added more water, and now I am boiling it down.

I had a starting amount of 50 ASA and the amount of water I used to dump it into was over 1600ml! Too much. Even if it was nice cold, it would contain all the picric acid. so I am just doing the recrystalization in the original liquid. Once it down to almost nothing I will be re-recrystalizing it since there is still a lot of acid in this stuff. From the fizzing I see when I stir it.

BlackPowderBoy - 2-12-2022 at 23:14

Ok so methanol is definitely the answer. The difference between acetone and methanol is NIGHT AND DAY. However as previously stated on this site, you must use MUCH more methanol in your recrystallization than if you were to use acetone. It took me around 350ml to dissolve 10-11 grams of ETN and even then I should've bought more as there was a small pile that remained undissolved in solution.

The methanol didn't settle out the second I crashed it into water like acetone does. The whole water solution becomes milky and stays that way. I also used room temp methanol. I know you're supposed to heat up the methanol beforehand so you can dissolve more ETN in solution. But personally I'm not going to invole heat and ETN until I want to detonate it. Maybe when I get better equipment and more cojones.

The end result is a very nice, fine powder. MUCH better than the crunchy acetone mess. The texture reminds me of powdered sugar and the appearance almost reminds me of "Artifical Snow." Or "Dry Snow."

[Edited on 3-12-2022 by BlackPowderBoy]

ManyInterests - 3-12-2022 at 00:08

Quote: Originally posted by BlackPowderBoy

Ok so methanol is definitely the answer. The difference between acetone and methanol is NIGHT AND DAY. However as previously stated on this site, you must use MUCH more methanol in your recrystallization than if you were to use acetone. It took me around 350ml to dissolve 10-11 grams of ETN and even then I should've bought more as there was a small pile that remained undissolved in solution.

The methanol didn't seperate out when I crashed it into the water like acetone does. The whole water solution becomes milky and stays that way. I also used room temp methanol. I know you're supposed to heat up the methanol beforehand so you can dissolve more ETN in solution. But personally I'm not going to invole heat and ETN until I want to detonate it. Maybe when I get better equipment and more cojones.

The end result is a very nice, fine powder. MUCH better than the crunchy acetone mess. The texture reminds me of powdered sugar and the appearance almost reminds me of "Artifical Snow." Or "Dry Snow."

[Edited on 3-12-2022 by BlackPowderBoy]

Did you heat your methanol? I was able to fully dissolve around 90 grams or so (forgot exactly how much) of ETN in around 500ml or so of methanol. I need to look up my (open) lab notes that I posted in another thread.

I heated the methanol to boiling point before dumping into the ETN for recrystalization. I actually didn't intend to recrystalize that much ETN, I wanted to do 30 grams at a time, but I did everything at once. It was a happy little accident.

Laboratory of Liptakov - 3-12-2022 at 00:18

Experience says that hot methanol is the best for recrystallization of ETN. But it is work with poison, or rather with its vapors.

ManyInterests - 3-12-2022 at 00:25

Quote: Originally posted by Laboratory of Liptakov

Experience says that hot methanol is the best for recrystallization of ETN. But it is work with poison, or rather with its vapors.

Yeah, I am aware of how nasty and smelly it is. I do it near my balcony door where air is rushing in and thus properly ventilates my apartment. The fumes aren't too much which is why I can do it this way, otherwise I would need to do it on my balcony.

BlackPowderBoy - 3-12-2022 at 00:43

No the methanol was room temp. I'll try heating up the methanol to boil next recryst, I'm just sketched out even if I took all the precautions...

After reading "Life After Detonation" I would almost rather spend more and use up more methanol just to avoid heating it to a boil and putting ETN into it.

Also Lip, Is hot methanol best for recryst because it takes less to dissolve more? Or does it do a better job at dissolving overall? Does it open up the crystals more efficiently so more acid can escape? Or is it just that you use less methanol when it's heated?

[Edited on 3-12-2022 by BlackPowderBoy]

Laboratory of Liptakov - 3-12-2022 at 02:14

Experienced researchers say, from many experiences, that acetone is too strong a solvent for ETN. Over many years of recrystallizations, methanol proved to be an ideal solvent for several reasons at once. Better neutralization, cleaner product, finer resulting fraction - the consistency of a fine powder. I don't remember the exact ratios between hot methanol and raw ETN.

Herr Haber - 4-12-2022 at 05:05

Quote: Originally posted by BlackPowderBoy

After reading "Life After Detonation" I would almost rather spend more and use up more methanol just to avoid heating it to a boil and putting ETN into it.

Happy Saint Barb day !
I thought these words of wisdome deserved a bigger font size.

ManyInterests - 4-6-2023 at 20:34

I think I might have melt cast my ETN by complete accident! I wanted to give it a very late wash with a hot sodium bicarbonate solution and while it was not boiling, it was kinda steaming. After heating the solution I transferred it to my 2 liter beaker and then waited a minute before adding my ETN supply...

and after giving it a stir... the stuff became a blob at the bottom and then kinda stuck there.

I wanted to give it a sodium bicarbonate wash because I never did that before and I thought 'better late than never' to make sure all acid is done and gone forever (even though I recrystalized this stuff TWICE).

Now I am scared... very scared. melt-cast etn is much more sensitive and I don't want to end up with another 'life after detonation' story. I must proceed with utmost caution.

edit: OK the big disk at the bottom came out without issue, but it is still solid... I am really scared guys...

[Edited on 5-6-2023 by ManyInterests]

Microtek - 4-6-2023 at 23:57

I don't think melt cast ETN is more sensitive than powdered ETN. It is more sensitive WHILE you have it heated/molten, but once cooled, it is not. Probably less so, in fact, than when crystalline.

Laboratory of Liptakov - 5-6-2023 at 00:15

Cast ETN processing........This process was tryied 10x
https://www.youtube.com/watch?v=YZSXL8xxzKs

ManyInterests - 5-6-2023 at 03:12

Quote:

I don't think melt cast ETN is more sensitive than powdered ETN. It is more sensitive WHILE you have it heated/molten, but once cooled, it is not. Probably less so, in fact, than when crystalline.

That was still a lot of ETN and it was large solid puck. breaking it up and grinding it would require some force. I am not taking that risk. But if it is actually less sensitive then... cool! I might piecemeal melt-cast my ETN this way in the future.

Quote:

Cast ETN processing........This process was tryied 10x
https://www.youtube.com/watch?v=YZSXL8xxzKs

Yeah I saw your video and downloaded it a long time ago. it had a LOT more ETN than that and it wouldn't be as easy to break it up without some force, so I didn't want to do it. But maybe next time.

At any rate, I remember that there is no reason not to recrystalize it... so I got some acetone and melt it all in there.

specialactivitieSK - 5-6-2023 at 06:47

https://youtu.be/fAMPtd0MKgo

Laboratory of Liptakov - 5-6-2023 at 09:46

ManyInterests.....Oh yes... hockey puck dissolved in acetone....Always is possible pour 5 grams on warm plate and evaporate acetone. And create thin layer for small experiments.... :cool:

OneEyedPyro - 5-6-2023 at 13:57

Quote: Originally posted by ManyInterests

I think I might have melt cast my ETN by complete accident! I wanted to give it a very late wash with a hot sodium bicarbonate solution and while it was not boiling, it was kinda steaming. After heating the solution I transferred it to my 2 liter beaker and then waited a minute before adding my ETN supply...

and after giving it a stir... the stuff became a blob at the bottom and then kinda stuck there.

I wanted to give it a sodium bicarbonate wash because I never did that before and I thought 'better late than never' to make sure all acid is done and gone forever (even though I recrystalized this stuff TWICE).

Now I am scared... very scared. melt-cast etn is much more sensitive and I don't want to end up with another 'life after detonation' story. I must proceed with utmost caution.

edit: OK the big disk at the bottom came out without issue, but it is still solid... I am really scared guys...

[Edited on 5-6-2023 by ManyInterests]

I think you're overreacting a bit. You can just dissolve in a solvent and crash it out the ETN to bring it back to a powder, it's rather fragile so I don't think very carefully crushing it poses too much risk.

Another option is to remelt it in hot water while strongly stirring on a stir plate, this breaks it up into tiny globs which harden as the water cools yielding a dense and coarse powder. This actually works to neutralize crude ETN if you use a hot bicarb solution, I believe a similar process is used for processing crude TNT.
I don't know how necessarily safe it is but it can be done remotely.and I've done it numerous times without issue.

ManyInterests - 6-6-2023 at 14:01

It's OK. I recrystalized it. It's fine. I also found that it did need a recrystalization. I remember when I did it last time I thoguht there was some undissolved ETN. But it turned out to be impurities. I filtered them out this time. So I got some very clean and super pure ETN now.