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Author: Subject: Erythritol Tetranitrate
B(a)P
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[*] posted on 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.
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[*] posted on 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.
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[*] posted on 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.




I now have a YouTube channel. So far just electronics and basic High Voltage experimentation, but I'll hopefully have some chemistry videos soon.
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[*] posted on 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.
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[*] posted on 13-11-2021 at 23:08


Quote:
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.


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]
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[*] posted on 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.
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[*] posted on 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.
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[*] posted on 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.
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[*] posted on 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.
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[*] posted on 14-11-2021 at 09:38


shit load of teflon tape maybe?



Hi, please read about exif data.
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[*] posted on 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.
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[*] posted on 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.



Joint1 (2).jpg - 1.8MBJoint2 (2).jpg - 1.7MB
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[*] posted on 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]
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[*] posted on 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]
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[*] posted on 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.
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[*] posted on 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.
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[*] posted on 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.
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[*] posted on 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]
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[*] posted on 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.
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[*] posted on 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! :D

[Edited on 16-11-2021 by ManyInterests]

[Edited on 17-11-2021 by ManyInterests]
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[*] posted on 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]
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[*] posted on 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.
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[*] posted on 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.
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[*] posted on 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.
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[*] posted on 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




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