Sciencemadness Discussion Board

What is this whole "nitration" thingy about?!

arthur2647 - 1-9-2015 at 21:03

Hi, I'm new here, just have a few questions. Before I give my situation and questions, i apologize if I'm interrupting. I tried to synthesize NG with more of dilute acids, around 40 percent sulfuric acid and potassium nitrate. I filled the beaker with around 50ml of the acid and added around 15 g nitrate to it. To this i added about 1-2ml of glycerin drop by drop. Shortly after adding I was presented with a subtly sweet smell which I guess is the NG. But i don't believe I ever achieved the tri- ester form. As well I could see a hazy zigzag line where the glycerin hit the acid as it trailed down to the bottom.
During the nitration which i left for about 90 minutes, I did see a few bubbles here and there form on the top and also some very slight haze in the top layer. However after i added some cold water to this, it all vanished and i was left with a clear solution. Actually to be honest, I did this experiment twice. The first time i was left with tiny clear bubbles (~20) spread out on the bottom after adding cold water, and they would not dissolve in water. The second time i was left with just that clear solution.

So in the end this got me really interested in terms of the action of these acid mixtures on the glycerin. It seems that the glycerin is acted upon almost instantly but I'm guessing the acid just loses potency quite fast. It makes me wonder how much more concentration do i really need to get a decent nitration.

If you guys have any ideas or input, thanks.

[Edited on 17-9-2015 by Bert]

[Edited on 17-9-2015 by Bert]

Bert - 2-9-2015 at 05:37

Start at the beginning of this thread, read the whole thing... Don't waste any more chemicals until you have done that.

Look for the Phokion Naoum book in the sciencemadness library:

http://library.sciencemadness.org/library/index.html

Read the relevant chapters (or better yet, the whole thing!).

FAR too dilute sulfuric acid.

Battery electrolyte?

http://www.sciencemadness.org/talk/viewthread.php?tid=19117

arthur2647 - 2-9-2015 at 15:52

Thanks...it is true, its from battery acid. But part of that large journal , it does mention if you add excess sulfuric acid it can counterbalance the lower hno3 amount. I have to say it doesn't really matter to me if i make the tri ester or not. I just want to understand the chemistry behind nitration more. It does seem though that the most concentrated acids are the best. I just don't see a lot of literature on potential of these lower acids. For example with excess sulfuric acid would it manage to make the di ester, since i know the first OH group is not hard to nitrate.

ecos - 2-9-2015 at 23:17

try to buy more concentrated sulphuric acid or you can concentrate it yourself by boiling or distillation :
https://www.youtube.com/watch?v=tgUH0HXrOKE

boiling is faster and would give you concentration till 80% as far as i remember !

FYI- avoid nitroglycerin since you don't have experience with EM. better to deal with nitrocellulose !

[Edited on 3-9-2015 by ecos]

Tabun - 3-9-2015 at 15:05

OK!I'm getting tired of this.These 2 names,TNT and dynamite has been so raped and they are so freaking popular that you can't google them without getting firecrackers,minecraft and the like : nothing on the subject(well...almost).Can somebody tell me about the tube dynamite is put in?How thick is it?What is it made of?Carboard or what?Is it pressed in there?
Yea...I know : "What dynamite?".Just try to make it general.

Hennig Brand - 3-9-2015 at 17:23

I think a lot of different things have been used, and I am not an expert on that, but I have found that common kitchen grade waxed paper works well. Make tubes by rolling 2 -3 layers, or whatever you deem appropriate, onto a former (e.g. cardboard tube or dowel of the right size). One end can be folded in and sealed and the dynamite can be spooned in and pressed in increments (normally fairly light pressing depending on dynamite type). Loading is very easy and fast especially once the cartridges get over 3/4" to 1" or so.

arthur2647 - 4-9-2015 at 18:02

so back to my last post, any ideas. dynamite is cool and all but i dont need that

Hennig Brand - 7-9-2015 at 04:01

Do some reading, there is a tremendous amount of information on NG even in this thread alone. The esterification of glycerin by nitric acid is an equilibrium reaction and I am fairly sure there is equilibrium data which you could avail yourself of if you searched a bit.

arthur2647 - 15-9-2015 at 15:13

well i did some reading, but my hope of coming here was that people would like to have a discussion about things. Basically i know i need concentrated acid to make the final nitrated form reliably. I just haven't come across in my reading much about dilute acids. All i found was mainly that dilute mix of acids can create glycerin mononitrate. But i haven't found if its possible to create more.

Joeychemist - 15-9-2015 at 15:41

Quote: Originally posted by arthur2647  
well i did some reading, but my hope of coming here was that people would like to have a discussion about things.


That would require you to have something worthwhile to discuss...

Quote: Originally posted by arthur2647  
Basically i know i need concentrated acid to make the final nitrated form reliably. I just haven't come across in my reading much about dilute acids.



Nitroglycerin and Nitroglycerin Explosives By Naoum

You might want to check out the chapters on nitratring acids and the Homologous and Related Nitric Esters ;)

ecos - 16-9-2015 at 00:33

Quote: Originally posted by arthur2647  
well i did some reading, but my hope of coming here was that people would like to have a discussion about things. Basically i know i need concentrated acid to make the final nitrated form reliably. I just haven't come across in my reading much about dilute acids. All i found was mainly that dilute mix of acids can create glycerin mononitrate. But i haven't found if its possible to create more.


do you have a problem to concentrate the diluted acids your self ?

you will find a lot of videos on youtube on how to concentrate nitric acid or sulphuric acid.

roXefeller - 17-9-2015 at 09:06

They do like discussions, but not leading questions on century old compounds that have been researched exhaustively. Sulfuric acid only has a role in dehydrating, so you should ask, how concentrated does it need to be to function as a dehydrator. The question isn't really about strength of nitric acid because it's water component effectively dilutes the sulfuric acid more. It is the same as adding 97% NA to 30% SA if you add 70% NA to 60% SA. Patent research that you should do, would indicate that industry finds little value in concentrations of SA below 70% as a dehydrator in these ester reactions. A tangent question would be, how is glycerin mono- or di-nitrate created and what strengths are employed there. You can find it. I (and the other advanced users and mod's) don't want to spoonfeed knowledge of dangerous compounds to people who aren't willing to research mundane details, it's an ethics and site liability thing. If you really want a discussion, ask questions that are more meaningful or match the experience of those whom you are probing.

Bert - 17-9-2015 at 10:03

Quote: Originally posted by arthur2647  
well i did some reading, but my hope of coming here was that people would like to have a discussion about things. Basically i know i need concentrated acid to make the final nitrated form reliably. I just haven't come across in my reading much about dilute acids. All i found was mainly that dilute mix of acids can create glycerin mononitrate. But i haven't found if its possible to create more.


First: go read the forum FAQ:

http://www.sciencemadness.org/madscifaq.html#2.1_Board_topic...


Next: Go to the forum library.

http://library.sciencemadness.org/library/index.html

Download these books for a start:

Phokion Naoum: Nitroglycerin and Nitroglycerin Explosives

Tenney L. Davis: Chemistry of Powder and Explosives

Read about your topic there. Come back and ask questions, provide references for WHERE the information you ask to clarify came from. Then, you may post outside of "beginnings".

And I GUARANTEE you, you'll get to have a discussion under those terms-

ave369 - 17-9-2015 at 11:02

Here's the resident forum researcher on Boiling the Bat! (battery acid). And a little how-to.

1. Flask

The best container to boil down H2SO4 is a round-bottom flask. If you have one, the heating method is a non-issue: you can even heat it directly on a kitchen gas stove, if you have a tripod or stand. If you have an electric stove, a conical Erlenmeyer flask could be preferable, but these are not as crackproof as round-bottom flasks. A thin sand bath is preferable if you use an Erlenmeyer flask on a kitchen electric stove.

If you do not have any flasks, it gets harder. Jars can be used, but they are very prone to thermal cracking, so a very thick sand bath is recommended if you use a jar. One of the best vessels for this purpose is a thick glass casseroling dish, it is nigh uncrackable.

2. Boiling chips

Pour the Bat into your chosen container. Toss some boiling chips into it once you start heating. Boiling chips are pieces of porous material that make the process of boiling continuous and calm, as opposed to not boiling, overheating and suddenly going "POOF!". This is called bumping, and sulfuric acid loves to do it. Without boiling chips, you will hear gunfire from your flask and the acid may even be forcefully ejected from it. So use boiling chips: small pieces of brick, pumice, some kinds of porcelain will also do. They will make your boiling calm, like you are boiling an egg.

One thing to remember about boiling chips is that heating should be continuous for them to be effective. If you boil your acid, let it cool down and heat it again, boiling chips may refuse to work. If this happens, toss some fresh ones in.

One final thing to remember about boiling chips: do NOT toss them in when the acid is already bumpily boiling! It will make it boil extremely vigorously and, possibly, be ejected from your vessel.

3. The Mist.

It's that Mist! The infamous, dreaded Mist!

What the Mist is? It is a mixture of H2SO4 vapors, SO3, H2O, and SO2. It starts to form when your boiling acid reaches the threshold of 80%. It is extremely noxious, carcinogenic and smells like pure pain and hell. It is milky white in color. You can usually smell the Mist long before it actually touches your nose (and it is not a good thing at all to let it anywhere near your face!)

What to do when you detect it? Depends on what do you need the acid for. If you need it for things like Glauber's acid syntheses, you can stop right here. 80% acid will be enough.

If you need it for nitrations, you need much more than that. You have to somehow get around the Mist. Here's a few common methods:

* Devise a remote control of your heating appliance. Once the Mist emerges, open all windows in the room, evacuate the room and watch over the process through the glass in the door. Turn off the heating when 30 minutes/1 hour/2 hours etc pass.
* Use a retort, and redirect the Mist into a trap flask filled with bicarbonate of soda. This will thwart the Mist and turn it into harmless steam.
* Put a reflux condenser on your flask when the Mist starts to form. This makes the Mist much less intense, but does not stop it completely (a reflux condenser long enough to stop the Mist right in its tracks also stops the boiling down of acid, returning all the water down).
* Distill the acid. You need very good glassware to do this.

I'm also researching various ways to get around boiling down over 80% and produce 98% or oleum another way. So far, I've yet to find an easy and fun way to do so. Pyrosulfate pyrolysis requires very high temperatures and sacrificial glassware. Distillation of acid mixture is so far a very experimental method, and I'm still unsure of what to expect from it.

[Edited on 17-9-2015 by ave369]