Sciencemadness Discussion Board - EU illegal chemicals -> useful legal ones?

EU illegal chemicals -> useful legal ones?

Dihydrogenmonoxide - 6-3-2023 at 11:43

For more than a year now, certain chemicals were made illegal to possess in the EU, some that are very essential and hard to make with pretty hefty penalties attached.

Let's say someone still had these and would like to modify them in a way to make them legal but keep most of their usefulness.

Being able to convert back is better than making a replacement is better than making something different which is useful

I'm most interested in

Sulfuric Acid 96% (banned > 15%)
Nitromethane 100% (banned > 16%)
Hydrogen peroxide 35% (banned > 12%)

Sulfuric acid:
A) make toluenesulfonic acid. Can be used as a sulfuric acid replacement for some reactions and is relatively straight forward to make.
B) Dissolve in a solvent that isn't water, preferably lower boiling point, inert to sulfuric acid and not azeotrope forming, so that it can easily be concentrated back to the original concentration. Maybe glacial acetic acid could work for this?

Nitromethane:
I guess the best option would be to dissolve in a high-boiling solvent that doesn't form an azeotrope and doesn't decompose under heating, so that the nitromethane can be distilled out as pure as possible. I know that castor oil is used for RC uses but maybe something like a parafin oil could also work?

Hydrogen peroxide:
I have read about the possibility of making barium peroxide, which in theory should be able to be converted back to hydrogen peroxide with somewhat concentrated sulfuric acid

. There is also the option of making calcium peroxide and gain hydrogen peroxide in a similar fashion, which should be cheaper. But I'm having a hard time to find detailed write ups of this process, so im not sure about the caveats in real life, like the instability of hydrogen peroxide.

What are your thoughts on the topic and what have you done to adapt to the new regulations?

Hexabromobenzene - 6-3-2023 at 12:04

Sulfuric acid difficult to be replaced. It can be easy obtained be electrolysis. If you afraid story it you can use acid immediately after preparation

Deathunter88 - 6-3-2023 at 12:10

The authorities have bigger fish to fry so if you already own the chemicals I wouldn't worry about.

Hexabromobenzene - 6-3-2023 at 12:20

If you have a hobby at home chemistry then it is better not to tell anyone about it. Most people dont understand you such a life.

Bedlasky - 6-3-2023 at 18:10

It's simple. If you have any of those chemicals, just don't tell anyone

clearly_not_atara - 6-3-2023 at 18:29

If the goal is homologation of benzaldehydes to one-carbon-longer amines, nitromethane can be "replaced" by hydantoin, produced by various methods. See attached, particularly Henze et al. Surprisingly, this also offers a reduction of benzaldehydes to the methyls.

Quote:

Sulfuric acid difficult to be replaced. It can be easy obtained be electrolysis.

As I understand it, the difficulty is with concentrating sulfuric acid beyond about 70%, at which point it begins to fume quite badly. Nicodem's suggestion of preparing tosylic acid with dilute sulfuric acid and excess toluene in a Dean-Stark sounds a lot less unpleasant, although I haven't tried it myself.

Quote:

There is also the option of making calcium peroxide and gain hydrogen peroxide in a similar fashion,

If it was practical to make calcium peroxide with oxygen, why did the old chemists bother with barium? That always seemed fishy.

Attachment: henze1940.pdf (408kB)
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Attachment: gaudry1948.pdf (241kB)
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Lionel Spanner - 7-3-2023 at 13:37

Hydrogen peroxide can be concentrated at relatively low temperatures by azeotropic vacuum distillation with xylene, which removes the water by forming a 60%/40% w/w azeotrope with it. In practise I've found the boiling point of the azeotrope is around 20-25 °C at 0.05-0.08 bar, and I've also found the water percentage is a little lower at low pressures, and reduces as the peroxide gets more concentrated.

Toluene will work as well, but is not as efficient; its azeotrope with water is 80%/20%.

CRUSTY - 14-3-2023 at 20:42

Hydrogen peroxide can be concentrated slightly by freeze distillation. It can also be concentrated by dessication with sulfuric acid... oh wait. It would be a lot of work but you could also dessicate using something like phosphorus pentoxide to reach higher concentrations of H2O2.

ave369 - 19-3-2023 at 05:40

If you want sulfuric acid, just boil the Bat. Buy dilute sulfuric acid (such as battery acid, hence "the Bat") and boil it down with boiling chips until fumes start coming out. Cool the solution, it's ~70% sulfuric acid, useful for many reactions. If you have a fume hood or a good distillation setup, you can boil the Bat further, concentrating it to 98%: use the fume hood or condenser to get rid of very dangerous fumes. If you use a distillation setup, make sure you use a two-stage condenser: first span is air-cooled where vapors pre-cool to about 100 C, second span is water-cooled, where they condense and safely drip down into the receiving flask.

blogfast25 - 20-3-2023 at 05:51

Quote: Originally posted by ave369

If you want sulfuric acid, just boil the Bat. Buy dilute sulfuric acid (such as battery acid, hence "the Bat") and boil it down with boiling chips until fumes start coming out.

In the UK/EU battery acid is now also restricted to authorised users.

But very low conc. SA is still available.

Fantasma4500 - 21-3-2023 at 09:08

well. NaHSO4- or just go for straight up nitric acid production through electricity- maybe im thinking purely in energetics, hm!

H2SO4 can be made by sulfates, even CaSO4 as demonstrated by one guy on here and YT with electrochemistry and a PVC membrane, otherwise S+O2 using vanadium pentoxide catalyst can form SO3, and essentially, potentially- make oleum even

or maybe we just wanna stick to selling things under the radar, since most chemistry eventually ends up illegal one way or another anyways
im more worried for when OTC truly dies and everything is getting put into a computer unless if you trade gold for chemicals

ave369 - 21-3-2023 at 09:27

Quote: Originally posted by blogfast25

In the UK/EU battery acid is now also restricted to authorised users.

But very low conc. SA is still available.

Can't see how it prevents people from boiling it down. No matter what the concentration, boiling down always works.

blogfast25 - 21-3-2023 at 10:37

Quote: Originally posted by ave369

Quote: Originally posted by blogfast25

In the UK/EU battery acid is now also restricted to authorised users.

But very low conc. SA is still available.

Can't see how it prevents people from boiling it down. No matter what the concentration, boiling down always works.

Legally speaking I don't know whether these prohibitions apply to buying or to possession or both.

Organikum - 23-3-2023 at 21:59

Quote: Originally posted by blogfast25

Quote: Originally posted by ave369

Quote: Originally posted by blogfast25

In the UK/EU battery acid is now also restricted to authorised users.

But very low conc. SA is still available.

Can't see how it prevents people from boiling it down. No matter what the concentration, boiling down always works.

Legally speaking I don't know whether these prohibitions apply to buying or to possession or both.

It depends somewhat on how the country you live in implements those EU regulations, but generally those are restrictions put on the trade, on sellers not on buyers.
It is illegal for anybody trading with those compounds to sell them to private entities. It is not illegal for private entities to own or aquire those things. So if you find somebody who sells you the stuff - get it. But be warned! There are for example clowns who sell Potassium Nitrate by the kg on German Amazon and virtually everybody who buys it gets a visit from the police shortly after.
But as told before, regulations are differently interpreted from country to country and if you find somebody anywhere in the EU who sells and sends you something as his country has no problem with it - buy it. You are not in the wrong by doing it, actually citizens are explicitly allowed to use different regulations in EU countries to their advantage. like running a business from Belgium for the lower taxes there even when most biz is done in Germany. Or using an Irish Ltd for its much cheaper to install and run then a German GmbH.

Chemgineer - 25-3-2023 at 13:35

Quote: Originally posted by Lionel Spanner

Hydrogen peroxide can be concentrated at relatively low temperatures by azeotropic vacuum distillation with xylene, which removes the water by forming a 60%/40% w/w azeotrope with it. In practise I've found the boiling point of the azeotrope is around 20-25 °C at 0.05-0.08 bar, and I've also found the water percentage is a little lower at low pressures, and reduces as the peroxide gets more concentrated.

Toluene will work as well, but is not as efficient; its azeotrope with water is 80%/20%.

I guess using a dean stark trap with xylene would work well for this?

[Edited on 25-3-2023 by Chemgineer]

Lionel Spanner - 26-3-2023 at 07:29

Quote: Originally posted by Chemgineer

Quote: Originally posted by Lionel Spanner

I guess using a dean stark trap with xylene would work well for this?

[Edited on 25-3-2023 by Chemgineer]

Very likely, but I found simple distillation works pretty well, provided that you don't mind the stopping and starting.

DocX - 3-4-2023 at 12:56

This peroxide business... I get conflicting statements about the possibility to simply evaporate off water to a 30% concentration from 12.
Some say it's perfectly possible, there's even Youtube videos of people demonstrating this https://www.youtube.com/watch?v=Hrv1FTq96LE.

Others say it's bogus, since too much peroxide would decompose by the heat (producing water, as it is) for the concentration to actually change very much.
So then he demonstrates his technique for ascertaining success:
https://www.youtube.com/watch?v=ScZKaD5mlCk

And if you like evaporators, you have this guy who cashes the freeze-concentrating technique that was mentioned above:
https://www.youtube.com/watch?v=_L2ecuDZwlA

Then we have this annoying guy. You just kind of want to synth some Xanax, force-feed it to him and put him in a corner somewhere to shut up:
https://www.youtube.com/watch?v=LhEYaovWxl4&t=600s

Vacuum distillation:
https://www.youtube.com/watch?v=nVAe__ToAOY

Chemgineer - 7-4-2023 at 05:41

Quote: Originally posted by DocX

Then we have this annoying guy. You just kind of want to synth some Xanax, force-feed it to him and put him in a corner somewhere to shut up:
https://www.youtube.com/watch?v=LhEYaovWxl4&t=600s

Hey that's Tom from Explosions and Fire, he's great!

blogfast25 - 7-4-2023 at 06:08

Quote: Originally posted by DocX

Then we have this annoying guy. You just kind of want to synth some Xanax, force-feed it to him and put him in a corner somewhere to shut up:
https://www.youtube.com/watch?v=LhEYaovWxl4&t=600s

Annoying beyond reasonably: just luuurrves the sound of his own voice...

But one man's music is another man's noise, I guess...

Amos - 7-4-2023 at 06:46

Quote: Originally posted by DocX

Then we have this annoying guy. You just kind of want to synth some Xanax, force-feed it to him and put him in a corner somewhere to shut up:
https://www.youtube.com/watch?v=LhEYaovWxl4&t=600s

Why, though? That's tdep here on the forum, he's actually super knowledgeable and either has or will very soon have a PhD in chemistry. And I love his channels. I'm not sure why we aren't allowed to have a dose of humor to go with our science...

Cathoderay - 7-4-2023 at 07:08

Part of it is that he's an Aussie. Some people don't mind it much.
https://www.youtube.com/watch?v=wRdnNN1N-zA