"Things I Won't Work With...." and the person who decides to work with it runs a channel named "Explosions&Fire" ...
From the article:
"We're talking high-nitrogen compounds here (a specialty of Klapötke's group), and the question is not whether such things are going to be explosive hazards. (That's been settled by their empirical formulas, which generally look like typographical errors). The question is whether you're going to be able to get a long enough look at the material before it realizes its dream of turning into an expanding cloud of hot nitrogen gas."
Notice how quantity is the main thing that matters with explosives.
You can make the nastiest thing imaginable but there's pretty hard limits on how much chemical energy can blow up in your face per milligram of reactants. On the other hand, even if you think something is "better behaved" if there's enough of it it will still do horrible stuff if anything goes wrong.
Yes, likely that's all of us here. ...But they're probably not worried, they'd know our planned actions would be once-off and self-limiting and never come to fruition. ;-)
This is a great video on Azidoazide Azide, explosions and fire is a horrifically entertaining and educational youtube channel. I say horrific because of the chemicals that he works with. But he seems like he knows what he's doing... Hopefully...
“So how does this composition get this reputation then? Well, it’s hard to make so other people don’t make it and test. And what the Germans in 2011 published is ”Hey, it’s too sensitive and we can’t test it because it’s below our threshold for sensitivity”… Which doesn’t mean suppose that’s a fucking zero then, it just means they have some cut off.”
I knew that was going to be Explosions&Fire before I even clicked the link. His videos are a lot of fun even though I can't follow most of the chemistry.
For those who care and that I’m not patronizing - this is the same kind of behavior you see in TNT (though way more extreme in this molecule). Basically the bonds in these molecules are so unstable they are teetering at the top of a hill and just need a nudge to roll down that hill and become far more stable and much lower energy nitrogen molecules (N2 as nitrogen a nitrogen molecule, not elemental N on the periodic table). When they roll down that hill they let off a huge amount of energy as the bonds break and reform. That energy can be translated to force, as it does in bombs. Just touching this stuff is enough to trigger the bonds to start breaking in a nasty chain reaction.
Amazing they were able to characterize this stuff (that is get the x-rays, NMR specs, etc). I think the only way this stuff could be useful is if it could be somehow completely immobilized in a liquid or solid until use. Sounds insanely dangerous!
TNT is much less sensitive in some important ways. You can heat it up enough to melt and pour it without it exploding, and you can subject it to a great deal of physical shock, too. You need to set it off with another (less stable) high explosive.
TNT is rather insensitive for an explosive. You need primers or high energies to set it off, you can melt it and it won't explode. In fact it's so insensitive that for decades people didn't realized it's an explosive and used it as a dye. And even after they did - it was exempt from most safety rules.
Shock sensitivity Insensitive
Friction sensitivity Insensitive to 353 N
Anegdoticaly - my grandpa told stories that after WW2 he and other kids found a lot of munitions in the forest and played with them. And TNT was so safe they used it as a fuel in stoves and it would just burn without exploding (and for quite a long time). Not sure how true it is, maybe it was a different material they just called TNT.
I think the energy in TNT mostly comes from the desire of carbon and hydrogen to join forces with the oxygen, which has a much higher activation energy than nitrogen leaving of its own accord.
All of the posts in Derek Lowe's "Things I Won't Work With" series are excellent and worth a read. Do be sure to read the comments as well, there's some gold in there.
I still see a "Category" panel on the right-hand side, and clicking on the name of a category (like "Things I won't work with") seems to show posts just from that category.
Not all of them are titled "Things I won't work with", but others seem still on-theme.
I can't find it now, but my favorite of TIWWW was this chemical that just smelled terrible and did so in exceedingly small quantities. Like, a stray drop of this gets the building evacuated kind of bad, and people are asking what that smell is a mile or more downwind.
> To convince them otherwise, they were dispersed with other observers around the laboratory, at distances up to a quarter of a mile, and one drop of either acetone gem-dithiol or the mother liquors from crude trithioacetone crystallisations were placed on a watch glass in a fume cupboard. The odour was detected downwind in seconds.
How is the smell able to travel so quickly? And through walls no less?
Nigel of the NileRed youtube channel has just the other day disputed this claim. Diffusion isn't very fast and the wind would have to have been going 15mph or more. He says he wants to create this compound and test it, as he has done with a few other "horrific smell" compounds.
However, there's a running theory that he has kinda burnt out his nose working with certain compounds, as he seems mostly unphased by smelly chemicals that other people very much struggle working with.
In the thioacetone TIWWW, Lowe says that "the workers in the laboratory did not find the odours intolerable". It sounds like in higher concentrations it just overwhelms and numbs a strong reaction people have at even extremely low concentrations.
> the wind would have to have been going 15mph or more
15 mph really isn't much for wind, though? In fact that's about how much wind there is where I am right now, so that doesn't strike me as an unreasonable condition.
Individual molecules of air travel at speeds in the hundreds of meters per second (https://pages.mtu.edu/~suits/SpeedofSound.html). So it seems quite possible that individual molecules may be found quite far away from their origin quite quickly, even if the bulk is much slower in mixing (I'm not an expert here and would love to hear more if someone knows more about this).
It sounds like this substance is bad enough that a couple of molecules per Litre would make the air smell awful, which together with the previous point may explain how the bad smell could be detected at such a distance so quickly.
There's a section of "Ignition!" where the rocket scientists try out mercaptans as a rocket fuel, and get exiled to the far end of a huge empty field for the duration of their experiments.
Ignition! is a fantastic read. Not related to mercaptans (or bad smells), but this passage from the book has always made me chuckle:
> [Chlorine trifluoride] is, of course, extremely toxic, but that’s the least of the problem. It is hypergolic with every known fuel, and so rapidly hypergolic that no ignition delay has ever been measured. It is also hypergolic with such things as cloth, wood, and test engineers, not to mention asbestos, sand, and water –with which it reacts explosively. It can be kept in some of the ordinary structural metals — steel, copper, aluminum, etc. — because of the formation of a thin film of insoluble metal fluoride which protects the bulk of the metal, just as the invisible coat of oxide on aluminum keeps it from burning up in the atmosphere. If, however, this coat is melted or scrubbed off, and has no chance to reform, the operator is confronted with the problem of coping with a metal-fluorine fire. For dealing with this situation, I have always recommended a good pair of running shoes.
I wish he had access to instrumentation that could verify that he actually made what he was trying to make. One of the comments makes a fairly convincing case that he ended up with a different compound that, while still violently explosive, was much less sensitive.
Given that he DGAF that his scale doesn't work, he probably isn't interested in building an NMR spectrometer in his shed.
For his cubane project he has been getting stuff sent off for NMR, obviously he can't send a hilariously sensitive energetic off for that.
I'm genuinely unsure what other product would be made if you react isocyanogen tetrabromide with sodium azide, you could get a mix of azide and bromide on the isocyanogen, but that's super unlikely (bromide and azide double displacement is favourable reaction in this case, the bromine being more than happy to fuck off with the sodium) and you would get a distinct bromine cloud off any detonation or deflagration of the product.
At school I synthesized a tiny amount of NI3 (nitrogen triiodide).
As it was late and the substance was still dripping wet I went home leaving it under fume hood to dry.
Next day I learned (to much amusement of my chemistry teacher) that it scared the hell out of a cleaning lady who managed to trigger it off accidently while cleaning the chemistry lab.
Kind of tangentially reminds me of "nitric acid acts on trousers", which afaict is from Ira Remsen's quote about nitric acid acting upon copper. Can't find a good link
> I'd call for all the chemists who've ever worked with a hexanitro compound to raise their hands, but that might be assuming too much about the limb-to-chemist ratio.
I love these Derek Lowe posts. Somehow he mixes highly technical details with down-home folksiness. Examples:
> Hydrogen sulfide, for example, reacts with four molecules of FOOF to give sulfur hexafluoride, 2 molecules of HF and four oxygens. . .and 433 kcal, which is the kind of every-man-for-himself exotherm that you want to avoid at all cost.
and
> Organometallic reagents come from large tribes, and there are always wild cousins up in the hills. A good place to look for the livelier ones is in the simplest alkyl derivatives, and you should go all the way down to the methyls if you want to know their real character. Ignore the halides. Methylmagnesium bromide you can get in multiliter kegs; they might as well sell it in Pottery Barn.
and
> ... compounds with lots of nitrogens in them – more specifically, compounds with a high percentage of nitrogen by weight – are a spirited bunch. They hear the distant call of the wild, and they know that with just one leap of the fence they can fly free as molecules of nitrogen gas. And that’s never an orderly process.
and
> perchloric anhydride (dichlorine heptoxide) [is] a liquid with a boiling point of around 80 C, and I'd like to shake the hand of whoever determined that property, assuming he has one left.
Apparently it's not as bad as they say.