Hittorf's violet phosphorus

It is also sold as a tile de-hazing and solid no fume concrete etchant product in the hardware store. Few bucks/lb, say 8$ ish here. For the electroplating could suspend it in a dollar store stainless bowl polarity protected. Just pour out acidic solution (*save for later not down drain) when not charged I would think. Stainless never took a hit from silver nitrate refining sol with suspended 925 bar plating Ag out on it.

For the other side of reaction where you had failure, why not cast iron? Standard for melting lead to make fishing weights. Just on the fly thinking, not sure if you would have other compatibility issues, as I am not all too familiar with your synthesis of violet P. Controlled here

*Edited for non polluting statement.

[Edited on 19-2-2017 by violet sin]

Of course, I wouldn't dump a load of lead waste down the bog!

I recycle almost everything. Everything bar organic generic tarry shite, which is pretty much beyond salvation. But I can't remember the last time I actually dumped any chemical waste, save for some bicarb solution used to catch HCl fumes and dilute HCl used to scrub NH3. Other than that, I've been continuously recycling everything more or less.

Electroplating? are you suggesting use of the lead rod that it'll end up producing as an anode and relying on it breaking down, electrolysing sulfamic acid solution?

And its watched everywhere, I just go for suppliers who won't snitch. Bought 2kg, enough to last for a decent few syntheses. PBr3 and possibly PCl3/PCl5 are on my to do list.

I wouldn't bother cooking meth from pseudoephedrine using the RP/I2 method, its messy, stinky and takes ages. Dirty as well IMO. Birch is far superior, cleaner, more tolerant of crap that one can't get out of the substrate until say, steam distillation of product. And its fast. Safety can be improved by doing an in-situ birch too, as NH3 is to an extent soluble in diethyl or diisopropyl ether. Takes longer than using condensed NH3, since one needs a lot more NH3, keeping the flask on a cryo bath, but the dark blue of solvated electrons indeed appears after prolonged bubbling and stirring, good contact of the NH3 stream with the Li is essential, but its a lot safer IMO than using pure anhydrous.

I'd imagine such an in-situ birch-benkeser reduction would work on reducing certain primary benzylic alcohols. Not that I'd do such a thing, of course

Its not quite as convenient as the classic way of doing a birch reduction, adding the substrate to the NH3 with a little alcohol as proton source, and slowly adding Li as little chips, with stirring, the blue forming and dissappearing as the Li is consumed and the solvated electrons reducing the substrate, so one can tell when its done. The in-situ way requires calculation of the molar quantity of Li to accomplish the reduction and preforming the solvated electron 'soup' Still, it works for doing that particular reduction method. The NH3 can be generated more or less anhydrous, certainly dry enough by using quicklime (CaO) as the base to liberate NH3 from the sulfate or phosphate, fertilizer grade works just fine, passing through a drying tube packed with CaO if finicky, but adding just a squirt of H2O to start the generation works well enough, the CaO is a powefull dessicant and dries the NH3 as its formed. And releases no H2O on displacing the NH3, so in this way is superior to NaOH. Although with a bit of excess Li, even that can be done.

The red phosphorus is quite safe from being used in that manner, not on that particular substrate that is. Can't currently think of anything I'd want to reduce in such harsh conditions, though.

[Edited on 19-2-2017 by tsathoggua1]

I was just covering my bum should others read this and assume I meant down the drain ya know. Never know when some one just passing through thinks its ok

And yes, If you melted the Pb/P together in such a way to do your synth... Electrochemically remove the lead to reveal the P beats just waiting for it to dissolve no? Sulfamic acid probably wouldnt like peroxide soo much -> ammonium bi sulfate and subsequently lead sulfate ppt. Which will happen on hydrolysis of sulfamic acid over 60'C (mentioned in the paper) anyhow. But hydrolysis is much slower at lower temps.

Basically lead bar in filter basket, electroplated to inside of containing ss bowl or cup. Will leave P in the filter with any contaminant from the Pb not soluble. Pb will likely be in the form of a spongy mass that settles, not super adherant to the container. SS container is usually fairly smooth any how.

That is not to say you will want to spend forever dissolving the thing, unless you did, but could be complementary to other processes. What about filtering through iron seive while molten and just cleaning off junk?

[Edited on 19-2-2017 by violet sin]

So after some reading, I'm feeling brilliant... This is sealed tube, high temp kind of thing not an open top cast iron crucible deal... You dont expect the P to just burn off here without pressure?

[Edited on 19-2-2017 by violet sin]

Yes, going to either seal the tube totally, or fill a copper pipe with lead, let it set, then drill a deep hole, hoping to grow a long crystal if I can. Then add P, squirt over a little argon just to cover the initial torching of the very top, to melt the lead. Move the torch down, until the lead above the level of the phosphorus melts, then keep the torch aimed at the point where the WP is. Hoping the pressure of the lead will exceed the vapor pressure of the molten white phosphorus. Trying it in a small improvised refractory sand-cast crucible there were definite fumes of WP coming out at the top, through the lead, which didn't adhere to the crucible walls and form a seal. The result was filling the tool-shed with P2O5 smoke.

I might try that sieve idea actually. Not sure if the violet P wouldn't revert to RP or more likely, willy pete again, and just ignite. Its not meant to be highly reactive, but theres a difference between not being flammable like red or white phosphorus and withstanding being blowtorched out of a stick of lead without reverting to one of the white polymorphs.

Say, anyone got that chart showing a phosphorus allotropic phase-diagram and the various different polymorphs and how to prepare them.

Also, interestingly it appears that there are two violet phosphorus allotropes. Hittorf's and one produced by subliming (i forget which) but IIRC red P from one high temperature zone to another heated area, some 500'C for the cooler area, in a vacuum chamber. The wikipedia entry shows two distinct violet phosphorus crystal structures, with differences in the 'puckering' of the polymeric chain.

With all the Pb (anyone know any really, really sensitive colorimetric tests for Pb?) removed, I'd be curious, given the similarity of Hittorf's phosphorus, to see if its conductive, and if so, whether its isotropic, like graphite or anisotropic.

Edit-bet that spongy lead could be used for something rather than discarded. Like I said, I recycle. All except a few things, organic tars beyond salvation and I'm fairly iffy about recycling diisopropyl ether, certainly that needs to be done damn carefully given its tendency to peroxidize, its a menace, diethyl ether needs peroxide testing yearly or so, whilst DIPE...three monthly at least.


And yes this is DEFINITELY one of those high-temperature sealed tube type jobs. I'm hoping the lead itself will seal it, as I'm unsure where the silver-cadmium alloy rods are so I can't braze anything together.

As it happens I went to look over the copper scraps salvaged from dumpster-diving where resources are to be had (often good finds. I've even found some really decent antiques, such as a solid silver jerusalem cross dating back I think to the 1500s or 1600s, scenes from the crucifixion (I'm not religious, but still, looks damn good) forged somehow into the back, thing, excluding the chain, must weigh a few oz at least. Tried to get it valued by jewellers, but they wanted it for melting down for scrap! which I consider more or less a crime in this case)

But I found a brass fitting of some sort with a relatively wide bore, and one end with a screw cap. The other end will have to rely on a long drill hole for the sample, and the weight of the lead on top holding back vapours.

This is a long rxn, its meant to take, from my reading, from about 18 hours, to two days. Thats going to mean a lot of propane and a lot of supplementary heating from the hotplate. Got a fresh gas tank, or rather my old man did, for the torch. Just hoping, that he isn't going to be too pissed when he realizes how much gas has been used.

Further experiments will be done with an electric heating system, possibly multiple lead-filled copper tubes if the reaction succeeds in producing any alpha-metallic violet phosphorus. The vacuum chamber sublimation prepared allotrope will need of course special preparation. The Hittorf's P allotrope should at least be doable by means of electrical heating with a coil of nichrome wire wrapped round the area to be heated. Would be a lot more efficient in terms of resources than blasting it with a gas torch for a day and most of a night. Its 6am here, and I'm about ready to get started.

Such is the life of a mad scientist..the itch never gets scratched does it? once your hooked, your hooked for good, even if it does mean being up at 6 AM buggering about distilling white phosphorus and torching the shit out of it in molten lead

There is a piece of slightly movable plastic in there, which I'm going to torch out, leaving me with the beginnings of a reaction vessel.


[Edited on 19-2-2017 by tsathoggua1]

Quote: Originally posted by SuperOxide

@tsathoggua1, any update on this? Sorry to revive an old thread, but I was curious how this turned out (contemplating trying some of the vP procedures myself). But, while im here, I may as well add something useful. In a separate thread, clearly_not_atara was able to point out that black phosphorus can be made by autoclaving red phosphorus in ethylenediamine: https://dlisv03.media.osaka-cu.ac.jp/contents/osakacu/journa... https://chemistry-europe.onlinelibrary.wiley.com/doi/pdf/10....

Quote: Originally posted by Tsjerk

tsathoggua1 is no longer with us. He died a couple of years ago.

Oh, wow. That's sad Thanks for letting me know..

Quote: Originally posted by Organikum

I am not sure though if the judge will believe your claim that your sole intention was to produce this mystical compound. /ORG