tsathoggua1
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Hittorf's violet phosphorus
Alrighty.
I'm about to attempt production of some violet (Hittorf's) phosphorus, using a combination of a gas torch and hotplate to keep a sample of lead
molten, in two layers, one with red P and the other with white P in the lead 'sandwich'
Problem is dissolving the lead after. I lack, although can buy some WFNA, and currently have no nitrates. Anyone know if phosphoric acid or HCl with
peroxide, or a dilute piranha acid will dissolve lead (9% H2O2 is the best I have)
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Texium
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Thread Moved
18-2-2017 at 17:55 |
Texium
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The acids that you mention will not work, as lead phosphate, chloride, and sulfate are not soluble. The only slightly practical thing that I can think
of that will dissolve lead other than nitric acid is peracetic acid, though a lot of insoluble white fluffy oxyacetate is also produced using this
method. If you have glacial acetic acid, you might be able to make do with a mixture of that and your 9% peroxide. Once all of the lead has dissolved,
add more acetic acid to allow the basic acetate to dissolve.
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tsathoggua1
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Need to get more GAA.
Got some 54% formic, if peracetic would work shouldn't performic?
Edit-bugger, looks like I am going to need a better crucible. The casting sand refractory cracked, and the lead flowed through the bottom, which of
course, given it was sat on a hotplate, and a blowtorch clamped in a vice aimed at it, set the phosphorus on fire and the place is FILLED with P2O5
smoke. When the crucible broke, that was to say the least, messy.
Before the breakage, there was a slight flaring at the top, that looked gaseous rather than bulk P catching fire, the lead was first added to the
bottom in a small quantity as cut up little chips, around 1mm thick and 1mm wide, melted with the torch, allowed to cool, then a generous couple of
scoops of phosphorus (red) added. topped off with more lead chips then molten lead poured from above. Then the heating started. When the breakage
occurred it was obvious the RP had converted to WP from the greenish-white flaring flames bursting out of the broken crucible.
How does a copper mold filled to the brim with molten lead, a hole drilled in the lead, and the bottom of the pipe sealed by hammering it shut,
creating a bend and hammering it firmly closed. Should prevent the Pb from running out. Drill a hole through the lead in the bore of the pipe, then
fill with RP, tamp down plenty lead to fill the hole and start heating the pipe from the side at the point the phosphorus is situated sound?
[Edited on 19-2-2017 by tsathoggua1]
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PHILOU Zrealone
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Formic acid should work...performic acid (PFA) is a bit more dangerous than PAA...so avoid too high a concentration...for both...and avoid too much
heat of course.
You may also try with HClO4 (perchloric acid)...lead perchlorate must be very soluble.
[Edited on 19-2-2017 by PHILOU Zrealone]
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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tsathoggua1
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Could probably make some perchlorate. Although with quite a lot of effort, chlorine gas into hot NaOH and electrolysis, followed by conc. H2SO4?
its not as if there needs to be purification or lab grade perchloric for this purpose.
I think I'll just include some WFNA and 70-80% HClO4 in my next chemical order.
Fucking hell though, that was still entertaining, in a manner of speaking, the amount of smoke produced by less than a teaspoon of WP.
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violet sin
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Sulfamic acid salt of lead is soluble.
https://www.google.com/url?sa=t&source=web&rct=j&...
Little pdf on lead electrodeposition
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tsathoggua1
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Thanks! thats useful to know. Sulfamic acid is sold OTC as a descaler for IIRC kettles. Will have to pick some up.
The current problem though is sorting out a suitable vessel for the rxn,
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violet sin
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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]
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tsathoggua1
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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]
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violet sin
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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]
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tsathoggua1
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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]
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tsathoggua1
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http://www.vidmeup.com/video_manage?vid=645955
Here is a quick view of the retort being set up. Its a simple improv job from a length of scrap brass pipe with an end cap on one end.
The lead is now setting and once it has done so, a well will be drilled in down the center of the lead, and filled with phosphorus. Then I shall seal
the well with lead, and get torching the area of the pipe containing the phosphorus.
The Pb is cooling now, going to give it a few minutes and finish my beer, whilst getting fresh batteries for the camera. Given the length of time
taken for this experiment, a day at least, I won't be filming the entirety of it, I'll take shots if anything visible changes or anything interesting
happens. Otherwise it'll be the chemistry equivalent of watching paint dry, only with a blowtorch and a piece of pipe.
[Edited on 19-2-2017 by tsathoggua1]
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JJay
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That link requires a login.
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tsathoggua1
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Bugger, anyone know of any other free video hosting sites? its too big to directly upload here.
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tsathoggua1
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This is now been postponed for a short time, given the impracticality of heating with a torch. Going to buy some short lengths of copper pipe and
end-caps etc, or if I can get wider pipes and caps to fit, semi-batch sized runs.
I've just ordered a molten metal bath capable of about 500'C, which should be ideal for heating up some custom-made retorts for the Hittorf's
phosphorus.
Actually, I'm not only after saleable crystals, but decided to make P the start point of a framed periodic table element collection, given how many
allotropes and polymorphs phosphorus has, it should give me some idea of the scale of the cells in which to hold the element samples. Its going when
done, to hang on the wall of the lab, intending to chase down everything bar astatine and francium, up to Np and whichever of the actinides can be
safely obtained and sealed in lead glass with a built in miniature geiger-muller tube that can be activated by an external switch. Just an idea I had,
for display of the radioactive elements. For the really unstable ones, I'd just have to have a placeholder, something that includes them in the
daughter nuclides created in the decay chain. A few atoms hanging around is better than none, and better than an empty display case.
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PHILOU Zrealone
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Ah yes I forgot to mention that red P is uncompatible with H2O2...
So violet P might also be....even if less reactive.
White P burst into flame upon exposure to air if dry and in sufficient quantity to self heat.
Red P is stable under the same conditions, but the powder burst into flame after a few seconds if you add H2O2 30% onto it.
I don't have Violet P so I don't know if it also react vigorously with H2O2.
There is also a Black P that is normaly the much stabler allotropic form.
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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tsathoggua1
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Thanks for the heads up. Will order some nitric, (not to mention the retort that just broke. Will recycle the tube for production of WP in a sealed
tube, tried one of the suggestions here to use hot water to melt the P as it distills over. Seems like my alembic quite possibly wasn't made of boro
glass, it warped way too easily. Ever seen a couple of hundred G of molten WP suddenly start spraying through a crack in a glass vessel? that was
quite the firework display. Unfortunately wasn't able to retrieve more than maybe a couple hundred mg using a long volumetric cylinder full of hot
water, lost too much as vapour.
And lets just say, now the lawn is going to be fertilized well down the line, but for now theres several patches and long streaks from flying WP.
Going to try with just the side-arm and weld it shut, fill with argon, the much thicker glass tube hopefully will serve for a use or two, breaking the
end off each time.
There are several black phosphorus allotropes, iirc a monoclinic and cubic form, theres aother if I remember right, but can't quite remember what form
it takes.
And what of the fibrous form mentioned on wikipedia. That sounds interesting.
I noticed that WP seems to change color under intense heat (propane brazing torch) when it starts to liquefy and run down the sides of the vessel,
from a pale to almost amber yellow. The retort itself was thoroughly purged with argon, so unless traces of O2 were responsible, seems to lighten as
it cools and take on a honey-amber look whilst its a liquid being heated and refluxing.
I have a distinct feeling that black P is going to be one of the most difficult of the allotropes to produce.
[Edited on 19-2-2017 by tsathoggua1]
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SuperOxide
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@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....
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Tsjerk
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tsathoggua1 is no longer with us. He died a couple of years ago.
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Organikum
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When the czech were running a certain red phosphorus and iodine reduction of a benzylic alcohol they were too lazy to filter off the phosphorus and
just added a shitload of NaOH at the end followed by steamdistillation.
The result was violet phoshorus left back in the flask, violet phosphorus, no black no red - violet.
I am not sure though if the judge will believe your claim that your sole intention was to produce this mystical compound.
/ORG
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SuperOxide
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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 |
And why would I be explaining that to a judge - ever? If you're implying that I'm after red phosphorus to make illicit narcotics, then doing
such a procedure is pretty senseless since there are far easier ways to get red phosphorus (and I have ~100g on hand already).
It's a little cynical of you to assume that, though.
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