phosphorus production

[zeocrash]

Ok i was looking for a method to manufacture phosphorus, i searched the forum and archives and found an old post by NBK about the manufacture of phosphorus from an old 19th century chemistry guide. one of the replies though mentioned the production of phosphorus by heating with coke and sand.
the reinhold chemical dictionary says that phosphorus is produced industrially using this method. in an electric furnace. the phosphorus is then apparently driven off and condensed under water. I was wondering if anyone had any ideas about how to do this practically in the lab. I was thinking of using a condenser, but the phosphorus would solidify in the condenser and bung it up. another idea i came up with was to use a column of water or something similar and pass the vapour up through the column to cool and condense, where i would skim the solid off the top (i think phosphorus floats). i could also use an inert gas to pass through the equipement to make sure the phosphorus does not combust. I was wondering if anyone knew anything else about this method, or knew an easier way of doing this.

[a_bab]

The WP won't float, it's heavier then the water. And assuming that your mini-furnance it'll be isolated from air, and it should be, there will be presure built in it because of the WP vapors. All you have to do is to drive these vapors in cold water; the vapors will be hot enough to heat the tube so there will be no problem concerning the solidification of WP in the tube.

[FadeToBlackened]

I'd just like to clarify something, heating coke+sand will not yield phosphorus, the sand is an addition to the coke+phosphate, which nbk (I think) said combines with residual calcium after the phosphorus has been driven off.

[THErAPIST]

I once read something in book at school that had the discovery and such of all of the elements on the table. When I read about phosphorous i remember something being said about a 5 gallon bucket being filled with urine and then it was set outside for a week or two untill worms and stuff started to crawl around in it. Then it was boiled untill all that remained was a crude form of phosphorous which had to be treated with alcohol or something of the sort. I'm not too sure about it so I'll find the book and post what it says if i can.

[Sparky]

There is a book called "The 13th Element" on the FTP. Phosphorous being the 13th element discovered. I think it is in the uploads section though. It is also on the Mad Science FTP. If you have a place to put it I can upload it somewhere. It is a bit over 1.8 megs.

Edit: I 'found' it on this webpage:
<a href="http://pyropage.cyberarmy.ca/13thelement/" target="_blank">http://pyropage.cyberarmy.ca/13thelement/</a>

<small>[ January 13, 2003, 08:26 PM: Message edited by: Sparky ]</small>

[nbk2000]

All that "fermenting till worms..." crap is unneccessary. Just set the piss out in shallow trays to evaporate and collect the phosphate salts the remain. Mix with carbon and sand, heat to over 1000*C, and collect the vapors in warm water.

A furnace capable of melting copper should be hot enough. The furnace is the hard part.

[megalomania]

There have been other threads concerning this matter not so long ago. I believe it was Polverone who tried an experiment very much like the one you have described. Obtaining P from urine is another matter we shall not concern ourselves in this thread.

The industrial reaction is more efficient in terms of producing more P from the same chemicals than using more laboratory means. There is another thread I believe that describes the production of P from ordinary chemicals.

I have given some thought in the past on improvising an industrial based setup, along with other methods. The first problem is making the electric arc. This is necessary to provide the high temperatures needed to initiate the reaction, but an electric arc is not essential, just more convenient to industry. You will have to have some type of high temperature furnace, which I do believe can be improvised. There are a few documents on the FTP that seem to indicate they are about making such furnaces, but I have not checked them out yet. You can use an iron or steel pipe with pipe caps screwed on to make a reaction flask (like a pipe bomb). The reactants are mixed in the pipe which is placed in the furnace.
The top of the pipe can be connected to an adapter letting you run a length of metal tubing under water. You may need a reducing adapter or two along with a pipe thread to flair fitting adapter to use a small diameter copper tubing that can bent, or use steel pipe with some elbows. Either way the intent is to lead the exhaust gas into a container of water.
The equipment is rather simple, the reaction not complex, the only problem will be getting it hot enough. Solve the furnace step first, and the rest should be easy. You do not need to use a regular condenser, and inert gas, or indeed any standard lab equipment. Any air in the setup will not last long. The only problem I foresee is the possibility of a suckback of water into the very hot metal pipe, a trap can stop this, but it may get filled with a little P. P may also condense on the insides of a tube if it cools off enough enroot to the water. These are problems that only experience with using such a setup can resolve, if indeed they happen at all.

[nbk2000]

I don't think water suckback would be a problem if you placed the condenser tube just under the water. Any water that did get sucked back up would be turned into steam in the hot condenser tube long before it got into the actual retort.

I don't see why it's so hard to make WP. They managed it back in the 17th century for Gods sake!

Polverone had the problem of the mix forming a glass in the retort. Perhaps if the retort was rotated along the horizontal plane, the reaction mix wouldn't be able to solidify into a solid cake, and would increase surface area for vaporization of the P.

[THe_rEaL_dEaL]

An idea! (holy shit!!!) :D

To keep the vapor from condensing on the inside of the metal tube on the way to the condenser you could just keep the tube at elevated temps.

This could be achieved with a resistance coil around the tube or a gas BBQ burner (the long narrow burners used on BBQS)

[Polverone]

There is hardly any problem keeping the metallic venting tube warm if it is emerging from a furnace and not terribly long. Resistance heating is not necessary. The glassy reaction products are a real bitch to remove mechanically and I didn't find (in my short search) any reagents that would attack the crap without attacking the reaction vessel itself. I have collected some documents and performed some preliminary experiments that indicate aluminum is a significantly better reducing agent than carbon for phosphorus production. Don't try using fine aluminum powder; it's too reactive and could present a real hazard if it were heated in confinement. Aluminum reduction wouldn't be cost-effective on an industrial scale, but I don't need 50000 kg/month of phosphorus. Another good idea, suggested by Vulture I believe, was to try using CaC2 as a reducing agent for phosphates. I have not yet tried this method. Oh, BTW, it seems to be a much better idea for the home experimenter to use metaphosphates as opposed to plain old phosphates, as they have much more reasonable melting points (to mingle them with the reducing agent). My horrible sticky-then-glassy something-or-other phosphate (some sort of metaphosphate, I would think) was produced simply by strongly heating diammonium phosphate (used as a nutrient in brewing).

I imagine (imagine, mind you) that phosphorus production would be pretty simple if I had a decent furnace on hand. But I don't have a decent furnace on hand, this rental didn't come with a machine shop (pity), and a gas burner just doesn't give the heat that I need. If I were out in the boondocks I would build a nice big fire in a pit and feed it air from a hair drier or the like. Does anybody here live out in the boondocks? Sure you do. C'mon, be a pioneer.

Edit:

See

SOME RECORDS OF THE YEAR'S PROGRESS IN APPLIED CHEMISTRY.1
Wm. McMurtrie;
J. Am. Chem. Soc.; 1898; 20(12); 967-987.

Tantalizing bit:

"Franck has likewise utilized the high combustion temperature of aluminum for the reduction of oxides both metallic and non-metallic and particularly the production of phosphorus. For this latter purpose he mixes the metaphosphate with silica and aluminum, and heats the mixture to start the combustion when the reduction proceeds quietly; the phosphorus distills readily and yields an excellent product particularly when the lime compound is employed."

Now to find out who this Franck was, learn the details of his process, and see if it's practical on a lab scale.

<small>[ January 14, 2003, 04:03 AM: Message edited by: Polverone ]</small>

[nbk2000]

So you think chunks of aluminum metal would be better than carbon? It'd certainly be easier to make a furnace capable of melting aluminium than one capable of melting copper (or iron).

I'd also think that having a large surface/volume ratio would help in allowing the P to volatilize off as fast as it was formed. If I remember correctly, your pipe retorts were vertically oriented?

[Polverone]

Not chunks, more like coarse powder or perhaps shredded foil. Something with decent surface area that can be mixed with the other materials prior to loading in the reaction vessel but that isn't so fine as to be dangerously reactive. Just after I edited that post I realized that I had (unknowingly) referenced Franck before in one of my other phosphorus posts. Sadly, the original article is in an old German journal. But I think there are enough details to try some experiments. Phosphorus from shredded foil, homemade calcium metaphosphate, and diatomaceous earth? This could be more fun than homemade cyanides if it works out :D :D

[nbk2000]

Think you could make a "jelly" roll out of reynolds foil and metaphosphate? Toss the roll into the pipe (horizontally, of course) and roast.

At the time of that journal reference, it was probably prohibitively expensive to use aluminium since it wasn't till the 20's or 30's that tha Alcoa process was discovered to make it cheap to make. Which is NOT a problem nowadays.

Machavelli is in Germany. Perhaps he could call some local universities and obtain a copy of the journal article and translate it? :D

Last I heard, RP was going for $1,000/Kg for use by meth cooks. Being able to whip it up yourself could put you in good finances. :)

With OTC cyanide and WP production processes in hand, you've got one of the (un)Holy Grails of IW...Nerve Gas. :D Ah, nothing like a whiff of Tabun in the morning to get the ol' juices flowing, eh? <img border="0" title="" alt="[Wink]" src="wink.gif" />

<small>[ January 14, 2003, 04:35 AM: Message edited by: nbk2000 ]</small>

[Polverone]

I imagine that using aluminum as an intermediate would still be industrially undesirable since it represents another step, produces more waste, and takes a lot of electricity but such economic considerations are of little importance to the home chemist. I spoke too hastily about the journal article. It appears to actually be in English and was posted on Usenet some months ago as part of a long discussion about thermite. Search for Franck in the "new adventures in cyanide" thread to find the text. It is fairly detailed, though not meticulously so.

Phosphoric anhydride, phosphorus halides, phosphorus as a catalyst, phosphorus as a reducing agent... Phosphorus opens up many synthetic possibilites. I doubt I'll ever be trying for homebrew Tabun, but there are many things I would like to use phosphorus for. At one time I believed that phosphorus production would very much ease the task of methamphetamine synthesis, but I now believe that HI reduction is a method whose days are numbered. Eventually the pills will no longer be OTC and the dumbest of the cooks will have to find an entirely different hobby. The better ones will just go after P2P as they have for years. In the short term, you are very correct that you could make a good living just peddling RP (if you're not caught).

The jelly roll idea isn't bad. The powder would need something to stick it to the aluminum while it was rolled up; maybe just a light misting of sugar water, spray-on adhesive, or the like. Dampen, coat, roll, dry at low heat, place in reaction chamber, heat intensely... and hopefully reap white phosphorus. That would make my day. It would make my whole month.

[Alchemist]

Hello all,

several years ago I had several grams of RED Phosphorus and tried to convert it t YELLOW by distilling it. I use a glass retort and put the end into warm water. After heating started the YELLOW Phosphorus started comming over just fine. After all the RED was converted I removed the heat. A lot of YELLOW Phosphorus had collected on the neck of the retort and as the system started to cool down the water did start to suck back into the retort. As I did not want to break my retort I (NOT THINKING) removed it from the water. As air rushed in and hit the hot Phosphous there was a load explosion and the retort went everywhere. I had glass cuts all over my face, but my eyes where ok (thank God).

The point here is to use caution, be aware of air leaks, metal pipes(etc) could be a real danger!

Good luck to everyone with this research, Phosphorus is a VERY needed element with many uses.

P.S., for a arc furnace see my upload to the FTP on making Calcium Carbide!

[Mr Cool]

Furnaces are easy to make, a google search will turn up loads of references, both on charcoal and gas burners. Even a bunsen burner can be converted into a little mini-furnace quite easily.
The simplest way would be to have a large flower pot full of crushed charcoal, with your reaction vessel inside, and blow hot air in the drainage hole at bottom from a paint stripping gun. These are available at DIY stores, and are GREAT. The one I have blows out air at something like 400*C (hot enough to ignite wood on its own, so it must be pretty hot), and when I blew it into a coal fire it got the temperature high enough to melt the end off a cast iron rod that's about 1cm diameter. Plenty hot enough for all your phosphorous/cyanide/CaC2 etc needs.
Checking my garden centre catalogue I see that monoammonium phosphate is £5/kg, which I'm sure is cheaper than buying it as a brewing nutrient, which I've never seen in more than 50g tubs. If you could get a 50% yield that'd be a fiver for 300g of WP, then sell it at $1000/kg to Hive bees... :D :D
The biggest problem that I see is how would you disassemble your apparatus for the next batch? You'd have to use metal with screw threads, which would get gummed up with this phosphate glass and Al2O3, forming a nice adhesive, and if you did get it off it'd immediately burst into flames!
Maybe you should have a pipe through which you can blow [insert any inert gas here] into the vessel, then you could get everything very hot, blow CO2 through, and this would vapourise and blow out the last of the phosphorous which, if there was enough, could be collected, or otherwise allowed to burn off. And you could then unscrew it while hot... so maybe it wouldn't be a problem after all.

"and heats the mixture to start the combustion when the reduction proceeds quietly"

Something like this would be nice - basically a mild pyrotechnic mixture that yields phosphorous during combustion. Then no furnace would be necessary, just an ignitor!

[Polverone]

I tried using calcium carbide to reduce sodium metaphosphate. It didn't work, at least not with a gas burner as my heat source. I still need to make another attempt with aluminum (hopefully silica too, next time).
</font><blockquote><font size="1" face="Verdana, Arial, Helvetica">quote:</font><hr /><font size="2" face="Verdana, Arial, Helvetica">Something like this would be nice - basically a mild pyrotechnic mixture that yields phosphorous during combustion. Then no furnace would be necessary, just an ignitor!</font><hr /></blockquote><font size="2" face="Verdana, Arial, Helvetica">No kidding. It would be another proud step on the path toward World Domination (or whatever it is at the end of this path I'm walking).

[knowledgehungry]

I read somewhere that the insides of flourescent lights were coated with P. I am not sure whether that was elemental P or a compound containing P. I doubt that this would be a cheap or efficient way of obtaining P but i thought that you might like to know.

[A43tg37]

knowledgehungry,
The insides of fluorescent lights are coated with phosphors, not phosphorous itself. The phosphors are chemical compounds (oxides, fluorides, and vanadates, to name a few, with some of the higher efficiency fluorescent lights using rare-earth compounds), not the element phosphorous. There may be some fluorescent lights that utilize phosphorous compounds (but it seems rather dangerous to put these compounds inside one, given that they can burst if hit by water, and the resultant mess would probably be toxic), but I've never heard of any. Even if there are lights that use phosphorous compounds, it seems better to stick with the production from phosphates or phosphate derivatives, as that method would yield larger amounts than could conceiveably be obtained from a reasonable number of fluorescent bulbs.

<small>[ January 18, 2003, 10:17 PM: Message edited by: A43tg37 ]</small>

[Machiavelli]

Polverone, if you give me the reference, I'll see whether I can get it.

[Polverone]

I was wrong about it being in German - sorry. The text can be found in the "new adventures in cyanide" thread, which drifted off-topic (as threads have a habit of doing) and started being about phosphorus production.

[FlaAlchemist]

For lab scale quanities, all you need is the iron pipe setup described in this thread . Instead of the furnace just heat the iron tube with the propane torch. It will work, but be very careful with the white phosphous obtained..and be sure to remove the receiver before blowing out the torch or the water will get sucked back into the pipe. The yield is not that great but it does work..
I do all my experiments on a semi-microscale 1st...then scale up after i get all the bugs worked out.

[nbk2000]

So then you'll post pictures of your WP? Because we'd all like to see this very much, as it's been such a hassle that none of us have succeeded at it yet.