Sciencemadness Discussion Board

Preparation of elemental phosphorus

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Nitro-esteban - 21-6-2013 at 12:58

It was just an idea... but I think its worth trying.

Direct Reduction of Phosphorus pentoxide to P4, possible?

Zachemophile - 15-7-2013 at 10:50

I would like to experiment with WP but I know the inherent difficulties of getting my hands on the stuff. Due to its use as a stand alone reducing agent in methamphetamine production it is not easily available in the modest quantity I would like. One option would be to obtain it from thermal decomp of red P, but this reagent is just as controlled for the same reasons. I have no intentions of converting cold pills to crank, but I'm sure they won't take my word for it.

As an alternative I have mulled over the idea of reducing the easily obtainable phosphorus pentoxide to condensable P4.

What dyu guys think? Id like to have a few pointers from more experienced chemist before I get started so that I don't waste my time / risk my life on procedures that won't work or will leave me severely injured.

Would LAH work as a reducing agent, or maybe Na + H2 (I think I would use amalgam rather than the pure metal)?

I'v heard carbon could work, in a kind of smelting type reaction, but I don't want to go anywhere near high temperatures when it comes to Willy Pete.

I realize the final product would contain quite a bit of oxide impurity, but I think I could get rid of most of it with a chromic acid treatment (although I've read from someone else's post that nitric would work the same or even better). Or should I condense it directly into acid solution?

Am I insane for even thinking this is possible? I've toyed with the idea of attempting the industrial kiln method of production (calcium phosphate, silicon dioxide, carbon and HIGH temperatures) but I'd rather not blow up.

Anyway just a little brain teaser for those of you that would appreciate a possibly easy way of producing WP at home or in the lab. If your advice is good I might live long enough to post my findings.


blogfast25 - 15-7-2013 at 11:03

Check out the sticky thread above.

BTW: in all likelihood: 'No heat? No phosphorus'.

Zachemophile - 15-7-2013 at 12:46

I would like to experiment with WP but I know the inherent difficulties of getting my hands on the stuff. Due to its use as a stand alone reducing agent in methamphetamine production it is not easily available in the modest quantity I would like. One option would be to obtain it from thermal decomp of red P, but this reagent is just as controlled for the same reasons. I have no intentions of converting cold pills to crank, but I'm sure they won't take my word for it.

As an alternative I have mulled over the idea of reducing easily obtainable phosphorus pentoxide to P4.

What dyu guys think? Id like to have a few pointers from more experienced chemist before I get started so that I don't waste my time / risk my life on procedures that won't work or will leave me severely injured.

Would LAH work as a reducing agent, or maybe Na + H2 (I think I would use amalgam rather than the pure metal)?

I'v heard carbon could work, in a kind of smelting type reaction, but I don't want to go anywhere near high temperatures when it comes to Willy Pete.

Am I insane for even thinking this is possible?

bfesser - 15-7-2013 at 12:57

Quote: Originally posted by Zachemophile  
Would LAH work as a reducing agent, or maybe Na + H2 (I think I would use amalgam rather than the pure metal)?
Wasting LiAlH<sub>4</sub> on isolating P? I don't even...

<img src="http://time2breakup.files.wordpress.com/2013/07/annoyed-facepalm-picard-l.png" width="300" />

Why don't you just read though this thread before posting strange ideas that likely won't work?

[edit]
Also, if you're going to continue saying things like "Willy Pete," we'll assume you're just a cook looking to be spoon-fed and your posts will be ignored or removed.

[Edited on 7/15/13 by bfesser]

Magpie - 15-7-2013 at 14:07

Quote: Originally posted by Zachemophile  

....easily obtainable phosphorus pentoxide ....


May I ask in what country (or continent) you live?

Endimion17 - 15-7-2013 at 15:07

IIRC, WP has nothing to do with metamphetamines. It's pretty useless for such things partially due to reason it's violently reactive.
It's RP together with iodine that's used to make HI in situ for various organic reactions (I think; I really never bothered to search on how to cook drugs), and while you can get small lumps of WP by thermal conversion and meticulous purification from RP, you can't really get RP from WP that easy.
In that regard, WP is less interesting to cooks, but it's also not very interesting to most k3wls as it's not something you can easily get and then force to react in a spectacular fashion without seriously jeopardizing health. It's more of a curious allotrope that glows in the dark and can make your life pretty miserable if you don't handle it with care. It's kind of like Gollum's precious. :)

But yeah, you won't get any allotrope unless you use heat, lots of it. There still isn't a process out there that is similar to the, now famous among amateurs, isolation of potassium without the whole mess.

Some things are still basically the same as when invented. Aluminium and phosphorus production, for example.

May I suggest reading at least 25% of this thread? It should not be that hard.

AndersHoveland - 15-7-2013 at 15:09

I had an idea. What if we reduced sodium phosphate with zinc powder in a closed iron container over flame. This would form zinc phosphide. Cautiously remove the residue, place in an enclosed flask with sealed tubing, add hydrochloric acid, and pass the resulting PH3 gas into a solution of FeCl3. This might oxidize the phosphine to phosphorous, though I do not know. I am not sure what other reaction could happen.

zed - 15-7-2013 at 15:39

Zachemophile,

The production of Red Phosphorus, via the reduction of phosphates via LiAlH4, has been reported on......here. As I recall, there is some, but too much information in the literature about it. Anyway, reputedly, it can be done.

Quite likely, if the reduction can be performed with LiAlH4, it can also be performed with NaAlH4. If you have a Parr-type pressure reactor, NaAlH4 can be produced. (And, if required, that material can be used to produce LiAlH4.)






AndersHoveland - 15-7-2013 at 21:32

I wonder... do you think it might be possible to reduce triethyl phosphate dissolved in ether with aluminum foil, by passing anhydrous HCl gas into the solution?

Afterwards, hydrolyze the ester to phosphorous acid, which might then be easier to further reduce than the phosphate. Woelen remarked something about this in another thread:
Quote: Originally posted by woelen  
Indeed, the highest oxidation state salts and acids usually are much less reactive than the salts (and acids) of lower oxidation states:
- nitrite is more reactive than nitrate
- sulfite is more reactive than sulfate
- chlorate is much more reactive than perchlorate
- bromate is more reactive than perbromate
- phosphite is more reactive than phosphate, although the difference is less than with the other examples above.

As an example, nitrite can act as either an oxidizing agent or reducing agent, it is fairly reactive. Sulfur dioxide typically acts as a reducing agent, but can readily oxidize H2S.

I wonder if it might be easier to reduce phosphite also.

[Edited on 16-7-2013 by AndersHoveland]

Nitro-esteban - 26-8-2013 at 13:07

Perhaps phosphorus can be obtained from malathion.

testimento - 28-9-2013 at 17:29

For all the chit-chat, it doesn't seem to be impossible to perform the industrial process in small scale:


2 Ca3(PO4)2 + 6 SiO2 + 10 C → 6CaSiO3 + 10 CO + P4

700g Calcium phosphate + 360g silicon dioxide + 120g carbon → 30 grams of phosphorus

Oh dear, heating a kilogram buttload of waste soil up to 1500C all only just for a neatly 30 grams of white waxy accumulant? Bring that all way up to 100 kilograms for getting only 3kg out? Aww f*....

Another source cites using microwave at 540C - possibly manageable with conventional heating too:

1 4H3PO4 + 16C → 6H2 + 16CO + P4

98g phosphoric acid + 192g carbon → 30 grams of phosphorus

I remember seeing a 25-liter trunk of decent quality phosphoric acid in some sort of cleansing ware shop so whenever I'd have a need for some phosphorus, I might give it a shot and let you know.

[Edited on 29-9-2013 by testimento]

elementcollector1 - 30-9-2013 at 16:11

Quote: Originally posted by testimento  
For all the chit-chat, it doesn't seem to be impossible to perform the industrial process in small scale:


2 Ca3(PO4)2 + 6 SiO2 + 10 C → 6CaSiO3 + 10 CO + P4

700g Calcium phosphate + 360g silicon dioxide + 120g carbon → 30 grams of phosphorus

Oh dear, heating a kilogram buttload of waste soil up to 1500C all only just for a neatly 30 grams of white waxy accumulant? Bring that all way up to 100 kilograms for getting only 3kg out? Aww f*....

Another source cites using microwave at 540C - possibly manageable with conventional heating too:

1 4H3PO4 + 16C → 6H2 + 16CO + P4

98g phosphoric acid + 192g carbon → 30 grams of phosphorus

I remember seeing a 25-liter trunk of decent quality phosphoric acid in some sort of cleansing ware shop so whenever I'd have a need for some phosphorus, I might give it a shot and let you know.

[Edited on 29-9-2013 by testimento]


In case the carbon isn't quite enough to bring the reaction up to the desired heat, one could always use silicon carbide powder from a rock shop.

The only problem I can see is the CO - what on earth would you do to get rid of that? Leave oxygen in the reactor to turn it into relatively harmless CO2?
Also, could I request that source?

[Edited on 1-10-2013 by elementcollector1]

12AX7 - 30-9-2013 at 17:22

CO would pass the condenser, at which point it could be flared off (along with any pesky P4 / PHx fumes), or just vented.

CO burns easily in air, sustaining a dim blue flame.

Tim

Metacelsus - 30-9-2013 at 17:32

Quote: Originally posted by testimento  


2 Ca3(PO4)2 + 6 SiO2 + 10 C → 6CaSiO3 + 10 CO + P4

700g Calcium phosphate + 360g silicon dioxide + 120g carbon → 30 grams of phosphorus



What if you used sodium hexametaphosphate (empirical NaPO3)?

4 NaPO3 + 2 SiO2 + 10 C → Na2SiO3 + 10 CO + P4

408 g NaPO3 + 120 g silicon dioxide + 120 g carbon → 30 grams phosphorus

As to the CO, can't you absorb it in concentrated NaOH solution to get sodium formate?

[Edited on 1-10-2013 by Cheddite Cheese]

[Edited on 1-10-2013 by Cheddite Cheese]

learningChem - 1-10-2013 at 20:23

According to Mellor, phosphoric acid is reduced with carbon in fireclay retorts "heated to redness".

What temperature would that be in celcius?


12AX7 - 2-10-2013 at 06:43

Around 700-800C (think MP of aluminum).

Tim

plasticraincoat1 - 5-10-2013 at 12:00

I have some yellow phosphorus for sale if any one is interested.

testimento - 9-10-2013 at 14:09

Quote: Originally posted by elementcollector1  
The only problem I can see is the CO - what on earth would you do to get rid of that? Leave oxygen in the reactor to turn it into relatively harmless CO2?
Also, could I request that source?


Presuming the CO won't react the gas phase / solidified phosphorus, it will be bubbled out of the reaction through the water trap, and it can be vented via tube outside, ejected via exhaust fan or directed into a separate burner air intake to be burned.

I remember this was actually cited in this very topic in some form of patent which dictated that reaction scale.

https://en.wikipedia.org/wiki/Black-body_radiation
http://911research.wtc7.net/cache/wtc/analysis/fires/metcolo...
http://physics.info/color/ (this one has excellent chart)

The black-body radiation is explained in this article, including the temperature color indicators. It seems to be the most common method of showing up the temperature chart since few people have access to high-temp thermoprobes, allowing them to actually measure the reaction temps anything in excess of 350C where conventional mercury thermometers compete.

[Edited on 9-10-2013 by testimento]

reduction of metaphosphoric acid

learningChem - 3-11-2013 at 20:34

I used a ceramic retort loaded with some 2 grams of metaphosphoric acid and carbon (burnt flour). There's phosphorous coating the glass tube but the yield was almost nothing.



p.jpg - 140kB

learningChem - 3-11-2013 at 20:40

pics

p2.jpg - 209kB p3.jpg - 93kB

Dr.Felix Strausser - 16-11-2013 at 10:00

A simple way to obtain a SAMPLE of white phosphorus is by scraping out the (impure) mixture of red phosphorus from the sides of matchboxes (or if you can obtain pure red P4 just as good). Now put the red P4 in a testube whose mouth has been firmly sealed with a piece of cotton. Take this apparatus and heat lightly for a few moments until you see a white-yellow substance condensing on the cotton. Voila, white phosphorus.

;)

woelen - 26-11-2013 at 00:51

Please post useful info or do not post at all. Your last post about boiling piss does not add anything to this thread, it just derails it and makes you look like a k3wl.

elementcollector1 - 5-12-2013 at 13:36

Quote: Originally posted by learningChem  
I used a ceramic retort loaded with some 2 grams of metaphosphoric acid and carbon (burnt flour). There's phosphorous coating the glass tube but the yield was almost nothing.



You know, looking at this I'm tempted to see what happens if you scale it up. The setup is fine, but the yield is, as stated, very low. The maximum possible yield of phosphorus from a mixture of (assuming) 1.3g H3PO4 and 0.7g C would be about 0.41g phosphorus, and because you didn't use vacuum or inert gas, your yield is likely much lower than that. So, if you scale it up to 50g phosphoric acid and 25g carbon, and assume a yield of 10% (a reasonable, if low assumption IMO), your expected yield would be 1.6g of phosphorus.

bismuthate - 6-12-2013 at 18:21

What was the heat of your reaction.
Also would this be a viable route (it seems to simple)
PH3+3NH3==>(NH4)P
and then decompose the ammonium phosphide (I cant find if it does decompose, but it seems likely)

learningChem - 7-12-2013 at 00:04

some notes...

I started with (NaPO3)6 and did

a) (NaPO3)6 + 3CaCl2 --> Ca3(PO3)6 + 6NaCl
b) Ca3(PO3)6 + 3H2SO4 --> 3CaSO4 + 6HPO3


Ca3(PO3)6 is a funny substance. It's a sticky mess. Doesn't look like an ordinary salt at all (I guess these P compoounds are some kind of polymer?)

I concentrated the HPO3 solution by heating. When it cooled down, I got a mass of crystals. See picture.

In theory that stuff is rather pure HPO3, but I'm not 100% sure.

The color of the retort was kind of orange, but not too bright.


ElementCollector
Quote:

because you didn't use vacuum or inert gas, your yield is likely much lower than that.


Well, apart from P, the products of the reaction are H2 and CO. Wouldn't those gases displace any O2 present? Also, I don't think there was any P2O5 to be seen.

If I recall correctly there was a fair amount of C left in the retort. Or at least a black slag, which should indicate that there was too much C or too little HPO3?

Anyway, I don't completely trust the starting materials, and I was more interested in finding out whether some kind of reaction would happen at all using my furnace.

I'll do a more careful test. Also, I might buy some phosphoric acid.

hpo3.jpg - 240kB

[Edited on 8-12-2013 by learningChem]

elementcollector1 - 7-12-2013 at 09:58

True that. Unfortunately, there was already air in the tube before the reaction, so it's not out of the question. Also, the hydrogen and carbon monoxide would have diffused into the air in the tube, so you'd likely get an unholy mix of the three.
I'm assuming you didn't distill off the phosphoric acid, which is normally clear crystals. Try a recrystallization if you're not sure about the purity.

DoctorZET - 30-1-2014 at 11:08

I found some papers (written by me), where I noted several experiments that I made in the past summer (or I intend to make).
I think that...these informations will be helpful:

sg0000.jpg - 359kB sg0001.jpg - 345kB sg0002.jpg - 331kB

Attachment: converted_to_.pdf (1020kB)
This file has been downloaded 1103 times

<!-- bfesser_edit_tag -->[<a href="u2u.php?action=send&username=bfesser">bfesser</a>: PDF]

[Edited on 30.1.14 by bfesser]

DoctorZET - 31-1-2014 at 10:07

I think I forgot to tell you something :) :
All operations involving white phosphorus should be conducted in the absence of light (especially short wavelength light) because white phosphorus can turn into red phosphorus, which is much less reactive.
...P4 molecule is freaking annoying :mad:

[Edited on 31-1-2014 by DoctorZET]

PeeWee2000 - 31-1-2014 at 10:38

Thats a pretty spiffy looking setup idea there ZET, carbon disulfide seems kind of exotic to me though is it necessary for capturing the phosphorus or could you eliminate it and try to just condense the phosphorus in cold water if you're willing to live with some impurities?
I've been wanting to be able to get ahold of phosphorus for some time but haven't bothered with all the attention it gets from the DEA and lack of need that I have for it but this method would be perfect for me if its really that simple!

elementcollector1 - 31-1-2014 at 10:54

Problem is, that conversion to RP is actually very slow - only the surface is converted, if I recall. So, light is fine.
Doc ZET, is this an experiment you did or one you plan to do? The theory looks fine from a surface glance.

DoctorZET - 31-1-2014 at 12:03

Hmmm...I think it should also work with carbon tetrachloride/chloroform/benzene/toluene (this solvents can easily dissolve white phosphorus) but be careful with first two solvents (because, phosgene can be formed in the CO+H2 output flame).
Also you can try to collect P4 vapors in cold water, then boil the water and release the white waxy phosphorus sample into the flask. I'm not sure that it will work , unless I don't try this method yet. (there can be traces of H3PO4 and other phosphorous acids in water, but not in CS2 or other nonpolar solvents)
And yes, I did this experiment (on a small scale). I have got only 2-3 grams of phosphorus ... but my goal was not to obtain phosphorus.
Guess who was my source of phosphoric acid? >>> Answer is seven bottles of Coca-Cola. :)
First, I boiled all of the juice for 2 minutes (to destroy the carbonic acid), then added 30 grams of Ca (OH) 2 to precipitate calcium phosphate.
Then I added calcium phosphate in concentrated sulfuric acid, I distilled the mixture and voila! A few grams of almost pure phosphoric acid from Cola! (almost dry).
My goal was to determine experimentally how much phosphorus is in Coca-Cola. ;)

To be sure, use acetylene instead of ethylene, but be careful! Acetylene can ignite/explode in the presence of an oxygen source (like NO2, N2O3, CuO, SnO2, PbO, H2O2 ,ClO2 ,HClO2 and, why not H3PO4 ) at that temperatures (600*C).

[Edited on 31-1-2014 by DoctorZET]

elementcollector1 - 31-1-2014 at 12:16

Interesting! What did you find in terms of yield of phosphoric acid from x bottles of Coke? (example, how many grams of Ca3(PO4)2)
I've had problems with sodium orthophosphate and sulfuric acid - mainly due to contamination with carbonates (calcium would not be an effective separating agent here...)
How did you add the Ca(OH)2? In solution, or solid? If solid, how did you separate this from the Ca3(PO4)2 - just by mixing stoichiometrically, or was there something else?
This sounds like a potentially more viable procedure than the usual high-temperature stuff, mainly because the reagents are (relatively) easy to find or synthesize, and the procedure itself looks sound.

DoctorZET - 31-1-2014 at 12:49

As I said (in the pages), the reaction between ethene and phosphoric acid at 600 * C in the the presence of CuO is exothermic, and if you try to scale up to much, you can get it out of control and produce phosphine, a toxic gas (smells like garlic when burned).
About the phosphoric acid in Cola...I don't remember the exact concentration...but I remember that if you add enough Ca(OH)2 in the boiled juice, the solution will turn basic and the calcium phosphate will start to decant at the bottom of the pot (along with the excess of Ca(OH)2 ).
Then collect the CaHPO4+Ca3(PO4)2+Ca(OH)2, remove the water from the mixture by heating it, and add the mixture to some fuming sulphuric acid (not to much, but a little excess).
After it reacts, you can distill almost pure phosphoric acid.
(CaHPO4 represent actualy some hidroxyapatite formed in the acid water solution, while the H3PO4 reacts with Ca(OH)2 )

[Edited on 31-1-2014 by DoctorZET]

PeeWee2000 - 31-1-2014 at 13:36

Awesome now I have a reason to get an acetylene tank! Now my welding supply company wont wonder why I only have an oxygen tank :) And toluene is definitely the most convenient for me, I can buy it by the gallon no problem. Cant wait to try this out!

I sure wish I had the patience and determination to want to figure out the phosphorus content of a bottle of coca cola, props for that ZET! Hope I get to see some more of those awesome sketches elsewhere on the forum too!

[Edited on 31-1-2014 by PeeWee2000]

DoctorZET - 31-1-2014 at 13:57

Thanks...but (just asking) ...you have read the section in which I said:

"Acetylene can ignite/explode in the presence of an oxygen source (like NO2, N2O3, CuO, SnO2, PbO, H2O2 ,ClO2 ,HClO2 and, why not H3PO4 ) at that temperatures (600*C)."

and, I also say that :

" the reaction between ethene and phosphoric acid at 600 * C in the the presence of CuO is exothermic, and if you try to scale up to much, you can get it out of control and produce phosphine, a toxic gas (smells like garlic when burned). "

so...using an acetylene tank for these procedure...it's a "little" bit dangerous...I think...(because you work with phosphorus, and with a lot of flames around, and with a HUGE source of acetylene, and with a 2-3 meters hot red copper tube in which some dangerous&exothermic reduction reactions take place)

[Edited on 31-1-2014 by DoctorZET]

[Edited on 31-1-2014 by DoctorZET]

DoctorZET - 31-1-2014 at 14:12

better use calcium carbide ;)
and there is another something:
3CuO+H3PO4+2C2H2 =(550*C)=> Cu3PO3+4CO+(7/2)H2+ [ KABOOM ],
where the 'kaboom' is the main problem...
then, the heat produced by first reaction activate this reaction:
Cu3PO3 <=(630-700*C)=> 3CuO+ P^
and the CuO is reintroduced in the process

[Edited on 31-1-2014 by DoctorZET]

[Edited on 31-1-2014 by DoctorZET]

PeeWee2000 - 31-1-2014 at 14:45

Yeah It might not have all been fresh in my head in that last post though ;) Luckily I'm only fantasizing right now, usually I'm pretty through with my safety though. And besides I dont actually have the money to buy an acetylene tank for a single reaction :cool:

testimento - 8-2-2014 at 20:33

Ok I spent 12 hours reading the topic and made some 11 pages of notes from what people were doing and thinking around there.

I noted that nobody didn't consider the Wöhler process of using electric furnace for this reaction. It certainly gives enough heat. My worry is that will the reaction mixture be conductive enough to allow current pass through. My idea is to make a tubular reactor as following:

electric furnace for WP.png - 16kB

The reactor volume would be 1-2L. To there, two tungsten electrodes with ceramic steel lined threaded plug is inserted according to picture. Also carbon rods could be used, but I've got some tungsten floating around. I would wanna test using direct microwave transformer pushing 1kW at 2000V to induce a gap width of about 10-20mm for electric arc. This way the arc wouldn't be dependent on the mixture's conductivity, but if it turns out it is well conductive once started, a voltage of 20-30V with high amperage(in scale of several dozens) should be used.

The electrodes should be inclined so the arc will initate at the bottom. A ballast of heating elements would be placed in the circuit so the fuse wont short out and the reaction energy is limited by the respectiveness of the mixture's temperature. The circuit would be fitted with power adjuster. The body of the vessel is stainless steel so it could become conductive and therefore require insulative placement.

Several reaction mixtures should be tested. First is the classic mixture of 10Al + 6 NaPO3 + 3 SiO2 ball milled. Another mixture consists of Ca3(PO4)2 + 3 SiO2 + 5 C. The heat from the arc should be more than sufficient to squeeze out what we want. No inert gas is required since at the moment of initiation, the small volume of the reactor is occupied by millimoles of reactive atmospheric gases and therefore burnt to oxides in the next second.

On the side would be the exhaust port where a steel tube is lead underneath water heated to 50-60C.

Another option consists the same reactor structure, but the heating is applied through the reactor wall, as in electric furnace or by coke bed. Steel merely holds up to 1200-1400C before becoming too soft and reactive, so it could be replaced with Al2O3+silicate or MgO refractory with proper fittings.

I'm interested in the practical scalability of this reaction, eg. could this produce WP in scale of several moles per run. In the posts regards towards too finely mixed reactants caused explosive initiation when the batch was scaled up slightly, which must be taken into consideration until bringing it up to several hundreds of grams, or even kilograms. The cost of the reaction is of another matter: if the reactants of Al and B could be substituted with carbon and SiO2, the cost and the trouble of making the reactants will decrease substantially. With the most expensive setup with fine Al and Boron, the cost and the trouble of making the reactants themselves can become a major limiting factor.

[Edited on 9-2-2014 by testimento]

jock88 - 10-2-2014 at 12:57


"Ok I spent 12 hours reading the topic and made some 11 pages of notes from what people were doing and thinking around there "


Great, you should put them online as a synopsis of a rather long winded thread.

elementcollector1 - 10-2-2014 at 17:17

That's kind of already been done?
http://www.sciencemadness.org/talk/files.php?pid=247779&...

jock88 - 11-2-2014 at 09:52


I stand corrected!

thebean - 7-3-2014 at 20:05

I had an idea while I was reading this thread, but it sounds insane. I"ll propose it anyways.
3 P4S10 + 20 Al -> 3 P4 + 10 Al2S3
My plan would entail loading the P4S10 and Al into a retort made of steel pipe or maybe borosilicate glass. Then I would heat the mix with the end of the retort in water. Maybe a different reducing agent would work better.

blogfast25 - 10-3-2014 at 11:34

Quote: Originally posted by thebean  
I had an idea while I was reading this thread, but it sounds insane.


Not necessarily. Have you at least checked whether the reaction is thermodynamically favourable?

Litmus - 21-3-2014 at 05:31

Ok Perhaps I'm just a dumb-ass. I've been following op on this +decade long thread as best I can. So far I've caught up to about 2010 or so so please understand me if I'm not up to speed on the recent posts. I eventually shall, but with such a phase lag involved it'll be a little while for me more to catch up. Perhaps a spin-off thread of sorts would be in order. I'm new here, so please fill me in for any my missing spaces as a newbie. So far the German garage chemist, blogfast, peach, Wack, and Roger have contributed so much in a "thread" that was pioneered more or less by Polverone and Bromic Acid long ago. These guys have poured heart and soul into making this fascinating substance, Phosphorus. which happens to be an element. Rather amazing how far mere scientific curiouity and perseverence will go. I've heard it before that the chemists were ahead of the physicists at the time in terms of new discoveries. Long Before the periodic table was discovered, chemists were at it discovering all sorts of things by mere good "detective work" .

About time there was a forum for chemistry like there's been for the Linux/GNU/BSD crowd forever.

Okay the facts from literature I know about Phosphorus:

Quote: from my old CRC Handbook of Chemistry and Physics, 62nd Ed 1981-1982
at. wt. 30.97376; at. no. 15; m.p.(white) 44.1 C, b.p. 280 C; sp. gr. (white) 1.82, (red) 2.20, (black) 2.25-2.69.
White P has twp modifications: alpha and beta with a transition temp of -3.8 C.
Discovered in 1669 by Brand, who prepared it from urine.
Never found free in nature, it is widely distributed in minerals.
Phosphate rock, which contains the mineral apatite, an impure tri-calcium phosphate, is an important source for the element.
Large deposits are found in U.S.S.R., in Morrocco, and in Florida, Tennessee, Utah, Idaho
etc, etc. Insoluble in water...

Yes, insoluble in ideal water, which contains no dissolved gases. Real water: O2(albeit slightly), and CO2(a lot).
An old edition of CRC, but doubt a whole much has changed...


Here's a naive thought to throw out to the crowd:
For a long time I've been reading posts about how this annoying obnoxious byproduct called phosphine is often obtained by all the prodigious attempts I've been reading here to make elemental phosphorus from crucibles at 500-100o degrees C. The thought comes to mind: can you make lemon-aid out of lemons somehow by reaction of phosphine, where P is in it's LOWEST oxidation state(P-III). and just oxidize that(perhaps in-situ somehow so you don't pass out by the fumes). with an alkene or alkyne, the simplest being ethylene or acetylene, respectively. If you get the stoichiometry and heat of reaction right, ought to get the stuff in gobs, right? Or...

Interesting that is NH3 so similar in ways on the PT dissolves in water easily while PH3 don't. If you thought PH3 is bad,
Arsine is insane: even more lethal, as gaseous, and less soluble than phosphine.
In any event, makes common sense the white form is waxy and less stable than the red form.
The P4 molecules are unlinked in white while they're somewhat polymerized in red. Question is, why does
that give it a red appearance and other difering properties such as solubility in Carbon Disulfide(if you're an organic
chemist, just about anything is soluble in CS2, but may not care since the stuff is so gross)
Perhaps it could be incorporated into some gift candle for some irritating relative :)
Could the paraffin "stabilize" the P like in the movies' pyro stuff :)

rcfunker - 23-3-2014 at 16:37

Thank you for sharing the link, looking forward to read it!
Quote: Originally posted by Polverone  
Wow, don't everybody try to answer at once. Anyway, I've just found a very interesting document: US Patent 6207024 (accessible through www.uspto.gov) describes the production of elemental phosphorus from pyrolytic carbon and phosphoric acid, using microwaves to heat the reactants. The reaction takes place at much lower temperatures than the conventional arc furnace process. The problem (or problems), of course, is that the phosphorus still needs to be protected from oxidation, you need a relatively heat-resistant and microwave-transparent reaction vessel, and it's going to be tough to condense and collect the phosphorus if you're trying to come up with something using a domestic microwave oven. Microwave ovens are cheap at thrift stores, but there are still obstacles to overcome for performing this reaction at home...

aga - 11-5-2014 at 11:06

Would elemental phosphorous float or sink in Liquid aluminium (i.e. molten) ?

If it sinks, the molten aluminium will protect it from Air as it cools ...

https://www.youtube.com/watch?v=0uhI0NwlnL4

[Edited on 11-5-2014 by aga]

Metacelsus - 11-5-2014 at 12:03

It will react to form aluminum phosphide.
https://en.wikipedia.org/wiki/Aluminium_phosphide

BromicAcid - 11-5-2014 at 12:03

Quote: Originally posted by aga  
Would elemental phosphorous float or sink in Liquid aluminium (i.e. molten) ?

If it sinks, the molten aluminium will protect it from Air as it cools ...

https://www.youtube.com/watch?v=0uhI0NwlnL4

[Edited on 11-5-2014 by aga]


<s>float</s>
<s>sink</s>
<b>react</b>

ScienceHideout - 12-5-2014 at 03:09

Are you sure that that is correct, bromic acid?

The delta H of AlP is negative.

When we are talking about the reaction with LIQUID aluminum, the delta S is certainly negative, because we have a liquid turning into a solid (m.p.=2530 C)

If both are negative, doesn't that mean that the enthalpy only drives the reaction, and the reaction is only favorable at low temperatures?


aga - 12-5-2014 at 03:26

if it does sink, and if this is right :
Quote: Originally posted by Polverone  

then if done in a crucible, the aluminium would protect the P from air.

Adding a hairdryer is a nice touch.

BromicAcid - 12-5-2014 at 03:44

Quote: Originally posted by ScienceHideout  
Are you sure that that is correct, bromic acid?

The delta H of AlP is negative.

When we are talking about the reaction with LIQUID aluminum, the delta S is certainly negative, because we have a liquid turning into a solid (m.p.=2530 C)

If both are negative, doesn't that mean that the enthalpy only drives the reaction, and the reaction is only favorable at low temperatures?



Then how about :

<s>float</s>
<s>sink</s>
<s>react</s>
<b>distill</b>

Although Hittorf's Violet is recrystallized from lead, that occurs at even lower temperatures than the melting point of aluminum. Some phosphorus might stay behind in the aluminum melt but as it cools then I would wager that the phosphorus would react.

Admittedly I did not take the time to consider the known thermal instabilities of metallic phosphides when making my previous comment.

Metacelsus - 12-5-2014 at 04:56

Reaction Delta H = -166.5 kJ/mol
I don't have specific data for the entropy.

aga - 12-5-2014 at 08:11

Quote: Originally posted by BromicAcid  

Then how about :

<s>float</s>
<s>sink</s>
<s>react</s>
<b>distill</b>


Looks likely.
But then, Distill is good isn't it, as in do-able ?

jsc - 12-5-2014 at 12:46

Phosphorus.—This is obtained by heating phosphoric acid with carbon, or bone-ash or mineral phosphates with carbon and silica. In this way the phosphorus is liberated from the compound containing it, and is distilled and condensed outside the furnace. As this operation must be carried on in the absence of air, the electric furnace is particularly suitable, and has practically replaced all others.

The old method of making phosphorus consisted in heating bone-ash (calcium phosphate) with sulphuric acid, thus obtaining phosphoric acid or calcium metaphosphate. This was mixed with charcoal and heated in clay retorts, phosphorus being liberated as a vapor and condensed under water.

Bone-ash or natural calcium phosphate can be smelted directly (without the sulphuric-acid treatment) to yield phosphorus, if silica is added to combine with the lime, as well as charcoal to reduce the oxide of phosphorus, but this process could not be carried out until the introduction of the electric furnace, as the temperature required was higher than could conveniently be obtained in a retort. At the present time, bone-ash, or the minerals rock-phosphate, apatite, or wavelite, are mixed with silica and charcoal, and heated in an electric furnace, yielding phosphorus vapor, carbon monoxide and a liquid slag of calcium silicate. In some cases, however, the sulphuric acid process is still employed as a preparatory step.



A suitable electric furnace is that invented by G. C. Landis, and shown in Fig. 144. It consists of an iron box lined with vitrified bricks and having an inner lining of carbon blocks which form one electrode; the other electrode, E, being vertical. The charge of phosphate, carbon and silica is introduced by means of the hopper H and inclined tube J. The phosphorus vapor and accompanying gases pass out by the pipe O to suitable condensers, and the fused slag is tapped out below. The furnace is made gas-tight with the aid of water-seals for the cover and for the gland admitting the electrode; the latter being insulated from the furnace body at the point F. The vitrified bricks lining the furnace are laid in a nonabsorbent mortar such as a mixture of silicate of soda and powdered asbestos; this being intended to prevent absorption of the phosphorus. The carbon lining is composed of two layers of blocks, so that the inner set of blocks can be replaced, when worn away, without disturbing the outer layer. The inner tapping hole for the molten slag is plugged with a piece of wood, without any luting; an outer plug, which is luted, prevents access of air to the inner wooden plug. Two sets of tapping holes are provided so that one set can be used when the other has become worn out.

About 80 per cent. or 90 per cent. of the phosphorus in the rock is extracted by this process, and the yield has been stated as 3.3 lb. of phosphorus per horse-power day.

aga - 13-5-2014 at 11:28

Superb !

Eagerly awaiting the photos of it in action in your backyard.

[Edited on 13-5-2014 by aga]

Motherload - 24-6-2014 at 14:34

This may have already been answered but I couldn't find it.
Can Sulfur be oxidized to SO2 by P2O5 resulting in Phosphorus ?
If so it is likely that the reaction me proceed at a lower temperature vs Carbon.

Litmus - 4-7-2014 at 22:41

Motherload, I couldn't say for sure but you may have something there. On the face of it, it seems reasonable to me the acid anhydride of a stronger acid could reduce the acid anhydride of a weaker acid. Unfortunately, procuring phosphorus presents a major obstacle for me :-), and I don't think I quite have the wherewithall to construct jsc's apparatus! For one thing, I don't think my backyard is big enough :-)

nux vomica - 12-8-2014 at 03:13

Managed to make a small amount of white phosphorus today i added 50 mls of 47 % rust killer to 25 grams of crushed heat bead, and heated the mix up until it was like black lumpy honey ,then put it in a s/s retort i made at work from odd and sods, i then put it in my electric forge and after 3 hours of bubbling and self igniting fumes i was left with 1 gram of white phosphorus ,great but scary stuff .

will try mono ammonium phosphate next ,did a trial run and managed to get a tiny amount of WP so looks promising.

cheers nuxy

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Magpie - 12-8-2014 at 09:25

Nice work. What kind of a flange closure system is that? It almost looks like a Victaulic. Does it require a gasket?

Is the assembly reasonably easy to clean?

[Edited on 12-8-2014 by Magpie]

nux vomica - 12-8-2014 at 17:27

There called triclover unions we use them in product pipelines in food and pharmacutical factorys, they can have a nitrile or viton seal and the pipe to ferrel weld is a purge weld cheers nuxy

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Magpie - 12-8-2014 at 19:03

I knew I'd seen those somewhere before - in a food processing plant I think.

For high temperature work you could likely get a gasket made of graphite. Was your gasket a problem when making P?

[Edited on 13-8-2014 by Magpie]

[Edited on 13-8-2014 by Magpie]

nux vomica - 12-8-2014 at 19:43

Not really magpie the nitrile gasket go hard after a couple of runs so i use a new gasket work has plenty of them, they smell a bit if the gasket burns when you open the retort after a run and the phosphorus remnants ignite. cheers nuxy


[Edited on 13-8-2014 by nux vomica]

nux vomica - 13-8-2014 at 03:13

Just tried using mono ammonium phosphate mix was 25 gm crushed heat bead 12gm map and 10 gm garden lime hoped lime would convert to ammonium carbonate and make the phosphate react better, total yield was .4 grm lost some probably .1 grm before weighing ,ph tested retort residue tested acid on ph paper. cheers nuxy

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[Edited on 13-8-2014 by nux vomica]

Magpie - 13-8-2014 at 08:52

I am now noticing that you are not using any SiO2 or boria and therefore likely not forming any insoluble residue. This would nicely solve the problem of how to clean your expensive apparatus. If you can get your yields up I think you are onto something here. ;)

Edit: Out of curiosity I calculated the %yields for your two experiments:

1st experiment. Assumptions: charge is 50ml of 47% H3PO4 and 25g of carbon. P content = 30.6g. %yield = (1g/30.6g)x100% = 10.3%

2nd experiment. Assumption: charge is 12g H2NH4PO4, 25g of carbon, and 10g of Ca(OH)2. P content = 3.2g. %yield = (0.5g/3.2g)x100% = 15.5%

Do these results look right?

[Edited on 13-8-2014 by Magpie]

Magpie - 14-8-2014 at 09:50

Quote: Originally posted by Magpie  


1st experiment. Assumptions: charge is 50ml of 47% H3PO4 and 25g of carbon. P content = 30.6g. %yield = (1g/30.6g)x100% = 10.3%


Correction to above post:

1st experiment. Assumptions: charge is 50ml of 47% H3PO4 and 25g of carbon. P content = 9.7g. %yield = (1g/9.7g)x100% = 10.3%

nux vomica - 16-8-2014 at 19:28

Will have to delay any more tests as the element in my forge has burnt out, anyone have any ideas on a more efficient condensing arrangement as i was getting lots of smoke from the phosphorus being carried through the s/s pipe and hitting the atmosphere instead of condensing, i see in a old book i have that the tubes dip under the surface of the water a fair bit, would the increase of pressure that it gives make the phosphorus condense easier, it says the water is hot so i don't think its a cooling effect, maybe i should have more expansion space so the vapors slow down enough to condense before they hit the water. cheers nuxy

nux vomica - 30-8-2014 at 21:46

Got the new element off ebay fitted and have changed the retort setup to try and use gravity to make the phosphorus flow out easier,
Used 30 gp heat bead mix that had been used for another batch but that batch was run until exhausted of phosphorus so there shouldn't be any map residue left in it but the lime mix was still in it so don't no how much there actually was in it, 15 grams of map in granules like sugar mixed together with spoon then welded the retort shut and turned on forge.

Run took 45 min to get first sign of phosphorus then rest was out in another 50 min got a yield of 2.25 grams:o works out to a 56.25 %yield would be more one big blob caut on fire on surface of water when i let the water get to hot and the end of the retort tube must of had some left where i couldnt get it with a wire scraper cos i had a nice fire burning out of the tube after i had shut down cheers nuxy


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[Edited on 31-8-2014 by nux vomica]

[Edited on 31-8-2014 by nux vomica]

Magpie - 31-8-2014 at 07:12

That's a great yield - the highest I've seen. Phosphorus is hard earned as it resists mightily its separation from oxygen. That piece of phosphorus sitting on your scale looks angry.:D

nux vomica - 1-9-2014 at 23:21

I knocked together a second retort today so i can run several batches in the one day, never bothered to have my own tig at home as i can always use my work tig on my own jobs at lunch time but i have to wait till I'm back at work to refill the retort now i have gone away from the triclover fittings.

Filled one retort with 15grm map and 30 grm heat bead mix, and the second one with 15 grm map and 30 grm heat bead mix plus 5 grms of garden lime interesting to see if there is differencece with the lime to no lime Other photo is a page from old book from 1920,s that has some info on phosphorus production . cheers nuxy

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Magpie - 2-9-2014 at 08:00

So, if I understand correctly, you are welding the retort pot shut then charging it with powder through the tube, right, or maybe charging then welding? If so, then how do you open the retort for cleaning and reuse? Do you have to cut off the retort floor, so to speak?

When heating the retort do you apply any heat to the tube or is conduction sufficient? How long is that tube and what is the diameter/height of the pot?

What's the purpose of the nut welded to the pot?

I can't read that old text. Could you try again with more light and perhaps a better focus.

It's nice to see someone experimenting again. But be careful, phosphorus is a backstabing bitch.

Amos - 2-9-2014 at 08:22

Here's the text in a clearer format, Magpie.

"Phosphoric acid is separated from insoluble calcium sulphate by filtration. it is then mixed with finely powdered coke or charcoal, concentrated to a thick paste, and heated to bright redness in clay retorts, A, placed in a furnace. Phosphorus distills over, and the vapour is condensed under warm water in D. The liquid obtained is allowed to solidy (in tubes?)"

"A" refers to the four retorts in the center of the furnace, "D" to the two containers of water on either side. Essentially, this described the originally posted process, with no addition of silicon dioxide. I think I may try this soon, my furnace will just need a couple of adjustments. That and I have to make a badass retort like nux's.

nux vomica - 2-9-2014 at 16:53

Magpie the main part of the retort is 50mm x 1.5 wall tube that is 50mm long the small tube is 12mm x 1.5 wall and is about 300mm long the nut is a standoff to raise the bottom of the retort off the firebrick.

I fill the retort first then weld the outlet end on if you look at my previous post there is a s/s mesh disk inside the retort to stop the contents from blocking the outlet.

If you want i can photograph more pages and not be so lazy and get them in focus.

Magpie - 2-9-2014 at 17:51

Thanks No Tears. I find it interesting that no silica or boria is being used. That way you can avoid the slag that is such a pain for cleaning. This may facilitate P gas escape also. The slag might also plug your screen.

I not sure what the addition of garden lime, Ca(OH)2, would do. I guess you will find out.

It would be nice if you could find a more simple closure system than welding: maybe a bolted flange with a graphite gasket, or maybe a screw cap with graphite gasket.

nux vomica - 2-9-2014 at 23:08

I find that the phosphorus was condenseing around the triclover fitting and not flowing out, a smaller tube hopefully makes the gasses flow through quicker and wont form a heat sink effect,

I thought that the lime would form ammonium carbonate but i see the heat makes the ammonia volitize out leaveing H3PO4 in the retort (took better photos of pages :D ).
cheers nuxy

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gdflp - 4-9-2014 at 11:30

@nux vomica
What temperature are you heating the phosphorus mixture at in your forge? Also, how easy is it for you to reuse one of your retorts?

nux vomica - 4-9-2014 at 23:15

Gdfp going by eye and looking at a temp chart it looks to be between 950 and 1000 C i have a 1200w element in it but i have a variable temp controller and its only putting out 1000w when running the forge, there seems to be no probs reusing the retorts just buff of any scale where you are welding, a tig can weld some pretty shitty covered steel if you have to but a cleaned up retort welds like new. cheers Scott

nux vomica - 13-9-2014 at 02:43

Right the results are in but not sure how accurate they are, for the retort with lime i got 1.35 gms of phosphorus, and for no lime 1.75 grms, the no lime retort seemed to also be really reacting well as there was a lot of phosphorus being wasted and burning up in the air after passing through the water:mad: used a new element and think temp was to high measured at 945 deg c with probe, you get the same effect if you heat the outlet with a gas torch the phos seems to volatile and wont condense and just passes through the system, will play with settings when i get a chance cheers nuxy

nux vomica - 25-9-2014 at 21:54

Had three more goes for the return of 2, 2.3, 2.65 grm phosphorus used a glass tube leading into the water and found the phosphorus condensed on the glass and will run down the tube if you heated gently with a gas torch occasionally much better way to do it.

Took a pic of map and coke mix didnt crush them up but mix and seal in retort, arc welded tube at home useing 2.5 m/s rods.

Cleaned all the phosphorus up in chromic sulfuric acid mix total is 15.48 grm dont even really need that much so might see if i can turn it into red phos seems a bit more usefull and stable than the white version cheers nuxy.

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[Edited on 26-9-2014 by nux vomica]

[Edited on 26-9-2014 by nux vomica]

Amos - 5-10-2014 at 20:44

Quote: Originally posted by j_sum1  
I'm late to the discussion and haven't read the whole thread so forgive me if this has been covered before.

If the purpose is to obtain a small sample for element collection (ie, volume created is not critical) then there is a straightforward method.

Red Phos can be gotten by scraping matchboxes after first loosening the glue with acetone. Tedious, impure, but possible.
Purifying and converting to white Phos is easy.
Place a small sample of red phos in a glass tube with sealed end or a small test tube.
Bung the other end with cotton wool or similar.
Heat the red phosphorus in a flame until it sublimes. It will deposit on the cotton wool. Removing the bung should demonstrate self ignition in air.
If you want to keep your sample then you need to use a longer glass tube. Place a cooling collar around the tube to force the phos to deposit in the location you desire. Then ampoule your sample by melting the tube on either side of the sample.

You won't get more than a few milligrams this way, but if that's all you need then this method is a cinch.


I'm pretty sure this is for larger amounts, like the ones nux vomica keeps producing above. It sounds as though this problem was cracked a couple of years ago; now all that remains is improving the syntheses that others have posted, and making them ever more accessible to the amateur chemist.

Azane - 14-10-2014 at 18:42

Perhaps phosphorus trichloride could be reacted with a metal phosphide...?

AlP + PCl3 --> 1/2P4 + AlCl3

Let me know if this is a terrible idea.

Arcuritech - 24-10-2014 at 09:05

Quote: Originally posted by Azane  
Perhaps phosphorus trichloride could be reacted with a metal phosphide...?

AlP + PCl3 --> 1/2P4 + AlCl3


This raises the problem of trying to obtain PCl3. It can't be made by the standard industrial route because that uses phosphorous as a precursor, and it's controlled as a schedule 3 under the chemical weapons convention so I'm almost certain nobody will sell it to a non-corprate and non-government buyer.

this worked

tim - 25-10-2014 at 04:19

Hi...I thought i would like to share this after just finding this site..Ive just joined up now !

I have been fascinated by phosphorus for years and tried a few things that didnt work..however this did...
I got some phosphoric acid from a chemical company (Also easy to make,which i have, by digesting bone ash (used in pottery and available from pottery supplies) in H2SO4) heated it in a glass beaker over a gas burner (with mesh) until it smoked meaning it was dehydrated to pyro,or is it meta? let it cool...added about 10 times the amount of finely ground activated carbon (thats all I had on hand.I originally intended to use charcoal) then stuffed some of the really thick paste a third of the way into a quartz domestic heater element that i had taken the coil out of and rewound on the outside (I used a variac but other elements in series would give the possibly needed control) and heated it for about 2 hours.
When it was cold i took it into the dark and there it was...a faint glow of green...It glowed a lot more brightly when I blew into it displacing the phosgene and other gasses protecting it from the air...I was stoked !!!....Ive been meaning to do it on a big scale but been to busy.. From what i learned one needs to slope tube slightly upwards as goo melts before reducing and tries to run out..Block end in which you put reaction mixture with some sealer and start winding wire 2 inches from said end so you can keep a damp rag around sealer to prevent it burning..(I used urethane but fireclay would be way better and no wet live rag either !!..Hope someone likes this...I did !!
Im very happy to join your great site...thanks (-: Tim New Zealand

nhindori - 5-11-2014 at 08:06

Im not sure if preparation of black phosphorus crystals has been discussed but I'm very curious as to how it its created. I know extremely high pressure is applied or gas phase transport.
Please share some info or refer to one of the 48 pages of this thread

Photo from smart-elements

[Edited on 5-11-2014 by nhindori]

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Pok - 6-11-2014 at 15:48

There is already a thread about black P: http://www.sciencemadness.org/talk/viewthread.php?tid=12196
This doesn't belong to "preparation of elemental P" because it's a transformation of an allotrope from another one which already is elemental P.

Monopotassium way?

Zarynga - 11-2-2015 at 03:47

Hello. I have read about the last twenty pages, but I couldn't found an answer. Is possible to obtain phosphorus from Monopotassium Phosphate KH2PO4 or from Trisodium Phosphate Na3PO4 using similar way to Ammonium Phosphate and coal method? I have only these two chemicals available.

[Edited on 11-2-2015 by Zarynga]

S.C. Wack - 11-2-2015 at 13:43

Add hydrogen chloride during the reduction.

Ramium - 4-3-2015 at 10:57

If u heated red phosphorus in a sealed test tube to convert it to white phosphorus then opened the test tube under water the white phosphorus would sink to the bottom.if u repeated this lots of times wouldent you get a nice amount of white phosphorus???

I dont know if this works or not.its just an idea

Do u think it would work???

Molecular Manipulations - 4-3-2015 at 11:22

Pyro did basically that except the test tube was bent but open, with the open end in the water. It seemed to work decently.
http://www.sciencemadness.org/talk/viewthread.php?tid=25653

Molecular Manipulations - 7-5-2015 at 06:37

You supply phosphates but think they were made from phosphorous? Common man, nobody makes phosphates from elemental phosphorous.

Magpie - 7-5-2015 at 08:17

Quote: Originally posted by Molecular Manipulations  
You supply phosphates but think they were made from phosphorous? Common man, nobody makes phosphates from elemental phosphorous.


Certainly not for phosphate fertilizer. But IIRC elemental P is used by the carbonated beverage industry for making phosphoric acid. This is likely a way to obtain the purity they require.




blogfast25 - 7-5-2015 at 08:26

Quote: Originally posted by Magpie  
But IIRC elemental P is used by the carbonated beverage industry for making phosphoric acid. This is likely a way to obtain the purity they require.


I'm not sure it is made by the carbonated beverage industry but high purity (incl. food grade) H3PO4 is indeed manufactured from burning phosphorus.

j_sum1 - 6-6-2015 at 02:51

Maybe this has already been covered in the multiple pages of this thread (not all of which I have read). If so, I apologise.
I came across this video which results in what looks like a yield in the tens of grams range.
Source of phosphorus is a food additive or water softener.
http://www.melbournefooddepot.com/buy/sodium-hexametaphospha...
http://www.alibaba.com/showroom/sodium-hexametaphosphate.htm...

I am still not extremely clear on the process: in particular the reason for the NaCl and SiO2 in the reaction vessel. I think the receiving vessel has water in it, but again I am not sure. Anyway, the whole process looks reasonably accessible. I'd love some more insight if anyone has any. (Or refer me back to the sections of this thread that I have missed.)

byko3y - 6-6-2015 at 06:21

j_sum1, this is a know reaction
Quote: Originally posted by blogfast25  
2 NaPO3 + SiO2 + 10/3 Al ---> Na2SiO3 + 5/3 Al2O3 + 2 P

and also
Quote: Originally posted by Rogeryermaw  

6(NaPO3) + 10Al + 3SiO2 = 3Na2SiO3 + 5Al2O3 + 6P

Quote: Originally posted by Rogeryermaw  
i have done it!!!!!!!! i will post pics soon as i clean and solidify it all. they will be up tonight!!!

However, I have no idea why he needed NaCl.
Quote:
6NaPO3 + 10 Al + 3 SiO2 = 6P + 5Al2O3 + 3Na2SiO3
Reduction is performed by heating in a heat resistant tube 25 cm long and 1-1.5 cm in diameter, connected from one side to a source of clean hydrogen (gas cylinder or kipp's apparatus), and from the other side to a tube, which passes gaseous products into a crystallization vessel filled with water.
The heat resistant tube is filled with a mixture made from 1 weight part of NaPO3, 3 pars of SiO2 and 0.5 parts of aluminium turnings. With a help of asbestos corks the tube is connected from one side throught a washing bottle, filled with concentrated H2SO4, to a source of hydrogen, and from another to an outlet tube.
After removal of air from the apparatus using a strong flow of hydrogen and making sure that exiting hydrogen is pure, the heat resistant tube is heated using a burner with wide nozzle. Phosphorus being formed by the mentioned reaction is distilled and condensed into small balls within crystallization vessel with water. In dark you can notice a slight glowing of the phosphorus in the tube.
After the experiment is finished, the apparatus is dissasembled only after it has been completely cooled down in a flow of hydrogen.
Obtained phosphorus is put in a bottle filled with cold water.
Sodium metaphoshpate can be prepared by ammonium sodium phosphate hydrate calcination by reaction:
NaNH4HPO4*4H2O => NaPO4 + NH3 + 5H2O
Ripan, R. and Chetyanu, I. (1972) Inorganic Chemistry
PS: although I have no idea why these very conditions are needed. Also I can point at the book which says NaPO3 + NaCl leads to HCl, Cl2 and small amounts of POCl3 at 800°C; and Lerner mentiones P2O5 + NaCl => POCl3 at 300-420°C with perfect yield.

[Edited on 6-6-2015 by byko3y]

blogfast25 - 6-6-2015 at 08:30

Quote: Originally posted by j_sum1  

I am still not extremely clear on the process: in particular the reason for the NaCl and SiO2 in the reaction vessel. I think the receiving vessel has water in it, but again I am not sure. Anyway, the whole process looks reasonably accessible. I'd love some more insight if anyone has any. (Or refer me back to the sections of this thread that I have missed.)


This video is by rogeryermaw, who posted his stuff higher up in the thread.

The NaCl is present as a 'flux', promoting contact and mass transfer between the reagents. The SiO2 is a bit of a 'relic' from the old Ca phosphate + C + silica method.

I'm not sure why he doesn't just use a large open pile of BBQ coal and lots of air (leaf blower, for instance).

Assured Fish - 20-9-2015 at 20:49

Does anyone know the exact temperature range at which this reaction takes place

2NaH2PO4 --> Na2H2P2O7 + H2O

And also the following

3Na2H2P2O7 --> (NaPO3)6 + 3H2O

I would guess its up around 700°C but the wiki doesn't specify nor can i find anywhere that does tell me.
I also realize that it would be a hell of a lot easier to just buy sodium hexametaphosphate but for the sake of science it would be good to know the temp range required to undergo hydrolysis of monosodium phosphate to disodium pyrophosphate and so forth just in case sodium hexametaphosphate cannot be aquired.

Assured Fish - 16-1-2016 at 18:06

Quote: Originally posted by Assured Fish  
Does anyone know the exact temperature range at which this reaction takes place

2NaH2PO4 --> Na2H2P2O7 + H2O

And also the following

3Na2H2P2O7 --> (NaPO3)6 + 3H2O

I would guess its up around 700°C but the wiki doesn't specify nor can i find anywhere that does tell me.
I also realize that it would be a hell of a lot easier to just buy sodium hexametaphosphate but for the sake of science it would be good to know the temp range required to undergo hydrolysis of monosodium phosphate to disodium pyrophosphate and so forth just in case sodium hexametaphosphate cannot be aquired.


Ok so this thread is old and dead but ill post here.
169C
2NaH2PO4 -------> Na2H2P2O7


blogfast25 - 16-1-2016 at 18:15

Quote: Originally posted by Assured Fish  


Ok so this thread is old and dead but ill post here.
169C
2NaH2PO4 -------> Na2H2P2O7



Any evidence for your assertion?

Bert - 17-1-2016 at 09:25

Quote: Originally posted by Assured Fish  
Quote: Originally posted by Assured Fish  
Does anyone know the exact temperature range at which this reaction takes place

2NaH2PO4 --> Na2H2P2O7 + H2O

And also the following

3Na2H2P2O7 --> (NaPO3)6 + 3H2O

I would guess its up around 700°C but the wiki doesn't specify nor can i find anywhere that does tell me.
I also realize that it would be a hell of a lot easier to just buy sodium hexametaphosphate but for the sake of science it would be good to know the temp range required to undergo hydrolysis of monosodium phosphate to disodium pyrophosphate and so forth just in case sodium hexametaphosphate cannot be aquired.


Ok so this thread is old and dead but ill post here.
169C
2NaH2PO4 -------> Na2H2P2O7



Why are you talking to yourself?

[Edited on 17-1-2016 by Bert]

BluePlanet1 - 8-2-2016 at 21:32

Hello all! I'm a new member and if it's ok with the forum I'd like to try a few different approaches to making white P4. I have a new camera coming in a few days for doing HD 1080P videos as my current one sucks. My plan is to tape the experiments then upload them to a proxied YT account. This way I can stay anonymous but also show people VIDEOS of this reaction going with many different tweaks to it.

There are mainly 4 different things I'll be doing here:

1) Using HHO (oxyhydro gas) + MAP coolant + AIR propane to test and run experiments at any temperature up to 2500C - 5000F. My HHO torch is 3 cells at 4-5 LPM (each cell) with 3, 12V-75A chargers. I finally fried a breaker a couple days ago so right now the torch is only running on 1 cell. What you see in the pic is a baby flame around 4-5LPM. Which on its own can boil & cut steel. But when everything is connected I get a surge of roughly 12-15LPM HHO on top of the MAP gas which is extraordinarily hot and cuts through 1/4" steel like butter. It really is powerful. When I change the tip to .035 the flame is at least 14+ inches. Which you'll see when I get my breaker fixed & get some advice from the electrician.

The main benefit of HHO is that the water (fuel) really does last forever. So there's no need to refill any gas tanks. The torches aren't really "cheap", but you can set up a powerful hobby torch for $150-$300 (or cheaper if you build the cells yourself). I should mention too, my goal is to use HHO just for testing. I want my final method to rely on simple air-MAP gas accessible by anyone.

2) Instead of using pure AL powder (500 mesh) I want to test a mixture of 50% AL, 20% MG, 30% C. I have a theory I'll talk about in #4.

3) When my camera gets here I'll be replacing all text & pics with video.

4) I'm going to start with a few "normal" reactions first. Then I'm going to set up a "rocket distiller". I believe one of the big problems with this reaction is the RELEASE of heat energy in the form of >>>pressure. I believe for every unit of energy that escapes in the form of pressure, that's 1 less unit the AL has to not only keep the sodium silicate and aluminum oxide molten and finishing their reactions.... but to CONTINUE & COMPLETE the process of reducing P4O10 to WP.

I believe this is a serious problem! Why? Because I've set this reaction of many times on a small scale by igniting it with either HHO or air-MAP. I notice the reaction will fire off (then I pull the heat away on purpose to see how far it goes on its own). Then when I add air-MAP the reaction starts up again. However, there is this weird threshold where the slag stops releasing WP with the air-MAP (at 1100C). I noticed when I add HHO at this point the reaction goes almost double the time. Like under it's own energy it goes for 3-5 seconds. MAP makes it go another 3-5 seconds as you see more WP liberate. But when you just keep the MAP there the reaction dies and the WP stops being liberated. When HHO is added the reaction goes off again vigorously for nearly double the length of time. Around 12-15 seconds.

My hypothesis is this:

AL - will burn up and get the reaction going as normal.
MG - will make the mix more reactive, will burn faster, hotter and create more pressure.
C - As the AL & MG are doing their thing, the C will be displaced as gas OUT of the vessel. This will conserve energy by lowering the weight of the slag and also add pressure that can be "recycled". Plus C produces cleaner WP.

I believe if this is done right, and I get the right %'s we may see some interesting things. For instance, if this goes off like a rocket there will be a very HOT & efficient afterburn. That should be capable of driving the reaction COMPLETELY to the right under it's OWN thermal energy.

My goal is to also make this reaction easier for people who don't have access to a lot of resources. For all we know, 1 tweak to the reducing powder or the way the reaction burns (making it burn like a rocket) may produce higher yields in much less time. This can also CONTROL the release of gas coming out of the distiller. And another issue is short distillers which is why I *may add a spiral distiller on my final model.

So far I've successfully ran this reaction many times but all on small scales under 5gms. Using a small retort with thin walls which I accidentally melted. I've also used tricalcium phosphate (mixed damp rid with TSP) + C + SiO2. Just to prove it works which it does but the available P4 is low, the reaction conserves no energy, my current retort can't handle the heat.... which is why I use NAPO4 now like everyone else.

Let me show some pics of things....


This is 1 cell of HHO (4+LPM) with a drip of MAP to color it blue.
bPe69Gr.jpg - 30kB

This is a thick steel reducer that I cut in half. Then I realized the camera was just a big white screen so I had to let it cool (you can see the back where it snapped off)
rx9msFl.jpg - 24kB

This is my HHO torch which is semi-dismantled at the moment.
yJxn9Ck.jpg - 55kB

THIS is what I need feedback on. I built 2 retorts. 1 big that's not done yet and 1 small. This is my smaller one that I want to begin doing larger chargers in (25+gms).
yopDzh2.jpg - 39kB

It's crude but I'm gonna hit the back cap with MAP gas and the middle with a cooled burst of HHO. I did NOT weld the copper distiller to the steel because the threads on that adapter connect to my bigger retort (it can be reversed for larger hundred gm charges).

What I did to connect the copper pipe is put it in the reducer with a small gap around the pipe (like 2mm). Then I used a small flat screwdriver and quite a bit of AL foil to pack it in tight all around the pipe down to the bottom. After that I poured SiO2 dust all around the pipe. Then I hammered the dust down hard ass possible going in circles packing it down. Then I put another layer of foil up top and hammered that down to sandwich the SiO2 dust between 2 layers of very tightly packed foil. So basically it's like a rock of SiO2 powder crammed between the pipes that effectively seals out air. This way down the line when I'm ready to scale I just hammer/wrench out the pipe and connect it to my bigger retort then use the small retort as the distilling side.

The thing is... I'm a bit worried as to whether a "seal" like this will hold up.

I've seen the amount of smoke just a few gms produces. The first time I tried AL I did it open air in my home with no ventilation... my whole house filled up with smoke. I immediately opened all the windows and threw fans in. Then I started testing the same volume in my bathroom in a small retort. With a respirator on my face and small fan vent on the ceiling.

My "ventilation" now is a fan in the window (bathroom fan isn't powerful enough for large charges). I can't do this outside. It's too cold. Nosey neighbords, etc. So it has to be done inside. I've already heated the pipe with MAP and HHO to see how it holds up and as long as I keep enough coolant in the line the pipe stays bright orange-yellow and doesn't melt. You can also bang on it and it doesn't deform unless you turn down the MAP gas. My concern though is at higher weight the reaction itself could melt the AL. Then I'm left with just SiO2 and I'm hoping worse-case-scenario that will stop any breach of O2.

Finally, I've thought about flooding the retort with CO2 gas. As I saw someone else in this thread do that and that will allow me to test the retort with smaller amounts first. The problem is he did that around 750C in a testube. I'll be slightly under the melting point of steel (1300C?). From what I understand, CO2 gas is no longer "inert" at these temperatures. As in, the AL with burn in CO2 like oxygen inside the retort? They say not to put out MG fires with CO2 so this has to apply to AL as well, right?

Sheesh, so many things that could go wrong I think I'll just start small maybe 15gms and see how that holds up.

My end goal is to build a "quick fire rocket distiller" so safety & engineering are huge concerns here. When I switch to the rocket model I'll test very small amounts first on video. I know many on here will be concerned with clogging. But I think good engineering will stop that.

If people have thoughts or comments feel free to LMK. :)

Thank you!

ps. I realize this thread is extremely old. But this is the ONLY THREAD on the internet that sufficiently covers this topic. And the 1 thing this thread really lacks is videos. So even if my hypotheses are wrong at least others will get to see this done on video in detail. With me tweaking as many variables as possible till I'm hitting 80% yields both consistently & efficiently as possible... in a way that is accessible to most people (my end goal is to make this work with only air-MAP and no HHO). Wish me luck. :-)

pss. I will continue with pics only until my cam arrives.





[Edited on 9-2-2016 by BluePlanet1]

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