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Author: Subject: Preparation of elemental phosphorus
Marvin
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[*] posted on 16-1-2004 at 09:37


I would like to see the Gmelin scanned, particulaly to do with the temperature of carbon reductions.

Your reference is from 'A comprehensive treatise on inorganic and theoretical chemistry' by JW Mellor.

The Brooman reference itself I think is a british patent number, so no luck there.

I will see if I can find info on electrolytic production of P, but its unlikley I have anything.
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BromicAcid
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[*] posted on 16-1-2004 at 11:20


Ask and ye shall receive... Scanned in Gmelin for the production of phosphorus.

(Sorry that it's a little big...)

[Edited on 1/16/2004 by BromicAcid]




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[*] posted on 9-2-2004 at 14:44


Quote:

If you can get hold of a phosphide and acidify it you get PH3. This will decompose on heating to give P4.

Funny thing, there was at one time an industrial process relying on this method. I ran across it today in the chemistry abstracts from the turn of the last century. Basically it was the reduction of calcium phosphate in the presence of excess iron and silica to yield iron phosphide which was then reacted with acid to yield the phosphine which was decomposed at high temperature. I will get the exact reference on Wednesday, although I really wouldn't want to work with phosphine, it is interesting.

Also when I was looking though the early chemistry abstracts today I repeatedly saw the regular reduction of calcium phosphate, usually with just silica and occasionally with silica and carbon and with silicon carbide. But... I also saw an iron phosphate catalyst being used, saying that its use lowered the reaction temperature, very interesting.... Maybe current literature neglects this because for the longest time now they have been using an arc furnace to make phosphorus and adding the catalyst only lowered the activation energy a slight amount.... to them! Heck, I'll use any advantage I can get.

Finally, my last find of the day. I found a reference for the production of phosphorus from electrolysis!!!

But... it's the electrolysis of bone ash in molten cryolite :( ... yeah... in case you don't know what's wrong with that I should point out the melting point of cryolite is about 1000 C, so you wouldn't save much in terms of how many BTU's you would need to make your phosphorus, and I really don't want to think about what's being evolved at the anode. Maybe there's an eutectic mixture that could be used, using the eutectic finder http://ras.material.tohoku.ac.jp/~molten/molten_eut_query1.p...
I found some that melted around 600 C, somewhat lower, but would they even work? The stuff is soluble in concentrated sulfuric, maybe dissolve it in 100% acid and as long as the ions are there it might facilitate electrolysis... I know, it's a stretch, but I'm still trying to figure out new ways to get to the phossy prize.




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[*] posted on 9-2-2004 at 15:54


I still think you had a great idea when you conceived of dissolving those phosphorus-copper alloys (used for making phosphor bronze) electrolytically. I know it isn't really a preparation, but it's the next best thing. I can't recall if cyanides complex copper strongly enough to dissolve the metal in aqueous solution... if they do, that could be an easier/faster way of dissolving considerable quantities of the alloy without simultaneously oxidizing the phosphorus.



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BromicAcid
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[*] posted on 9-2-2004 at 16:07


Here's another one about dissolving metals. The electo-less nickel plating is high in phosphorus, much higher then the phosphor bronze, like anywhere from 3 - 12% by weight. Not only can you buy it because the phosphorus adds desired properties but you could make it in an electro-less plating bath. Then you perform electrolysis between two pieces of nickel to purify them like you would to refine copper, the phosphorus would sink to the bottom of the anode, or if you did it industrially you would wrap the anode in a bag to prevent the phosphorus from getting out into the solution. I thought I already posted about that but I guess I just had it in my notes.... That's a good idea now that I reflect on it.... and as a by product you could nickel plate things, the more I think about it the better it sounds... Weird...



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[*] posted on 13-2-2004 at 11:20


Quote:

....particulaly to do with the temperature of carbon reductions.

I found a reference to reaction temperatures the other day for carbon. Straight calcium phosphate with carbon in the form of coke begins at 1000C and is complete by 1600C.

If someone were to go the method of production involving the high temperature decomposition of phosphine might it be possible to do a dissolving metal reduction of a phosphate to yield phosphine? I know that using antimonates and arsenates you get stibine and such so wouldn't phosphate produce phosphine?

Oh, and I hit the library again, went though the chemistry abstracts from vol 1 to vol 21, they were all covered in dust and looking through them gave me a sore throat. :D Anyway, I was getting really really sick of seeing almost every abstract for a new modification of reduction of calcium phosphate with either carbon, silicon dioxide, or aluminum oxide to yield some form of slag that could be used for concrete but I came across some interesting stuff.

Patent 1988387 has some interesting designs for phosphorus producing apparatuses. Reduction of phosphorite containing 1-2% moisture with a 10-15% excess carbon charge yields phosphorus in a nearly theoretical amount a 500 - 600C which is really low.

Reduction of bone ash with peat moss yields CaCN2 and Phosphorus or just the regular reduction with an excess of Carbon under a nitrogen atmosphere yields cyanimide.

[Edited on 2/13/2004 by BromicAcid]




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[*] posted on 24-4-2004 at 12:24
It's the season of phosphorus!


I decided that since I might be doing more experiments soon that I would post pictures of the evolution of my phosphorus production apparatuses so here they are in chronological order. (I remade all the apparatuses of parts I had handy so they are not the originals except for a few parts however they convey the concepts used in the designing of each incarnation)

My Oldest design

For this one I thought that clay would be the way to go. So I got one of those pots with the high magnesium content and I got one of the clay bottoms to sit it on. I drilled out the bottom to make it into a lid and put a ran a 3/4 inch pipe through it and put a flange on it and held that in place with screws. Then I drilled 4 holes evenly spaced along the edges. I bought 4 hooks with threads and put them in the holes. They hung down with the hook part at the bottom and the threads at the top. I put the pot in place and put the hooks under the bottom rim of the pot and tightened the bolts on the ends of the hooks to hold the pot in place. Within minutes of heating though the pot started to crack. Further heating produced more cracks and I tried to add fire place mortar for a repair but it was falling apart too quickly so I took it of the heat and never tried using pots again.

My First Design That Worked

I got results with this one. This is similar to the design that I used in my somewhat infamous description of phosphorus production gone wrong. With the exception that the exit was exactly at the same height as the bottom of the original container. Phosphorus was produced in the bottom of what is pictured here to be a propane can and from there the gaseous phosphorus traveled upward and into the downward pipe where it went down and into water to condense. This design was subject to burn through and corky phosphorus which I rectified on later designs by adding a piece of screen around the exit gas area on later designs. (That bolt in the back ground along the condenser pipe is just being used to prop up the pipe to take the picture.)

This One is More Stout

The whole of the reaction area is somewhat thicker metal then I was used to so the problem of burn through was more distant then before. Still the rest of the apparatus stayed the same. Except the vessel that it lead to full of water had a stopper on it and the only way for gasses to exit or enter was through the one-way gas valve that I had made (not pictured) this also prevented suckback which although not a point of previous experiments (the large diameter pipe prevented it somewhat) was still a concern from time to time. In addition I started to burn my exit gasses by placing a torch so that the flame was positioned over the exit point.

My Radical New Design

The charge that makes the phosphorus will be placed in the bottom of the pipe on the far left. That will be the section that is heated. The elbow on the bottom to the right will be filled with water a little past the bend to force the phosphorus rich gasses to bubble though it and condense out the phosphorus. Finally there is a one-way gas valve on the end to prevent air from reentering the system. Less can go wrong in this one in that it is all self contained. At the end open the end with the one-way valve and dump out the water probably full of colloidal phosphorus.

Now I just need to design my apparatus for the reduction of lead phosphate with hydrogen.




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[*] posted on 24-4-2004 at 13:49


Quote:

If you can get hold of a phosphide and acidify it you get PH3. This will decompose on heating to give P4.


PH3 made this way is usually spontaneously flammable in air because of P2H6 content. Not to mention the toxicity of PH3.

In Belgium DIY store sell a rodenticide that uses Al (german dark it seems!) to reduce calciumtriphosphate to calciumphosphide, which then slowly reacts with moisture to form PH3.

I dissected one of these things, but didn't further investigate because the toxicity of PH3 is/was worrying me.

I might just go for P2O5 + Al.




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[*] posted on 24-4-2004 at 21:14
a thought for your safety


Don't get me wrong - I love pipefitting, but looking at your apparatus scares me -as you are depending on a check valve for a vent. If I was going to heat an enclosed pipe system I would feel a lot better about it if it included a rupture disk and/or a pressure indicator.
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[*] posted on 24-4-2004 at 23:33
But it has to be one way....


All things considered Bromics' design is superb.

The gravity ball valve is contemporary technology and is the valve of choice for high pressure/hard vacuum.

And If I'm not mistaken the rupture disk you speak of could act like a burst diaphram. In this instance, the consequences of the vessel exploding really isn't that much more severe than having the contents splatter all over the inside of the phossy kiln.

The wisdom of the "Normal" safety procedures for pressure vessels get a little fuzzy when working with anthing more dangerous than your average pressurized vapours or gases.

In short, flying bits of metal puncturing major organs might actually be a plus when a man is running around in circles in his yard with his facial features running down his shirt.

Did you see the look on the Nazi's faces when they opened the Ark of the Covenant in Indiana Jones and the Raiders of the Lost Ark?

I'm certain they would have agreed.

In all seriousness, (not that gouts of White Phosphorus vapour condensing on your delicate fleshy parts is a joke) but Bromic has explained to me, his device in no small detail and I feel very confident in his ability to acheive success safely.
:cool::cool::cool:




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thumbup.gif posted on 29-4-2004 at 06:42
Good Work


Bromic Acid: Well done on your new apparatus! I have been contemplating making my own for a while now, but couldn't decide what I should make it from... What material did you use for the pipes? I'm assuming that it is standard plumbing (?) - the photos look somewhat like stainless steel... And what reaction did you end up using? Some phosphate + Al for reduction and sand? I have read that this reaction can be done without the sand, but it only yields about a third as much - what sort of yeild have you produced?
It would be interesting to see what happens with the hydrogen / lead phosphate reaction you mentioned. I have read somewhere about using 'catalytic hydrogen', this is a bit more advanced to the sort of reactions I'm used to... (I'll keep reading!)

Cheers
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[*] posted on 29-4-2004 at 12:27
Not sand!


You want very fine silica. Either go to a ceramics supply place and pick up some 300 mesh silica there, or make sodium silicate from your sand with NaOH, acidify the sodium silicate solution, and wash/dry the precipitate to yield clean SiO2 dust.



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[*] posted on 29-4-2004 at 13:13


Yes (playsand will not work unless brought to ungodly temperatures 1500C+), the finer the SiO2 you use the faster/better the reaction. The finest silica you can find is fumed silica. I bought some and 100g takes up nearly 500 cubic centimeters. Very very light powerdery stuff. The best reaciton that I used to produce phosphorus I mentioned further up thread:

6(NaPO3) + 10Al + 3SiO2 ---> 3Na2SiO3 + 5Al2O3 + 1 1/2P4

Zinc can also be used and I bet magnesium could be used but the reaction might get violent.

One other interesting reaction that I found that I may have mentioned before is R.A. Brooman's procedure, he heated a mixture of silica, iron, coal, and calcium phosphate, this formed a fuseable slag and iron phospide. He took the phosphide and heated with sulfur and distilled the phosphorus.

[Edited on 4/29/2004 by BromicAcid]




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[*] posted on 1-5-2004 at 03:32
Excellent


Thanks for the info, I'll give it a try soon...
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[*] posted on 3-5-2004 at 07:05
Arc furnace


Just in case anyone is interested in building an Arc Furnace (ie temp 3000C+)

I found an article posted on the Popular Science site:

http://www.popsci.com/popsci/science/article/0,12543,611070,...

They give a brief description of using an arc welder connected onto graphite rods to yield extreme temps (if you want to melt tungsten, etc).

Perhaps it could be scaled down? Maybe put the electrodes into a mixture of powdered carbon + [the material you want to heat] ?

We already have easier ways to make phosphorus (thanks guys!!!), but maybe this will be helpful to someone...
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[*] posted on 3-5-2004 at 18:11
calcium carbide


Maybe this is the way to make some calcium carbide. I understand you need a furnace reaching 3000 deg C.
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[*] posted on 4-5-2004 at 03:36


Hmmm... I think that the phosphide ion is an intermidiate in the phosphorus preparation. The aluminium/carbon/else strips the phosphate ion of oxide ions, and the electrons from the reductant transfer to the ion, this happens step by step untill a phosphide ion is obtained. This then comes into an equilibrium:

3PO4--- + 5P--- <=> 12O-- + 8P

The oxide ions are scavenged by silicon dioxide, which drives the equilibrium to the right. If no silica is present, the phosphorus produced immediately disproportionates, and eventually all the phosphate is reduced to phosphide so no equilibrium can establish.
The phosphide is the general product if a reductant is present, but no acidic oxide like SiO2. Production of calcium phosphide by carbon reduction works at 1200 C, while production of phosphorus requires 1400 C.

Just my theory so...

Edit: Hold on:

"Reduction of bone ash with peat moss yields CaCN2 and Phosphorus or just the regular reduction with an excess of Carbon under a nitrogen atmosphere yields cyanimide."

Ca3(PO4)2 + x => 3CaCN2 + 2P + 8H2O/4CO2 ?

Ca3(PO4)2 + 7C + 3N2 => 2P + 3CaCN2 + 4CO2 ? Some temperature you need for that...

Ca3(PO4)2 + Ca(CN)2 => 2CaCO3 + 2P + 2CaO + N2?

Ca3(PO4)2 + Ca(CN)2 + 2SiO2 => 2CaCO3 + 2P + 2CaO + N2?

[Edited on 4-5-2004 by Theoretic]
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[*] posted on 5-5-2004 at 07:24
1600C+ furnace


hmmmm.... just found a site with a home-made furnace capable of 3000F+ (ie 1600C+) from gas!

http://www.reil1.net/Furnace.shtml

May be useful for making phos and melting certain metals, too...
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[*] posted on 18-5-2004 at 18:49


This is in response to chemoleo's advice on the thread "nerve damage" suggesting as i had made WP to post here.

I have made about 5 grammes of WP a few days ago, by painstakingly scraping off the striking strips from safety match boxes. I filtered off the paper from the RP using nail varnish remover, then filtered the red P off.

I then placed a large amount of RP in a test tube, with a tube for distillation into cold water and condensed the WP.

This works fairly well, but a warning, Don't even let the smallest trace of this touch your skin, this happened to me, I accidentally got a small streak of white P on my right hand which I immediately scrubbed off. 2-3 days later and I cannot write at all and can hardly move my arm, due to great weakness, this also affects the grip of my hand too. Just be careful not to touch WP, even in the smallest quantities.




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[*] posted on 18-5-2004 at 21:48


Quote:
Originally posted by Lestat

I have made about 5 grammes of WP a few days ago, by painstakingly scraping off the striking strips from safety match boxes. I filtered off the paper from the RP using nail varnish remover, then filtered the red P off.


Daym that a clever synthesis, the more so given that the strips on safty match boxes contain a phosphorus sulfide AND NOT RED PHOSPHORUS.
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[*] posted on 18-5-2004 at 22:50
whoopsie-daisy


No, the strikers really do contain red phosphorus. If you burn one in, say, the inverted bottom of an aluminum soft drink can, and then rub your fingers in the sticky residue (ahh, healthy!), your fingers will smoke a bit and glow in the dark from the WP in the residue. The glow/smoke will be more intense if you rub your fingers together, at least until the phosphorus is consumed.



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[*] posted on 19-5-2004 at 13:49


i gotta admit i was talkin from memory of the uses of Phosphorus - charcogenide glasses in greenwood and earnshaw. Having had a scratch around the web Ive found stuff that says the striker is P4S3, red P and EVEN white P:- none of these are really concisely written, and i wouldnt trust any of these as much as G and E. However I may well have to eat humble pie on this one.
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[*] posted on 19-5-2004 at 13:59


Meth heads make their speed using a red P/I2 reduction of pseudoephedrine. The red phosphorous is obtained mainly from match strikers. Yields are poor. About 2 grams per 250 strikers, or something like that anyway. I've never done it, but I recall it being pretty sad.



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[*] posted on 19-5-2004 at 13:59


If you want to see it in very small amounts for yourself, just scrape the powder off about 5 boxes of safety match strips, put it into a neat little pile on top of a lid from a tin can and ignite, when the smoke has died down, knock away the ash and scrape the stain on the metal with a toothpick or sumthing, you will see sort of expanding rings of burning P as it gets consumed wrim the center.

Thats how i first did it, out of curiosity from the way the above said meth heads obtained their red P :P

[Edited on 19-5-2004 by Lestat]




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thumbup.gif posted on 31-5-2004 at 09:26


"My plans

On the Sunday I plannig to prepare P from H3PO4 + C = H20 + CO + P.
I have real 600-650C in my glove

Good luck
Flayer
Sorry for my bad English."
by Flayer.
This was his first and last post at MSDB.
I'll tell you why.
When carbon reduces an oxygen atom off the H3PO4 molecule, H3PO3 results. That disproportionates quantitatively back into H3PO4 and PH3, which he wasn't expecting... so the guy's liver probably gave way in a dramatic fashion, terminating him on the spot.

Half-joking :) but...
This could be used for phosphorus production after all.
Phosphine would react with CuCl2 or FeCl3 and reduce them to the metals, while turning into white phosphorus vapour, a byproduct is HCl gas.
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