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Author: Subject: Preparation of elemental phosphorus
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[*] posted on 23-12-2011 at 06:56


what does that have to do with anything??? i hate commercials...
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[*] posted on 1-1-2012 at 18:08


Has anyone ever experimented with fusing Hexasodium metaphosphate with Sodium acetate? I did a little while ago just messing around and the mixture liquified rather quickly and a strong smell of garlic was released. It seemed like the NaOAc was acting as a rather good carbon source and a flux because once the melt was fluid there was a large release of Phosphorus at a pace much faster the I have seen in the past using a number of the following.....powdered carbon, powdered Aluminum, Magnesium(the most potential IMO) I can't help but wounder if Sodium acetate could become very helpful in creating White phosphorus.

What is every ones thoughts on such an idea?





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[*] posted on 1-1-2012 at 18:39


That's an interesting observation. I suppose you're speculating the following:

2NaC2H3O2 + heat ----> Na2O +3H2O + 2C

Did you see any evidence of water vapor or condensation?

Na2O would indeed be a good flux, and the C is then available for reduction of the metaphosphate to P.

What kind of vessel did you use for the experiment? How hot do you think it was when it liquified?

I wonder what would happen if you added a stoichiometric amount of SiO2.

BTW I have never smelled garlic when making P. I hope that is because I had good containment within my apparatus. And/or a good fume hood.




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[*] posted on 1-1-2012 at 18:48


Quote: Originally posted by Magpie  
BTW I have never smelled garlic when making P. I hope that is because I had good containment within my apparatus. And/or a good fume hood.
Magpie, in my opinion you have the best fume hood owned by any of us on Science Madness. My hood works just fine, but yours puts mine to shame!
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[*] posted on 1-1-2012 at 20:48


It was just a small open Stainless steel cup, I have a bunch of them for doing little melt test and what not. I just got propane for my torch for the first time in a couple months so of course I was playing around ;).

I didn't even put to much thought into what it taking place reaction wise I just noticed that where normally I will get a bubble pop here or there using most other reducing materials this was more like a fine sheet of tiny bubbles glowing on the surface of the melt. It was just a crude experiment and run on a very small scale but I figured I would report what I seen here and let you all make your own conclusions about it. I have an IR thermometer so I will repeat it and test the temperature.

At first I seen water vapor but that was just because my NaOAc was not totally dry. Im going to run out and check the temperature, BRB.





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[*] posted on 1-1-2012 at 21:18


Ok so testing it with the IR isn't exactly easy on such a small scale but I will give you the numbers I got. Keep in mind these are rough estimates but there was some stability in them.

At around 375 degrees C I started to smell garlic, There was some sputtering as waters seemed to leave and the NaOAc carbonized. The temperature kept rising to about 490 degrees C at which point the reaction became very fluid, once total fluidity was achieved is when the temperature quickly dropped down to around 380 and remained rather stable as many many small bubbles popped on the surface of Phosphorus. Also there did not appear to be much carbon at the time the temperature dropped and the majority of the Phosphorus seemed to be produced. I don't know what to make of it but given the crappy setup it might just be superficial and mean nothing.

I wish I could give you more data but my setup leaves alot to be desired and I was just toying around at first. I can't go much further with any experiments until I make a better setup to avoid poisoning myself with Phosphorus. Hope this helps folks.





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[*] posted on 30-1-2012 at 22:15
Conclusion?


Wow that's a lot posts. It took me all night to get to the end of page 2. I'm very familiar with bone ash, sand, and coke but was there a common consensus of a method that doesn't take white heat to evolve P4?

And just in case anyone was interested this Handbook of Chemical Technology by Johannes Rudolf Wagner has industrial methods for P4 synthesis from bone ash starting on page 537.

[Edited on 31-1-2012 by alphacheese]
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[*] posted on 31-1-2012 at 06:23


"This is just my opinion, please do not get mad.
Using aluminium for any home chemical project is cheating ! Aluminium is more difficult to make than phosphorus. Using aluminium to make phosphorus is like buying red phosphorus then turning it into white phosphorus and bragging that you made white phosphorus. Its like getting someone else to make you some concentrated nitric acid and glycerin, then bragging that you made nitroglycerine.
If you use aluminium, the aluminium factory has done three/quarters of the work for you. Any post that talks about using aluminium, I do not even read it."

I don't know why you would hold this opinion. Everyone here has a different level of competency and so what is cheating for you may be a very high bar for others.

In your example above about nitroglycerine, let's take your reasoning to it's absurd logical conclusion. That is, YOU can make nitro by "not cheating" because you are so godlike in your capacities that you can drill your own oil, build your own refinery in the back yard, crack that oil, collect the sulphur waste, make your own h2so4.

At which point you amble out to the pile of cow manure you've been lovingly stacking up for the last year and start boiling that down to collect the potassium nitrate you'll use to make your nitric acid. In your spare time you'll be fabricating your own glassware/reaction vessels.

Once all that's done (whew!) you'll go out to the pasture, shear your sheep, wash the wool, and collect the glyceriney goo for purification. THEN you're off to make your nitro.

Anything less, dear, and you will be cheating.....

To the point of this thread: smelting of bauxite is simple, easy, and straightforward. It's EXPENSIVE to do in the back yard both because of the quality of refractories necessary and because of the wattage consumed. But it is a btdt, and I'm not a chemist by any stretch. Given the massive brain power in this thread, and the trouble that brain has been having getting this done, I'd say that using aluminum is very far away from cheating.

The halfway point, I guess, would be not to buy your aluminum powder but to giveyour 8 year old a file and send her out to the aluminum can bin.
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[*] posted on 31-1-2012 at 16:36


I don't see how using aluminium is cheating. For most of us, we could only dream of having phosphorus to perform certain syntheses, regardless of the production methods employed.
Phosphorus is rarely an end product in and of itself, it is oftentimes a precursor.




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[*] posted on 7-2-2012 at 08:56


The above process will make white or red phosphorus
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[*] posted on 7-2-2012 at 14:01


Quote: Originally posted by Vikascoder  
The above process will make white or red phosphorus


[sarcasm] No, really? I didn't know that this thread was dedicated to making phosphorus. The title is really misleading. [/sarcasm]




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[*] posted on 16-2-2012 at 03:02


Quote: Originally posted by shannon dove  
This is just my opinion, please do not get mad.
Using aluminium for any home chemical project is cheating ! Aluminium is more difficult to make than phosphorus. Using aluminium to make phosphorus is like buying red phosphorus then turning it into white phosphorus and bragging that you made white phosphorus. Its like getting someone else to make you some concentrated nitric acid and glycerin, then bragging that you made nitroglycerine.
If you use aluminium, the aluminium factory has done three/quarters of the work for you. Any post that talks about using aluminium, I do not even read it.


calling aluminum a cheat is rather silly. this entire site is dedicated to the idea of the home chemist doing what can be done with the chemicals that are available to us. so many of the interesting choices have been stripped from our hands. however, i challenge you to go to any major grocer or hardware store and find that aluminum is not readily available. it may take sturdier equipment and a lot more energy to purify, but the process itself is not much more complicated than the production of elemental phosphorus. it is perhaps easier when you consider the extreme danger posed by exposure to P4 and its fumes and gaseous compounds. yes, claiming to have made P4 by distilling P2 is a bit of a cheat since the concept is to start from no pure form of the element, but taking advantage of the position of Al in the reactivity series is just good chemistry sense.

by your logic, your posts are cheating if you did not build your computer, your monitor and generate your own electricity, run your own cabling, launch your own communications satellite with a handmade rocket and write your own software to tie it all together.

[Edited on 16-2-2012 by Rogeryermaw]




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[*] posted on 20-3-2012 at 13:33


There was a method talked about a few pages back, that is mixing bone ash and charcoal then heat to redness, then pipe in hydrogen chloride gas, there is supposed to be immediate release of phosphorous.
I guess the HCl replaces the sand in the common industrial method.
I think maybe we should take another look at this method. It might work at a lower temp than the sand/charcoal/boneash method, but it probably will not work as good as the aluminum method. But its good to know different methods. Does anybody else think we should research this method further?
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[*] posted on 27-3-2012 at 09:45


I was just wondering if anyone knows of a temperature (and pressure) for the vacuum sublimation of red phosphorus to the white allotrope. I know woelen demonstrates this at atmospheric pressure (sublimation temp according to wiki is about 416*C), but I was hoping for something a little more "gentle" - preferably below 250*C. I am unsure whether it may be calculated from standard data tables using thermodynamic equations.
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[*] posted on 14-4-2012 at 10:57


Well I don't see why everyone is looking that far to make phosphorus it's actually very common and you've hold it in your hand. Matchbox!

The sides of the box should contain phosphorus and glass. The head of the match should be potassium chlorate with possible sulfur , pyrotechnic binder (ex:dextrin) and maybe some other possible chemicals but haven't found them yet in the head of matches. I am talking about safety matches by the way (NOT strike anywhere matches).

So Ive done alot of research and expirements of getting a fairly pure and reasonable amount of phosphorus from matchboxes. Ill describe here my "tactic".
So first I tried to scrape off the phosphorus with just a knife but I would get ALOT of cartidge from the matchbox with it so ive tried alot of ways to avoid it and the best is to weathen it with acetone. Just dipping it for two seconds in acetone and you can easily scrape the phosphorus off with a creditcard. Then I came up against another problem , red phosphorus just isn't soluble in any material that I tested (ether, alcohol, water , carbon disulphide, alkali solutions) but I found it only soluble in concentrated nitric acid (best is fuming nitric acid but 70% (made by fract. distilation worked also for me)). So then I made a satured solution of it and filtered it through the finest filters I had. It worked perfectly!

So thats how I obtained my red phosphorus it isn't a very cheap method but you buy the cheapest match brand. Here in Belguim it's quite cheap (10small packs for 1.50euro) maybe check ebay or amazon for bigger amounts.

If you would have critism or any questions,suggestions please ask !
Btw: I will post a video about the whole proces on my youtube channel soon. And sorry for possible grammar faults, im from Belguim=)
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[*] posted on 15-4-2012 at 09:44


@CrEaTiVePyroScience The purpose of the methods described above is not so much to obtain phosphorus, rather, the purpose is to demonstrate that phosphorus can be made at home. It is the process rather than the end result. To be honest, even though elemental phosphorus is chemical that is "nice to have" it doesn't have that many uses, especially for the amateur.

Question, do any of you have a concrete use for phosphorus (any of its allotropes) in any kind of synthesis?





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[*] posted on 15-4-2012 at 10:08


Quote: Originally posted by White Yeti  

Question, do any of you have a concrete use for phosphorus (any of its allotropes) in any kind of synthesis?


Both white and red phosphorus can be used to make the phosphorus halides, PX<sub>3</sub>, PX<sub>5</sub> and POX<sub>3</sub>, which opens up a lot of synthetic routes not normally accessible to the amateur.




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[*] posted on 15-4-2012 at 10:11


@White Yeti.
Well that's true but I "collect" all chemicals Ive made and obtained just small samples of them in those 25ml duran glass bottles (at 174 now).
But I used it to make white phosphorus and to make the armstrong mixture and do experiments with armstrong mixture but besides that I don't really use it..
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[*] posted on 15-4-2012 at 14:13


Quote: Originally posted by CrEaTiVePyroScience  
Then I came up against another problem , red phosphorus just isn't soluble in any material that I tested (ether, alcohol, water , carbon disulphide, alkali solutions) but I found it only soluble in concentrated nitric acid (best is fuming nitric acid but 70% (made by fract. distilation worked also for me)). So then I made a satured solution of it and filtered it through the finest filters I had. It worked perfectly!


You dissolved the red phosphorus in nitric acid? You have just oxidized it to phosphoric acid.




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[*] posted on 16-4-2012 at 07:47


@Polverone Ow that might be right ill do some extra experiments now and find out , ill let you know
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[*] posted on 7-5-2012 at 15:58


Tying up some loose ends.

As I read through the thread I found some blank spots in terms of information presented that could be filled by my somewhat recent acquisition of:

Mellor, Supplement to the Comprehensive Treatise on Inorganic and Theoretical Chemistry: Vol VIII Supplement III - Phosphorus. Longman Group Limited, 1971

Of special interest is the reduction of phosphates using hydrogen. Lead phosphate reduction is covered in patent literature but I haven't seen much on other phosphates so I will present that here:

(pgs 111-113)
Quote:
...many phosphates can be reduced by hydrogen at temperatures between 300° and 750°C. Metals which do not form phosphides, or give phosphides which are easily dissociated by heat, are the most susceptible to this reduction. In these reactions the metals is formed and the oxygen of the phosphate is quantitatively converted to water. Lead phosphates are particularly easy to reduce by hydrogen. For example, pyromorphite, 3Pb3(PO4)2*PbCl2, starts to react at 300°C and is completely reduced at 850°C.


Here is a reproduction of the table provided listing phosphates that are reduced at low temperature to phosphorus, the temperature listed is the temperature at which the reaction becomes rapid which was determined by looking at the increase of the partial pressure of water formed by the reaction:

Phosphate ........... Decomposition Temperature (°C)
BiPO4 ..................... 425
Ag3PO4....................425
SbPO4......................450
Pb4(PO4)2................575
3Pb3(PO4)2*PbCl2...600
Hg3PO4.....................600
Hg3(PO4)2................600
SnO2*P2O5..............600

Whereas metals that do form phosphides reduction with hydrogen will give a phosphide as an end product. A similar table is below reproduced in part:


Phosphate ........ Decomp. Temperature (°C) Products
Ni3(PO4)2.........................450........................P + Ni2P
CuPO3..............................600........................P + Cu3P + CuP2
Fe2P2O7...........................600........................FeP
Cu3(PO4)2........................300........................CuPO3 + HPO3
H3PO4 + SiO2...................550........................P

Onto another subject, thermal decomposition of phosphides. It was postulated early on by madscientist that heating certain phosphides could result in disproportionation to give a different phosphide along with elemental phosphorous. His example was:

4Cu3P2 ----> 4Cu3P + P4

Noting that heating copper (II) chloride gave copper (I) chloride and chlorine.

The text gives an equation showing disproportionation (pg 295) but no temperature is listed and a melting point is listed as 900°C for CuP2.

Heats of disproportionation are listed for several phosphides but decomposition temperatures are not listed for many.

Some examples of iron phosphides illustrate that perhaps these disproportionation reactions might not be the easy ticket that they appeared at first:

4FeP(s) ----> 2Fe2P(s) + P2(g) deltaH= + 72 kcal t=1200°C
4FeP2(s) ----> 4FeP(s) + P4(g) deltaH= + 66 kcal t=930°C




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[*] posted on 11-5-2012 at 13:35


Apologize ahead of time if this is out of place...but it is interesting.

I recently prepared this sample for a collector in California.
After working with Cs, this was a tame lil' pussycat.

wppaul - Copy.jpg - 88kB

[Edited on 11-5-2012 by Zan Divine]
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[*] posted on 11-5-2012 at 15:48


Quote: Originally posted by Zan Divine  

I recently prepared this sample....


That's a fair amount of P. Did you make it, or just ampoule it?




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[*] posted on 12-5-2012 at 15:12


Quote: Originally posted by White Yeti  
@CrEaTiVePyroScience The purpose of the methods described above is not so much to obtain phosphorus, rather, the purpose is to demonstrate that phosphorus can be made at home. It is the process rather than the end result. To be honest, even though elemental phosphorus is chemical that is "nice to have" it doesn't have that many uses, especially for the amateur.

Question, do any of you have a concrete use for phosphorus (any of its allotropes) in any kind of synthesis?



On the contrary, reaction of phosphorous with bromine or chlorine will give rise to phosphorous trichloride/phosphorous pentachloride, which can be used when wanting to synthesize custom phosphine donors, or when wishing to synthesize acyl halides or anhydrides.
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[*] posted on 14-5-2012 at 06:15


Quote: Originally posted by Magpie  
Quote: Originally posted by Zan Divine  

I recently prepared this sample....


That's a fair amount of P. Did you make it, or just ampoule it?


I just purified the crude commercial material which was obtained, as initially condensed, under water. The P was melted, clarified by filtration through a SS screen to remove unmelted solids, ash and black specks, drawn up into 10 mL plastic syringes and allowed to freeze. The syringe fronts were cut off under water and the slugs were extruded using the plunger. This sample is 100 g and I would dearly have loved to treat it with chlorosulfuric acid to make it white instead of yellow before the owner took posession, but this acid requires oleum to make. And, yes, I know I could make the oleum but you have to draw the line somewhere and my current fascination is black P.
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