Sciencemadness Discussion Board - New Easy Way to Phosphorous!

New Easy Way to Phosphorous!

hodges - 31-3-2005 at 17:19

When one thinks of making phosphorous, high temperature furnaces and dangerous condensation procedures come to mind. Indeed, the way phosphorous has been prepared historically is to heat phosphates to a high temperature with carbon in a coal furnace. However, at the time phosphorous was first discovered, the majority of chemicals that are today available to the mad scientist were not available. I thought about this situation, and what chemicals are available to us today. Sure enough, I was able to come up with a new way to produce phosphorous that requires no high temperatures or elaborate condensation procedures.

One of the most chemically active reducing agents available is aluminum. We don't think much about aluminum, because we see it everywhere. It is in our cars, our lawn furniture, and even in our cooking (aluminum foil and aluminum pie plates). The reason aluminum does not generally show its reactivity is because it forms a thin coating of aluminum oxide (Al2O3) on the surface. This thin oxide coating renders the aluminum metal inert. Yet given the right conditions, aluminum is quite active (as anyone who has made thermite before knows). While thermite involves very high temperatures, this is not the only way to get aluminum to react as a strong reducing agent. If you've ever used Drano you realize that aluminum, in alkaline solution, is a strong reducing agent at room temperature. Drano consists of a mixture of sodium hydroxide, sodium nitrate, and aluminum. When water is added to this mixture, aluminum reduces the nitrate ion to ammonia as follows:
5NaOH + 3NaNO3 + 8Al + 18H2O --> 8NaAl(OH)4 + 3NH3

I got the idea that aluminum might reduce phosphates, much as it reduces nitrates. Experiment verified this to be correct. The apparent reaction is (using sodium phosphate as an example):
2NaOH + 2Na3PO4 + 8Al + 22H2O --> 8NaAl(OH)4 + 7H2 + 2P
To perform this reaction, add sodium hydroxide and a phosphate to water. Once the phosphate has dissolved, add small balls of aluminum foil. After the reaction is complete, the sodium aluminate solution is decanted, and the precipitated phosphorous is washed several times with water.

A couple of precautions are in order here. First, be careful to avoid excess sodium hydroxide, as this will react with the phosphorous to produce phosphine gas (PH3), which is both flamable and poisonous. The first time I tried this reaction, the escaping gas caught fire with a "pop" several times, and the phosphorous yield was very small. I was able to remedy the problem by using less sodium hydroxide, although this resulted in not all of the aluminum being used up and a phosphorous yield that was less than theoretical. I found that keeping the reaction cool with an ice bath, and removing the phosphorous as soon as hydrogen production has ceased provides a better yield. Either way, the reaction should be done outside, and care should be taken to avoid inhaling the vapors (which have a strong garlic odor). A second precaution concerns the phosphorous itself. As it is a very fine precipitate, some of it tends to float on the water after it is washed. At the very least, this could result in harmful phosphorous vapor being released into the air. In the worst case, the phosphorous could conceivably ignite if enough of it floated on the surface. I recommed that the phosphorous in water be heated lightly in order to melt the phosphorous and fuse it into one solid chunk which will no longer tend to float.

Although phosphates are not too hard to find, there are other alternatives besides buying them. Recall that urine contains phosphates; indeed phosphorous was first prepared using fermented urine. I have found that feline urine works as well as or better than human urine. I simply take some used kitty litter (the clumping kind works best) and add it to the sodium hydroxide solution. I was able to significantly increase the amount of phosphorous I could extract by feeding my cat a diet of "high phosphorous" dry catfood (made especially for older cats). While this may sound gross, there is nothing wrong with using biological reactions to provide chemicals; it has been done since the early days of chemistry. A few months back, I even had an idea which would allow me to produce hydrazine, using my girlfriend's vagina. Unfortunately, my girlfriend broke up with me shortly after I proposed the idea, so I never got a chance to test it.

Anyway, I'm sure that the above reactions will be of use to those desiring to prepare phosphorous tomorrow.

Enjoy,
Hodges

How suspiciously interesting.

Polverone - 31-3-2005 at 17:57

I fear that this is an early April Fool's joke, like last year's "strange lead compound." I have had the same idea before, but I didn't succeed in noticeable production of phosphorus or phosphine from the nascent hydrogen produced by aluminum acting on an alkaline phosphate solution. I believe BromicAcid has tried it as well. Post further experimental details if this isn't purely a joke.

rift valley - 31-3-2005 at 18:28

Quote:

Originally posted by Polverone
I fear that this is an early April Fool's joke, like last year's "strange lead compound." I have had the same idea before, but I didn't succeed in noticeable production of phosphorus or phosphine from the nascent hydrogen produced by aluminum acting on an alkaline phosphate solution. I believe BromicAcid has tried it as well. Post further experimental details if this isn't purely a joke.

Yeah its a joke hodges also wrote strange lead compound at almost the exact same time one year ago (or was it two years?) It isn't even April yet!

budullewraagh - 31-3-2005 at 18:43

i dont think the phosphate would be reduced, really.

awhile back i did think of the following:
Al+Na3PO4-->Al2O3+Na2O+P
but that wouldnt work at reasonable temperatures

Darkblade48 - 31-3-2005 at 18:46

The strange lead compound thing was last year

Chris The Great - 31-3-2005 at 22:04

Obviously this needs to be tried in a furnace of some sort

cyclonite4 - 1-4-2005 at 02:48

I was under the impression that Drano was just sodium hydroxide, but if hodges is telling the truth about that, well... you learn something new everyday.

12AX7 - 1-4-2005 at 04:25

I was under the impression that Drano was lye and aluminum shavings (well, certain kinds of it).

Tim

Darkblade48 - 1-4-2005 at 04:31

Quote:

Originally posted by 12AX7
I was under the impression that Drano was lye and aluminum shavings

Tim

Lye is (usually) sodium hydroxide, though it can also refer to potassium hydroxide

cyclonite4 - 1-4-2005 at 04:41

I think 12AX7 was suggesting he was unaware of sodium nitrate being present in drano, not confusing lye with sodium hydroxide.

BTW hodges, I don't blame your girlfriend for disagreeing with your proposal.

Natures Natrium - 1-4-2005 at 05:49

Quote:

Originally posted by hodges
Although phosphates are not too hard to find, there are other alternatives besides buying them. Recall that urine contains phosphates; indeed phosphorous was first prepared using fermented urine. I have found that feline urine works as well as or better than human urine. I simply take some used kitty litter (the clumping kind works best) and add it to the sodium hydroxide solution. I was able to significantly increase the amount of phosphorous I could extract by feeding my cat a diet of "high phosphorous" dry catfood (made especially for older cats). While this may sound gross, there is nothing wrong with using biological reactions to provide chemicals; it has been done since the early days of chemistry. A few months back, I even had an idea which would allow me to produce hydrazine, using my girlfriend's vagina. Unfortunately, my girlfriend broke up with me shortly after I proposed the idea, so I never got a chance to test it.

lol! That is some of the funniest shit I have read in a long time.

hodges - 1-4-2005 at 18:31

Quote:

Originally posted by cyclonite4
BTW hodges, I don't blame your girlfriend for disagreeing with your proposal.

Yeah, I figured that might be a tipoff as to the validity of the rest of the message (that and today's date

BromicAcid - 1-4-2005 at 19:50

Actually, I never tried this in basic medium, so... you had me going for a bit until I read the next message

tom haggen - 2-4-2005 at 11:33

You got me good with this one.

kryss - 2-4-2005 at 14:46

Good one best april Fools Ive seen. Def taking the piss as it were! Have you guys any idea what cat litter would smell like if you digested it up with caustic - apart from any Phosphorus there there's loads of Nitrogen too so you'll have stinking cat piss giving of loads of ammonisa fumes too!

future cats

roamingnome - 31-1-2007 at 11:51

after cracking up about hodges methods, chance would have it that it offered a great solution for kitty problems....

a particular kitty would pee in one corner and was too good for the other places.... only pee though... another person put litter there but cats flick this everywhere and no one wants to step on litter in the kitchen...

then in a thirft store. i saw charcol air filter pads for like 40 cents. i said awsome...

so i put one of these charcol pads in a tray and covered with a paper towel for some reason.... just the other day it was so deliteful to see that kitty had used her new space pad from the year 2000.

i hope this will form the microcosmic salt and after collecting a few pads will heat it up to sodium phosphite

then in some ceramic retort all the way to 'icy noctiluca' as Boyle called it.. back in shoot 1680

you probably have to collect a real lot huh?

Levi - 1-2-2007 at 06:41

Well, phosphorus can be prepared from urine but I have no idea how a vagina would aid in hydrazine production. The idea of combining chemistry and sex sorta reminds me of that Seinfeld episode where George manages to combine sex and food into one, uncontrollable urge. Maybe someday the pr0n industry will catch on to the appeal and film the worlds first chemistry themed porno film.
"Is that a test tube or are you just happy to see me?"

YT2095 - 1-2-2007 at 07:55

Joking aside for a sec, I wonder if it`s possible to strip Phos from Phosphine in much the same way as is done with H2S in biogas filtration for the sulpher?

the recent biogas thread made me wonder.

EDIT: This thread; http://www.sciencemadness.org/talk/viewthread.php?tid=7631

[Edited on 1-2-2007 by YT2095]

garage chemist - 1-2-2007 at 09:10

Yes, partial combustion of phosphine yields phosphorus. I read something about it somewhere here.
It would also be possible to brominate it to PBr3/5 and then reduce it with mercury as Sauron is planning to do with commercial PBr3.
Water is easier reduced than phosphorus (at 900°C in the gas phase, P will react with steam to H3PO4 and H2), so reduction of phosphates in aqueous solution is not possible. Also, white P reacts with alkalis to PH3 and hypophosphite, so PH3 would be the only product if the Al reduction would work. Acidic or nearly neutral solution with Al amalgam would be required, but as said, it is not possible in water.

I have said it several times before: Phosphides are easily made from phosphates by reduction with magnesium or aluminium powder! The reaction is similar to thermite, only less vigorous. No furnace needed! Just a crucible which is covered to prevent entry of air. Ignition via Mg ribbon.
Adding water or acid to the reacted mix releases PH3.

[Edited on 1-2-2007 by garage chemist]

YT2095 - 1-2-2007 at 09:28

yeah, I was thinking along similar lines, Phosphine is reasonably easy to obtain, so to break that down also May be another way to go.
2 smaller problems is better than one Big One sometimes.
I know my Attempt at making Phos the hard way worked once, but I think that was more Fluke and impurity than judgement on my part, I`ve never managed to replicate it since using Pure ingredients

it`s a tenacious little beasty is Phos!

unionised - 1-2-2007 at 11:35

I'm pretty sure PH3 can be broken down by simply heating it.

garage chemist - 1-2-2007 at 11:51

I read up on Phosphine in Ullmann, and it surprises me how easy it is:
"Above 375°C, it decomposes into the elements".

I am positive that a doable OTC preparation method for phosphorus will go via PH3 as the intermediate.

Get a phosphate salt, reduce it with Mg or Al, hydrolyse to phosphine, lead this through a heated glass tube to obtain elemental phosphorus.

Of course, this will yield the white modification since P boils at 280°C and condensing P vapor always yields the white form (though white P is always colored orange or red when not purified, so never assume you have red P when the condensing drops are red!).

YT2095 - 1-2-2007 at 12:33

yeah, I had that before when trying to make Phosphides in a CO2 atmos, it didn`t work and only succeeded in distilling the phos into an orange waxy substance I later found out to be impure phos.

garage chemist - 1-2-2007 at 12:45

"Orange waxy" is an appropriate description of what I obtained from sublimation of red P.
It is white phosphorus of high purity!
A more fitting name for P4 is yellow phosphorus.
It is extremely difficult to obtain white phosphorus that is actually white, and this turns yellow in light in a matter of seconds.

garage chemist - 2-2-2007 at 00:59

I might give this a try in the holidays (in a few months), just to see if I can make elemental P.
*puts 15mm diameter quartz tube on list of things to buy from the glassblower*

The generation and decomposition of phosphine will have to be carried out in inert gas atmosphere (I'll use CO2). The explosion limits of phophine in air are 1,6- nearly 100%, so exclusion of oxygen is essential to avoid blowing up the apparatus as soon as the heating is begun.

vulture - 2-2-2007 at 14:29

Quote:

The explosion limits of phophine in air are 1,6- nearly 100%, so exclusion of oxygen is essential to avoid blowing up the apparatus as soon as the heating is begun.

Not to mention its rather high toxicity...

[Edited on 2-2-2007 by vulture]

garage chemist - 2-2-2007 at 15:03

Fume hood takes care of that, plus its smell is very strong and already noticeable at concentrations that do not pose immediate danger.
Of course, working with PH3 as intermediate is not the ideal way. A phosphine- free method is always preffered, but this is too difficult (high temperatures) so we have to look for alternatives. Going via PH3 is the most promising one.

It is exactly the same as with making cyanides via HCN as the intermediate: it is easy and yields a very good product. The only downside is the added danger.
But for cyanides, doable HCN-free methods exist, while for phosphorus, doable PH3-free methods do not seem to exist.

unionised - 2-2-2007 at 16:35

"The generation and decomposition of phosphine will have to be carried out in inert gas atmosphere "
That doesn't require an inert atmosphere; just a reducing one. A flow of H2 would do.

garage chemist - 3-2-2007 at 01:15

I think CO2 is easier to fill the apparatus with (heavier than air) than hydrogen. Also, if the atmosphere isnt oxygen-free there will be a more powerful explosion with the hydrogen in there (the phosphine will ignite long before it starts to decompose, not to think of the phosphorus itself which ignites at 50°C). Also, the hydrogen definately won't reduce any formed P2O5 from oxygen impurities in the gas back to phosphorus.

For those reasons I am sure that an inert atmosphere is required. A reducing one just won't do with phosphorus, because P is a stronger reducing agent than hydrogen.

[Edited on 3-2-2007 by garage chemist]

S.C. Wack - 3-2-2007 at 02:45

Either that or the reduction of phosphate with hydrogen has been known for over 50 years, is mentioned in several books on phosphorus, is patented (with some additional goings-on leading to other P cpds.), is mentioned in the very first page of the P thread, and linked to later on.

garage chemist - 3-2-2007 at 03:02

This contradicts with the statement in Ullmann that phosphorus will react with water vapor at high temperature to phosphoric acid and hydrogen.
The reduction of phosphates with hydrogen probably relies on the equilibrium shift by the high temperature which removes the phosphorus as it is formed.

guy - 3-2-2007 at 15:20

If I did my calculations correctly,

21H2O + 3PO4(3-) + 8Al --> 8[Al(OH)4]- + 3PH3 + OH-

should have a Eo value of 1.09V. That's pretty good.

BTW, just to let you know, diphosphine is responsible for the explosive behavior, not phosphine. Diphosphine is analogous to hydrazine in structure.

[Edited on 2/3/2007 by guy]

chemrox - 3-2-2007 at 16:22

Elemental P comes in two common forms. Which one would be produced?

(This assumes the post is not a joke but I thnik it must be)

guy - 3-2-2007 at 17:11

Quote:

Originally posted by chemrox
Elemental P comes in two common forms. Which one would be produced?

(This assumes the post is not a joke but I thnik it must be)

White always occurs naturally. It takes more effort to convert to red.

And why does this sound like a joke? Its very probable that phosphine will at least be produced.

guy - 5-2-2007 at 21:28

Possible way to make aluminum phosphide?

16Al + 6Na3PO4 --NaOH--> 5Al2O3 + 9Na2O + 6AlP

Then treat AlP with water to get PH3 (this PH3 will be free of diphosphine, which is explosive).

madscientist - 5-11-2010 at 11:01

Something interesting:

Quote:

When triphenyl phosphate was reduced with a solution of LiAlH4 in carbitol, which was prepared as described in [9], the formation of red phosphorus was observed and not even traces of phosphine were present.

Attachment: phosphate ester reduction lialh4.pdf (216kB)
This file has been downloaded 1720 times

Random - 6-11-2010 at 00:41

5NaOH + 3NaNO3 + 8Al + 18H2O --> 8NaAl(OH)4 + 3NH3

2NaOH + 2Na3PO4 + 8Al + 22H2O --> 8NaAl(OH)4 + 7H2 + 2P

I think PH3 would form

NaOH + Na3PO4 + Al + H2O --> NaAl(OH)4 + PH3

this could actually happen

zed - 6-11-2010 at 05:38

Well, Madscientist.....Normally, using LiAlH4, ain't the preferred way to do anything.

But, Red Phosphorus is so hard to buy, or make by conventional means....This method really could be considered "Easy Phosphorus".

Too bad the Authors of your paper, seemed hell-bent on making phosphine, and didn't give much detail about their red phosphorus adventures.

As in....... "Darn it! We were trying to make Phosphine, but alas, we only got Red Phosphorus!"

madscientist - 6-11-2010 at 12:40

It made me wonder if other, more accessible reducers may effect a similar transformation. And I agree - it's too bad they failed to investigate further!

zed - 6-11-2010 at 23:21

The result of many experiments, I fear.

Authors fail in achieving their original objective, but none-the-less...get results that
are extraordinarily interesting. But alas, generally, to no avail.

Scientific tunnel-vision, makes it impossible for them to see their triumph.

Give credit to the fellow that originally discovered Phosphorus. He was trying to refine Gold from urine, but ended up with Phosphorus instead.

He could see that he hadn't achieved what he wished to, but he was clever enough to also see that he HAD achieved something unique and valuable.