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Author: Subject: Phosphorus - Life & death of a 2.5g lump
Zan Divine
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[*] posted on 7-7-2012 at 13:10
Phosphorus - Life & death of a 2.5g lump



OK, let's just drop any pretense that this thread is a real contribution other than to provide a few yucks.

I hear such hushed reverence for the demon phosphorus that I thought a few pictures might be useful to the uninitiated (and I count myself in that group)...

Pic 1 Time 0 m, 2.5 g WP wet with a little water.

Pic 2 Time 3 m, The WP has self-heated, fusing the two pieces.

Pic 3 Time 5 m, The WP was moved to a less heat absorbent surface after this pic, which shows very little activity so far.

Pic 4 Time 7 m, That was the trick....by this point the WP was bubbling and getting shiny as the surface liquified.

Pic 5 Time 8 m, WP simultaneously liquified and ignited with a ferocity approximating gasoline. The spread down the side of the log was extremely rapid, the viscosity must drop in a pretty drastic fashion. The spread was every bit as fast as a gasoline fire.

Impressive amount of fire from the small lump!

It seems that small factors can drastically alter the behavoir of pyrophoric WP. If the heat gets sucked away, it couldn't do much (at this scale).

(I've tried a half dozen times to insert the pictures in the correct order and they insist on coming up randomly. I'm too disgusted to try anymore. I think the sequence is obvious, but in case it isn't, the website prefers the sequence 8m, 7m, 0m, 3m, 5m).








t 8 m (Small).jpg - 87kB t 7 m (Small).jpg - 130kB t 0 (Small).jpg - 102kB t 3 m (Small).jpg - 106kB t 5 m (Small).jpg - 105kB





[Edited on 8-7-2012 by Zan Divine]




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m1tanker78
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[*] posted on 7-7-2012 at 13:38


Where's the 'like' button? Thanks and don't sweat the sequence too much. :D



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Endimion17
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[*] posted on 7-7-2012 at 14:29


Sexy. :D

Dude, you have to try this at night, and summer is just the season for it. Spread it across a warm concrete floor (outside, of course) like butter and watch the glow. It's amazing.
You can put a small piece on the floor and cover it with a cotton ball, and just smear it around. It looks like a sea of light, shimmering with a ghastly green color.
Or put a small piece (<0.5 g) in an ampoule, heat it under warm water to melt it and then smash it on the floor during the night. You get an amazing starry night scene. Toxic as shit, dangerous, but beautiful.




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Rogeryermaw
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[*] posted on 12-7-2012 at 21:52


put a small lump in a vial with some benzene and shake for a few minutes. only a few milligrams will dissolve. pour the benzene on the surface of your choice(within reason and in a dark place or outside at night)and as the benzene evaporates, you will be greatly rewarded.

an example i made of this:

http://www.youtube.com/watch?v=XA02M9yf1qg&feature=plcp

[Edited on 13-7-2012 by Rogeryermaw]
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[*] posted on 13-7-2012 at 07:38


I recently put some RedP in the end of a long tube and heated it with a torch and was amazed at how the vapors looked like fireflys as it flickered in the night. I did not expect it to flash as the smoke blew around the way it did.




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[*] posted on 13-7-2012 at 08:08



I WANT PHOSPHORUS!!

If an animal is buried in marsh ground a green shimmer can be seen over the place at night. It's called 'willow the wisp'. (I believe) cause by the phosphorus coming from the decaying bones.
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[*] posted on 13-7-2012 at 08:31


will o' the wisp (will of the wisp)so called due to the myth that the wisp could "will" travelers to follow its eerie glow, often to their detriment or doom: http://en.wikipedia.org/wiki/Will-o%27-the-wisp#Scientific_e...
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[*] posted on 13-7-2012 at 09:34


I have never heard of that theory on will o' wisp but I must say thats what I would expect them to look like. It was a hell of a sight.




Knowledge is useless to useless people...

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[*] posted on 13-7-2012 at 10:36


Quote: Originally posted by dann2  

I WANT PHOSPHORUS!!

If an animal is buried in marsh ground a green shimmer can be seen over the place at night. It's called 'willow the wisp'. (I believe) cause by the phosphorus coming from the decaying bones.


No, there's no phosphorus coming from the decaying bones. It takes a hell of a lot energy to pull elemental phosphorus from calcium phosphate. It's impossible in such conditions.

What comes out (presumably!) is dirty phosphine that spontaneously ignites upon contact with oxygen, although I don't really see the possible mechanism behind it.

And no, if an animal is buried in marsh ground, nobody will see anything. This luminous phenomenon is quite rare. If it was that simple, many people would've already taken lots of photos and videos of it.




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[*] posted on 13-7-2012 at 10:57


Quote: Originally posted by Endimion17  

What comes out (presumably!) is dirty phosphine that spontaneously ignites upon contact with oxygen, although I don't really see the possible mechanism behind it.

Microbial reduction. I think phosphine can still luminesce in air, without actually igniting. Or perhaps it is from traces of P2H4. Phosphorous-phosphorous bonds are very weak and easily oxidized.

[Edited on 13-7-2012 by AndersHoveland]
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[*] posted on 13-7-2012 at 14:15


Quote: Originally posted by AndersHoveland  
Quote: Originally posted by Endimion17  

What comes out (presumably!) is dirty phosphine that spontaneously ignites upon contact with oxygen, although I don't really see the possible mechanism behind it.

Microbial reduction. I think phosphine can still luminesce in air, without actually igniting. Or perhaps it is from traces of P2H4. Phosphorous-phosphorous bonds are very weak and easily oxidized.

[Edited on 13-7-2012 by AndersHoveland]


It would happen more often if it was that simple, and it does not.
Bacteria don't really mess with phosphorus in such ways. They want it and they eat it because it's not exactly something to waste like the plentiful nitrogen which can be pushed out in the form of ammonium cation, ammines, etc.




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[*] posted on 13-7-2012 at 19:11


E17 has hit on part of the theory of the phenomenon. quite a lot of methane is released from decaying organic matter. if a miniscule quantity of phosphine (pyrophoric) were to be released into a cloud of methane, IGNITION! there is your will o' wisp.

by all accounts it is an incredibly rare occurrence and has never been photographed so it may only be a theory anyway. we can put it up there with ball lightning, superman, aliens and god. great and fun ideas, but who really knows for sure.

there is a small experiment i would like to try with some of the P4 i have. i know red P and chlorates are unstable and very energetic. how would it go with white P? if i get the balls to try it i will post the video.

[Edited on 14-7-2012 by Rogeryermaw]
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[*] posted on 13-7-2012 at 23:20


Quote: Originally posted by Rogeryermaw  
there is a small experiment i would like to try with some of the P4 i have. i know red P and chlorates are unstable and very energetic. how would it go with white P? if i get the balls to try it i will post the video.


Just hide behind a wall and drop the P4 using a clench.




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[*] posted on 14-7-2012 at 03:46


Quote: Originally posted by Rogeryermaw  
E17 has hit on part of the theory of the phenomenon. quite a lot of methane is released from decaying organic matter. if a miniscule quantity of phosphine (pyrophoric) were to be released into a cloud of methane, IGNITION! there is your will o' wisp.


Well that hypothesis is useless if there's no proposed mechanism. There might be, but I haven't heard of it.
Also, phosphine itself isn't pyrophoric. When produced by the reaction of white phosphorus and a strong base, it contains some P2H4 which is pyrophoric.


Quote:

by all accounts it is an incredibly rare occurrence and has never been photographed so it may only be a theory anyway. we can put it up there with ball lightning, superman, aliens and god. great and fun ideas, but who really knows for sure.


A theory explains stuff in a proven way, stuff that's been documented.
Here we have something that could very well be a lie or a misinterpretation. The whole phosphine thing is merely a weak hypothesis for a doubtful phenomenon.

Ball lightning is essentially in the same category, though unlike will o' wisp, it has been produced in the laboratory and witnessed by more people.
Superman is an invented being from a comic book, aliens probably exist (somewhere in the universe; the whole UFO stuff is probably a hyped up product of the media), and god is a phylosophical concept without a proper definition, therefore useless for any discussion.
So no, will o' wisp is not in the same category as these things.


Quote:

there is a small experiment i would like to try with some of the P4 i have. i know red P and chlorates are unstable and very energetic. how would it go with white P? if i get the balls to try it i will post the video.


I've thought about it, too, but I don't think it can be done safely. Red variety will explode if in the highly divided form and mixed intimately with a dry chlorate, but if you don't mix them, a deflagration occurs.
You can't exactly make a WP powder. It would take a very cold argon box in order for WP to stay brittle, but as its reactivity is way greater, it would probably detonate while it's being mixed with the salt.
In normal circumstances, you'd only get a violent sputtering flame.

Burning RP produces some WP on the bottom of the flame, so if you put some RP on a small pile of chlorates and light it, it will give WP which will react violently.




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[*] posted on 14-7-2012 at 06:29


Well, I know a very impressive way of demonstrating this reaction: Put a coin on a thin alumina sheet (about half a mm thick), and the alumina sheet an a piece of wood. Pour a little pile of finely ground potassium chlorate on the coin and wet it with a satured solution of white phosphorus in carbon disulfide. Wait... (15 - 30 minutes). If the ambient temperture is high enough, the detonation will occur spontaneously; if it does not, use a long wooden stick and a candle to initiate the reaction... By far the most spectacular way of doing coinage.;) Of course only recommended to experienced chemists...
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[*] posted on 14-7-2012 at 09:52


Quote:

Also, phosphine itself isn't pyrophoric.


according to air liquide from: http://encyclopedia.airliquide.com/Encyclopedia.asp?GasID=51

"Major Hazards

Major hazard : Inhalation and Fire
Toxicity (Am. Conf. Of Gov. Ind. Hygienists ACGIH 2000 Edition) : 0.3 ppm
Flammability limits in air (STP conditions) : Pyrophoric
Odour : Garlic or Onion-Like
UN Number : UN2199
EINECS Number : 232-260-8
DOT Label (USA) : PG & FG
DOT Hazard class (USA) : Poison A"
Quote:
Ball lightning is essentially in the same category, though unlike will o' wisp, it has been produced in the laboratory and witnessed by more people.

from wiki: http://en.wikipedia.org/wiki/Will-o%27-the-wisp#Scientific_e... "Chemists have replicated the lights by adding some chemicals to gases from rotting compounds."


[Edited on 14-7-2012 by Rogeryermaw]
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[*] posted on 14-7-2012 at 10:53


Quote: Originally posted by Heuteufel  
Well, I know a very impressive way of demonstrating this reaction: Put a coin on a thin alumina sheet (about half a mm thick), and the alumina sheet an a piece of wood. Pour a little pile of finely ground potassium chlorate on the coin and wet it with a satured solution of white phosphorus in carbon disulfide. Wait... (15 - 30 minutes). If the ambient temperture is high enough, the detonation will occur spontaneously; if it does not, use a long wooden stick and a candle to initiate the reaction... By far the most spectacular way of doing coinage.;) Of course only recommended to experienced chemists...


That's a fairly good substitute, forgot about the solvent. Quite dangerous, indeed.


Quote: Originally posted by Rogeryermaw  
according to air liquide from: http://encyclopedia.airliquide.com/Encyclopedia.asp?GasID=51

"Major Hazards

Major hazard : Inhalation and Fire
Toxicity (Am. Conf. Of Gov. Ind. Hygienists ACGIH 2000 Edition) : 0.3 ppm
Flammability limits in air (STP conditions) : Pyrophoric
Odour : Garlic or Onion-Like
UN Number : UN2199
EINECS Number : 232-260-8
DOT Label (USA) : PG & FG
DOT Hazard class (USA) : Poison A"


Well it's wrong. Pure phosphine won't start burning. Thénard has proven it, and it's not something I've found online, but an established fact from actual paper books. Diphosphine is pyrophoric, phosphine is not.


Quote:
from wiki: http://en.wikipedia.org/wiki/Will-o%27-the-wisp#Scientific_e... "Chemists have replicated the lights by adding some chemicals to gases from rotting compounds."


Have you missed the [citation needed] mark? Nobody ever produced it. It's a disinformation clearly made by someone into this thing.
There's a PDF in the references below where dome Italian dude is monitoring PH3 levels on cemeteries. No positive results.




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[*] posted on 14-7-2012 at 14:24


with an auto ignition temperature of only 38C and lower explosive limit of 1.8%, perhaps it would be wise to consider phosphine as dangerous as any "pyrophoric" substance. technical PH3 always has some percentage of impurity in it which heightens the danger.

anyway, i don't have an electrolysis cell so i am in the process of boiling down some bleach. i will report after i give this a try(milligram scale).
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[*] posted on 14-7-2012 at 14:39


I forgot to mention: for the experiment mentioned above usually aroung 4 g of potassium chlorate are used (if I remember well). That is much, however you don´t need to mix the two compounds by hand and as long, as the mixture is still wet, it is probably (more or less) insensitive, so it´s OK.

Quote:

anyway, i don't have an electrolysis cell so i am in the process of boiling down some bleach. i will report after i give this a try(milligram scale).

I have always found it easier to introduce chlorine (which can be generated in large amounts from technical calcium hypochlorite or trichloroisocyanuric acid) into a hot solution of NaOH, followed by precipitation with KCl (and recristallisation).

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[*] posted on 14-7-2012 at 15:57


Quote: Originally posted by Rogeryermaw  
with an auto ignition temperature of only 38C and lower explosive limit of 1.8%, perhaps it would be wise to consider phosphine as dangerous as any "pyrophoric" substance. technical PH3 always has some percentage of impurity in it which heightens the danger.

anyway, i don't have an electrolysis cell so i am in the process of boiling down some bleach. i will report after i give this a try(milligram scale).


Yeah, but if no diphosphine is produced, it can't burst to flames. Bacteria producing diphosphine is even more far fetched idea.
Marshes produce wet methane, ammonia, hydrogen sulphide and carbon dioxide. Also some volatile organics, but they aren't pyrophoric.




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[*] posted on 30-7-2012 at 22:52


finally tried the experiment with KClO3. turns out i didn't have to. someone beat me to it. anyway here it is: http://www.youtube.com/watch?v=I_ZE4UwPObM&feature=youtu...
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[*] posted on 31-7-2012 at 09:02


The explosion of WP+chlorate was demonstrated for us back in the good old days by our chemistry master. At the back of the class, behind us, he put several grams of chlorate on an asbestos gauze supported by tripod. He poured on it a CS2 solution of WP and continued his lecture. The resulting sudden explosion 20 mins later was impressive and blew a hole in the wire gauze. So be careful!

As to RP + chlorate, several times I made small mixtures of fine ground Chlorate and RP as a teenager, by mixing with a feather! Aim, to make a percussive mixture more impressive than with sulphur. It worked. Then one day I repeated same but the RP had gotten damp (it’s hygroscopic). The mixture deflagrated when touched and singed eyelashes and eyebrows. Don’t do it! The reason was probably due to acid formation on the RP, causing the chlorate to be sensitized.

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