Sciencemadness Discussion Board

First attempt at making WP + clusterfuck

Pyro - 8-4-2013 at 13:24

Today my RP arrived! it is (was) a floury burgundy powder.
When I took it to my lab I tried to make WP. It went extremely well and I had lots of dark yellow blobs of it.
the reason that the WP on the pictures is such a strange shape is because The water was cold. after that I heated it and it melted.
That's where the good news ends.

here's the bad stuff:
I was transferring the RP from the big container (800g!!!) into a smaller one and the bloody thing just caught fire, it almost exploded! I figure it was WP contamination as it smelt of matches. I jumped back, dropping the bottle on the floor and table, that ignited and started making P2O5 smoke. I quickly got my CO2 fire extinguisher and tried putting it out, but it just spread the fire so I collected up my half burnt camera and coat and got out of there. just then my dad arrived. I closed the door hoping for the fire to burn itself out fast. but 20 mins later it was still on fire and the P2O5 smoke had filled the entire area so densely that I couldn't see my hand 1ft. in front of my face. Then I made a mask out of a wet towel, It worked quite well but then my dad wanted to go down and have another go with the fire extinguisher and wouldn't let me come so he took the towel and went down while I waited above the stairs I heard him walking, then I heard a clang, then the fire extinguisher spraying, then coughing and stumbling, then a thud and nothing so I raced down and found him lying unconscious on the stairs so I grabbed him and started pulling and apparently told him ''don't die on me'' but I don't remember, then he seemed to wake up and I half dragged him outside. the fire is out now and we talked a bit. his story was: he went down, fell over the fire extinguisher and lost the wet towel, the sprayed the fire and started coming back, but he was disoriented and ad to follow my shouting, then he says he doesn't remember anything until I shouted at him to not die.

That's the story, now I smell like matches and feel a bit sick, might be from all the adrenalin.
tomorrow I am going to ask for another bottle from the seller as mine is burnt up and it's his fault.

To recap:the synth. of WP went perfectly. the RP spontaneously ignited, there was no flame nearby and the only heat source was a 100* hotplate keeping some water hot The plate was actually 100*) What do you guys think caused it? WP contamination, friction (I had the 800g bottle over the smaller bottle and was geltly turning it to make it fall into the small bottle) or something else?


Endimion17, you must be proud coaching me to make such nice WP first time around! dark yellow, a little lighter than the glob you used in your video: phosphorus chemiluminescence and pyrophoricity. so thank you, hopefully there will be a little RP left over from the fire that I can distill while waiting for the thing from poland
WP.jpg - 181kB WP2.jpg - 162kB

[Edited on 8-4-2013 by Pyro]

elementcollector1 - 8-4-2013 at 13:52

Well... that's... interesting. You might want to get you and your dad checked out by a doctor, phosphorus poisoning can be pretty nasty.
As for contaminants, I would imagine WP is not an issue (decays to RP upon exposure to light, if I recall).
Was anything destroyed in the fire?

Lambda-Eyde - 8-4-2013 at 13:55

Holy tits, dude. That could have gone horribly wrong, it's good to hear you're both safe. I don't have anything else to add, really...

Pyro - 8-4-2013 at 14:01

Well, It's not P poisoning, it's P4O10.
It came in a cardboard box wrapped in black plastic. and when I opened the bottle there was a strong WP smell.
I have no idea, last time one of us went even near the table he nearly died! you can't see a thing, I just left it until tomorrow.
Well, you can get phossie jaw from frequent exposure to P4, but i don't know about P4O10. Pulmonary edema might be a problem!

Any theories on the cause of the fire? I really think it's WP contamination

Mailinmypocket - 8-4-2013 at 14:08

I've never really handled much RP so I'm not an expert on its properties in person. Is there a possibility that the container it was in (or box) was of the type of plastic prone to creating static buildup? Again, I didn't think P was that sensitive to static, but perhaps finely divided dry material could be prone to ignition if you were to say, pour enough (800g) of it out and it developed enough charge to make a spark?

Glad to hear you are both okay though, wow.

Pyro - 8-4-2013 at 14:10

It was a HDPE container, and i didn't pour 800g, I poured maybe 50g before it went up in flames. I had half filled a 120ml packing jar

Simbani - 8-4-2013 at 14:22

WP contamination is very likely, due to the production method of RP. Ignition by friction can most likely be excluded, because you need more than a light tap to ignite RP.
I never heard of RP igniting in such a manner by itself, either. I would look for another seller in your case, where you can be sure to get a clean product.

Anyway, I´m glad to hear that you suffered no real damage, low amounts of phosphoric acid won´t kill you :) If you or your dad have to cough the next days there is a
chance of a pulmonary edema, maybe a doc won´t hurt.

Magpie - 8-4-2013 at 14:39

I got very uncomfortable reading your story. Burning P way out of control is a scary situation - I have flirted with this myself.

WP will spontaneously catch fire at room temperature in contact with air. I have seen it happen. I have not seen RP do this.

I'm so glad you and your dad are OK. Also, I admire your determination to not let this accident stop you.

I guess with bad actors like P one cannot do too much planning for worst-case scenarios.

DraconicAcid - 8-4-2013 at 14:41

I could have sworn I read a reference somewhere about having to treat red phosphorus carefully, as it has been known to spontaneously convert to white phosphorus, but I'll be damned if I can find it now.

Be careful- or we'll have to rename you "Pyrophosphate".

Endimion17 - 8-4-2013 at 14:55

Acute poisoning is possible because phosphorus fires quickly bring down the partial pressure of oxygen to low values, so lower oxides are being formed, as well as lingering phosphorus fumes. If there was no light in the room, you could've probably seen a chemiluminescent fog in the room. Luckily for you, you've acted fast.
CO2 extinguisher won't help at all. It's just fanning the fires. Closing the container will help.

You could've easily been killed both, but it would be because of the suffocation and desiccant, acidic efect of the pentoxide upon your alveoli. A gruesome death indeed.
Do not return to the lab yet. Throw a dripping wet towel inside and close the door. Don't come inside for a few days. The towel will absorb the smoke and any lingering P vapors will oxidize. After that, put on a damp cloth on your mouth (very dry air in the room!) and slowly pour water into the container to cover it all up. There's probably more WP inside, and it would ignite if you poked it without water.
After that, ventilate the room and start with the cleanup. There'll be a lot of acidic residue all over the place.

Under different circumstances, I'd recommend you to press charges against the douchebag the seller, but you should keep a low profile. That's a lot of phosphorus, way more than I've ever seen with my eyes in my entire life, so yeah... Keep quiet and be thankful you're alive.

The motherfucker who sold you the vessel obviously got hold of industrial raw material. When RP is being made, it is made from WP and the conversion is never 100% over. There's a balance reaction.
That's why RP is being milled and boiled with lye, to remove nonconverted white allotrope.
I have no idea how the hell he got his hands upon something that's not even for sale. Maybe he bribed someone, or stole it from the chemical plant?

The ignition was a spontaneous combustion of WP. No static electricity. RP is always too damp for that to happen.
It obviously caught fire after being exposed to air for some time. You should've recognized the immediate huge danger you were in when you've opened the bottle and smelled WP, but now you know. Let this be a lesson for you and whoever reads this.

I hope you don't have any burns.

edit: a steel bucket filled with sand is a must in chemical laboratories. It's one of the first things I've obtained. If something is burning, you toss it into the sand. If there's a powder burning on the floor/desk, you cover it with sand.
Inert and very handy.

[Edited on 9-4-2013 by Endimion17]

Endimion17 - 8-4-2013 at 15:00

Quote: Originally posted by DraconicAcid  
I could have sworn I read a reference somewhere about having to treat red phosphorus carefully, as it has been known to spontaneously convert to white phosphorus, but I'll be damned if I can find it now.

Be careful- or we'll have to rename you "Pyrophosphate".


It does convert to WP, but there won't be any buildup of the material. It happens together with moisture, and the result is phosphoric acid and RP mud.
Of course, every sample of RP contains traces of WP, but what happened here was because the seller sold raw industrial material that needed to be processed.

RP is being sold in large drums and if it's processed, nothing happens.

Damn, this makes me so angry. Some people are so reckless, as long there's money involved.

chemcam - 8-4-2013 at 15:09

What on earth do you need that much RP for? Sounds interesting if it is not for drugs. You are very lucky that the damage was not extensive. I too, would think WP was the culprit.

Magpie - 8-4-2013 at 15:12

Quote: Originally posted by Endimion17  

I have no idea how the hell he got his hands upon something that's not even for sale. Maybe he bribed someone, or stole it from the chemical plant?


My brother used to live where phosphorus was being produced on an industrial scale. He said the workers would smuggle RP out of the plant in their lunchboxes. I guess you know what they wanted it for.

Endimion17 - 8-4-2013 at 15:30

Magpie, such occurrences are probably the main source of RP for drug makers and I'm surprised the security is not strict enough to prevent it.

Pyro, when the container bursted into flame, the worst thing you did was to jump back and drop the bottle. You should've been ready. All you had to do is to put it on the table or the floor and close it. I've prevented a similar accident from turning ugly when a dumb student shoved a spoon with bits of burning RP into the bottle. What you need to do is to close it immediately and cool the bottle with wet cloth. The bottles are often plastic so acting quickly is of utmost importance. If the plastic melts, and you don't have anything to cover it with (large steel pot, large glass beaker, bucket of sand), it's evacuation time.
When it cools down, never open the container at once. The rush of air might start a new fire. Just slide the cover and introduce water. Aerosol dispenser works great if you want to save the bottom half of the dry powder, because the upper part will be layers of acid, RP and WP that are difficult to salvage by inexperienced experimenter/technician.

DraconicAcid - 8-4-2013 at 15:37

Quote: Originally posted by Endimion17  
Pyro, when the container bursted into flame, the worst thing you did was to jump back and drop the bottle. You should've been ready. All you had to do is to put it on the table or the floor and close it.


That's really easy to say, but anyone can be forgiven for panicking or reactive reflexively when the unexpected happens. We can't be expected to expect the unexpected all the time.

Pyro - 8-4-2013 at 15:39

Well Endi, I dropped the bottle when the thing caught fire in my hands, and then the spilt RP caught fire, it didn't burn in the bottle.
I thought of spraying in water when I saw the sea of white fumes, It was like rising water, rippling and running exactly like it.
I didn't throw in the towel, but it is very damp in there, I'm going back tomorrow to see if I can get in there to open a window.

My dad and I were discussing liability if the fire dpt. got called. I said it would be the polak's fault, he says it would be our fault. what do you think?

But how about the good part? what do you think of the distillation?

I am writing a mad letter to him asking for another bottle because this one caught fire in my hands, if he sends it I will top it up with water as soon as I open it, then dump in a beaker and boil I guess, with some KOH. 32 eur/800g is a super price!

I was incredibly fucking lucky! there was a huge burst of flames and I jumped back, dropping the bottle. my hands and all are burn free, my camera however, is fucked!

Yeah, we are getting sand tomorrow. and a bucket of water.

I am considering recuperating it, but haven't decided yet. I'll see how I feel tomorrow.

When I smellt the WP I had no idea how much dangerous it was. you and Woelen have warned me about it but I had no idea what WP smelt like (''Matches'' is not very accurate, it smells a little plasticky too) and thought that might be the norm.

Chemcam, I couldn't let a deal like that pass up! 800g/32 eur. even WP laced, it's worth it, I'll just boil it with KOH. all I want is to make WP and some P compounds.

Any idea why I feel so sick? adrenalin leftovers? or poisoning?

elementcollector1 - 8-4-2013 at 15:54

Quote: Originally posted by Pyro  
Any idea why I feel so sick? adrenalin leftovers? or poisoning?

Adrenaline doesn't stick around for 2 hours; SEE A DOCTOR!

Pyro - 8-4-2013 at 15:59

too late now, it's 2AM. I'll go tomorrow if i'm sick.
adrenaline might not, i thought it might be an aftereffect

Endimion17 - 8-4-2013 at 16:16

Quote: Originally posted by DraconicAcid  
That's really easy to say, but anyone can be forgiven for panicking or reactive reflexively when the unexpected happens. We can't be expected to expect the unexpected all the time.


Nobody expects the Spanish inquisition, either.

After all, it's 0.8 kg. Enough to make anyone squeamish.
Quote: Originally posted by Pyro  
Well Endi, I dropped the bottle when the thing caught fire in my hands, and then the spilt RP caught fire, it didn't burn in the bottle.
I thought of spraying in water when I saw the sea of white fumes, It was like rising water, rippling and running exactly like it.
I didn't throw in the towel, but it is very damp in there, I'm going back tomorrow to see if I can get in there to open a window.

So the last time you saw the bottle, it was not burning, but - where is it? If it's somewhere in the lab, opened, it's a ticking time bomb. If you find it undamaged, close it and put it in a steel sand bucket.
Quote:

My dad and I were discussing liability if the fire dpt. got called. I said it would be the polak's fault, he says it would be our fault. what do you think?


If you want your father to stand before a judge in a court, accused of negligence of a minor, go for it. That's probably what would happen.
Quote:

But how about the good part? what do you think of the distillation?

Knowing how easy it is to suffocate that fire just by closing the cap, and the fact it won't catch fire immediately, I'd use a spoon and transfer the stuff (without dispersion) in smaller bottles while the original is in a steel bucket, partially buried in sand, where it should remain sitting. But that's me, and I have experience with it.

It can be used for the conversion, but the risk of it spontaneously catching fire is known only to you. I can't really evaluate the risk without knowing exactly how does the thing behave.
Quote:

I am writing a mad letter to him asking for another bottle because this one caught fire in my hands, if he sends it I will top it up with water as soon as I open it, then dump in a beaker and boil I guess, with some KOH. 32 eur/800g is a super price!


Good luck with the purification. Don't do it all at once.
Quote:
I was incredibly fucking lucky! there was a huge burst of flames and I jumped back, dropping the bottle. my hands and all are burn free, my camera however, is fucked!


I still don't understand why would it would make a huge burst. You should've used a spoon. Transfering dusty, flammable material by pouring it through air is not a smart idea. Maybe you're responsible for the ignition. If there was a hotplate near you, and RP aerosol is lingering around... Maybe you've caused some friction, too.
I don't know. I'm not a CSI "genius".
Quote:

When I smellt the WP I had no idea how much dangerous it was. you and Woelen have warned me about it but I had no idea what WP smelt like (''Matches'' is not very accurate, it smells a little plasticky too) and thought that might be the norm.


Realistic RP samples smell. That's fact. If the smell was very intense and there were visible fumes upon opening the container, that would've give me a strong clue that shit is about to hit the fan.
Quote:
Any idea why I feel so sick? adrenalin leftovers? or poisoning?

What does it mean "feeling so sick"? Nausea? Fear? Vertigo?
If your father, being exposed a lot more, lacks the symptoms, it's probably anxiety. Get it? Probably.
Adrenalin rush doesn't last more than a couple of minutes.

How long have you been in the pentoxide atmosphere? Have you been holding your breath?
Did you take a shower? Do you still smell like matches? Does your breath smell?

Again, I can't evaluate this because there isn't enough info. If you feel sick, go to the doctor. "I was playing with Chinese fireworks, big bada boom", standard story.

[Edited on 9-4-2013 by Endimion17]

S.C. Wack - 8-4-2013 at 16:32

I imagine there aren't many manufacturers of RP who sell product that ignites in air, in the last hundred years that is.

BTW even RP with no WP but gets wetish can generate PH3. Some RP is treated to slow this down.

[Edited on 9-4-2013 by S.C. Wack]

plante1999 - 8-4-2013 at 16:35

I talk with pyro via another mean then the forum, and he told me as dad was having good problems with his lungs...

I do think it is pyro's fault, since like S.C said, nobody want to sell spontaneously flammable material that make toxic fumes... Especially that I never heard of spontaneous RP combustion...

Endimion17 - 8-4-2013 at 16:50

Quote: Originally posted by S.C. Wack  
I imagine there aren't many manufacturers of RP who sell product that ignites in air, in the last hundred years that is.


Unless it has been stolen from a factory. Even then, it wouldn't come as powder. Freshly made RP is a gunky mess that easily cakes up. There's enough WP inside to probably cause weak glowing, fuming and spontaneous combustion.
After it's processed, washed and dried, it's fluffy and dry if kept away from humidity. It doesn't catch fire just by itself. If left exposed to air, it will eventually turn into acidic goo, but it takes a long, long time. Months.

There's something wrong with this story. I do think it's probably his fault, though I can't be sure.
Quote: Originally posted by plante1999  
I talk with pyro via another mean then the forum, and he told me as dad was having good problems with his lungs...


"Good problems" as in "heavy problems"? That might be oedema forming. It's a medical emergency...
Quote:
I do think it is pyro's fault, since like S.C said, nobody want to sell spontaneously flammable material that make toxic fumes... Especially that I never heard of spontaneous RP combustion...


That's simply not true. :)

plante1999 - 8-4-2013 at 17:10

yes, as heavy problems... Well, for some money I guess, but he would be better to warn that it spontaneously burn making toxic fumes. At least I would warn if I were to sell something like this.

Pyro - 9-4-2013 at 05:58

Well, I held my breath most of the time or breathed through a damp cloth, but got a few big lungfuls while dragging him up the stairs. now I feel fine, must have been anxiety.

to clear up on the ''pouring'' thing, I held the neck of the RP bottle just above the neck of the empty bottle, and was gently turning it to make the powder fall into the smaller bottle. I have no idea how big the burst came to be, It was right in front of me, so maybe it wasn't that big. the hot plate was maybe 1m away.

The smell might of been intense, but that was the first time I had smelt WP so I had no idea how strongly it smelt. there was no fuming.

I don't see how this might be MY fault Endi.

I feel fine now, he has a little pain breathing. I might go check today to see if the smoke has settled, otherwise i'll check tomorrow.

Mixell - 9-4-2013 at 07:50

Was your RP Polish by any chance?

Pyro - 9-4-2013 at 08:18

yes. why?

Endimion17 - 9-4-2013 at 09:14

Huh, the plot thickens.

Although I don't see any real danger with careful and neat pouring of RP, I'd always choose steady transfer by spoon.
I'm trying hard to imagine the required conditions for spontaneous combustion of plain regular RP and I don't see them. I worked with fine grain RP and powdered RP and never ever saw anything like it, even with stronger rubbing. Friction will cause pentoxide fumes and the smell of matches, but that's it. If it was any different, matchboxes would be very dangerous items.
Your lab is damp, RP is always damp unless freshly prepared and kept in sealed containers... Static buildup is basically out of the question. It's not like there was dry atmosphere and prolonged friction between dry powder and some polymer sheet so that sparks would occur.

Can you describe the container? Or take a photo of it...

Fantasma4500 - 9-4-2013 at 09:49

wow.
quite some drama there.. well red phosphorus by itself is friction sensitive to some degree, but pouring it doesnt sound like a legit reason for it to selfignite... i would go with WP contamination aswell..
but yes phosphorus is pretty good for creating some dense smoke (:

http://www.youtube.com/watch?v=Yg7RR82NQOU

really cant imagine this inside a room!! always heard about the danger of handling phosphorus even in small amounts.. if you do this another time have some water you can dump it in even with very bad accuracy..

Mixell - 9-4-2013 at 11:38

I am planning tu purchase RP and other stuff from the same supplier, if he will ship internationally of-course.

But yea, what can you expect when you purchase 300g of it for 6$...

Adas - 9-4-2013 at 12:25

Oh, you mean strzaly.pl? I was about to buy some red P from them. :| But that's not 32€/800g but 16€/900g.

Please tell us who the seller was, so we could be informed.

plante1999 - 9-4-2013 at 12:49

Well, doctorofphilosophy and I baugth a 800g bottle of RP from the same ebay seller as Pyro, it should be here in a month or so... I will try to find the link for it.

Found it:

http://www.ebay.nl/itm/EMPTY-BOTTLE-RED-PHOSPHOR-ROT-PHOSPHO...

[Edited on 9-4-2013 by plante1999]

Pyro - 9-4-2013 at 12:52

Wow! those are cool smoke grenades! they are commonly 200g, so imagine 4 of those in a small space, I couldn't see my hand 1ft. in front of my face and could hardly see a light 3m away! Is that you throwing those grenades?
I was extremely lucky he collapsed on the stairs or i would never have found him!

Well endi, Transferring by spoon would have been messier, i opt for gently turning the bottle at an angle and use the Archimedes screw effect. My RP was a free flowing powder.

And no pic. of the container for you, where the container was there is just a blackish spot. the damage was minimal, a burn spot on the table and a black spot on the floor. Thank God the fire wasn't nearer to my bottle of propane! 10,5 kg of propane would be a nice complement to a P fire :D
All my glassware is clouded though, but that is easy to fix. I am worried about my hot plate. Any ideas on stopping it from being fucked by all that H3PO4.
the air in there is clear, but a bit painful to breathe. tomorrow i'll start cleaning up.
I did wash about 30g in boiling water and filtered it. It's on the filter now, and i hope it won't dry enough to ignite. that brings me to a question for you Endi, can I load it in a test tube damp and distill it damp as to not waste what tiny bit I have? I wrote a mad letter to the seller telling him it's his responsibility to warn about WP contamination and asking for a new bottle as reimbursement.

Anyone who wants his name just PM me, he is an ebay seller.

It was really nasty in there, like some Vietnam film

Mixell - 9-4-2013 at 13:07

Yea, I was talking about strazaly, do you know what his international shipping policies are?

Endimion17 - 9-4-2013 at 13:44

Quote: Originally posted by Pyro  
Well endi, Transferring by spoon would have been messier, i opt for gently turning the bottle at an angle and use the Archimedes screw effect. My RP was a free flowing powder.

It shouldn't be messy. After all, using spoon won't contaminate the neck.

If it was free flowing powder, then perhaps it was super dry? Static electricity comes back to mind.
Quote:
And no pic. of the container for you, where the container was there is just a blackish spot. the damage was minimal, a burn spot on the table and a black spot on the floor. Thank God the fire wasn't nearer to my bottle of propane! 10,5 kg of propane would be a nice complement to a P fire :DAll my glassware is clouded though, but that is easy to fix. I am worried about my hot plate. Any ideas on stopping it from being fucked by all that H3PO4.the air in there is clear, but a bit painful to breathe. tomorrow i'll start cleaning up.


So everything burned down? Almost 800 g burned down? Jesus have mercy... :o
I'd recommend opening the window slightly, let the breeze do its work for a few days, and then wipe everything.
I doubt your hotplate will suffer a lot. Phosphoric acid should will passivate any exposed iron. Just to be sure, wipewipewipe, dry, apply WD-40.
Quote:
I did wash about 30g in boiling water and filtered it. It's on the filter now, and i hope it won't dry enough to ignite. that brings me to a question for you Endi, can I load it in a test tube damp and distill it damp as to not waste what tiny bit I have? I wrote a mad letter to the seller telling him it's his responsibility to warn about WP contamination and asking for a new bottle as reimbursement.


If you think ignition might occur, secure it with something impossible to ignite. I'd put it in a steel bucket in the middle of the room.

Slight water content is not a problem as long as you heat it very gently to avoid frothing and excessive translation of the material in the retort. In fact, liberated water vapor will push out most of the air, so the usual initial ignition probably won't happen.
Quote: Originally posted by plante1999  
Well, doctorofphilosophy and I baugth a 800g bottle of RP from the same ebay seller as Pyro, it should be here in a month or so... I will try to find the link for it.

Found it:

http://www.ebay.nl/itm/EMPTY-BOTTLE-RED-PHOSPHOR-ROT-PHOSPHO...

[Edited on 9-4-2013 by plante1999]


Damn, this is hilarious. Illiterate and funny. "I'm sure you understand." LOL :D

There's even a serial number. That's not very smart. Those numbers make it traceable.

Mailinmypocket - 9-4-2013 at 13:56

Oh my... 800g of RP to our good old Canada eh? I'm anxious to hear how customs deals with it! Although not as paranoid as the US, I'm not sure how almost a kilo of the stuff will jive with them.

plante1999 - 9-4-2013 at 14:44

Well, hopefully doctorofphilosophy send him what I told him. I told the guy to send it as iron III oxide and we dealed outside of ebay, since we didn't wanted to be tracked down.

Pyro - 9-4-2013 at 15:48

Seems he bent his HKPD cuff links when he collapsed. No more blood for now, everything seems better.
Endi: we thoroughly enjoyed the spanish inquisition, we had laughing fits followed by coughing fits :D

Mixell - 9-4-2013 at 15:58

plante, don't think that the customs employees are easily fooled...
They have equipment that can easily detect traces of drugs and precursors, and disposable test kits for verification.
Trying to fool them on such matters may have more serious consequences than just package seizure.

If it's not strictly forbidden, then just send it as what it is and hope for the best. If you try to trick them, they will assume you have something to hide.

Pyro - 9-4-2013 at 16:06

Oh it is strictly forbidden in CAN.! but my package got opened, the seller had wrapped the bottles in black plastic, customs opened it and must have seen the clearly marked bottle stating it was P, they just closed it up and sent it to me!

plante1999 - 9-4-2013 at 16:48

Well, I had shipped things that should not be "allowed" and I don't think they find out... Canada is not strict like US taught.

The shipper could also have shipped it without my consent... Or someone is trying to get me locked down...

Magpie - 9-4-2013 at 19:57

Quote: Originally posted by Pyro  
Seems he bent his HKPD cuff links when he collapsed. No more blood for now, everything seems better.
Endi: we thoroughly enjoyed the spanish inquisition, we had laughing fits followed by coughing fits :D


I'm glad to hear that your dad is getting better. Here's some more inquisition fun to cheer him up. It's one of my favorites. :D

http://www.youtube.com/watch?v=NUMkcBctE7c

Pyro - 9-4-2013 at 20:07

hey, thanks!
here's something funny, real story:after I dragged him outside the first thing he did (after having a cough) was to start wiping off his suit ''Oh shit, look at my suit, it was really expensive!'' It just felt so out of place to after you just almost died to start worrying about your suit. but It's all dusted off and the cufflink can be fixed.

And this is copied from skype between plante and I:
[4/9/2013 1:42:33 AM] FGD: you know you may be dying while we talk...
[4/9/2013 1:43:17 AM] Alexander Birra: I guess that's another way out of the desperate situation in which i find myself

But he's still not out of the woods!
thanks for all the feedback.

[Edited on 10-4-2013 by Pyro]

woelen - 10-4-2013 at 04:09

Pyro, good to read that this near-drama did not end in a full drama. Let's all consider this as a serious warning about the use of impure red P. Pure red P only has a faint smell of white P, which is noticeable clearly, but not overwhelming and definitely does not self-ignite on contact with air.

I have done an experiment with red P to see how it behaves on storage. I have taken a sample of 5 grams (my red P is a dark red/brown/purple powder with a weak odour) and put this in a glass beaker at a dust-free place in direct contact with air. It already is there for more than a year and it has become somewhat wet in that time, but it did not liquefy and still burns well when ignited. It cannot be easily mixed with other chemicals though, because it is sticky. This is exactly what Endimion17 describes. Red P slowly reacts with air over the months (or even years!) and becomes wet. I expected this reaction to be much faster. I still have the sample of red P standing there, and I'll leave it like that for another long time, just to see what happens.

Also, red P is quite flammable, but I need heating to well over 200 C before it inflames. So, there is nothing like spontaneous ignition at room temperature. Pyro's sample of red P must indeed have been contaminated with lots of white P.

[Edited on 10-4-13 by woelen]

Pyro - 10-4-2013 at 12:59

Update:
I went to my lab, there are no fumes anymore. but EVERYTHING is coated in a thick layer of sticky H3PO4. any tips for cleanup?
here are pictures of the damage:

FLOOR.jpg - 178kB
This is the floor where the bottle was, RIP :D
TABLE.jpg - 181kB
This is the table where I dropped the bottle before it rolled off.
E17 bottle.jpg - 159kB
This is a bottle containing S, the bottle is identical to the one that had the RP in it
BOTTLE.jpg - 208kB
This is the bottle I was pouring the RP in to. It seems like I will be able to recover a good amount.
Willie Pete.jpg - 167kB
this one is my first ever batch of WP,l not bad for a beginner! pure nerd porn!

Eddygp - 10-4-2013 at 13:31

Quote: Originally posted by Pyro  
Well, I held my breath most of the time or breathed through a damp cloth, but got a few big lungfuls while dragging him up the stairs. now I feel fine, must have been anxiety.

to clear up on the ''pouring'' thing, I held the neck of the RP bottle just above the neck of the empty bottle, and was gently turning it to make the powder fall into the smaller bottle. I have no idea how big the burst came to be, It was right in front of me, so maybe it wasn't that big. the hot plate was maybe 1m away.

The smell might of been intense, but that was the first time I had smelt WP so I had no idea how strongly it smelt. there was no fuming.

I don't see how this might be MY fault Endi.

I feel fine now, he has a little pain breathing. I might go check today to see if the smoke has settled, otherwise i'll check tomorrow.


These mistakes are very harmful for your health... I don't mean you could have predicted it or not done that whatsoever, but I know of a man who died because of inhaling asbestos, a woman who died because of inhaling hlorine (NaClO+HCl, you can imagine)... and, well I suppose this is no nonsense either. Hope it's all right!

Pyro - 11-4-2013 at 11:28

update.
I got this from the seller after sending him a letter explaining what happened:

Hello,
I DO NOT UNDERSTAND!
I packed and shipped nearly 1,000 bottles. there was no problem.
I do not have and never sold the white phosphorus!
I'm getting into very clean. I know what is the red phosphorus! there is no possibility of contamination with me!
I think that you know how to do the red phosphor!
when you buy other items once you join free 400g phosphor red.
it is impossible to me to contaminated red phosphorus!

anybody who speaks polish and can make a little sense from this? i think it right from google translate

DraconicAcid - 11-4-2013 at 11:36

Quote: Originally posted by Pyro  
update.
I got this from the seller after sending him a letter explaining what happened:

Hello,
I DO NOT UNDERSTAND!
I packed and shipped nearly 1,000 bottles. there was no problem.
I do not have and never sold the white phosphorus!
I'm getting into very clean. I know what is the red phosphorus! there is no possibility of contamination with me!
I think that you know how to do the red phosphor!
when you buy other items once you join free 400g phosphor red.
it is impossible to me to contaminated red phosphorus!

anybody who speaks polish and can make a little sense from this? i think it right from google translate


I don't speak Polish, but it makes sense to me. He doesn't understand how what he sold could have burst into flames. He's sold nearly a thousand bottles of red phosphorus and never had a problem. He doesn't sell white phosphorus, so it's impossible that he sent you a bottle of the wrong material. His stuff is never contaminated (don't we always believe that our work is always perfect?). You must have mishandled the red phosphorus for it to burn like that.

And if you order another batch of chemicals, he'll throw in a bottle of red phosphorus for free.

Pyro - 11-4-2013 at 11:39

riiight...

this just in:
OK
you are in my 400g red phosphor for free. I will be most careful.
but you can also watch the phosphor rot! It can be bad in you and in me!
Greet. [DELETED]

think he might just want to give it to me :), maybe.
it's not 800g, but better than nothing

DraconicAcid - 11-4-2013 at 11:45

Quote: Originally posted by Pyro  

you are in my 400g red phosphor for free. I will be most careful.
but you can also watch the phosphor rot! It can be bad in you and in me!

He will check the bottle to make sure he's not sending the wrong stuff or a contaminated bottle. You have to be careful with red phosphorus (not just the white), as it, too, can be very dangerous.

(I'm assuming "rot" is a typo or mistranslation of "red", as in German, rather than him claiming that red phosphorus will decompose....)

Pyro - 11-4-2013 at 11:49

how do you figure that? :D
I just hope it gets replaced. I don't see why I have to order something to get it! i guess i'll have to fight

Endimion17 - 11-4-2013 at 12:05

So now he'll be transfering 400g out of its original bottle. It would be ironic if it bursts into flame. :D

Pyro, when you get your sample, use a spoon and take a detailed macro photo of the sample. Look for any evolving fumes against light.

Pyro - 11-4-2013 at 12:18

I hope he'll send me a new one! that would be very ironic!

I was hoping to pour on water as soon as I opened it! I really hope your right and he'll send me a replacement

[Edited on 12-4-2013 by Pyro]

DraconicAcid - 11-4-2013 at 12:20

Use a long spoon so you can take out some without picking up the bottle (you can't drop it if it's not being held). Put the lid back on the bottle ASAP.

Or, as you say, dump it into some water as soon as you get it.

Endimion17 - 11-4-2013 at 12:30

Nah, don't pour water in. What if this batch is ok? You wouldn't want to ruin it.
Take a long glass rod (or a thickwalled tube) and flamework it into an almost vertical spoon, and let that be your way of removing the substance from the container.
When opening the cap, unscrew it and then slide it away, slowly, keeping in mind that you don't want to grind the cap against the neck as it might be dangerous. Don't open it by lifting the cap to avoid mixing the air inside, which is possibly deoxygenated, with outer atmosphere.
Before opening, gently tap the bottle against the ground to ensure compactness of the powder.

Try to recreate your accident using small batches.
I wouldn't pour water inside just because something happened with the last bottle. It's much too valuable.

Inspect the neck and the cap's inside screw for the powder remains. Remove it with a damp cloth if there's any.

DraconicAcid - 11-4-2013 at 12:43

Quote: Originally posted by Endimion17  
Nah, don't pour water in. What if this batch is ok? You wouldn't want to ruin it.

I didn't think red phosphorus would react with water. White phosphorus is generally stored underwater, isn't it?

Maya - 11-4-2013 at 13:02

I would pour water into the container ASAP after I opened it and would not pour the contents into water.

The stuff may have a tendency to float on top at first from air bubbles caught between particles.
Then I would close to cap and gently swirl it to dislodge the air particles and let the RP settle to the bottom.

The water will not hurt it at all and can easily be removed under vacuum

Pyro - 11-4-2013 at 17:43

I think Endi means it would be wet. I'll take a scoop out for you guys when it arrives!
tomorrow: lime spreading on the floor and salvaging of RP

I only just noticed I have become an international hazard! doesn't seem fitting, it's more like hazard to self and family! Next time it will be inernational! don't worry! :D

woelen - 12-4-2013 at 02:19

This does not sound good at all. I do not agree with Endimion17. Why would this batch be better than the previous one? This seller just could get his hands on a huge pile of red P (tens or maybe even hundreds of kg) and I seriously doubt that the picture he shows on eBay is from his batch he is selling. He simply repackages from bulk into bottles of 800 grams and does this to stay just under 1 kg for shipping. He also sells 400 gram bottles and even 3 kg packages. As pyro writes, he wraps his 800 grams bottles in thick black tape before packaging it. He also sells 900 grams of NaNO2 in exactly the same type of plastic bottles (I have one of these, I ordered NaNO2 from this seller) and these are not wrapped in thick plastic tape, so he can sell 900 grams of NaNO2 in order to just stay under 1 kg total weight.

I would open the bottle in a bucket of water, under the water surface and SLOWLY let some water run in and allow bubbles of air to escape, while the cap is still loosely screwed on the bottle. SLOWLY, because otherwise when all water at once gulps in, it may cause a big bubble of air to escape with a large amount of the contaminated red P as a dust cloud and a possible tremendous flame! BE CAREFUL!!! Keep in mind that all this hassling around with crappy red P is not worth risking your health or even risking your life or your family's life!

This seller does not know very well what he is selling. He sells red P with a high white P content, period! Of course he did not add contamination himself, but he does not know enough of the chemical he sells and that the manufacturing process inherently may introduce a lot of contamination. For such low prices you can't expect good quality, but low quality should not be the same as insanely dangerous. I purchased his NaNO2 (which is less than EUR 4 per 900 grams) and do not expect it to be very pure, but it is not dangerous and is good enough for certain synthesis reactions (e.g. dyes, organic nitrites). Exactly the same I would expect with his red P.

[Edited on 12-4-13 by woelen]

Endimion17 - 12-4-2013 at 05:02

But Pyro's RP ignited when he poured the powder through the air. The surface available for the reaction was huge.
I'm almost sure nothing would happen even if he took a spoonful of the powder (of course, Pyro, don't transfer a spoonful at a time) and placed it on a flat surface. Even if it ignites, it won't be soon, and it won't be spectacular. RP fires are calm.
The fireworks he was were because of the "powderfall" from the main container which then ignited when fell from his hand.
One of the things that contributed is tilting the container. If it sits upright, and there's no wind, the fresh air doesn't enter by convection.

Before making attempts to make RP wet (it just delays the problem - WP is still inside) and thus subscribing to more tedious work in the future, I'd make few experiments. I'd try to cause an accident in a controlled condition, with small batch (cubic centimetre at most). I'd test for WP by observing fumes and glowing.

In the unlikely event of the upright container catching fire when picking up RP using a vertical spoon, water aerosol dispenser would take care of it. When RP catches fire in a container, it creates an area of pentoxide aerosol and oxygen depleted air which sits above it. Unlike flat surface fires, this one isn't spectacular. I've seen it and dealt with it. Its heat output is poor, so it takes like half a minute or more to seriously weaken the plastic container. It's more like smouldering.
Gentle sprinkle of water and closing the cap extinguishes it for good.

Submerging the container in a bucket of water and opening the cap might send up a fireball, as woelen said. I wouldn't do that.
The only RP available to reaction is the topmost layer. Nothing below will burn. The fire won't spread throughout the material, therefore water aerosol dispenser is enough.

If, after controlled testing, the material proves to be highly contaminated and pyrophoric, I would add enough water to cover it, and then process a small batch using lye to remove the contamination. But that's just me.

Someone mentioned wetting the powder and removing water using vacuum before using it. Baaaaaad idea. I'd say that would make it even more pyrophoric.

[Edited on 12-4-2013 by Endimion17]

Adas - 13-4-2013 at 12:30

Be aware! When you want to purify it with NaOH solution, it produces phosphine which may even kill you! I wouldn't try this for safety's sake..

Pyro - 20-4-2013 at 12:11

Cleanup session finished.

I spread slaked lime on the floor to remove acid traces. later I am going to brush it up and whitewash the walls.

The sliding door of my scales was open and H3PO4 got in! but It hasn't visibly corroded anything. I just hope it hasn't gotten in the mechanism. That's the pan, you can see all the H3PO4 on it, it's that thick everywhere.

All the gloves in the top of the box are covered in H3PO4 and smell a little strange, I just tripled them and used them to clean up.

I put water in the brown bottle the I was pouring the P into and it warmed up a bit (P4O10 I guess) and then I smellt REALLY strongly of P4 so I put it on the floor and buried it in slaked lime to make combusion impossible.

My boat that was inthere to keep it fry because all the varnish was striped off now has H3PO4, any idea if this is bad for it? I calculated there ust be a bit more than 2,5kg's H3PO4 there!

quick question:there is no shortage of water vapour in my lab, it's next to the river and the floor is below the water level. how dilute does H3PO4 become before it isn't hygroscopic anymore?

H-80 1.jpg - 152kB

Endimion17 - 21-4-2013 at 06:38

I think your scales have been filled with aerosol. You might want to do something about it.

The bottle got warm because of concentrated phosphoric acid, not because of the pentoxide. Solid pentoxide detonates if you pour water on it.
Now that you've got a shitty, toxic and flammable gunk inside the bottle, you should go to an open field, pour it all out and light it on fire. Step away from it and wait. Occasional poke with a stick is needed to expose every piece of WP. Then cover it with dirt or bury it in a shallow pit. There will still be residual WP/RP, but that will oxidize over the time to form phosphates.
You need to give plants phosphates. Plants love phosphates. (see what I did there? :D)

I don't know what will happen with your boat. Phosphoric acids reacts with cellulose. Higher concentration and temperature increase the rate of this reaction. It's like a phosphorilation inside biological systems, only there's no enzymatic catalysis that makes it spontaneous at physiological temperatures, pH and concentrations.
Wash your boat thoroughly with water. I meant to ask if you've got a drain, but then I've realized the floor is below the river water level.

blogfast25 - 21-4-2013 at 11:43

Buying things from an eBay seller who sells 'empty bottles, nudge nudge, wink wink, know wov I mean?', especially potentially dangerous ones, isn't really smart IMHO...

[Edited on 21-4-2013 by blogfast25]

Pyro - 22-4-2013 at 14:17

Well blogfast, it's not about safety, it's about money :)

Endi: My dad went to his local pharmacy and she apparently knew everything about WP and the treatment of it. Since they used WP in both WWI and WWII and there was heavy fighting in Belgium they have included it into medical training!
I am going to open them up and see if i has gotten into the mechanism, If it has I will have to send it back to Mettler Toledo. (Or perhaps a watchmaker could do it)
I was hoping to be able to recover it to convert into WP. how about washing it in CuSO4 to make the present WP a little more inert so I can remove most of the moisture?

soon I need to sweep up the slaked lime from the floor, I think it will stay white for a long time :) hope the owner's ok with it! :D

and thanks for all the help

blogfast25 - 23-4-2013 at 05:16

Money??? You don't think it was a bit of a false economy, to say the least?

Maya - 23-4-2013 at 10:26
Quote:

Someone mentioned wetting the powder and removing water using vacuum before using it. Baaaaaad idea. I'd say that would make it even more pyrophoric.



Don't know why you say that. Only a complete moron would regass with
oxygen. The norm is nitrogen or argon.
Alternatively, you could use KOH or P2O5 to dehydrate, but that'll take a millennium....

In Any case, there is WP in that product. IT NEEDS TO GO UNDERWATER!

Endimion17 - 23-4-2013 at 11:31

Quote:
Quote: Originally posted by Maya  
Someone mentioned wetting the powder and removing water using vacuum before using it. Baaaaaad idea. I'd say that would make it even more pyrophoric.



Don't know why you say that. Only a complete moron would regass with
oxygen. The norm is nitrogen or argon.
Alternatively, you could use KOH or P2O5 to dehydrate, but that'll take a millennium....

In Any case, there is WP in that product. IT NEEDS TO GO UNDERWATER!


It's a bad idea because it would probably leave WP deposited in activated, surface phase. WP is soluble in water, though poorly, but under normal circumstances that's not important because it oxidizes quickly.
Wiki can sometimes be terribly incorrect. It says it insoluble, but its solubility is 2.4 mg/L (Spanggord et al. 1985), or 3 mg/L (Stich 1953). I'll have to correct that.
If it was insoluble, water covering WP wouldn't smell and wouldn't give off fumes at certain conditions.

Who ever mentioned regassing with oxygen? I think you meant to say air? Introducing oxygen could lead to violent reaction. Air would probably cause a spontaneous ignition in the form of smouldering.
Anyway, introducing air to an evacuated vessel with probably weakly pyrophoric material (weakly because it obviously takes some time and air dispersion, unlike some organometallic compounds) is a stupid idea, but it's something most people would do because they either don't know enough chemistry, lack laboratory skills or simply don't have inert gases available.

plante1999 - 24-4-2013 at 03:58

Ok, I got this as my last message from the tracking of the phosphorus, I'm woried by the translation by google translation.

Wyslanie przesylki z polski

Does anyone can translate to english?

Thanks

Pyro - 24-4-2013 at 04:05

plante, that's off topic! try google translate.
dispatch charges of polish...

tips on making the P4 less reactive while handling that bottle of crap to make it useful for WP?

woelen - 11-1-2019 at 02:09

Pyro probably does not read your message anymore. This is 6 years ago. I mentioned this thread in the other thread on buying red P in the EU, just as a warning. Not all red P is safe. Stuff, which is highly contaminated with white P is very dangerous. Some bad sellers, however, sell this as 99.9% or so purity of phosphorus. Technically they are right, it indeed is very close to 100% phosphorus, but it is not close to 100% red phosphorus!