Sciencemadness Discussion Board - Preparation of elemental phosphorus

Preparation of elemental phosphorus

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Rogeryermaw - 17-10-2010 at 14:32

Quote: Originally posted by garage chemist

Just some other experiment I found: a demonstration experiment to show that bones contain phosphorus.
It is from a german site, the adress is here:
http://cc.upb.de/studienarbeiten/seidel/allgem_chem/versuche...

Translation of the important part:

Cleaned, boiled and dried chicken bones are burned with a bunsen burner on a fireproof surface and directly heated with the flame until they have turned into white ash.

2g of this bone ash are mixed with 0,5g magnesium powder and 0,5g kieselgur.
The mix is heated in a test tube which is plugged with a glasswool plug. After the reaction has finished, it is left to cool and the glasswool plug is removed in a darkened room and observed closely.
A glow is visible on the glasswool.
When the residue in the test tube is mixed with water, gas bubbles are evolved which self-ignite on contact with air. They are phosphine.

Reactions are on the site that I posted.

The important feature here is the use of magnesium instead of the often- used aluminium. Mg reacts at a much lower temperature than Al.
The SiO2 must be finely dispersed in the mix, hence the use of kieselgur. Quartz sand is not fine enough, even after good grinding.

The reaction of calcium phosphate with Mg is very exothermic.
Good heat is still necessary though.
The following reaction, the reaction of the phosphide with SiO2, is the actual phosphorus producing reaction, and the important bottleneck in DIY P manufacture.
The use of kieselgur promotes the reaction by increasing contact area due to its fine microporous structure.
The ingredients should also be grinded together very well, due to this reason (dont use too fine Mg powder though, otherwise it might be more of a pyrotechnic mix. But the SiO2 and bone ash should be intimately mixed.).

according to garage chemist this would indicate that the use of SiO2 is an absolute necessity in this reaction. i have been using silica sand. i wonder if this is a hindrance and i should perhaps acquire some silica flour? i am not as concerned over the use of Al vs Mg since temp is not a major issue for me but the finer SiO2 may be a link to increasing the yield. thoughts on this musing?

jgourlay - 18-10-2010 at 05:48

Would silica flour be a good substitute for Diatomacious earth?

12AX7 - 18-10-2010 at 08:00

Yes, most likely.

redfox87 - 18-10-2010 at 21:15

I was curious if Charcoal would burn sufficiently hot for the Calcium phosphate method?
" Charcoal may be used to smelt a variety of metals from aluminum to copper as it burns at the necessary temperature: 1,100 °C (2,010 °F)."

I realize thats around the threshold, and am uncertain if it is just enough or just a bit short.

Lambda-Eyde - 18-10-2010 at 21:21

If you blow air through the burning coal in a proper fashion, it can melt iron.

I speak from my experience with metalsmithing.

Rogeryermaw - 18-10-2010 at 22:18

charcoal briquettes have other chemicals in them that make them suspect for this reaction. you would be better to use natural wood charcoal. coal is carbon and carbon (coke) is what they use in industry along with calcium phosphate and silica. the problem is that with most setups available at home, the temp needed to run the reaction is out of reach. you need a pretty strong furnace and a retort capable of surviving it. the sodium hexametaphosphate with aluminum reducing agent and silica sand or silica flour have been the most viable route so far as it has shown some success. polverone, blogfast, magpie and others made this discovery years ago in this thread. i recently scaled up their efforts and had some decent success. these reagents are cheap and plentiful and perform fairly well. the industrial method with carbon and calcium phosphate uses temperatures in excess of 1500C. see my youtube channel for a detailed process.

http://www.youtube.com/user/rogeryermaw

redfox87 - 22-10-2010 at 13:18

Your videos are appreciated!

I had another thought. Could a graphite crucible be used to ignite thermite with calcium phosphate. Then pipe the vapors using a graphite pipe (graphite rod drilled to make a tube) to a ice bath to collect phosphorous. What kind of problems might this method encounter. I think this could be the quickest route to elemental phosphorous and could probably be scaled up fairly easily or perhaps a valve to further add more calcium phosphate to the reaction as it proceeds.

bbartlog - 22-10-2010 at 19:54

Quote:

What kind of problems might this method encounter.

For starters, making a whole working assembly out of graphite is not as easy as you make it sound. You speak of a crucible and a single tube. Even assuming that your 'crucible' is actually a hollow graphite vessel with a suitable opening, and that you have some way of making a gas-tight connection between two graphite pieces, I wonder whether you think this tube points up or down. Briefly, it needs to be bent, so that the vapors travel up out of the melt and then down under the water's surface. And graphite (for our purposes here, I don't need to hear about graphite fiber sports equipment) doesn't bend. Of course you can get around this by assembling multiple tubes and a machined elbow, again assuming you have some way of joining things properly. Graphite, for what it's worth, is not trivial to work, and produces very fine dust that must be dealt with. In short your proposal is either very expensive (if you plan to order all these parts made to order) or else requires extensive special expertise (and even then the graphite blanks are not cheap compared to steel tubing).

Quote:

could probably be scaled up fairly easily

Yes, because when I want to move up from a 4" outside diameter graphite reaction vessel to 8"all I need to do is order a $400 graphite blank and then somehow machine out a hollow within it. You want something that scales easily? Design around cheap materials like steel and firebrick. Also, thermite as a heat source is not something I would associate with scalability.

Quote:

add more calcium phosphate to the reaction as it proceeds.

And the heat to decompose this new material will come from where? Also, despite the outgassing of various products, I don't think in general that the reaction frees up a lot of space in the reaction vessel. And while adding more phosphate to a very hot vessel without also letting in air or letting out toxic gas is not something that would be a problem industrially, it's not all that easy to rig it up at home.

Quote:

I think this could be the quickest route to elemental phosphorous

Well, you're certainly welcome to demonstrate it if you want to have a go. Sounds fanciful to me.

redfox87 - 22-10-2010 at 20:51

graphite crucibles are very cheap...
graphite rods are very cheap...

It does not need to be air tight for the connection, it simply needs to provide the path of least resistance. Graphite piping is not necessary, but I thought it provided the best material to withstand the high temperatures of the initial vapors. I'm sure a metal condenser(water cooled or otherwise) would work fine, and I don't think the vapors are going to be near as hot as the temperature of the thermite reaction.

also if the graphite pieces were clamped together with sufficient force I would think the crystal lattices being identical would stack fairly nicely to make a decent seal (perhaps not air tight but close enough). As for scaling up I don't see why a wider diameter would be needed, why not just a deeper cavity?

The heat to react more calcium phosphate will be at the site of the boiling aluminum perhaps, or did all that heat just disappear as soon as the first round of calcium phosphate was vaporized (I would not think so). Perhaps adding more calcium phosphate would prove problematic, so the simple answer is don't add more. If the reaction is efficient and cheap just run it again.

As for the gasses. The gasses would be released through the water of course and if addition of further gases was desirable an inlet could be rigged up easily. Perhaps run an inlet tube through the exhaust pipeline.

Spending 50 bucks on graphite(it is MUCH cheaper then you make it sound) and making some thermite for a few bucks seems far less fanciful then feeding an expensive arc or tube furnace with large amounts of gas.

I suppose my question on the matter would be will the vapors from this reaction melt steel. Are there any propositions for alternative piping methods. My main concern is the temperature of thermite, I do not want to melt any piece of the apparatus, so some scheme or knowledge to ensure this does not happen is essential. I think steel piping might be adequate if it is adequately far enough from where the thermite is igniting. Perhaps a coolant gas (one of the nobles) could be utilized for this purpose.

Now your going to make me shell out to try and prove a point lol. Might take me a few weeks but I promise I will get around to this.

[Edited on 23-10-2010 by redfox87]

[Edited on 23-10-2010 by redfox87]

Rogeryermaw - 26-10-2010 at 01:28

personally i'm dying to see your results. yield notwithstanding, i think my 6 dollar and change retort kicks the shit out of any other idea i have tried so far. i hold all the ideas i have seen in this thread in high regard but for efficiency,and reproducible, that little cheap ass wood furnace is doing well. even if i had to buy everything i have used new, and specifically for this project, considering how many runs it has survived, no competition for cheapness and simplicity. the major flaw with graphite is that it IS expensive. one thing you should consider is that success requires experimentation and a $50 piece of graphite is not what i would call expendable. will it survive the heat? will it survive chipping the slag out of it for successive runs? every time you have to move it and take it apart will you damage the joints? what i'm using may not be ideal but it is cheap and expendable and i have at least 18 grams of white nasty from it. personally, i think the "best" method for home use would be a steel tube retort of heavy wall construction and an induction heater.

for those of you waiting on the latest result, sorry it took so long but i have been ill and suffering some truly fucked up allergy attacks at the same time. i think my guinea pigs are getting to me...well their hay anyway. going to try orchard grass and see if it helps. i hope so because getting rid of them is not an option. i love those little boogers! on top of that i gave myself the worst headache the other day...got a little dab of nitroglycerin on my arm and now i know what a migraine feels like. NEVER AGAIN!!! i'm not big into pyro anyway. just having a bit of fun which i paid for

i have some small data. the usual measurements. roughly 6.5 grams of output. longer down pipe may be helpful but deeper submersion is ill advised. it may not be a problem normally, but if for any reason you should have to turn your back on your furnace for any length of time, suckback will ruin your chances of good yield. steam explosion no but wet reactants and subsequent phosphine yes. sorry for the poor video but it was around 2:30 am, pitch black and i am a bit tired:

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those of you on the phosphorus path have seen phosphine and know what you are looking at. ignore the flying cinders...i do and they're flying at me! however, through the collector, you can see the yellow, orange flashes. obvious phosphine. the more greenish ones are escaping phosphorus.

what this leads me to believe is that to truly increase yields, this will have to be done with a LONG temperature controlled condenser that will drop P in its liquid state into an oxygen free collector of water cool enough to solidify the goo as it drops. otherwise there will be losses. and having an oxygen free space for it to drop between the condenser and the collector will eliminate any possible suction issue. conversely, those of you i know i can trust can send me a few bucks for a new retort and i would be glad to produce it for you. have to ship overnight to reduce prying eyes. of course this applies to the u.s. since 1. getting it out of the country would require an intrepid soul who is quite liberal with his anus and 2. most other countries can purchase red P (if even with some difficulty) and convert it.

[Edited on 26-10-2010 by Rogeryermaw]

Eclectic - 26-10-2010 at 04:58

The advantage of phosphoric acid and activated carbon heated by microwaves and contained in borosilicate glass, fused quartz, or ceramic is that there would be no slag, just CO and P.

blogfast25 - 26-10-2010 at 05:06

Roger:

Hear, hear!

The main improvement of your apparatus would actually be (apart from the collector problem) an easier and cleaner heating method. Propane is still an option but propane furnace design to reach the right temperatures will not be so easy.

Microwave heating remains for this purpose and pardon the pun, a 'pipe dream'... ;-)

metalresearcher - 26-10-2010 at 06:08

Quote: Originally posted by blogfast25

Roger:
Propane is still an option but propane furnace design to reach the right temperatures will not be so easy.

With forced air (a $10 air mattress inflater) I get 1400oC easily with a propane furnace even when using cheap autoclaved cell concrete (for inner walls) as refractory.

How I did it:

www.metallab.net/ytongfurnace.php

Rogeryermaw - 26-10-2010 at 06:11

i have to wonder...if one were to use a graphite crucible...would it not become part of the reaction?

metalresearcher - 26-10-2010 at 06:16

A graphite crucible is what I use for melting metals. But for other things such as distilling off P4 you can use the same vessel as in your wood fueled furnace.

Rogeryermaw - 26-10-2010 at 07:39

what i mean is, since carbon is used in the industrial production of phosphorus, were you to use a graphite crucible, would it not react when the other reactants start and the temp spikes? when the reaction starts, temp rises in the retort. would this not cause the graphite(carbon)to partially react as well? wondering if this possibility makes the use of a carbon based vessel less feasible...

blogfast25 - 26-10-2010 at 09:38

Quote: Originally posted by Rogeryermaw

what i mean is, since carbon is used in the industrial production of phosphorus, were you to use a graphite crucible, would it not react when the other reactants start and the temp spikes? when the reaction starts, temp rises in the retort. would this not cause the graphite(carbon)to partially react as well? wondering if this possibility makes the use of a carbon based vessel less feasible...

It would, superficially, but that wouldn't matter. They use graphite crucibles for melting gold (get them on ebay quite cheaply) and these crucibles also slowly burn away due to oxygen in the furnace. It limits the lifespan of the crucible, that's all...

But there's no need for graphite here: good old steel does the job. If it ain't broke, don't fix it!

[Edited on 26-10-2010 by blogfast25]

redfox87 - 26-10-2010 at 19:55

The issue with the microwave is that your going to have some issues with the phosphoric acid eating at your glassware.
I tried the microwave with nalgene reaction vessels and that failed quickly as the nalgene melted quickly.

Graphite should remain largely un-reactive, and its high melting temp is really attractive, it is only attractive for an experiment with something like thermite though as its an excellent insulator and will not transmit heat very well.

I was thinking about the use of a graphite crucible. What if one used a graphite crucible, had two lines feeding in oxygen and propane, utilizing an exhaust for the P4 to be cooled. Would this be viable or would the direct contact of the oxidizing gas' prove to be a problem.

If that didn't work perhaps an iron or steel container within the graphite crucible with the gas' burning. (the crucible would be used as a heat shield mainly). I used to blow chemical glassware and am aware that by adjusting the ratio of propane to oxygen you can essentially adjust the temperature of the flame, meaning an ideal temperature that would not be detrimental to the reaction vessel could be calibrated. Perhaps I'll just get a larger pipe to place the smaller pipe in to ensure I do not lose that oh so precious heat to the atmosphere.

I will work on gathering reagents for my experiment and keep the board posted. I'll try to record it, so whether it be success or failure it will be an interesting watch.

Rogeryermaw - 28-10-2010 at 17:50

i really do think blogfast and metalresearcher are onto something there. graphite is all well and good but i think a furnace of refractory brick made to fit with less than an inch or so of space around a heavy walled steel reaction vessel, with propane injection and forced air may be just the ticket. blogfast i am wondering about the use of a flux in this reaction...it seems to help with the speed of the process overall but from looking at the product post reaction...it may either be contaminating the phosphorus or causing some of it to come over as red P. i will show some comparison pics by tomorrow to illustrate what i mean and solicit opinions. the products of the reactions with salt have been darker than my earlier attempts.

blogfast25 - 29-10-2010 at 11:58

Quote: Originally posted by Rogeryermaw

i really do think blogfast and metalresearcher are onto something there. graphite is all well and good but i think a furnace of refractory brick made to fit with less than an inch or so of space around a heavy walled steel reaction vessel, with propane injection and forced air may be just the ticket. blogfast i am wondering about the use of a flux in this reaction...it seems to help with the speed of the process overall but from looking at the product post reaction...it may either be contaminating the phosphorus or causing some of it to come over as red P. i will show some comparison pics by tomorrow to illustrate what i mean and solicit opinions. the products of the reactions with salt have been darker than my earlier attempts.

Roger:

Have you ever seen melted salt? It loses salt (vapour) like water loses water vapour! So it's very likely some will distil over with the P. Of course it also has a higher MP and BP, so it condenses and resolidifies before the P. But your P is very likely quite badly contaminated with all sorts of things and strictly speaking needs a purifying distillation (good luck with that!) to get to decent purity...

Eclectic - 29-10-2010 at 13:57

You may be getting phosphorus chlorides and oxychlorides using NaCl as flux. Heating P2O5 and NaCl was a mentioned production method in other threads.

Rogeryermaw - 29-10-2010 at 19:24

here's a look at the color differences:

purity2.JPG - 50kB

no flux

with flux

side by side

pretty huge difference huh? it shouldn't be too hard to re-distill these with an inert test tube large enough. i did some messing around with making the trichloride and found that CO2 is suitable for an inert atmosphere so it should be doable. how hard is it to remove the phosphor coating from fluorescent tubes? perhaps i can bend one of these into a suitable vessel for the job...

[Edited on 30-10-2010 by Rogeryermaw]

blogfast25 - 30-10-2010 at 04:22

Quote: Originally posted by Rogeryermaw

pretty huge difference huh? it shouldn't be too hard to re-distill these with an inert test tube large enough. i did some messing around with making the trichloride and found that CO2 is suitable for an inert atmosphere so it should be doable. how hard is it to remove the phosphor coating from fluorescent tubes? perhaps i can bend one of these into a suitable vessel for the job...
[Edited on 30-10-2010 by Rogeryermaw]

No, not huge, but certainly significant, I'd say.

Getting the phosphor off TL tubes wouldn't be the problem, but the glass wouldn't be suitable AT ALL: too thin, too brittle and not borosilicate. Forget trying to bend it.

If you're venturing into distillation of either P or PXn, you'll need a small 'professional' boroglass still for safety. And vacuum or argon (I wouldn't trust CO2 with P: too reactive...)

Rogeryermaw - 30-10-2010 at 09:18

how about a borosilicate retort?

retort3.jpg - 8kB

i happen to have a couple of these. one hole stopper in the top with glass tube to run nitro or argon perhaps? i also have some distillation equipment and smaller flasks that may be easier to heat evenly but i hesitate to run P gas through equipment with joints that may freeze with solidified product. then to find a suitable heating fluid in which P is not soluble in case of a glass failure. water is out due to inability to reach the BP of P. P is somewhat soluble in most oils. solvents are mostly too volatile for the job and who wants to heat a solvent like that anyway...melon scratcher...

woelen performed a distillation of phosphorus under CO2 atmosphere with no ill effects as seen on his website here:

http://81.207.88.128/science/chem/exps/RedP2WhiteP/index.html

this is what prompted me to use CO2 to inert the apparatus to re-distill this white P. for some reason it's not appearing as a link so just copy-n-paste it i suppose.

[Edited on 31-10-2010 by Rogeryermaw]

peach - 31-10-2010 at 05:37

Bah, my intensive decorating means I've lost out on following this, so I need to have a back read.

But, in terms of purification, wouldn't sublimation be a better plan than distillation? Less glass involved (so less chance of it breaking / money being lost), do it under vacuum (squirt some inert gas in there first as well if you have some) to reduce the fire problem, no fractioning needed.

Probably won't be super pure given the lack of fractionation, but it should get it most of the trace gunk out.

{edit}Depends what you plan to do with it downstream as well. If you're going to be making phosphorus compounds with it, it may be far easier to go straight to those with the impure phosphorus and then purify the resulting product, which may be better behaved (boiling at lower temperatures, not bursting into flames and so on). The transition to the product, depending on what is it, may also help clean it up with much less involved methods; e.g. the contaminants may not even interact with the reagents and so will more easily get left behind as solids in a liquid (filtration) and so on. If the goal is the trichloride, using hydrochloric for that will produce phosphoric acid, so you'd need to be using chlorine (hydrochloric on manganese dioxide). Then some pure oxygen to go to POCl3. A respirator and some practice with gas handling / scrubbing / neutralization would be a good idea for those bastards. Definitely want the kids at school or asleep for that one.

[Edited on 31-10-2010 by peach]

Rogeryermaw - 31-10-2010 at 07:25

red phosphorus sublimes but i believe white boils so i may have only that as an option.

metalresearcher - 31-10-2010 at 08:46

A borosilicate retort won't work above 700oC it melts like plastic. And making P requires, as you know, a LOT more. These are OK when doing experiments not above the 500 or 600s (dull red glow).
Maybe a quartz retort might do the job but this participates in the reaction.
EDIT:

http://www.qsiquartz.com/

sells quartz labware.

[Edited on 2010-10-31 by metalresearcher]

blogfast25 - 31-10-2010 at 12:27

Quote: Originally posted by metalresearcher

A borosilicate retort won't work above 700oC it melts like plastic. And making P requires, as you know, a LOT more.
[Edited on 2010-10-31 by metalresearcher]

We're talking about distilling the product of Roger's efforts, NOT about using glass retorts for the production of P. White P has a boiling point of 280 C, still quite high for a dangerous substance...

Roger: for a one stage distillation your retort would be fine. And that would get rid of most of the junk...

Rogeryermaw - 31-10-2010 at 18:48

of course the main concern here would be an even temp inside the retort or the P would just reflux...wonder if this might be a good time to try that questionable design with a free or cheap junkyard microwave. no...with the need to inject inert gas things could get to complicated to keep safe. perhaps woelen's test tube method has more merit in this case...of course as peach pointed out, i could use the P for synthesis and distill the products of that synthesis to obtain a purified secondary product leaving the crap behind(in theory).

i do agree that this is a very high boiling point for a dangerous substance but we're reaching the same temps here as trying to purify sulfuric acid which can be just as scary as far as what it will do to you in the event of catastrophic failure. i would hate to have either substance on my skin. so...face shield, elbow neoprene gloves and full body covering. with the added risk of extremely horrid fire, i think this may have to be an outdoor venture.

perhaps i could fill a production style retort with the product and run it like a production run. there will be loss but the P would distill over like normal only cleaner...thoughts?

[Edited on 1-11-2010 by Rogeryermaw]

peach - 1-11-2010 at 09:56

With your sublimation point in mind, I'd go for the PCl3 and distill that at 76C.

The worrying thing about distilling the raw phosphorus is the flammability, the way it interacts with the atmosphere even as a solid and the high temperatures involved.

Both are not good to breath in, with the PCl3 being more so. But dealing with the toxicity of the latter would be easier, for me, than the risk of it bursting into flames with the added bonus of being slightly less dangerous to breath in.

PCl3 isn't a fire hazard, at all, according to the NFPA fire diamond.

Also, you'll probably want to clean up the PCl3 anyway, which may mean another distillation at the end. So it may be easier to skip the first, go to the PCl3 and clean that up on it's own.

[Edited on 1-11-2010 by peach]

Rogeryermaw - 1-11-2010 at 11:20

that makes sound sense. i do have enough of the product that fairly clean to give it a go on a small scale.

Interesting idea?

Enantiomer - 2-11-2010 at 18:48

I have not ready the entire thread - it's huge! And if what I'm about to suggest has already been discussed somewhere I appologize in advance.

In the very first post in this thread the guy mentions, near the end of the post, something about using aluminum or magnesium powder. I'm not extremely knowledgeable about chemistry. Specifically, I'm not real keen on what is meant by "reducing agent" in this context - since this is what he is referring to in this part of his post. An idea did occur to me though that I would like to put forward.

Magnesium is flammable. Anything that burns has it's own temperature that it burns at. The need for high heat is an issue with the traditional methods of priducing phosphurs. Perhaps there is some powder (maybe magnesium powder, maybe somthing else) that is flamable and that burns at about the right temp for the traditional ways. If this were included in the mixture and ignited one would have an interal heat source that heats in the right temp range. This is something that could considerable simplify and speed up the process (if it worked). I can also see the possibility of a few problems with this idea too though. Such as: what kind of gasses the thing you were using for the heat souce emit and contamnation of the final product; side rxns with the same, etc.

Any thoughts on this?

Enantiomer

12AX7 - 2-11-2010 at 22:19

Somewhere in this thread, you'll see thermite type mixtures used, where aluminum or magnesium reduce the phosphate directly. The phosphate itself is a fine source of oxygen, no gasses required.

Tim

Good ol' Tim

Enantiomer - 3-11-2010 at 15:11

Sweeet!! I'll have to look for that.

Enantiomer

blogfast25 - 4-11-2010 at 12:58

Quote: Originally posted by 12AX7

Somewhere in this thread, you'll see thermite type mixtures used, where aluminum or magnesium reduce the phosphate directly. The phosphate itself is a fine source of oxygen, no gasses required.

Tim

Unfortunately that didn't really work though. I tried the direct reduction of calcium orthophosphate with Al powder, lit like you would light Classic Thermite TM but I couldn't get it to ignite...

plante1999 - 31-12-2010 at 16:13

Quote: Originally posted by blogfast25

Quote: Originally posted by 12AX7

Somewhere in this thread, you'll see thermite type mixtures used, where aluminum or magnesium reduce the phosphate directly. The phosphate itself is a fine source of oxygen, no gasses required.

Tim

Unfortunately that didn't really work though. I tried the direct reduction of calcium orthophosphate with Al powder, lit like you would light Classic Thermite TM but I couldn't get it to ignite...

this type of thermite rection need extremly high temperatur to go you could try to melt the alu with the orthophosphate, liquid have very high surface area.

blogfast25 - 2-1-2011 at 14:13

Quote: Originally posted by plante1999

this type of thermite rection need extremly high temperatur to go you could try to melt the alu with the orthophosphate, liquid have very high surface area.

I tried lighting the calcium orthophosphate ‘thermite’ with a mixture of Al/KClO3/S as ignition pill. That ignition mixture burns to well above 2,500C, if that doesn’t light it then I dunno what does. I think the dissociation temperature for Ca3(PO4)2 === > CaO + P2O5 is too high, much higher than for metaphospates (used throughout this thread) like Calgon.

Sedit - 5-1-2011 at 12:04

I'v done it,

Well sort of but you will see why im atlest a little giddy about it.

I took something called Nu-Calgon which is something that is used in micromat systems assuming it at this point to be Sodium hexametaphosphate and shreaded Aluminum foil in a stainless steel crucible.

I laid out a layer of Aluminum and placed the Calgon product on top. I noticed sometime back that as this substance melts that when Al or Zinc is place in it some form of gas came out that burned green on contact with air. When the material melts it has the consistancy of melted glass and these gas bubbles where getting trapped on cooling only to ignite when the melt was crushed. The strong garlicy smell lead me to make a melt of this and then quench the reaction with water when the most material seemed to be trapped.

After a few minutes to cool down I started to break the cake away from the stainless steel vessle and kept it in water to see if I could dissolve all of the Calgon and leave some residue to perform test on.

After removing the melt and placing the stainless steel vessle aside I started to get a strong garlic smell after about 20 seconds and I could see vapors rising from the still slightly damp bowl.

I took this into a dark place and to my delight the bottom of the bowl was glowing like a firefly.

===========================================================

Thats awsome looking and I hope I can make something of it in time but right now im a bit concerned about all that garlic smell I was just around now assured I have contacted White Phosphorus I must take a few steps back and regroup my means of performing this synthesis to ensure my safety.

Any thoughts?
If I can perform this reaction at a low enough temperature im woundering if I can trap all the formed phosphorus under a water soluble layer of melt.

blogfast25 - 5-1-2011 at 13:34

Quote: Originally posted by Sedit

I'v done it,

Well sort of but you will see why im atlest a little giddy about it.

I took something called Nu-Calgon which is something that is used in micromat systems assuming it at this point to be Sodium hexametaphosphate and shreaded Aluminum foil in a stainless steel crucible.

Can you describe the Nu-Calgon product better?

Sedit - 5-1-2011 at 13:59

Im attempting to do so now.

Im not 100% sure but I believe this is the MSDS of the stuff I have,
http://www.nucalgon.com/assets/MSDS/English/4243.pdf

It states that its Sodium Phosphate tribasic. So if that is to be trusted, which its not until I pull up some more information from the container then its nothing more then Trisodium Phosphate. The reason I don't really trust that is because it list no hazard decomposition products but I have clearly seen it turn to what appears to be Phosphorus by boiling it with a blow torch. Adding Al, Mg, Carbon or Zn have increased the production of the flammable gas I have been seeing. I still have to figure out what temperature this reaction is taking place at as well and as soon as I get my IR thermometer back here which will be later tonight I will check it.

I tried to make it into a retort and capture the off gas in H2O but have so far had no luck.

blogfast25 - 5-1-2011 at 14:28

So Na3PO4. Yes, that would react with Al or Mg at elevated temps. to yield P4. But isolating the P is the whole art, Sedit...

Sedit - 5-1-2011 at 16:23

Isolation, esp on a small scale will be a task in itself without a doubt. I know the TSP is soluble in water so thats a start but then there will be other contaminations to deal with.

Like I said I tryed a simple retort but can not seem to get anything to come out which strikes me as odd because it can be seen forming rapidly in an open system yet getting anything to come out the other end seems like a no go.

On a larger scale and a good enough heat source I don't think it will be that hard to produce P4 at all but I still have some small scale test to run before I wrap a retort made of pipe fitting in nichrome wire and jack the heat up. The who Potassium thread has got my brain scambling for means of performing something simular in a solvent based lower temperature setting.

S.C. Wack - 5-1-2011 at 17:12

Quote: Originally posted by Sedit

The reason I don't really trust that is because it list no hazard decomposition products but I have clearly seen it turn to what appears to be Phosphorus by boiling it with a blow torch.

Well I don't think those conditions apply to the msds. Perhaps your product is not virgin pure and in fact contains something organic.

Perhaps checking the pH can aid some in identity.

Sedit - 5-1-2011 at 18:12

Im highly doubtful of organics because it looks like shattered glass. Im almost positive now that what I have is TSP but your right and a PH test would be good, I just hope my PH tester is still working because I stuck it into to strong of an acid the other day and it started to bubble violently. I may have to resort to PH strips.

Either way Im just excited to see elemental Phosphorus glow.

Polverone - 5-1-2011 at 18:42

Looks like glass, easily melts under torch flame, MSDS reports solution is only faintly alkaline... this is not trisodium phosphate, despite a message to that effect later in the MSDS. It's some sort of polyphosphate/metaphospate. That's good news, actually. It's similar to what Rogeryermaw has used with success before.

Sedit - 5-1-2011 at 19:15

That is great news, Let me look for his synthesis and ill try to repeat it word for word.

Magpie - 5-1-2011 at 19:34

Here's some more information from Nu-Calgon's website:

http://www.nucalgon.com/assets/prodlit/3-70.pdf

This is good news if it is reasonably priced and OTC.

The old consumer product Calgon ("Calgon take me away") doesn't seem to be available anymore. Most likely due to concerns about phosphate contamination of surface waters.

Sedit - 5-1-2011 at 20:20

I just did a quick search since I do not know the price since its been sitting in my shop for about 5 years or more but the search shows them selling 8oz packets for 24$. This is not what I have but I believe the same product. Mine is contained in a one liter jug or so. Im pretty sure your local Ace or plumbing shop would have it and I would not doubt Large chain stores to have something simular.

Now I must find a good source of fine Silica if I want to proceed since I have read in this thread it would increase yeilds to something I may be able to capture.

blogfast25 - 6-1-2011 at 04:07

Silica: finely ground sand (preferably desalinated and decarbonated) or dry ground silicagel (these little sachets you get with electronic appliances) will do. Grind in a granite mortar and pestle.

Overall reaction:

12 Na3PO4 + 18 SiO2 + 20 Al === > 18 Na2SiO3 + 10 Al2O3 + 3 P4

Try heating a fine mixture of Nucalgon, silica and Al powder in a steel crucible on direct flame (Bunsen). Once reaction starts (stop heating!), burning jets of P4 should boil off, forming P2O5 smoke. Do it in the dark (to see the phosphorescence) and outside (don’t breathe the P2O5).

That’s what happened when I used NaPO3 (Na metaphosphate – ‘old calgon’) in that set up.

For ideas in P4 isolation read this thread! Trust me, it’s the HARDEST bit!

Jor - 6-1-2011 at 04:24

I recently bought a lump (about 20 grams) of white phosphorus. It is covered with some red material. Is this red phosphorus?

woelen - 6-1-2011 at 04:57

It probably is. If it is really read, then it must be very old material.

Cleaning white P can be done by immersing it in a cold acidic solution of K2Cr2O7 of low concentration (take 0.5 grams, dissolve in 50 ml warm water and add 1 ml of H2SO4 and then add the white P). Assure that the liquid becomes hand-warm, such that the white P does not melt.

Jor - 6-1-2011 at 05:25

Are you sure? Is the red P attacked by acidic dichromate and white P is not?
Why can't I allow it to melt? Because it will be contaminated with chromium?

I will do this when I get home.

blogfast25 - 6-1-2011 at 09:30

White phosphorus does indeed gradually convert to red P. Takes quite a while at RT, I'd imagine...

hkparker - 2-2-2011 at 08:21

Hey so I have phosphorus question, and I figured I could post it here without starting a new thread. Sorry if this has been adressed earlier and I couldn't find it.

Matchbox strikers contain red P. Do you think I could distill it out? I would heat it in a test tube and the red P would boil off as white P, which I would collect by leading the fumes from the tube into a beaker of cold water. If not, perhaps I could dissolve it out with CS2.

bbartlog - 2-2-2011 at 09:05

They contain exceedingly small quantities of red P. Yes, if all you want is a small quantity of phosphorus, you could probably remove the strikers from several hundred matchbooks/boxes and extract it. It's not a promising approach for any sort of scaling up.

hkparker - 2-2-2011 at 10:02

Ok, thank you. I'm looking for a more OTC approach, but ill probably have to make it. Has someone made a comprehensive review of our progress here so far like woelen did for the potassium thread?

Rogeryermaw - 3-2-2011 at 00:05

you probably want to clean it before distilling the P4. there will be glue mixed in with it as removed from the strikers. perhaps an acetone wash would dissolve the glue but i am uncertain as to what solvent will work best.

Jor - 10-2-2011 at 14:20

Quote: Originally posted by woelen

It probably is. If it is really read, then it must be very old material.

Cleaning white P can be done by immersing it in a cold acidic solution of K2Cr2O7 of low concentration (take 0.5 grams, dissolve in 50 ml warm water and add 1 ml of H2SO4 and then add the white P). Assure that the liquid becomes hand-warm, such that the white P does not melt.

I did exactly what you described. Most red material is removed this way, but still some red material is not removed. But it ok for my purposes. I use the white P for small experiments (so reactions with other elements and such, and ofcourse burning the stuff

Sedit - 12-2-2011 at 16:17

I was thinking of making a Phosphorus run sometime soon and I had a question.

I was going to make the flask out of ceramic but was going to connect to that with a copper tubing until I realized it may pose a problem by forming Copper Phosphide. Is this a major concern or no?

After the fact I wanted to convert it to Red phosphorus by bottling it up and setting it out in the sun for a long time. I figured it would be good to place it in an organic solvent and I know CS2 is perfered but its not avalible. What would be the best UV transparent solvent to use. It does not have to solve alot of phosphorus just enough to keep the surface clean instead of having Red P form on the surface slowing down the conversion.

blogfast25 - 13-2-2011 at 11:22

Quote: Originally posted by Sedit

I was thinking of making a Phosphorus run sometime soon and I had a question.

I was going to make the flask out of ceramic but was going to connect to that with a copper tubing until I realized it may pose a problem by forming Copper Phosphide. Is this a major concern or no?

After the fact I wanted to convert it to Red phosphorus by bottling it up and setting it out in the sun for a long time. I figured it would be good to place it in an organic solvent and I know CS2 is perfered but its not avalible. What would be the best UV transparent solvent to use. It does not have to solve alot of phosphorus just enough to keep the surface clean instead of having Red P form on the surface slowing down the conversion.

Copper phosphide? I think that needs much higher temperatures to form. Using a copper tube as a collector may cause some mild attack on the copper but not much to worry about, I’m pretty sure of it…

Sedit - 13-2-2011 at 20:00

Thats exactly what I was thinking as well. At the most I would worry about it reacting slightly which I was thinking may do something akin to passification so it wasn't to much of a concern. I just didn't want to go on a hunch just to have it fail in the middle spraying Phosphorus fumes all over the place.

blogfast25 - 14-2-2011 at 09:48

Quote: Originally posted by Sedit

Thats exactly what I was thinking as well. At the most I would worry about it reacting slightly which I was thinking may do something akin to passification so it wasn't to much of a concern. I just didn't want to go on a hunch just to have it fail in the middle spraying Phosphorus fumes all over the place.

The chances of 'spraying' P all over the show are pretty slim: this is not a fast reaction, even at red heat. As the experience of this whole thread shows, the trick is to keep the P hot enough without solidifying prematurely.

I believe that much can still be gleaned from the oil painting of Hennig Brand’s discovery of phosphorus:

http://www.google.co.uk/imgres?imgurl=http://mcclellan.yolas...

Of course the picture must have been somewhat ‘airbrushed’ but won’t be that far removed from Brand’s actual experimental set up…

Sedit - 17-2-2011 at 13:02

I got exciting news, for me anyway

I made another incarnation of the tube furnace from this thread,
http://www.sciencemadness.org/talk/viewthread.php?tid=9705&a...
(I will try to retrieve them pictures BTW they where on my website that got taken down.)

Im using the formula from page one given by Polverone using Al/ SiO2 / Metaphosphate. I placed the reactants into an old Iron Tube with the bottom sealed with a cap. Once the furnace reached 900 degrees C I placed the tube (which had the top open so I could watch) into the furnace. It took about 5 minutes before I started to hear a crackling noise. Within 10 minutes or so the melt was fluid and like clock work every second there was a pop due to P4 vapors igniting. Now all thats left to do is add a couple elbows and some more pipe to lead these vapors into water.

This is great because it means that anyone with a hair dryer, some old Iron pipe and creativity will be able to make Phosphorus quickly. The only limitation will be the size of the pipe your using and how much reactants it will hold. When I get time I am going to pretty it all up and make it self contained so that all I will have to do is add the reactants and plug it in. Within a matter of minutes start collecting the Phosphorus vapors comming off.

How come I don't see anyone else using Nichrome to perform this reaction? It seems like the obvious choice here. Also I think instead of Silica flour being used one could possibly get away with using fiberglass since it in itself is just very fine silica anyway the only difference is its in a thread and not a powder.

blogfast25 - 17-2-2011 at 13:49

Glass is, very simply put, sodium silicate. At high temperatures Al powder will reduce the disodium oxide in it. But it's worth trying...

Sedit - 17-2-2011 at 15:34

No glass is Silica with various fluxes added, water glass is sodium silicate but I do agree and its something I was thinking about where using a sodium silicate mixture to seal up a retort earlier. It doesn't really matter because I need to go pick up some 345mesh SiO2 for my ceramic work Saturday anyway so thats no problem at all. I think they sell Magnesium powder there as well so I may just pick that up and use it instead. Sheesh I love being into ceramics the list of over the counter chemicals becomes many factors larger then it normally is. I may even pick up a new roll of Nichrome while im there so I can do this the right way.

I can't wait to give this a larger run tommorow its now to late for me to make a new furnace. Im making one with a 2" opening and inside 1.5" diameter reaction vessle slides in. I already got the pipe work setup for it and its looking good but tommorow I have to setup the elements and insulation around the new form so it can fit the new setup. I estimate I should be able to produce atlest a few grams of Phosphorus per run to say the lest but I have no clue how long it will take per run to run it dry. It seems like it could run at a pretty good rate as it heats up but I did not want to let it run to long because I could taste the Phosphorus in my mouth while working with it. It taste like Copper.

Melgar - 17-2-2011 at 15:56

Quote: Originally posted by hkparker

Ok, thank you. I'm looking for a more OTC approach, but ill probably have to make it. Has someone made a comprehensive review of our progress here so far like woelen did for the potassium thread?

Probably the most OTC approach is this:

1) Get a bunch of bones, preferably from pigs or cows, but chicken bones will do in a pinch, you just need more.
2) Heat these in your oven at its highest setting for like two hours.
3) Grind the bones into a powder, pretending you're a medieval alchemist. This powder is a mixture of carbon and calcium phosphate, mostly.
4) It's probably not quite enough carbon though, so grind up some lump charcoal, about half the volume of your bone powder.
5) Get some white sand and measure out about half the volume of your carbon. Mix the powdered bones, charcoal, and sand together very thoroughly.
6) Get one of those short pieces of cast iron pipe with threads on both ends, that looks like it'll hold all your powder.
7) While you're at the hardware store pick up some steel brake line. Also, get two cast iron caps that fit your pipe. Try not to look like you plan on making a pipe bomb, although that is kinda what it'll look like. Try and make it wider rather than longer since that'll be easier to heat.
8) Drill a hole in one of the caps such that you can barely force one end of the steel brake line in it.
9) Get a coffee can, and line it with fiberglass (ok) or rockwool (best). Set your pipe bomb thing in there so the insulation comes up to just below the top pipe cap. Then move some of the insulation out of the way so you can aim a torch so it hits the pipe and not the cap.
10) Get a flask half full of distilled water. Put it next to the coffee can and bend the brake line so its end is near the bottom of the flask.
11) Get your torch and aim it at the spot on the pipe. This isn't pressurized so it's not going to explode, but still be careful.
12) Heat it until bubbles start coming out the brake line, and watch for a white residue to form. Once new white residue stops forming, turn off the torch. Pour out the water. There you have it, elemental phosphorus!

I think the reason more people don't use nichrome wire is a) you can't use it with metal vessels since touching would short circuit it and b) it tends to melt if you turn up the power too high, and c) torches are really cheap and easy and fast.

Sedit - 17-2-2011 at 16:48

Torches are a pain in the ass for maintaining temperatures that high I have tried it many times in something almost exactly like your suggesting and it hardly manages to reach temperature. The outter surface gets plenty hot but it seems to have heat transfer issues thru the Iron pipe. It can be done with a torch im sure but I can assure you its much more of a pain in the ass and produces a lower temperature then electric heating.

Im using a metal vessle, I scraped the ceramic tube I was going to use for this because the temperature rise is so fast it risk cracking and I like to be able to crank that baby up and let it go, all thats needed to avoid shorting it out is a very thin layer of fiberglass wrapped around the tube. I coat fiberglass in clay to make it harder and resist melting. If you have an issue with Nichrome melting its because your using to thin of nichrome or you do not have a long enough run of it.

Im thinking of taking apart my old toaster oven and using the thick .25" elements that it contains. There are 4 of them and they will be much more stable then wire Nichrome. This was bought from the Good Will for around $4 so its no big loss. These also come with a Voltage controlling noob and connections with ceramic ends to make the entire process much simpler and more professional contruction in the end.

I have experimented enough now that im very confident that my next setup will yeild success. The only variable is going to be the Iron form that the nichrome will be around. I normally use Copper tube which is much thinner but I think the only issue its going to cause using Iron pipe will be that it will take slightly longer to heat up. Since it reaches the needed temperature with ease in around 10-15 minutes im not to concerned with a little extra time added to the reaction.

Melgar - 17-2-2011 at 19:21

You definitely need the insulation; have you tried it with rockwool? That worked for me, although my yield wasn't that great, but my ratios were all screwed up too so I figured that was why. Iron is conductive enough, the problem is you're losing heat faster than you can add it.

Sedit - 17-2-2011 at 19:40

I use a furnace cement known as Cal-coat which is a mixture of Kaoline, fiber glass, and some calcium materials to act as a flux most of the time but recently I found adding Kaoline to fiber glass to be much better at retaining heat and after the first firing it become rock hard yet porous enough that less then a half an inch is all thats needed to heat one side and keep my hand on the other. Calcium in the cal-coat causes the mixture to melt to low for my liking and around 2000 degrees F it starts to liquify.

I still would recomend anyone to try what im talking about with the Nichrome wire to see the difference, the heat is more direct and instant and it quickly turns the iron or copper tubing into a white hot glowing mass and thats at only half power controlled with a light dimmer switch. This causes all of the temperature issues normally associated with Phosphous production to go out the window and the contruction of the tube is simple enough that I made the one earlier in under an hour.

Melgar - 18-2-2011 at 04:20

So do you use this CalCoat to put a thin layer over the iron, then wrap it with nichrome, then put a thick layer on after that? That was the problem I typically had, was how to wrap a conductive metal object with nichrome wire.

Still, I don't remember needing the retort heated to more than an orange glow in order to generate phosphorus. Although I used ammonium phosphate fertilizer, not bones like I said to use. I suppose that might make a difference.

Anyway, to help out, here's a nice chart correlating glow color with temperature:

Sedit - 18-2-2011 at 05:43

The thin layer is that pink insulation you find in you house dipped into a watery suspension of clay. A piece of insulation fluffed up to about 1.5" will flatten down to a layer a little over 1/8 of an inch and when its dry and fired it turns into a rock. I then wrapped the old one in some round Galvinized duct like what the heat in your house flows and packed the Cal-coat in it. This time I just used a mixture of Fiberglass, clay, and sand. I know the temperature I reached is well over whats needed but I was just playing with it any way. I honestly would put the color of the thing between a mix of the light straw and the Orange-Yellow. The reaction im performing is said to work at around 550C which would be around the slight Red range.

madscientist - 18-2-2011 at 11:27

Perhaps I'm overlooking something obvious, but it seems the use of SiO2 with the NaPO3 reduction is unnecessary.

3NaPO3 + 5Al ----> 3NaAlO2 + Al2O3 + 3P

The fusing of Na2O with Al2O3 and the fusing of Na2O with SiO2 are both similarly enthalpically favorable.

Sedit - 18-2-2011 at 12:54

Meglar I got wounderful news, those new elements I spoke of are called Calrod and here is a picture of them,

The great thing about these is that they are already ceramic coated and non conductive on the outside. It is the same type of elements that used in electric stoves.

I just made a quick run with the ones I ripped out of an old toaster oven and within 10-15 minutes the Pyrometer was at 2000F and the Copper tube started to melt away so I stopped.
Amazing down right amazing.

Anyone that wants to make Phosphorus needs to use these, they will save you time and hassle no doubt.

@ Madscientist.
Heres the explination from the first page of this thread, the reaction without the SiO2 only produces roughly 30% yeilds where as with the Silica it frees the remaining P and gives almost quantative yeilds.

Quote: Originally posted by Polverone

Aluminium as a Reducing Agent, &c.
L. Franck. Chem. Zeit. 1898, 22, [25], 236-245.
In:- The Journal Of The Society Of Chemical Industry. 17, [6], 612-613.
June 30,1898

Action of Aluminium on Phosphorus Compounds—Phosphorus vapour when led over powdered aluminium, heated to a dull red beat in a current of hydrogen, combines with it with incandescence, forming a dark greyish-black unfused mass, which is decomposed in contact with moist (normal) air, forming PH3, and leaving a greyish-white powder. It is decomposed also by water, aluminium also by water, aluminium hydroxide and a brownish-black residue being left ; and by acids and alkalis, which dissolve it almost completely with evolution of PH3. The compound remains unaltered when heated in air.

At more or less elevated temperatures, all phosphoric, acid compounds (meta-, pyro-, and ortho-salts alike) are decomposed by aluminium. Metaphosphates, however, undergo the most complete change, according to the equation—

6NaP03 + 15AI = 6NaAl02 + 2Al203 + Al5P3 + P3

The addition of silica effects the release of the remaining phosphorus, thus :—

6NaPO3 + 10AI + 3Si02 = 3Na2Si03 + 5Al203 + 3P2

Calcium and magnesium salts are as efficacious as those of sodium, but the superphosphates of commerce are not available for the production of phosphorus in this manner. If, however, bone ash be decomposed by hydrochloric acid instead of by sulphuric acid, a material suitable for the purpose is obtained.

Hence phosphorus may be produced, with almost quantitative completeness of yield, at relatively low temperatures...

Sedit - 23-2-2011 at 23:14

Ok so,

I didn't have much time to play this weekend since all that partying got in the way but I did learn a few things that will move this process along to success in short order as long as I dedicate the time to it.

I tryed to use the setup I was going to which involved a piece of 2" Iron pipe with another slightly smaller one fashioned into a retort to place inside of this setup. Theory was that it would act just like a simple kiln and fire that bad boy up to temperature in no time however reality proved otherwise. Yes, the temperature was rising pretty well inside of the pipe but it was going very slow even with added insulation. I concluded after observing it a few cycles that it could indeed reach the desired temperature and produce Phosphours however I have seen that these temperatures can be reached much quickers and with a more stable pace using a thin walled material like what I did in my initial test using Copper tubing.

The solution was a simple one and it links back to one of the very few people in this extremely long over discussed thread where the fellow used an old can of some sorts and a fire pit to produce the Phosphorus temperatures thru a simular reaction which I am about to undertake.

I made some rapid alterations and wrapped an old empty CRC electronic cleaning can in insulation and nichrome wire to see what it was able to accomplish. I cut the top off so I could examine the internal reaction and from what I seen if one was able to fashion a simple replaceable, reusable retort out of a container such as this using my sort of setup then the production of Phosphorus would be as simple if not extremely more so then the process put forth by the person using a firepit and a retort who IIRC waited sometime, possible in the order of hours, for everything to reach temperature. I observed my setup, which in the end will be almost the same as that persons, reach the same temperatures in a matter of minutes or less instead of hours of waiting, watching, and stoaking a fire.

I promise you all simple Phosphorus without a doubt folks. I have felt for some time that this reaction has been given way more bad juju then need be and it seemed that everyone would rather cry about high temperatures instead of just over comming them with simple materials. Your Getto master Sedit promises he will make sure that if you follow his lead Phosphorus will be within the reach of even the dumbest of chemist, after all... if I manage it.... its already been made by the dumbest of all chemist.

.... Wish me luck.

blogfast25 - 24-2-2011 at 12:48

Good luck. You'll need it.

Sedit - 24-2-2011 at 13:24

I know, im such a chicken shit its not even funny.

I wanted to run it today but I started to have concerns that if there is to much air in the vessle I could risk fire even though I doubt it would really be a major problem. Then I have fear of Phosphine generations on top of concerns about the vessle being able to hold up under the reaction conditions because if it failed while full of Phosphorus vapors it would be bad. The one that was run using a stoked fire and covered with sand does not have the same issues I have here because if the container fails in the fire its one thing where as if it fails in my case its going to drop molten reactants everywhere while releasing White Phosphorus...

All in all I have decided that when I do run it I am going to cover the entire vessle in sand, which would aid in heating anyway, so that if things go wrong atlest there is a little something to contain the reactants. I would then heat it as slowly as possible so that I don't get everything to hot to quick incase things start to go wrong I could turn off the power and it would cool to a safe temperature quicker.

Now I really feel all thats left to do is grow big enough stones to set it up nice and stable and plug it in. Im afraid its going to be just like Ketene where im sure I could pull it off, and I really really want to but lack the guts to start it in the first place. I always try to lean on the side of caution which I guess is a good thing but sometimes there comes a point where you just have to go for it. I find myself all to often not hitting that point even if I want to more then anything.

Melgar - 24-2-2011 at 13:59

The air in the vessel will oxidize the carbon first, which just makes CO2 bubble out of the tube, and slowly at that. I wonder how hot you could get it with a makeshift furnace fueled by bbq charcoal?

Sedit - 24-2-2011 at 14:26

Thing is there won't be any carbon around. The reaction im speaking of is Metaphosphate, Aluminum(or magnesium), and Silica. Details are laid forth on the first page of this thread by polverone and many simple experiments have showed me Phosphorus vapors bursting out of the melt and igniting as well as being able to trap a very small amount in order to watch it glow. I know it can be formed and it does so at a reasonable temperature of 550 degrees C as stated in Polverones reference. I have not checked the exact temperature at which it starts producing Phosphous however but I can tell that it is in no way the high temperatures normally associated with Phosphorus production. A dull red glow as noted a few post ago in this thread is all thats really needed. I got to thinking that it might just be possible to do all this on top of a stove to be honest. Not something I would want to attempt but I think they heat might just be high enough to get it going.

Even though this reaction does not call for carbon it may be a good idea to add a layer of it on top of the reactants just for the exclusion of air from the mix. I cant see how it could really hurt at all by having it there so perhaps that would be a good way to go. I have seen Phosphorus forming in the past by melting the metaphosphate and adding a little carbon so indeed all it would do is add some extra reducing agent to the mix while at the same time scavenging avalible oxygen.

captaindrum - 27-3-2011 at 05:23

Hi guys! I've been visiting this forum for a long time. I've read every single post of this topic and since I have some experience to share, thought that it is time to register and contribute! Here goes my first post:

I ordered a kg of sodium hexametaphosphate for about $10. Nearly everything else was in my posession, so I had some really cheap experiments.

In both of my attempts, I used Na-HMP, powdered charcoal and SiO2 sand from a water-purifier (stochiometric amounts, about a total of 100 grams). I found the purifier in the basement. Cleaned it up and bam! There was silica sand (about 1mm pellets), activated charchoal and here we have a reaction vessel (as seen in the picture).

The heating took place in two different barbecue sets, respectively. First attempt included some stronger heating and better insulation, and the reaction vessel was a column of the purifier. In the condenser, a lot of bubbles immediately formed which i believe was the expanding air. After about half an hour, a colorful smoke came out from the condenser, and some whitish solids started to form.

Maybe because of the cooling of the condenser with a LOT of ice, the solids floated on the surface ( as seen in the picture). After the reaction(?) was complete, I took some pictures and heated the water of the condenser. It melted at around 50C and after cooling the solids tend to sink.

The second vessel was a paint solvent can which had its cap drilled and had a tube of the purifier fit with a proper nut. A lot of effort was put on in order to make the apparatus gastight; a roll of teflon tape used. I still haven't investigated the residue since I couldn't find the proper time and space, but the second one did not have any smoke or a disturbing odor like the first one.

PS: Both of the heating procedures were performed with charcoal (several kgs of it in the first experiment). Both of the experiments took place in the open air and safety measures had well been aware of.

PPS: I doubt the solids may also consist of paraffin as well, but I'm not sure of either...

Take care people,
Respect,
cpt. drum

blogfast25 - 27-3-2011 at 05:55

Hi and welcome!

Glad to see someone else wanted to have a stab at this, this time trying to walk in the footsteps of the Bringer of Phosphorus, Hennig Brand, himself…

Can you provide some more info on your heating method?

Have you tested your goo? Is it phosphorus? Take a small blow torch to it and see if it burn brightly with white P2O5 smoke?

captaindrum - 11-4-2011 at 11:29

I was out of town for a convention/seminar, sorry for responding this late..

I heated the stuff, even tried burning it but it had so little difference than plain wax if any. I distilled wax guys. Sorry

(

In my previous post, there is a barbecue grill in the first picture. I used a deeper one for the heating. Used some sheet metal to cover the top for insulation; and the thingie also had a good venting/exhaust system itself.. I could easily see a bright red color with a few pounds of charcoal. Spent 4 kgs for the experiments in total..

Thanks blogfast, your hospitality made me feel that I am in the right place; here in this site

)

blogfast25 - 11-4-2011 at 12:45

Ah well, if at first you don't succeed...

...disembarrassed of the charcoal...

The WiZard is In - 12-4-2011 at 09:36

I was hunting down refs on arsenic in wall paper and
hapend upon this.

Improved method of extracting- Phosphorus from Bones.—Le
Genie Industrial describes a process recently patented by II. Cari
Mantrand, of Paris, for extracting phosphorus from bones more
economically than by the processes heretofore employed. The
calcined bones, reduced to a fine powder, are mingled with a
sufficient quantity of pulverized charcoal to combine, as carbonic
oxide, with all the oxygen of the phosphate. The mixture is placed
in an earthenware cylinder varnished on the inside, filling the
cylinder to three-fourths of its capacity. The cylinder is then heated
red hot, and a current of hydrochloric acid gas is blown into it. The
phosphate of lime is immediately decomposed, forming chloride of
calcium and carbonic oxide, while the liberated phosphorus is
evaporated and driven through a copper tube, which leads into a
vessel of cold water, where the phosphorus is condensed. The
chloride of calcium, disembarrassed of the charcoal, in contact with
sulphuric acid, regenerates hydrochloric acid for a new operation.
The labour of pulverizing the bones may be saved by digesting
them with a solution of hydrochloric acid; using for this purpose the
water of the condenser from the preceding operation.

The Chemical news and journal of industrial science, Volumes 3-4
May 4 1861

blogfast25 - 12-4-2011 at 12:00

Very... erm... disembarrasing, indeed!

Jokes aside, it shows considerable chemical ingenuity for its time...

ScienceSquirrel - 12-4-2011 at 15:01

Quote: Originally posted by The WiZard is In

I was hunting down refs on arsenic in wall paper and
hapend upon this.

Improved method of extracting- Phosphorus from Bones.—Le
Genie Industrial describes a process recently patented by II. Cari
Mantrand, of Paris, for extracting phosphorus from bones more
economically than by the processes heretofore employed. The
calcined bones, reduced to a fine powder, are mingled with a
sufficient quantity of pulverized charcoal to combine, as carbonic
oxide, with all the oxygen of the phosphate. The mixture is placed
in an earthenware cylinder varnished on the inside, filling the
cylinder to three-fourths of its capacity. The cylinder is then heated
red hot, and a current of hydrochloric acid gas is blown into it. The
phosphate of lime is immediately decomposed, forming chloride of
calcium and carbonic oxide, while the liberated phosphorus is
evaporated and driven through a copper tube, which leads into a
vessel of cold water, where the phosphorus is condensed. The
chloride of calcium, disembarrassed of the charcoal, in contact with
sulphuric acid, regenerates hydrochloric acid for a new operation.
The labour of pulverizing the bones may be saved by digesting
them with a solution of hydrochloric acid; using for this purpose the
water of the condenser from the preceding operation.

The Chemical news and journal of industrial science, Volumes 3-4
May 4 1861

I assume that you have tried this out and it works?
The process is only 150 years old.
An author claim to distill spiritus sanctus de la sange de l' agneau from donkey shit and you would publish it as truth.

The WiZard is In - 12-4-2011 at 16:43

Quote: Originally posted by ScienceSquirrel

Quote: Originally posted by The WiZard is In

I was hunting down refs on arsenic in wall paper and
hapend upon this.

Improved method of extracting- Phosphorus from Bones.

The Chemical news and journal of industrial science, Volumes 3-4
May 4 1861

If you want posts Kitchen tested you could do us the favor
and run this experiment through your lab.

Take your time and do a good job.

Cæsium.
AT the last meeting of the Chemical Society, Dr. Roscoe gave a
short account of Professors Kirchhoft and Bunsen's spectrum
researches, and mentioned that the new alkali metal which they
had discovered by that means had been named Cæsium, from the
Latin word casius, signifying grayish-blue, that being the tint of
the two spectral lines which it shows. By working with the residues
from twenty tons of the mineral waters of Kreuznach, Professor
Bunsen had succeeded in obtaining about 250 grains of the
platinum salt of the new metal. Cæsium is closely allied to
potassium in its chemical characters, the chief point of difference
being the solubility of its nitrate in alcohol. Its equivalent number is
117,—exactly three times that of potassium.

The New Alkaline Metal, Cæsium.

BUNSEN has discovered in the waters of several mineral springs, a
new alkaline metal, the existence of which was first detected by
the spectral method of qualitative analysis. The new alkali exists in
these waters, together with potassium, sodium, and lithium, and
its presence may be shown by the spectral analysis with the
greatest facility, although only a few milligrammes are contained in
several kilogrammes of the material. The author gives only a very
brief preliminary notice of the new metal, promising a more
extended investigation. The chloride may be distinguished from the
chlorides of sodium and lithium by the yellow precipitate which it
gives with chloride of platinum. It is distinguished from potassium
by the solubility of its nitrate in alcohol. The vapours of the
compounds of this metal, when heated so as to become luminous
, give an extremely characteristic spectrum, which at the same
time exhibits the remarkable simplicity of the spectra of the other
alkaline metals. Its spectrum consists of only two blue lines—a
weaker line, corresponding with the blue strontium line, and
another which lies only a little farther toward the blue end of the
spectrum, and which vies in intensity and sharpness of definition
with the red line of lithium.—Journal fur prakt. Chemie.

The Chemical News and Journal of Physical Science (With which is
incorporated the “Chemical Gazette”)

A Journal of Practical Chemistry In all its applications to Pharmacy,
Arts, and Manufactures.

Edited by William Crookes, F.C.S.
London 1861

djh
----
Good thing Herr. Bunsen invented his burner/clamp or
his name would have been lost to history.

Reminds me of — The Battle of Balaclava which most remember
only for 3 reasons.

A poem.

A quote of General Pierre Bosquet —
C'est magnifique, mais ce n'est pas la guerre.

And (sorry if I offend as it is not PC to mention this) a woman
who spent 20-years in bed.

jgourlay - 10-5-2011 at 05:07

All, I have wanted to contribute to this thread since it's inception. But, being as I'm more of a vinegar and baking soda volcano kind of chemist, I've had nothing. But now I have something tiny to contribute.

At Lowes, in the paint section, I ran across "DAP TSP". MSDS says it's 30-60% Phosphate, tribasic and 10-30% Sodium Carbonate (so what's the rest, I wonder?).

Point is...it's a source of TSP readily available. And, at $10 for 4lbs, it's cheap and you don't have to pay shipping.

symboom - 10-5-2011 at 05:34

Quote: Originally posted by jgourlay

All, I have wanted to contribute to this thread since it's inception. But, being as I'm more of a vinegar and baking soda volcano kind of chemist, I've had nothing. But now I have something tiny to contribute.

At Lowes, in the paint section, I ran across "DAP TSP". MSDS says it's 30-60% Phosphate, tribasic and 10-30% Sodium Carbonate (so what's the rest, I wonder?).

Point is...it's a source of TSP readily available. And, at $10 for 4lbs, it's cheap and you don't have to pay shipping.

ah neat another source of phosphorous by far one of the interesting source of element phosphorus i made was from bones from this great baby back rib i had well did not want to be wasteful so i just used the bones to make phosphorous. First tried crushing it up with a sledge hammer found out i have to heat it i guess the heat helps break it down ad it was a lot easier to crush. luckily i was sunny charcoalized some wood with my big ass Fresnel lens then crush that up mix it with the bones put it in my reaction vessel (used up non refillable oxygen tank) drilled out cylinder put on some elbow pipe that lead into water then point that lens and heat the crap out of it was more worrying about melting the container
because it started to glow red hot so i had to move back the focal point. Anyways that's my experience on that defendantly more involved than making sodium from electrolyzing molten sodium hydroxide

pip - 18-5-2011 at 05:58

Is there a reason everyone still wants to try the "furnace" method over the "beaker" method? I have LiAlH4 and carbitol but can't find the triphenylphosphine only triphenylphosphate.

Has anyone actually performed this synthesis as I am guessing no due to its lack of documentation here but if so was your triphenyphosphine purchased or made?

edit: as soon as I say somthing I find it on ebay. I swear it wasnt there last time I checked.

[Edited on 18-5-2011 by pip]

Rogeryermaw - 18-5-2011 at 13:06

Quote: Originally posted by pip

Is there a reason everyone still wants to try the "furnace" method over the "beaker" method? I have LiAlH4 and carbitol but can't find the triphenylphosphine only triphenylphosphate.

Has anyone actually performed this synthesis as I am guessing no due to its lack of documentation here but if so was your triphenyphosphine purchased or made?

edit: as soon as I say somthing I find it on ebay. I swear it wasnt there last time I checked.

[Edited on 18-5-2011 by pip]

my guess would be that not everyone but many, still like the furnace idea because 1. there is much documentation about it here, 2. it is proven to work, and 3. the reactants are super cheap, easy to source and, in their non-reacted form, they are pretty harmless.

also the videos of the process on my you boob page pretty much answer all the questions about how to carry the process out in detail. those with ingenuity know that the furnace i use is a lot more than is really necessary for the task. a small desktop job made of refractory and powered by propane and an airbed inflating pump can do the same job if you use a retort similar to the first one i had success with. it was constructed of E.M.T. 1" pipe about a foot long, hammered flat at one end and welded shut. to the other end weld a rigid steel nipple and then screw on a reducing 90 degree fitting and from that a 4"-6" half inch nipple submerged in water about one half to three quarter inch.

pip - 18-5-2011 at 18:30

Cool, hopefully I get around to doing "the other way" and we'll have pics of both.

edit: turns out I have the phosphine but need the phosphate, thoughf it was the other way around but I checked and its the phosphate.

[Edited on 19-5-2011 by pip]

Rogeryermaw - 21-5-2011 at 22:14

anyone heard of this yet?

http://www.omicron.de/en/products/deco-/instrument-concept

looks and sounds quite interesting but where to get gallium phosphide...(GaP)

i wonder if this technology, or at least the concept may be adapted for use on a home scale?

[Edited on 22-5-2011 by Rogeryermaw]

peach - 1-6-2011 at 14:34

That's a Knudsen cell type furnace used for spraying molecular beams of dopant at semiconductors in ultra high vacuum chambers.

Definitely works but, as they're working at the 99.9999%+ purity end of the spectrum, the price will make your eyes water .

ngoclan4ever - 18-6-2011 at 13:18

Hello,

My first post:
Based on the article "Method for Preparation of Small Amounts of P4", I mixed: 35g NaPO3 + 15g Al + 10g SiO2 to get 60g mix.
After 3 runs of 20g each, I am now a proud owner some P.
However, They are not at the same color. Each one weight in at a whooping 0.2g (yes, 200 milligram). The article use 3g to obtain 0.5 g of P.

Why are they different in colors and why are the yields are terrible low?
Any thoughts?

Have a super day everyone.

Strepta2 - 19-6-2011 at 07:18

@ngoclan4ever: describe your source materials and methodology in more detail. Did you use pyrotechnic Al? How well did you incorporate the chemicals--ie, How fine were the chemicals prior to mixing? How did you mix them together? did you use a blender or coffee grinder? Did the resultant mix ignite and self-sustain after heating? Did you use a glass tube as the reaction vessel? If so did you see the phosphorus migrate to the cooler section of the tube.

I never ran a batch as large as you're describing, but I always obained yields in the 40-50% range.

ngoclan4ever - 19-6-2011 at 23:04

@Strepta2: Thank you very much for your comments. Your yields are what I'm trying to achieved.
For the source materials, I'm not sure about the Al since I brought it long time ago. It looks gray and is 35 µ, 425 mesh. The SiO2 is 200 mesh. The NaPO3 is coarse so I use a blender to chop it into a fine powder. I then dried the 3 ingredents by baking them, sepereately, in a 275 degree F oven for a few hours. I then mixed them together using same blender.
The mix then put into a 1" by 8" glass test tube, filled with CO2. When apply the heat using propane torch, I can see the resultant mix ignite to a big red blob and self-sustant after heading. The phosphorus are condensing at the cooler section of the test tube (I wrapped the end of the tube with 2" paper towel with a tail and pump ice cold water to it. The tail drips the water back to the pump reservor).
Not sure which ingredient is the source of the problem. And, my materials are not lab grade. Do you think I should try to get the pyrotechnic Al? or try with a smaller batch?

Strepta2 - 20-6-2011 at 16:30

I would suggest the following: grind the SiO2 and the NaPO3 to be as fine as the Al. When thoroughly incorporated (intimately mixed), the resulting mix should act much like a liquid—If you have a tt about 1/3 full and sharply rap it on a table top it should spurt up like a liquid.

I heated the tt in a horizontal (nearly level) position, with the charge spread along about one-third of the tt nearest the closed end and leaving at least half of the volume of the tube above the charge free for expansion of the residue of combustion. I heated the mix along its length but more intensely near the open end of the tube which caused ignition to begin there and progress toward the closed end. I continued heating the area of the combustion after it ignited to ensure the any free P4 would be likely to migrate away from the reaction site. How long did you maintain heating the tube after the reaction appeared complete? Also, you state you filled the tt with CO2—was this a continuous flow? You must have provided an exit path as the internal pressure rises on ignition. Can you provide a photo or diagram of your tt and how you fixtured the protective atmosphere?

ScienceHideout - 23-6-2011 at 06:46

I know this is a bit off topic, but are there any methods using TSP?

ngoclan4ever - 23-6-2011 at 14:26

@Strepta2: My set up consists of a tt with 2 holes stopper fitted with 2 tubes. The end of the first tube connected to a CO2 generator. The CO2 generator is a 16 oz bottle filled with some baking soda and has a side tube for the vinegar to drip-in. The end of the second tube immersed partially in a flask filled with water to capture anything which may escape from the tt.

The CO2 is not a continuous flow. To start, I just tilted the tt about 45 degrees and generate the CO2. When enough bubbles escaped from the tt (as seen from the flask), I stop the flow of the vinegar which in turn stops the flow of the CO2, put the tt in horizontal position then perform the experiment. At the end of the reaction, I continue heat the tt at the bottom and at the side for about 2-3 minutes to drive any residual P to the cool end of the tube.

I think www (what went wrong) is that most of the time I headed the tt from the bottom (the close end) and the material is not as fine as they should be and I did not allow enough room for the expansion which might have prevented the P to escape.

I ran out of the big tt. So, naturally, I've ordered some. But I can't wait. I'll will try again this weekend using 15x150mm tt with your advice. Please let me know if you have any additional comments/suggestions.

Thank you very much for your help!

sternman318 - 1-7-2011 at 08:57

Does anyone else find it humorous that some dude a few hundred years ago cooked his piss with sand and carbon in an attempt to make 'the philosophers stone' and made phosphorous, yet the modern home chemist is having much trouble making it themselves, despite having superior equipment, materials, and knowledge?

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