Sciencemadness Discussion Board - Preparation of elemental phosphorus

Preparation of elemental phosphorus

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WGTR - 1-3-2017 at 19:22

That's why my obsessive thinking about collecting it under a vacuum. The idea of sealing the end of a very hot tube with water makes me nervous, as I imagine scenarios where the water can get sucked into the tube, flash boil, and blow burning phosphorus everywhere. However, perhaps this will provide some fodder for thought. Instead of sealing the tube leave it open, and use a condensor that is so cold that not only the phosphorus freezes, but any air moisture freezes as well, ensuring that the phosphorus freezes into a matrix of ice.

The condensor could be made from two different sizes of copper tube, sealed on the ends to make a jacket. Low temp solder could be used to provide the thermal bridge from the jacket to the iron pipe, with the advantage that the pipe could be removed by melting the solder and sliding it out from the jacket. Higher temp solder could be used to assemble the jacket itself, so that it wouldn't fall apart if the pipe was replaced.

Perhaps a lead plug or teflon sealed pipe cap could be used on the other end of the iron pipe. A similar water/oil cooled condenser could be used on that end to keep the cap from getting overheated. If the cap is removable, there is an advantage that a rod could be rammed straight through the iron pipe for cleaning.

My first thought for freezing the phosphorus would be liquid nitrogen, as I'm sure this would be more than cold enough, but perhaps other coolants would work. The phosphorus could be collected afterwards by submerging the pipe in warm water, and scooping it out.

macckone - 1-3-2017 at 19:27

Silicones are still one of the better bets, they will glassify at high heat.
An expanding clay putty is what was traditionally used to seal phosphorus
retorts. Of course the retorts were also clay.
And traditionally they were disposable.
I suspect they where made, sealed, allowed to dry then fired as one process.
Firing, sealing, and then firing again seems wasteful of fuel.

BluePlanet1 - 2-3-2017 at 00:40

Ok I'm in a super rush to get to bed so I'm gonna upload 4 pics and respond to everything else tomorrow.

And the cap for the bigger furnace I just torched a hole in the compression cap that came with the can (not shown). So it holds the retort center whenever the the larger steel retorts get here... which are shorter but wider than the copper one shown.

Some great stuff posted here I'll respond tomorrow.

ps. I have 3 other baby forges that are all different lengths than stumpy there. And the perlite in the white forge will be relined or rebuilt with the cheaper more superior aluminium silicate kitty litter clay.

[Edited on 2-3-2017 by BluePlanet1]

Magpie - 2-3-2017 at 10:33

Here is Part#3 of my retort/condenser assembly. EMT (electrical metallic tubing) is the standard galvanized electrical conduit available at hardware stores. The 90° elbows are standard parts. I think this is a great material as it is lightweight steel. Thanks to Rogermeryaw for suggesting its use in making phosphorus further up in this thread. Here's a pdf with some dimensions for the standard elbows:

http://www.calconduit.com/submittal-sheets/EMT_90_ELBOWS_sub...

condenser for P.bmp - 703kB

yobbo II - 2-3-2017 at 13:11

I seem to do nothing but criticize!

<STRIKE>Will the P not condence and solidify in the condenser and plug it.</STRIKE>

Just seen the 75C water in.

Reading up in the thread I realize that a steel retort will not suit using Phosphoric acid as the starting material as it is corrosive to steel , bummer, or would it be OK for a run or 2 since the mixture of carbon and phosphoric acid is 'reducing' mixture.

[Edited on 2-3-2017 by yobbo II]

WGTR - 2-3-2017 at 14:07

If you're going to add an inlet for an inert gas purge, then perhaps it's unnecessary to dip the condenser tube beneath water to collect your product. Simply let it drip into the water from the condenser. A purged container with an allowance for a small bleed hole could keep slight positive pressure of the inert gas in the collection vessel, and keep oxygen away.

[Edited on 3-2-2017 by WGTR]

BluePlanet1 - 2-3-2017 at 19:59

These designs are awesome! I love watching smart people engineer things straight from their brain.

So far we've had designs submitted that use...

1) Steel plates & bolts for compression fitting. This is an interesting idea & very simple idea. The end plates could be grinded round to fit better in a circular furnace. But I'm highly suspicious that flat steel plates on the end of a pipe... even tightened hard with screws.... that this would create an air tight seal without some type of circular rim on the plates that protrudes into the pipe. Like imagine this is the plate now: _________

I think it would have to be changed to: ___/--------\___

I've seen P4 easily escape tightly threaded caps that were screwed on TIGHT and SEALED with a mixture of water glass & perlite dust (fired before the reaction). But even with all that pressure the P4 slipped out like the snake it is.

Still I like this idea due to how easy it would be to clean & refill the retort. And I think it could work IF I take a large drill bit the same exact diameter of the pipe, carve a shallow, circular recess into the steel plate.... then pack that recess with dry betonite rocket clay. Because if I can get dry clay between the plate & pipe before it's compressed I guarantee that would work. Dry, packed bentonite clay is impossible for P4 to get through. It holds up against rocket exhaust under unbelievably high pressure. But my old sodium silicate-perlite dust seals break down in the threads soon as its heated.

I'm putting this on my list of things to test... likely with a drilled recess & hopefully will get around to it next week.

2) Magpies retort & gasket idea. Aside from the jacket and gasket that looks like the design I've been using that's been failing over and over lol. The idea of using threads was first inspired by that (swedish?) college student on page 8 who used oxy-ace with those "exotic" red pipes. But then he casually disappeared from the forum forever so I can't pester him about exactly what type of pipe that was or IF he used a sealant, what sealant and more generally - how he avoided leaks.

I've been doing this reaction under the assumption that the AL reaction quickly burns any O2 out of the vessel, leaving nitrogen... which should be no (not much) different than adding a N2 feed.

Then my assumption with coal is CO2 is produced in the vessel immediately which should also prevent any burning. But who knows? P4s affinity for oxygen is unbelievably strong... maybe purging is something I can't skip although I'd love to avoid drilling any more holes.

3) WGTRs vacuum idea. That sketch is awesome & innovative. I stared at your picture idk how long but I'm trying to approach this experiment with a strict doctrine of "social accessibility". This thread has been going on for >>>15 years now which unbelievable to think about.

And when I first came here (before registering) I remember reading up to the page about microwaving phosphoric acid with coal and thinking "this shouldn't be like astrophysics" then left the forum for a long time before coming back. I was that intimidated by the level of skill some people have on this forum.

Also, not to be political but I'm trying to "liberate" this reaction so it's accessible to amateur chemists. 15 yrs ago I was 19, going to college and doing Grignard reactions in my mothers basement. It's unbelievable how EASY it was to get so many different chemicals back then.

But today, science & innovation... basic elements & chemicals... the things that use to make science FUN & EXCITING... it seems like they've been regulated out of existence. Which has made science excruciatingly boring for kids. Maybe I'm getting old but I'd love to start a science revolution that puts the DEA out of business. They regulate phosphorus and watch anyone who buys it cause of a few idiots methheads. Then those methheads go blow up labs with ammonia & curious kids start doing dangerous things just to procure basic elements that yes are dangerous but it's always the danger that excites & inspires kids. Like blowing up HHO balloons in a classroom. I did that when I was 16 not in a lab but right in front of the class my teacher let me do that. If you did that today the FBI would probably raid the school....

----------------------

READ THIS IF YOU READ ANYTHING

Back on topic - Solution 1: I learned something new today which are the thermal expansion coefficients for steel & copper.

My retort-distiller passed an air compression test at room temperature. Then I put the steel retort in my freezer and the copper in boiling water. I came back, did an air test and guess what? An immediate breach of air.

I clearly see what's happening now. It's not thermal expansion that's the problem it's ignoring this fact that's the problem.

The threads on the steel are on the OUTSIDE. The threads on the copper are on the INSIDE. So if I fire this the copper expands at a much higher coefficient than the steel, causing the copper threads to PULL AWAY from the steel threads. And the solution I think is very easy. Reverse the threads. If the steel is tapped to have threads on the INSIDE and copper on the OUTSIDE, then the EXPANDING COPPER will expand >>>into the steel.

Every reaction I've done the threads have been the opposite direction. And since steel is denser than copper if any threads get ruined it's more likely to be the softer, bronze alloy (I keep saying copper but mean bronze).

But I don't think the threads will be ruined that fast and even if they are I only have to replace the cheap bronze distiller (Lowes), the steel from ebay should last much longer.

Solution 2 - This is getting long so I'll be brief AP. If solution 1 doesn't work as planned I thought of something simple. Why not just copy roger on a smaller scale? He was able to stop leaks merely thanks to the clay-dirt environment he was working in. Where in the video he packs dirt AROUND the distiller.... and just like that the P4 has no chance of escape.

So I picked up one of those large black tubberware boxes at the dollar store. It's like 16" L X 12" W X 5" deep.

If solution 1 fails I'm filling up that tubberware box with my fine, kitty clay. Which packs down much harder than what roger used (it's that rocket nozzle clay). Then I'll dig a hole in the clay and place the furnace in it sideways. I'll pack the dry clay down hard with my hands around the distiller and dig out a hole for the exhaust flames. Then dig another hole for the water collector.

I really think this idea is the best since I'm just stealing rogers environment, using higher grade clay ($4 for 25lbs at ShopRite) and replicating it in a smaller sand box. And I'll still test other designs but right now I'm putting my money on the sand box and reversing the threads... although I won't touch the threads till I'm done playing in my sandbox. This could work as it is.

Will update soon & cheers to all.

ps. For anyone wondering why I froze the steel rather than heat both it's because I didn't wanna torch it yet and was more focused on how much bronze actually expands which is A LOT.

[Edited on 3-3-2017 by BluePlanet1]

WGTR - 2-3-2017 at 20:55

Sorry, I have several different ideas running through my head all at once. The drawing I posted actually doesn't use a vacuum, it's just a straight piece of iron gas pipe, with a condenser/cooling jacket on either end. On one end is a condenser cold enough to freeze phosphorus and (hopefully) be cold enough to prevent it from reacting with oxygen during the course of the reaction. On the other end it's possible to have a teflon sealed pipe cap, with a cooling jacket that keeps the temp around 100C or so, enough to maintain some phosphorus vapor pressure on that end.

I'm posting on a smart phone right now. Unfortunately my writing isn't usually very coherent on the first draft, but it's very difficult for me to edit things on this tiny screen. I don't personally care to "stick it to the man" or anything; I'm more interested in the science of it all. I'm not quite sure what use I'd have for phosphorus even if I made some, although I am curious if solid phosphorus will withstand atmospheric conditions if kept very cold. If so, how cold does it need to be? The last time I just made mg quantities under vacuum, and watched the glass tube glow in the dark as I let oxygen slip in. That was cool. Then I went on to something else...

Magpie - 3-3-2017 at 07:44

For my design the coarse threads are not meant to act as a seal. They are there to allow making a tight seal at the gasket - this is common industry practice. This is the same function as the use of bolt threads on Yobbo's design.

Solid P will just sit there at room temperature, slowly oxidizing. After sufficiently self-heating it will self-ignite.

[Edited on 3-3-2017 by Magpie]

yobbo II - 3-3-2017 at 16:51

I went to make a retort via some box iron and welding. I cannot attempt to implement the idea of the bolts
holding on two end plates on a pipe idea as my furnace is too small. It is only the size of a single
alumina brick.
As a modification to make it a bit smaller, I was simply going to weld on the bottom plate and bolt
the top plate onto the pipe
by welding a flange with nuts welded on the inside and a plate bolted on to it as the removable lid.
I was going to lap (grind very flat) the lid and the flange to form a seal. It sounded like a lot
of work when I actually thought about it so I went with what is in the picture.
Consists of one pipe slid
inside another pipe. The pipes are a fairly good fit for each other. The inside pipe has the output
pipe welded to it. I am hopeing that fire clay (hardware shop) will be the seal.
There is a very large distance between one end of the seal and the other end so I think this will work?
The gas will have a very large distance to travel if it wants to excape in the wrong place.
The to pipes will be pulled apart (after I have made my P!) fOR cleaning out. It may take some pulling
and pushing and perhaps it will seize altogether.
My pipe is box iron btw about 2 by 2 and 8 inches long (it just fits into the oven and no more).

Now all I need is P compound. All I have is phosphoric acid which I hope to neutralize with NaOH
to get a compound that I can put into the retort. What compound will I have exactly can someone
tell me?

Thanks,
Y II

BluePlanet1 - 3-3-2017 at 17:23

Thanks WGTR & Magpie.

Last night I made the most significant advance after 1 1/2 yrs of obsessing about this reaction. Then I came back shouting in joy & posted the solution with pictures. Then after 2 hrs I deleted the post.

I decided it's too important to spoil until I'm completely done modifying what I have to.

THE SOLUTION IS...

1) As simple as it gets.
2) Extremely accessible, practical and scalable.
3) 100% fail proof w/no exceptions.
4) So fail proof it'll work on a bad connection from your retort to distiller.
5) Takes minutes to do and undo after every reaction.
6) Revolutionizes this reaction forever.
7) I'm not exaggerating at all.

Finally, I can start firing off as many reactions as I want on any scale I want nor do I need a giant sandbox or any of the mess I thought of before. And it has a few other benefits but I might spoil this too soon.

I really really think the forums gonna love this.

I'm gonna put a lot of time into filming & editing the first introductory video. Follow up tests will be shorter. I just need 1-2 days for a pic of the final design. Then 3-5 days should be enough for the 1st video. :cool:

edit: yobo, you somehow slipped in as I was typing. Looking at your design I'd highly recommend you pause what you're doing till you see how I engineered mine. Phosphoric acid + NaOH I believe gives Na3PO4 vs the NaPO3. Since that compound has more sodium it will need more sand to form the intermediate and likely more AL/C to reduce it. Though clearly right now you can just mix till neutral, purify and dry the Na3PO4 then we can do the math later if you want?

[Edited on 4-3-2017 by BluePlanet1]

BluePlanet1 - 3-3-2017 at 22:31

I wanted to add something I haven't seen talked about much in this thread. Which is the synthesis of sodium hexametaphosphate.

According to wikipedia this stuff is fairly easy to make. And since it's the preferred phosphate it would be nice to synth a batch just to see how it's made.

Wikipedia says that monosodium phosphate is made by the "partial neutralization" of phosphoric acid. That the pKa of monosodium phosphate is 6.8-7.2. With pKa just being the PH of that salt in solution. Which is a bit confusing because the avg of 6.8 + 7.2 = 7... which is neutral. Not "partially" neutral... although pKa is not the same as PH (I'm no expert on this).

But based on wikipedia, if you "partially" neutralize phosphoric acid with sodium hydroxide you get the monosodium phosphate.

Then if you extract the monosodium phosphate and heat it to 179C it converts to sodium acid pyrophosphate.

And if you heat the sodium acid pyrophosphate even further (doesn't mention what temperature) it converts to sodium hexametaphosphate.

The dozens of different sodium phosphate salts have always confused me.

But apparently to make sodium hexametaphosphate you just "partially neutralize" phosphoric acid which can be bought at Home Depot, extract the salt & apparently at some hot temperature it releases H2O & breaks down to the prefered hexametaphosphate.

The only 2 things I don't get is why they call it "partial neutralization" if the PH of the pyrophosphate in solution is suppose to be around 7. What exactly would be "full neutralization"? (question 1)

And furthermore exactly what temperature it converts to the hexameta. I'd assume somewhere between 400-600C would be good since the hexameta is fairly stable? (question 2)

Personally I have 3lbs of NaPO3 & doubt I'll run out but it would be cool if someone could explain exactly what "partial neutralization" means? A pKa of 7 is a PH of 7 with the monosodium in solution. But that sounds like full neutral to me not partially neutral. Here are the pages for reference:

https://en.wikipedia.org/wiki/Monosodium_phosphate
https://en.wikipedia.org/wiki/Disodium_pyrophosphate
https://en.wikipedia.org/wiki/Sodium_hexametaphosphate

j_sum1 - 3-3-2017 at 23:24

Phosphoric acid is triprotic: meaning it can donate up to tree H+ ions. A neutralisation reaction is to react these H+ with a base to eave a salt. In this particular case only one of the three H+ is reacted hence only a partial neutralisation reaction. The fact that it occurs at a pH of 7 is pretty much a fluke and largely irrelevant. The term neutralisation refers to the acid-base reaction and not to the pH of the product solution.

And yeah, there are heaps of different phosphates. I am like you and have not gotten my head around them yet. I am doing well if I can remember all of the sulfates. Sodium hexametaphosphate is available as a water softener IIRC. Given that phosphoric acid and pure phosphates are not readily available OTC where I live, I figured that when it is my turn to make some phosphorus I would simply buy what I need.

BluePlanet1 - 4-3-2017 at 02:37

Quote: Originally posted by j_sum1

Phosphoric acid is triprotic: meaning it can donate up to tree H+ ions. A neutralisation reaction is to react these H+ with a base to eave a salt. In this particular case only one of the three H+ is reacted hence only a partial neutralisation reaction. The fact that it occurs at a pH of 7 is pretty much a fluke and largely irrelevant. The term neutralisation refers to the acid-base reaction and not to the pH of the product solution.

And yeah, there are heaps of different phosphates. I am like you and have not gotten my head around them yet. I am doing well if I can remember all of the sulfates. Sodium hexametaphosphate is available as a water softener IIRC. Given that phosphoric acid and pure phosphates are not readily available OTC where I live, I figured that when it is my turn to make some phosphorus I would simply buy what I need.

That explains it perfectly, thank you!

I just read through a 5 page patent for converting TSP / Na3PO4 into NaPO3. Since in the US most water softeners are just NaCl and TSP is the only accessible phosphate.

The patent with images is here: https://www.google.com/patents/US4777026

HERE'S CLIFF NOTES FOR ANYONE WHO CARES -

The reaction happens in 3 stages with strict temperature and PH control.

TSP / Na3PO4 is added to water at 60C, CO2 gas is bubbled through and the temp is slowly brought down to 30C while monitoring the PH from 13.5 to 9.2.

This produces Na2PO4 and NaCO3.

Then the temperature is dropped to 20C to freeze out the disodium / Na2PO4.

The disodium phosphate is washed with cold water & added back to the recycled sodium carbonate water solution at 50C.

CO2 is again bubbled through the solution as the temp is again slowly brought down from 50C to 20C monitoring the PH from 9.2 - 7.5. This is when disodium phosphate splits into a mixture of di and monosodium phosphates.

Then the temp is further lowered and the sodium hexametaphosphate separates out.

So in essence it can be done at home but is a serious PITA. Not worth the time I'll just reup on ebay.

Will update tomorrow!

JJay - 4-3-2017 at 07:13

I had always thought you could just use a couple of pipe nipples with an elbow and a cap, putting some bone meal in one end and capping it, leading the other end into water, and heating the closed end with a torch. I guess it's not that simple....

BluePlanet1 - 4-3-2017 at 17:36

Quote: Originally posted by JJay

I had always thought you could just use a couple of pipe nipples with an elbow and a cap, putting some bone meal in one end and capping it, leading the other end into water, and heating the closed end with a torch. I guess it's not that simple....

A while back I tried calcium phosphate (TSP + damprid) + sand and coal. When the crucible cooled down a bit I took off the lid and saw P4 glowing & burning with a distinct garlic smell. But the amount that burns off is nothing compared to NaPO3.

I've also burned chicken bone with my oxyhydro torch (just to see what happens)... it makes the foulest, most disgusting stench I ever smelled in my life. Like a mixture of burning flesh and phosphorous oxides. I remember wanting to vomit & will never burn bone again lol.

-----

QUICK UPDATE:

I'm making good progress on the new design what's taking up the most time is just taking pictures of everything in stages with good lighting then cropping and resaving all the photos.

I'm taking pictures of EVERY part of the process from ingredients used (2), where you can get them (everywhere), how I process them (blender), the ratios I use (1.1), how I bang & pack the clay, how I quickly remove the coffee can without distorting the wet clay, how I drill the 6 holes (new design needs 6 holes in 3 different places) how I fire it to get it rock hard (oven first while wet at low heat then torch 24 hours later), then I'll get to retort-distiller and how everything comes together tomorrow.

It may sound complicated but it's real simple. You just buy 2 bags of material (under $20), blend them, mix them dry (I shake in tubberware), wet them, pack it in, drill, fire.

It took LOTS of testing to settle on these 2 ingredients... and using any other form of silica (like silica gel or regular sand) will give you a weak, inferior fire brick.

Overall about 90 mins of work.

If you like the quality of the firebrick (you will) and wanna melt metal then build a 2nd forge for that purpose.

If you DO NOT want to build a forge the only other stuff I'd recommend is k-26 alumina-silica fire brick: http://www.ebay.com/itm/like/201220850196?lpid=82&chn=ps...

That firebrick will also work perfectly. You can buy the firebrick, 25gm and 45gm CO2 cartridges and NaPO3 all on ebay for around $50. If you want to make larger amounts of P4 then I'd buy the 45gm and 90gm CO2 cartridges. These 90gm are pretty big & can likely do 10+gms of P4 per synth. Figure around 4-5gms for the 45gm and 2-3gms for the 25gm.

I'll be back later tonight or tomorrow with pics.

Oh and monday-tuesday I'll be swamped with work so I likely won't fire till wed-thurs then figure around next weekend for the first video. After that I'll start rapid firing and testing for purity & yield.

Cheers!

BluePlanet1 - 9-3-2017 at 17:39

OK! Furnace is done.

I'm working on a long post with lots of pics, will probably take 2+ hours to edit & put everything together so if it gets late I may have to finish tomorrow.

I just want everyone to stay tuned because the forums gonna love this.

Also, just for context the post is going to be split into 2 sections. The first section will be the post I deleted last week. Which is just 7 bullet points and 2 pictures. It was THAT POST which triggered this innovation so if you read that first you'll understand exactly why I arrived to this conclusion and why I believe this design is the best.

Be back soon...

yobbo II - 9-3-2017 at 18:32

Made a modification to my reusable retort.
A second 'barrier' was added in parallel to the inside barrier.

See picture.
Another way of explaining what is happening is that the (square in my case) pipe that holds the stuff slides up into the 'lid'. The lid is sort of double walled and the P will have twice the length to travel before it can go where it is not wanted.
I will be using fire clay as the sealer.

It's a rather big job to make this retort. Better to just have a pipe. Weld on a flat lid at the bottom. Same at the top + output pipe. Charge via the (fairly large dia) output pipe. When you are finished the run, cut the pipe (the retort) in half fairly tidy, clean out and reweld.

Yob

[Edited on 10-3-2017 by yobbo II]

BluePlanet1 - 9-3-2017 at 21:49

UPDATE:

This is a C&P of last weeks deleted post...

--------------------------------------------------------

OK I JUST CRACKED THIS WIDE OPEN!!!

This just changed the nature of this P4 game and is so stupid simple I can't believe how long it took to think of this. I 100% guarantee this will not only work but it will work with a horrible connection from your retort to the distiller.

Here's the answer:

1) You turn the retort upside down, connect distiller from the side.
2) The forge keeps 1 hole on the bottom for the distiller.
3) The forge gets another hole on the opposite side, up higher for the exhaust.
4) Forge walls will be built to extend above the bottom of the retort.
5) Since all threads & all connections now sit directly in the middle... YOU PACK DRY BENTONITE CLAY (OR BLENDED PERLITE DUST) IN THE BOTTOM. AROUND THE SIDES OF THE RETORT. That seals off all connections from air.
6) Turn the forge upside down now and you fire it from the BOTTOM.
7) P4 has no choice but to come straight out the distiller.

Tomorrow I'm going to make a new forge but just look at these 2 pictures and it should click immediately.

I'm so freaking pumped now! I'm officially ready to start small & large scale testing, I can begin filming now I just need a longer forge and extra hole.

--------------------------------------------------------

PART 2 - THE NEW DESIGN

I'm not going to go crazy going into detail I'll just post all the pics with captions.

An empty, drilled out coffee can.
1, 1/2" hole for the distiller.
4, 3/8" holes for the gas injection and exhaust.

Wrapped a spray can with thick paper, hot glued the edges.

Blended perlite dust in top left can.
Blended aluminum silicate (bentonite kitty clay) from Shoprite on top right.
Mixture in larger bottom can.

Front of completed forge.

You see the distiller on the bottom and 2 exhaust holes.

Back of forge. Gas can be injected in either hole. Then the free 3 holes help regulate the exhaust. It's not necessary to have this many holes but it regulates the pressure/exhaust better and also allows you to flip the forge sideways OR upside down to inject gas from the sides or "top" which becomes the bottom.

Vertical look down into the forge.

The space between the 4 higher holes and 1 lower (distiller) hole is where you pack your clay or perlite dust. You just dump in a few scoops and pack it down around the bottom.

To pack and close the threads you can just use perlite dust.

Or you can use a 50/50 mix of perlite dust and kitty clay.

All I know is you can pack either material on the bottom. It gets hard like a rock while dry just by packing. Then you can turn the forge side ways or upside down to position the distiller in water.

This allows you to use not so good connections. Then you scrape / break out the packing agent with a screw driver. And so people are aware, I already tested perlite on one of my first retorts & know it blocks P4 (as does rocket clay). I was just using in a really bad way that took hours to set up for every burn... and I quickly lost my mind using that design.

This design is like a compact propane hybrid of what roger did.

All I need to do now is patch the cracks. The forge works fine as is and the cracks only go down 2-3" but aesthetically I hate looking at them. And by this weekend I'll film my first fire along with measuring yield, cost, time, efficiency, etc.

ps. Quick note. The distiller pipe I used is 3" I have a longer 6" one in my tool box and will use that for the reaction with the forge turned horizontal.

[Edited on 10-3-2017 by BluePlanet1]

yobbo II - 10-3-2017 at 07:25

Just to recap. What are the co2 cylinders made from as I have not been able to get a clear answer.
Also is copper up to the job. It melts at 1085c and it is close to the 'action'.

Some photo's of my one and only.

[Edited on 11-3-2017 by yobbo II]

BluePlanet1 - 10-3-2017 at 19:23

Quote: Originally posted by yobbo II

Just to recap. What are the co2 cylinders made from as I have not been able to get a clear answer.
Also is copper up to the job. It melts at 1085c and it is close to the 'action'.

Sorry. If anyone has any questions feel free to ask.

All the CO2 cylinders are made of stainless steel. And I checked them with a magnet just to be sure.

From the bottom of the copper tube to the the bottom of the exhaust holes (how thick the silica will be packed) is 1 1/4".

From the top of the copper to the bottom of the exhaust holes is 3/4".

So for the copper to melt, that bright yellow heat would need to penetrate more than 3/4" deep.

And when the forge gets hot the deepest I've seen the liner glow is maybe 1/4". Then also, (when the forge is completely dry) the liner vitrifies to clay glass about 2-3MM deep. And it seems like after that glass layer forms in the liner it makes it much harder for heat to penetrate.

Thus I expect the same will happen to the packing agent. The surface will probably melt and vitrify 2-3MM deep. Then I'll have to poke through that surface like ice to remove the shell and packing agent. And I'll lose a bit of a perlite everytime I fire not that big a deal.

edit: Just saw your setup. That's a pretty cool design and your welds look much cleaner than mine. If those joints hold up to P4 must say I'll be pretty damn impressed.

[Edited on 11-3-2017 by BluePlanet1]

BluePlanet1 - 13-3-2017 at 02:33

Quick update.

I wanted to make my forge look "pretty" before filming so I repaired all the cracks and leveled off a few bumps & things before giving it it's final fire. The forge looks great now and the liner finally changed black to white so it's dry enough to fire the coal redux.

I also made a couple 2" frisbee escalators. So it fires 25gm CO2 cartridges as is. 45gms with 1 frisbee up top. And 90gm with 2 frisbees.

Only problem now a blizzard is coming tomorrow. So I have lots of chores to do but should have off tues-wed and will likely start filming after the blizzard begins tomorrow.

Will update soon!

BluePlanet1 - 20-3-2017 at 05:00

Ok, it took longer for the forge to dry than expected but it's getting hot as heck right now.

I'll be proceeding forth with the carbothermal redux as follows:

2 (NaPO3)6 + 15 C + 6 SiO2 = 6 Na2SiO3 + 15 CO2 +3 P4

Amounts will be:

34G NaPO3
5G C2
10G SiO2

Theoretically expected to produce:

20G Na2SiO3
18G CO2
10G P4

Unlike the Al redux, the byproducts should be >>>28G lighter.
So if you think about it, we're removing 58% the weight of the entire slag (more than half).

Instead of the formation of 28G Al2O3... which appears to do nothing but lock up the slag & potentially react with free P4.... we'll get 18G CO2 that leaves the vessel along with a highest theoretical yield of 10gm P4.

That leaves much purer Na2SiO3 in the steel retort. With a melting point of 1088C.

So like I've noticed (from previous smaller reactions) the end product IS much more brittle, highly water soluble and doesn't lock up to the formation of alumina. And if you just think about this logically the increased formation of almost 60% Al2O3 by weight (in the Al reduction).... just the initial "blast off" I believe it fuses all that alumina to the silicate and EVEN IF you're pushing the temperature up REAL HIGH, just the presence of so much alumina should be locking up lots of P4. That's my theory at least.

With the carbothermal redux, only Na2SiO3 should be left in the retort.
Which melts at 1088C.

So the sodium silicate will most definitely REMAIN MOLTEN in the steel retort as long as the forge is on.
There will be no alumina to lock up the silicate.
And the production of 18G CO2 should help "unlock" and carry out more P4.

This is all just theory of course but I'm getting everything together now and we're gonna see if carbon produces higher yields.

j_sum1 - 20-3-2017 at 05:12

Ok. I see what you are doing now.
How does the thermodynamics look? Meaning how do the heats of reaction compare? I would have thought that inclusion of aluminium would provide significant energy for the reaction and make it more likely to proceed.

charley1957 - 20-3-2017 at 20:07

Some of us are still following your progress. I'm especially interested to see how this turns out without the aluminum. I've been quietly following this entire thread since I discovered it a few weeks ago, and steadily building my own setup. I've not participated in the discussion or asked questions as most all my questions have been answered by others here. Here's hoping you indeed break this whole thing wide open.

WGTR - 21-3-2017 at 08:37

Can't access the references page of this book, but here's some info for you. You'll likely have to use an excess of carbon, with carbon monoxide as a product instead of carbon dioxide.

Also, in coal or charcoal there's going to be some hydrogen in there, which likely means phosphine production.

clearly_not_atara - 22-3-2017 at 13:13

A eutectic of tin and zinc phosphates forms a glass with softening temperature approximately 440 C. These are much cheaper than barium or silver as was discussed before. However there is still the unfortunate possibility that the melt will react with Pyrex :p

http://repository.kulib.kyoto-u.ac.jp/dspace/bitstream/2433/...

As WGTR notes, you want to use plenty of carbon. CO is the waste product.

BluePlanet1 - 23-3-2017 at 20:18

Thanks everyone for the responses. I doubled the weight of carbon but still got a few small issues to figure out.

Like packing the reagant into the retort. I have to "drop pack" it in, then turn it sideways and it still spills out too close to the neck.
Although I could just use less powder I'm trying to pack it as much as possible. So there's less air in the retort and also to test
how easy it is to clean out large loads.

What I'm doing is lightly plugging the retort with tissue before screwing the distiller on.

My hope is that the heat will burn out the tissue to flakes BEFORE CO gas starts spewing out.

Otherwise if pressure builds up too quick it could be dangerous.

So right now I need to run a few dry fires just to time how lightly I need to pack the tissue so the seal breaks before the reaction begins.

It's a small detail but I need to get this right so hopefully by the weekend I"ll be ready. :-)

[Edited on 24-3-2017 by BluePlanet1]

clearly_not_atara - 26-3-2017 at 23:37

Interesting. I hope your phosphorus synthesis works out.

This may sound like a bit of an odd request, but if you happen to have some tin and iodine handy, I'm deadly curious to see what would happen if the phosphorus stream were condensed in the presence of SnI2. It might have to be done under anhydrous condition or in a hot solvent to prevent disproportionation (SnI2 >> Sn + SnI4), but under the right conditions, condensing phosphorus vapor in the presence of SnI2 produces black phosphorus -- and it would be nothing short of incredible if this could be done with a freshly synthesized stream of phosphorus. If you do produce black phosphorus, it would be worth tens of dollars per gram, AFAIK.

A bit of a crazy idea -- no need to try it, right? :p

yobbo II - 3-4-2017 at 08:30

Finished making retort. Filled slot with fireclay. Had to force the two halves together using a bottle jack and two walls!
All looked well. Heated very slowly for to cure the firclay.
Let cool and tested the retort for air tightness by submerging in water and blowing into outlet. Air bubbles came out the joint. Not too many but not 100% air tight. Would possible do the job but I am not going to run with it.

RETORT = BUMMER.

Far too much bother and trouble and leaks air.
I will simply dismantle, weld together and go with that. It would be far handier to weld and cut each time I need to reuse the retort that to be messing with the fire clay, bottle jacks and heating to cure etc etc.

edit

Battered (and battered and battered) the retort to get the lid off. I ended up cutting the 'lid' off.

Rewelded and am nearly ready to go. I have to weld some holes that are on the anti suck back funnel.
I am using a Magpie condensor (steel with 80 degree water).

Hope all goes well. I am looking forward to selling large quantities of black P :cool:

Yob

[Edited on 3-4-2017 by yobbo II]

Elemental Phosphorus - 26-4-2017 at 04:35

I just realized that iron phosphide may make an excellent precursor for the production of phosphorus, since it is not controlled, and I found a supplier for it for about $5/kg plus shipping. According to Wikipedia, it is soluble in nitric acid, so maybe a solution of it could be made, and a stochiometric amount of chlorine bubbled in to oxidize Fe3P2 to 2FeCl3 + 2P (if that reaction works). Also, it could be burned and the resulting P2O5 reduced with aluminum powder

j_sum1 - 26-4-2017 at 05:12

Seems like an interesting idea. Per gram it seems rather cheap.

Si Da Sci Guy - 26-4-2017 at 06:36

great idea Elemental Phosphorus, not sure what will happen with the nitrate ion ( from the HNO3 ), but if it works you'll be a hero. Just remember... SAFETY FIRST

Elemental Phosphorus - 26-4-2017 at 06:58

Yeah, I was worried about the nitric acid oxidizing the phosphorus to the pentoxide, and dehydration of the remaining acid to N2O5. An ideal solvent for the reaction would maybe be chloroform, unfortunately wikipedia lists iron phosphide as soluble in HF, nitric acid and aqua regia. Chlorination of a molten bath of phosphide is out of the question, but maybe the iron phosphide can be converted to an easier-to-work with zinc phosphide by zinc metal.

Si Da Sci Guy - 26-4-2017 at 07:17

I was thinking perhaps I could use urea phosphate, dissolve it in water and then chemically destroy the urea, then reduce the phosphate with carbon to phosphorous.
Any thoughts on that guys?

Elemental Phosphorus - 26-4-2017 at 09:23

That should work, but only at high temperatures. (above the boiling point of water) Phosphate is very resistant to reduction, and this reaction would likely take a few hundred degrees celsius to proceed.

Aqua-regia - 26-4-2017 at 09:35

Quote: Originally posted by Elemental Phosphorus

I just realized that iron phosphide may make an excellent precursor for the production of phosphorus, since it is not controlled, and I found a supplier for it for about $5/kg plus shipping. According to Wikipedia, it is soluble in nitric acid, so maybe a solution of it could be made, and a stochiometric amount of chlorine bubbled in to oxidize Fe3P2 to 2FeCl3 + 2P (if that reaction works). Also, it could be burned and the resulting P2O5 reduced with aluminum powder

Do you have some reference abouth this? Iam sceptic that P will unattacked by chlorine.

clearly_not_atara - 26-4-2017 at 09:58

Fe3P2 may not be a very good precursor for phosphorus, but it could nonetheless be an excellent precursor for phosphorus halides, and therefore also for triphenylphosphine.

IMO triphenylphosphine is the real prize -- it opens the door to a lot of safe replacements for otherwise dangerous or inconvenient reactions, notably the Appel and Wittig reactions, as well as hydrogenations utilizing Pd(Ph3P)4 and Cu(Ph3P)6H.

It might however be possible to use FeCl3 rather than chlorine to digest Fe3P2:

6FeCl3 + Fe3P2 >> 9 FeCl2 + 1/2 P4

This has a higher chance of producing elemental phosphorus, since I don't think P will reduce iron trichloride, and the comproportionation of iron chlorides is favorable IIRC.

Elemental Phosphorus - 26-4-2017 at 12:50

I am skeptical as well, but if the amount of chlorine was controlled, and only enough to produce FeCl2 was added, it might work. Also, the iron phosphide could be reduced to zinc phosphide with zinc metal, and then the zinc phosphide could be chlorinated to ZnCl2, or alternatively, oxidized to ZnO and phosphorus with careful control of the oxygen.

Aqua-regia - 26-4-2017 at 14:02

Quote: Originally posted by Elemental Phosphorus

I am skeptical as well, but if the amount of chlorine was controlled, and only enough to produce FeCl2 was added, it might work. Also, the iron phosphide could be reduced to zinc phosphide with zinc metal, and then the zinc phosphide could be chlorinated to ZnCl2, or alternatively, oxidized to ZnO and phosphorus with careful control of the oxygen.

This theory is a joke. How do you think if even some phosphorus relased these sitting in the bottom of flask ,and waiting for other phosphorus molecule, while chlorine / oxygen is very polite and reacting only with zinc and giving a shit for free phosphorus? Science and fantasy are different things.

[Edited on 26-4-2017 by Aqua-regia]

Elemental Phosphorus - 26-4-2017 at 17:48

But, phosphorus halides are very reactive, whereas metal chlorides are certainly not. Think about this:
Zinc reacts in HCl to give hydrogen and ZnCl2, since it is a good reducing agent.
Phosphorus does not react in HCl, as it is not as powerful of a reducing agent.
Phosphorus halides hydrolyze, ZnCl2 does not. Zinc's electronegativity is 1.65, whereas phosphorus's electronegativity is 2.19. I think it is ludicrous to suggest that chlorine would react with something 1 away in electronegativity rather than 1.5 away. Come on, do you think you could reduce ZnCl2 with phosphorus?

I guess we'll see when I finally get my hands on some phosphides then...

clearly_not_atara - 26-4-2017 at 20:06

It is possible that phosphorus will react first simply because it encounters the chlorine molecules first:

http://en.wikipedia.org/wiki/Thermodynamic_versus_kinetic_re...

The reaction of metal phosphides with chlorine is kinetic. So if stoichiometric chlorine is used the result may be that half of the iron phosphide is converted to iron and phosphorus halides while the other half remains unreacted.

However, phosphorus halides are, of course, valuable in and of themselves, and it may be possible to reduce them to the pure element.

It may be possible to reduce PCl3 with a metal amalgam or possibly molten tin.

[Edited on 27-4-2017 by clearly_not_atara]

Aqua-regia - 26-4-2017 at 23:56

Quote: Originally posted by clearly_not_atara

It is possible that phosphorus will react first simply because it encounters the chlorine molecules first:

The reaction of metal phosphides with chlorine is kinetic. So if stoichiometric chlorine is used the result may be that half of the iron phosphide is converted to iron and phosphorus halides while the other half remains unreacted.

[Edited on 27-4-2017 by clearly_not_atara]

This is the point.

You can chlorinating red phosphorus in CCl4 suspension to PCl5. The reaction is very exothermic even in -20 degrees. The white one is more reactive.

If we examine the phosphide properties i would suggestion the termal decomposition of PH3. This is not enough stable molecule. Generate PH3 stream, destroy the evolving diphosphine with HCL and lead the gas into hot glas reactor tube. I fulfilled this in microscale a couple year before. This is workable. Nasty work of course, cause PH3 is very poisonous and extrem flammable. This is definatelly not for beginner!

Elemental Phosphorus - 27-4-2017 at 04:24

I am inclined to simply chlorinate all the way to the phosphorus chloride and metal chloride and then distill off the phosphorus chloride, since the main reason I wanted phosphorus was to generate its halides, although I think the halide could be reduced with magnesium metal.

Edit: The chloride could be refluxed over Mg metal turnings or powder

[Edited on 27-4-2017 by Elemental Phosphorus]

Aqua-regia - 27-4-2017 at 05:55

My suggestion: do it. The name of process experimental chemistry

BluePlanet1 - 10-5-2017 at 21:09

Ok folks, I'm back!

FIRST LARGE SCALE CARBON-PHOSPHATE TEST FIRE WAS DONE LAST NIGHT.

I may post pictures later but things didn't go as planned and I still have tweaking to do.

I packed the retort with coal, phosphate, silica and then wrapped thread around a tiny cotton ball (like a tampon) to plug the end of the retort. This way I could pack the sand base layer in (that seals the threads)... pull the thread through the distiller... and after the pipes are screwed / sand is packed, I turned the whole furnace sideways, mounted the exhaust cap, pulled the thread and cotton ball out to unblock the outlet then fired it off.

Within 1-2 minutes gas started coming out the distiller. Everything looking great.

After 3-4 minutes the furnace gets yellow.... then CO2 gas starts coming out with a good degree of force.

After 5 minutes it got bright yellow-white... and now CO2 is spewing out of the distiller so damn fast I start getting nervous.

After 5 minutes the gas was coming out at such an unexpectedly high volume, with so much unbelievable force and speed that my hands start shaking uncontrollably. As I thought "I really should have built that torch mount".

Around 6-7 minutes the gas expulsion was now a nonstop torrent. The bubbling sound from the distiller stopped. The distiller was about 1/2" under the water. I looked to see what happened and the gas was coming out so fast that the surface of the water couldn't hold it back anymore. It's now gurgling like a drain. As this torrent of super heated CO2 starts launching water out of the collector and now the distiller was barely submerged about 1/4".

Around 8+ minutes the CO2 would not let down at all. And this is when I noticed trademark phosphine explosions. But these explosions were no joke. Like 5-10 explosions every second in different angles dancing around the surface of the water which blew more water out of the collector. So now my right hand is shaking real bad. I grab water to level off the collector and as I'm pouring the water in the rapid fire phosphine explosions ERUPT INTO A JET OF FIRE AND SMOKE. A stream of fire about 8-12" high is now pouring from the surface of the water.

As I'm watching I think, "no way this is phosphine." This was pure P4 vapor burning off like one of those bombed oil wells in Iraq. Producing tons of white smoke.

I hesitated about 30 seconds trying to figure out what to do with my shaking hand vs the reaction. I looked in the collector thinking "is ANY P4 condensing", I look. It's milky white. I think "great", looks like it's.... kinda working. Except so much damn phosphorus is burning off straight from the water I realize this dynamic can't be changed (mid reaction). And that most of the P4 would burn off and not condense.

Then right as I'm about to lower the propane gas, my hand shook so bad it knocked the furnace off it's magnet mount and out came an explosion of black coal dust right out of the distiller. The milky white water turned pure black. I got mad as hell and shut it down.

As I pulled the collector from the distiller the fire on the surface of the water isolated itself and wouldn't go out. I grabbed the sides of the glass and noticed the water was hot as hell. It was fairly cold when I poured it in.

So I ran and grabbed ice, threw it in the water, stirred, then yay the fire went out.

With the coal reaction using an insulated furnace and propane-air.... the CO2 gas comes out so hot so fast at such high volume it heats the water up in the collector unbelievably fast.
That's the first thing I learned. I did NOT need an icebath for the Al reaction ever. But the CO2 reaction absolutely needs one.

Second thing I learned is where the Al reaction often condenses P4 in the distiller or clogs it.... the carbon reaction wants to do the opposite. It throws out so much CO2 so fast that unless you have the distiller submerged fairly deep in really cold water.... the P4 vapor barely condenses and is carried straight out the distiller, hits the surface of the water and burns in a stream of fire.

I saved the collector water but the bottom is about 1/2" of coal dust. And I know P4 is in there somewhere because everytime I open it the water smokes and stinks like it. Just not sure how to separate it yet.

THE GOOD NEWS I'D SAY IS THE FOLLOWING:

1) The coal redux clearly works at air-propane temperatures.
2) Perlite dust as a packing agent also works GREAT. The threads on my pipes didn't even match (there were small air gaps) but it still stopped leaks 100%.
3) The perlite packing agent does melt a bit on the surface. But all I did was fracture it with a screw driver and was quickly able to dislodge the retort.
4) The brass adapter and distiller did not melt at all.
5) There was virtually no corrosion on any of the threads or pipes.
6) The part of the distiller that comes out the furnace did corrode a bit. And so did the stainless steel retort in the forge but after a quick wirebrush I saw no oxide or flakes peel off. Just a darker color change.
7) The reaction didn't complete but the "slag" inside the retort wasn't a slag at all. It was all black powder with lumps here and there that broke down and poured out quick.

In regards to temperature.

I got these #s from an accurate source but am citing them off the top of my head.

The carbothermal redux kicks off approximately 1080C-1100C.
Around 1250C the highest potential yield is limited to between 50-60%.
The full conversion range for a 99% yield is pretty high at roughly 1400C.

I'm still not sure how hot my forge is getting but I'm assuming it's mid range around 1250C. Maybe higher maybe lower.

According to the data I think a good yield would be 50%. And I can try to push the temp up higher in various ways but I'm thinking it may be smart to get this reaction nailed down right first. Build my torch mount. Longer distiller. Ice bath. Figure out my current yield (on next fire). Then maybe, slowly reverse my way back to adding a certain % of Al.

This could reduce the max yield temp. And also reduce the insane gas output. It's just a question of how much carbon I need to stop Al from locking up the slag. And I haven't even experimented with adding NaCL like Roger did.

That's about it for now. Just wanted the forum to know I did my first large scale (50gm) carbon test fire. And though it failed a lot of P4 burned off that I will collect next time. I think yields will be pretty decent and much preferable to pure Al due to how quick everything can be disassembled and refired.... that alone is a huge step forward imo.

I'll be back soon & hopefully on camera next time. :-)

clearly_not_atara - 11-5-2017 at 00:13

Ow, damn, glad you're ok... It requires some bravery to do this.

Maybe we can calculate the heat that will be produced and corresponding volume of water required to quench it... Mighr be pretty high.

jgourlay - 11-5-2017 at 03:38

Blueplanet: that's an old school successful disaster! Awesome!

yobbo II - 11-5-2017 at 04:38

If you had more controlled heating would that help. If you held the temperature at say 950C for some time before going on upwards would that help with the gas output?

Magpie - 11-5-2017 at 08:44

Very interesting experiment.

Where's all the oxygen for the CO2 coming from - the phosphate? Coal contains a lot of hydrogen and is probably responsible for all that phosphine (PH3).

clearly_not_atara - 11-5-2017 at 11:02

Quote:

If you had more controlled heating would that help

I don't think so... the observations indicate a self-sustaining exothermic reaction. The best you can do is calculate the yield, both heat and volume of gas from the ideal gas law, and use those estimates to make sure your setup can contain it. You can probably slow the reaction down a little by adding an inert "solvent" such as sodium bromide which will neither be oxidized nor reduced but absorbs heat.

Also if you dissolve the CO2 in the water the P4 will be less able to escape because there will be less gas to carry it; only thing is, I'm pretty sure the gas it CO, not CO2, but I could be wrong on this point.

CO2 can be scrubbed by using alkali, weak alkali being preferable to prevent the production of phosphine. Ethylenediamine, ethanolamine, sodium phenolate, etc are applicable.
CO on the other hand might be scrubbed by iron (II) salts or something, I'm not sure.

Possibly using a metal carbide could reduce gas production while still producing a "useful" amount of CO/CO2 evolution.

Magpie - 11-5-2017 at 11:51

Commercial furnaces use coke (mostly carbon) rather than coal. Use of coal could produce all kinds of by-products like coal gas, etc. Coal gas is flammable. I suggest replacing the coal with carbon.

What exactly was your charge composition, including quantities?

[Edited on 11-5-2017 by Magpie]

NeonPulse - 16-6-2017 at 23:05

Been quite busy the past couple of weekends trying to get some P4 in OK yield. finally i had some success! after using the small scale method devised by strepta i found the product was hard to recover and not enough. there had to be a better way. it has taken me quite some time to read this thread in it's entirety but the knowledge discovered has been vital to success. using my gas powered forge i heated up the classic mixture of NaPO3, SiO2 and dark Al powder plus a little NaCl flux as suggested several pages back. Also using a variation of the steel can retort Magpie was using for a while was a great idea. previously i had tried a retort made from welded steel tube and plumbing bits but this failed. my forge was actually too hot and melted holes in the steel. it easily pushes 1200C when it is warmed up. figuring that a brute force heating is not needed nor was the thick steel tube setup i opted to go with the steel 500ml paint can. it is good to have it finally working but i wish the yields were better. i did another run today with the retort exit tube deeper in the water and also a cone of steel mesh around it to try to break up the bubbles a bit better. the results were better and there seemed to be bits of P4 caught in the mesh, however i pushed the limits of the retorts capacity and had it breach. next i will line one with refractory of some sort.
Pretty keen to try other methods. i have a 500ml bottle of 85% phosphoric acid i bought over a year ago which i hav barely used 10mls of. also have a bunch of mono ammonium phosphate.
maybe a carbon based reduction in the near future once i make a better setup. I also have everything I need to build an electric furnace including Hi temp fire bricks, kaowool, Kanthal elements, PID and SSR, thermocouple and steel angle. I just need to find the time to put it together.
Here's a couple of videos:

Attempt by strepta's method: https://www.youtube.com/watch?v=Xljfwz1UMWE
a successful run: https://www.youtube.com/watch?v=mhFyVDBmDVk

And a couple of pics :

metalresearcher - 2-10-2017 at 11:34

I watched your videos and tried it out.
I don't have NaPO3, but I have Ca3(PO4)2. I mixed 31 parts of it with 18 parts SiO2 (hardware store fine silica sand used for mixing with stucco) and 9 parts Al powder.

6 Ca3(PO4)2 + 18 SiO2 + 20 Al => 18 CaSiO3 + 10 Al2O3 + 3 P4.
weight parts: 1860 : 1080 : 540 = 31 : 18 : 9.

I heated it to 1000 C in a steel tube retort after flushing it with Ar gas with the nozzle under water and after a few minutes bubbles appeared and then a few flames above the water with white smoke. That should be P4, but was unable to capture it.

Here a video of the cooled retort emanating white smoke, probably slowly burning P4 to P2O5.

https://www.metallab.net/jwplayer/video.php?f=/clips/P2O5_fr...

[Edited on 2017-10-2 by metalresearcher]

metalresearcher - 3-10-2017 at 11:06

Another try, I used black pyro Al powder instead of gray stabilized.
After Just a few minutes after starting to heat it in a small propane furnace it started bubbling heavily in the beaker (left on the photo) and saw a bright light with a pop, presumably P4 vapor / air mixture which had a small explosion.
After that bubbling stopped even after increasing retort temp to 800-1000 C so after 5 minutes I shut it down.

It appears that the reaction takes place in a kind of 'burst mode' : very quick reaction releasing all the P4 and then it stops.

On the photo: the white blanket on top is kaowool to keep the heat inside.

Next time I'll capture the P4 vapor in a closed tube (e.g. upside down test tube) filled with water to prevent escaping and force it to condense.

[Edited on 2017-10-3 by metalresearcher]

clearly_not_atara - 3-10-2017 at 17:36

I think that more water is in order from the looks of your setup.

But since deeply submerging the outflow pipe in the flask led to clogging in previous trials, maybe one way to prevent P4 from condensing and clogging the tube might be to insulate the tube from the surrounding water with e.g. a few layers of foam tape. This should keep the inside of the tube hot enough to prevent condensation. Then you can put it in deeper water.

You could also consider a multi-stage condenser, with a pipe leading into one flask and the outgas from that flask led down another pipe into the next, etc... hopefully condensation will then occur on the walls of the flasks and not in the tubes. Unfortunately this might not be the easiest thing to construct.

A solution of NaHCO3 in the collection flask -- particularly in the first stage of a multi-stage setup -- would generate CO2 outgas that could help keep the pipes in the later stages clear and thus allow them to be submerged deeper, while at the same time inhibiting combustion. This is a little more speculative I guess.

[Edited on 4-10-2017 by clearly_not_atara]

Magpie - 3-10-2017 at 17:50

I think the pops and bright flashes are phosphine, PH3, burning.

metalresearcher - 4-10-2017 at 08:50

Quote: Originally posted by Magpie

I think the pops and bright flashes are phosphine, PH3, burning.

That can indeed be, but after cooling and removing the retort nozzle from the flask, the retort started emanating white smoke which tells that elemental P4 should be present (in small quantities).
clearly_not_atara: I don't think the retort tube was clogged, otherwise the clogging content would be spewed out at the time when the pop and flame appeared.
I can put hot water (>44ºC, mp of P4) in the receiving flask to keep the P4 at least liquid.

[Edited on 2017-10-4 by metalresearcher]

metalresearcher - 4-10-2017 at 11:29

Now tried with carbon.

FAIL :-((

OVERHEATED !

6 Ca3(PO4)2 + 18 SiO2 (fine silica sand) + 30 C(harcoal powder) =>
3 P4 + 30 CO + 18 CaSiO3
weight ratio is 31 : 18 : 6.

I mixed 1.5g + 0.9g + 0.3g and put it into a 15mm OD steel tube of which one end is welded. That end I put in another short 30mm OD steel tube to as a double layer due to the extreme heat.

I had to heat it up to 1200 - 1400 C in the same mini propane forge.

I put the nozzle into hot water of 60 C and started the run.
Soon i started bubbling which continued about 10 minutes and the inside of the furnace was blinding yellow.
Suddenly the bubbling stopped so I decided to shut it down and took out the yellow hot retort which sparked a bit, which means it is close to the melting point of steel.
I let it cool and saw indeed that there is a leak in the inner tube and there were traces of melting of the steel / scale (Fe3O4, which has about the same mp as steel). It must have been at least 1400 C.

Next time a little cooler ....

clearly_not_atara - 4-10-2017 at 12:41

Have you considered using sodium to reduce phosphate? It could allow a much lower-temperature reaction if you're lucky...

Magpie - 4-10-2017 at 15:05

Wow T= 1200-1400°C! If you get your condenser right you should be able to get P like clappers. This is the industrial temperature for P production.

NaPO3 allows making P at about 800°C.

Industry makes briquettes to allow the efficient passage of gases, including gaseous P.

Temperature control of the condenser is important. Nice work.

metalresearcher - 5-10-2017 at 11:56

Another Fail :-(

I made a new double walled retort with a 3mm thick walled outer tube and silica sand between the outer and inner tube, the latter being the retort, filled with Ca3(PO4)2, SiO2 (silica sand) and charcoal powder.
I heated it 20 minutes and now it kept bubbling, hoping some P4 vapor would appear, but it stopped again.
After shutdown and cooling it revealed a partially molten outer steel tube and leaking inner tube, so the temp must have been close to 1500 C ! With a simple DIY natural gas burner (not propane as I said earlier) with forced air on a simple domestic supply of 30mbar (1/2 psi).

Next time a retort from iridium ;-)

I think I would revert to aluminum as reducer as the temperatures required for carbon reduction melt and destroy my steel retorts.

Magpie: How to make NaPO3 ? Or can I order this from Ebay ?

[Edited on 2017-10-5 by metalresearcher]

Magpie - 5-10-2017 at 15:47

"Magpie: How to make NaPO3 ? Or can I order"

Order sodium hexametaphosphate from Kyantec.

FYI: mp for Ca(PO4)2 is 1657°C. With (NaPO)6 mp is about 800°C IIRC.

clearly_not_atara - 5-10-2017 at 16:59

Wikipedia gives the mp of sodium hexametaphosphate as 628 C (1160 F), a good bit cooler than 800. Whether it will react at this temperature is less obvious.

Sodium hexametaphosphate can be prepared by thermolysis of sodium dihydrogen phosphate, NaH2PO4, which is obtained by combining stoichiometric quantities of sodium bicarbonate and phosphoric acid in a 1:1 molar ratio and heating to drive off water.

[Edited on 6-10-2017 by clearly_not_atara]

metalresearcher - 6-10-2017 at 02:21

Why does it need to melt ? More intimate contact ?
Do powdered solids not also have 'intimate contact' as the phosphate / SiO2 / Al powder mixture does react at 800 C ?

Magpie - 6-10-2017 at 07:47

yes, I believe the intimate contact provided by molten aluminum/SHMP greatly augments the reaction rate. I don't understand how Monsanto and FMC get such good production using Apatite, sand, and coke at 1200°C. Perhaps the apatite is molten at that temperature.

I wish I could find a simple way to make briquettes about 1/4" in diameter.

metalresearcher - 6-10-2017 at 13:17

What about adding a solvent such as NaCl ?
This melts at 800 C and the phosphate gets ionized. Does that work ?

metalresearcher - 8-10-2017 at 06:46

I tried it again, but still no P4 yet, but the flames are PH3 or P4 vapor ?

See this vid (with a slo-mo of the flames at the end taken with a GoPro Hero5 at 240 fps).

https://www.metallab.net/jwplayer/video.php?f=/clips/Failed%...

clearly_not_atara - 8-10-2017 at 15:02

I don't know if you got the "more water" bit up there considering you used the same amount of water... but really it doesn't matter what the flames are, probably a little of both. You need more water. (when I mentioned clogging, I was referring to problems other people had, not you)

I'm not sure if phosphates will dissolve in molten NaCl or simply form a cement... but it looks like you're getting way above 800 C anyway with your setup so I'm not sure it matters.

[Edited on 8-10-2017 by clearly_not_atara]

Magpie - 8-10-2017 at 15:22

Damn that retort is hot, metal researcher! Thanks for this fine video. Yes, that is PH2-PH2 burning. P would be making copious white smoke.

Can't you get some Calgon or sodium hexametaphosphate or apatite? When you get the right combination you are going to be making P like nobody has seen before!

clearly_not_atara - 8-10-2017 at 15:31

Magpie: H3PO4 is also the product of P2H4 combustion is it not? I'm struggling to think of a mechanism for his P4 to be converted to PH3 -- unless the phosphate salt he's using is hydrated?

Magpie - 8-10-2017 at 16:37

Yes PH3 is due to the presence of water. I don't know how phosphine is formed from water and P.

Burning phosphine:

2 PH3 + 4 O2 → P2O5 + 3 H2O

Dry all raw materials in a hot drying oven.

[Edited on 9-10-2017 by Magpie]

[Edited on 9-10-2017 by Magpie]

metalresearcher - 9-10-2017 at 10:00

Quote: Originally posted by Magpie

Dry all raw materials in a hot drying oven.

Good idea. That might help, and flushing the retort with Ar gas before.
I limit temperature to 1200 C as otherwise the retort melts down, I have destroyed already a few steel retort tubes due to heating to 1400 C.

SWIM - 9-10-2017 at 16:19

Quote: Originally posted by Magpie

Damn that retort is hot, metal researcher! Thanks for this fine video. Yes, that is PH2-PH2 burning. P would be making copious white smoke.

Can't you get some Calgon or sodium hexametaphosphate or apatite? When you get the right combination you are going to be making P like nobody has seen before!

Seems they've been screwing around with the Calgon formula.
I found an msds for Calgon water softener powder saying it's sodium citrate and 'carbonic acid, sodium salt (2:3)'

Wikipedia says it's currently zeolite and polycarboxylate.

Assured Fish - 10-10-2017 at 22:08

Seems to me that the way forward is by using the carbothermoreduction method.
The major drawback of this it would seem is simply that the process produces waaaay too much gas to be controllable at a large scale.

So the obvious solution would be to find a way to remove the hot carbon monoxide/dioxide without removing the desirable P4, sooooo why not set up a refluxing system above the receiver.

Like you can see in my professional looking drawing.

I realize dropping the temp of the condenser down to below 280*C is no gonna be easy, my drawing suggest using air cooling but if the column between the receiver and retort was long enough then i see no reason why we cannot use water.

The stopcock would allow control over the amount of gas being let out and could be closed if too much phosphorous was escaping out the stopcock as it would be clearly visible as phosphorous pentoxide.

The only major problem i see is that the condenser may not be enough to drop the P4 out of the gas flow, however i would imagine if there were enough space inside and the condenser were tall enough then it should be enough to remove the P4 before it gets to the stopcock.

You wont be able to remove all the gas i know but provided the receiver was submerged deep enough you should be able to get a less intense flow of distillate.

Obviously this would be a much larger engineering project than a typical retort but building a steel condenser and stopcock is nothing too complicated for somebody who has a wielder.

Just my suggestion :cool:

Magpie - 11-10-2017 at 04:23

I like your design, but would make a few changes:
1. Change carbon to aluminum.
2. Monitor all condensers for temperature and control to the optimums.
3. Incorporate cyclone separators where needed to separate gasses from the liquid Phosphorus.

metalresearcher - 11-10-2017 at 09:20

This would be a rather compled design. It needs indeed strict temperature control in the condenser. But what is actually the problem that CO and P4 arrive together in the condenser? They don't react with each other and can easily be separated by condensing the P4, as CO remains a gas.

Magpie - 11-10-2017 at 10:27

My suggestions are for producing clean P at high yield, not for convenience of the operator.

Use of carbon vs aluminum will greatly increase gas formation, and decrease the necessary retort temperature. My experiences with aluminum and SiO2 produced a nasty voluminous slag that contaminates the P.

Use of a centrifuge for gas-liquid separation would be wonderful but indeed too complicated. A cyclone might work just as well and be far simpler.

[Edited on 12-10-2017 by Magpie]

Assured Fish - 11-10-2017 at 21:54

@metalresearcher i think the problem is that the combined pressure of the gasses being produced and the high temp make condensing the P4 a quite challenging, a liebig type condenser may not be enough to condense all the P4 and a large amount may possibly be lost out the top (hence my idea of using a stopchock).

Unfortunately I have no idea just how quickly the reaction proceeds beyond what BluePlanet1 described, what he described seems quite intense.

A possible simple solution, if the condenser is not enough would be to pack the condenser with a material with high surface area such as glass wool.

@Magpie i do like the cyclone idea but im a tad confused as to its operation.
Is the spinner supposed to rotate solely by the pressure of the gases being pushed through or would it have to be electrically driven.

j_sum1 - 11-10-2017 at 22:32

A cyclone has no moving parts. It spins the gas into a vortex. Denser material is flung out to the edge and funnels to the bottom. Light gas leaves at the centre top so that gas flow is maintained.

Assured Fish - 13-10-2017 at 11:42

The cyclone separator would appear to be a lot easier to engineer than i had originally thought.
One problem though: from what ive read on them cyclone separators are only capable of separating particulates or liquid droplets from a gas flow, they cannot separate 2 gasses at all.

This means that we would still need to condense the P4.
A water jacket around the cyclone housing would be the minimum required to accomplish this. Achievable but it makes other methods look more appealing.

clearly_not_atara - 13-10-2017 at 12:09

I'm really confused as to why the "just use a longer pipe and submerge it very deep in water" method is not being taken more seriously. Using water eg one meter deep should condense most of the phosphorus. It's not like you have any other condensates to worry about.

Magpie - 14-10-2017 at 00:11

First the P4 must be condensed using a proper condenser. Then it will drop out the bottom of the cyclone into a water filled receiver. Gasses will leave the top port of the cyclone, hopefully relatively free from P4. Cyclone design will be important, as well as condenser design and temperature.

wg48 - 14-10-2017 at 02:50

Quote: Originally posted by Magpie

First the P4 must be condensed using a proper condenser. Then it will drop out the bottom of the cyclone into a water filled receiver. Gasses will leave the top port of the cyclone, hopefully relatively free from P4. Cyclone design will be important, as well as condenser design and temperature.

So is the problem believed to be that the phosphorus condenses to a fine mist or dust that does not easily settle?

Looking at the short exit pipes and large bubbles in the water I would think cooling is the main problem. One end of the exit pipe is at +1000C with the gaseous CO and P even higher and only about 200mm of air cooled pipe to get the temperature down to say 200C.

The large bubbles so near the surface probably don’t wash out the P or cool it very efficiently particularly given the flow of CO.

Magpie - 14-10-2017 at 03:40

Yes, condenser design is important and less than optimum design was the cause of many of my troubles. Even though I generally used aluminum as reductant the gas/P/slag rush could be explosive. I used an air condenser made of 1/2" electrical conduit (EMT).

Gruson did excellent work with the help of his science teacher and some welding craftsmen. Here is a link to his work: https://www.sciencemadness.org/whisper/viewthread.php?tid=65...

Unfortunately his photos are no longer available.

e14 - 8-2-2018 at 03:27

Shouldn't this thread be erased? The DEA lists it. So, how easy is this stuff easy to make?

Sulaiman - 8-2-2018 at 03:45

Compared to the risk of the experiment I would not worry about the DEA, unless you plan to go into production.

wg48 - 8-2-2018 at 03:51

But don't do it on your front lawn or poison your neighbours .

Assured Fish - 8-2-2018 at 16:28

Quote:

Shouldn't this thread be erased? The DEA lists it. So, how easy is this stuff easy to make?

The DEA can go fuck themselves, phosphorous is an element and a fundamental one for life, why the hell would we restrict information because a bunch of degenrate apes want to misuse phosphorous for illegal or immoral purposes.

That aside, the items on that list are not illegal, we are technically allowed to make them, however the DEA or other government agencies from what i understand do also have the right to lay charges on us if we are caught with possession of those materials.

If you spend some more time lurking the older threads you will likely come across several threads discussing the preparation of scheduled compounds such as lysergic acid and anthranilic acid.
The forum cares little for the bickering stupidity of mortals.

Bert - 8-2-2018 at 17:13

e14 is one of a number of low post, dormant accounts that reactivated recently, posting gibberish or, if intelligible, quite different from their earlier activity.

Rogeryermaw - 2-3-2018 at 10:12

derped. sorry

[Edited on 2-3-2018 by Rogeryermaw]

Rogeryermaw - 2-3-2018 at 10:18

mmmm phosphorus! deelish! man...this thread has moved quite a bit since i've been away.

Quote: Originally posted by clearly_not_atara

I'm really confused as to why the "just use a longer pipe and submerge it very deep in water" method is not being taken more seriously. Using water eg one meter deep should condense most of the phosphorus. It's not like you have any other condensates to worry about.

it doesn't take much fluctuation in temperature to cause a suction. i would be afraid of a steam explosion blasting hot slag and gaseous phosphorus all over.

zed - 2-3-2018 at 11:54

Easy to make? Hard to make?

Seemingly impossible for some of us to make Phosphorus, but not very difficult for Rogeryermaw.

Has a nice series of Youtube videos. https://www.youtube.com/watch?v=mibM4WUx74Q

NeonPulse - 13-6-2018 at 21:31

I haven’t seen anyone try this in this thread yet so I thought I’d give it a go.
I just did a little experiment with P2O5 and some dark Al powder. I wanted to see it the Al reduced the oxide and it seems to. But very quickly. So what I did was mix small amounts of Dark Al powder and P2O5 maybe 100-200 mg of each but a little more oxide than metal. not stochiometric amounts though. I did not measure them as I wanted to see what happened just as a quick test. The powders were mixed quickly before moisture affected the oxide too much and put the mixture into a 50cm quartz tube with a plug in one end and proceeded to heat the mixture with a MAPP torch from below. After about 30 seconds there was a wispy white smoke coming from the pile and a moment later there was a quite energetic reaction and a release of gas which kind of acted like a cannon. The whole tube was coated in what I assume to be red phosphorus and it was instantaneous.
The observation of the tube after was interesting. There was a bit of smoke in the tube and some white phosphorus residue which was smoking. The tube had the unmistakable odour of phosphorus. It appears that the reaction is way to fast to be of any use to make white phosphorus this way. I may try again with some 400mesh bright Al and see if it slows any and maybe reduce the heat a bit. I don’t have Time at the moment but maybe tomorrow. Here’s a couple of pictures.

1FEB46C7-6CCA-4556-A8A8-81227741FE25.jpeg - 2.4MB

0516358E-C6D7-4423-9015-92AECC70FE1E.jpeg - 1.3MB

B315EF2E-4F4D-4897-8680-FC1E6C8361AC.jpeg - 3.1MB

[Edited on 14-6-2018 by NeonPulse]

elementcollector1 - 13-6-2018 at 21:43

Maybe add a heat sink like CaF2, or some other reaction-slowing mechanism? I seem to remember it working for blogfast25's attempts at manganese thermite, where the manganese metal would boil off - and this seems quite similar in general principle.

draculic acid69 - 12-8-2018 at 23:35

Looking at the short exit pipes and large bubbles in the water I would think cooling is the main problem. One end of the exit pipe is at +1000C with the gaseous CO and P even higher and only about 200mm of air cooled pipe to get the temperature down to say 200C.

The large bubbles so near the surface probably don’t wash out the P or cool it very efficiently particularly given the flow of CO.

From the videos I've seen on YouTube one guy has a gal steel pipe coming out of his furnace 2 foot in length total going into the bottom of a 250 ml erlenmeyer which is open to the atmosphere and the flask let's off flames that snap and crackle with white smoke which is probably p4 vapors igniting.if he used a longer steel pipe and a CHILLED bubbler system ie: 4 much larger flasks or bottles he would probably quadruple his yield.he only got like one or two grams a run.I reckon most of it burned off.

[Edited on 13-8-2018 by draculic acid69]

Getting ready

JScott - 31-8-2018 at 05:33

You may have seen that subject line, how the heck do you remove accidental postings?

Anyhow, after seeing NeoPulse's 'proof of concept' video I wanted to recreate that. I don't have access to a tank of Argon, but I can easily get a small can of Ar intended for wine preservation. About 15$ on Amazon/Ebay.

I made this small balloon 'equalizer' to make use of this gas. A small hose clamp to bleed off a small flow of Argon. I wouldn't think it would be much, just what is needed to be certain all oxygen has been removed from the tube, correct?

So I bent a few tubes and I'm waiting for enough time to get it done. Here's the 'apparatus'. Will there be enough gas in this balloon to get through the procedure? I should probably consider another hose to top off the balloon mid way should I run low.

Anyone else familiar with this video? Have any suggestions?

Hunterman2244 - 1-9-2018 at 05:20

I think refluxing a mixture of magnesium, SiO2, charcoal, and phosphoric acid, should yield white phosphorous. Maybe a metal paint can on a hot plate, a metal pipe coming off the top cooled by a fan, and some tubing leading into water. If you use clear tubing, either sunlight or a uv light could convert it to red. Maybe instead a tube, a one way valve off the top of the pipe that leads into a container of water to stop the P from getting stuck in the tubing. Like one of those things for making beer that lets the CO2 out, but keeps it sealed. Epoxy it onto a hole in the bottom of a tall contained so it bubbles through as its own condenser.

JScott - 1-9-2018 at 07:21

@Hunterman2244,

Thanks, when I scale up, it is my intention to work in a metal apparatus. However, I am a ways from there at this point. As mentioned, I really just wanted to recreate what I had seen in that video. Though it only appeared to be partially successful, I thought for me, it would make a good first step.

Partial successes can be instructional, and a bit more fun than absolute failure ;-) Further, I have been stymied by not having any inert gases on hand. I was sent down this path when I found that wine connoisseurs used Ar to replace the air in opened bottles. Though I'm sure 15$ for that much gas is a gouging, it's a lot cheaper than buying even the smallest refillable canister of Argon.

Any experience I can gain using these small, easily located cans of Argon will be helpful until I can afford more substantial supplies.

Still, your advise is right on point and very much inline with what I hope to do as I move further along in my studies. Thank you very much for getting back to me.

[Edited on 9-1-2018 by JScott]

Hunterman2244 - 1-9-2018 at 10:57

Quote: Originally posted by JScott

@Hunterman2244,

Thanks, when I scale up, it is my intention to work in a metal apparatus. However, I am a ways from there at this point. As mentioned, I really just wanted to recreate what I had seen in that video. Though it only appeared to be partially successful, I thought for me, it would make a good first step.

Partial successes can be instructional, and a bit more fun than absolute failure ;-) Further, I have been stymied by not having any inert gases on hand. I was sent down this path when I found that wine connoisseurs used Ar to replace the air in opened bottles. Though I'm sure 15$ for that much gas is a gouging, it's a lot cheaper than buying even the smallest refillable canister of Argon.

Any experience I can gain using these small, easily located cans of Argon will be helpful until I can afford more substantial supplies.

Still, your advise is right on point and very much inline with what I hope to do as I move further along in my studies. Thank you very much for getting back to me.

[Edited on 9-1-2018 by JScott]

Thanks. My intention was to eliminate the need for inert gasses due to the production of CO2. It also reduces the potential for accidents due to the fact it's not an energetic redox. I hope to try it out myself.

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