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Author: Subject: Preparation of elemental phosphorus
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[*] posted on 3-9-2005 at 17:45


Every post since ChemicalBlackArts' sarcastic post, posts have been straying from the topic at hand, preparation of elemental phosphorous. Indeed, conversion of the white allotrope to the others and the properties of the white allotrope are indeed things that could be covered under this heading, but it seems to me the discussion of these things would be more sutible for some of the other threads hanging around here, let's save this thread for actual experimentation and ideas for the preparation of elemental phosphrous and keep these other discussions in other threads more suited for this such as:

what's the usual way to make phosphorus? (white, then red from white, then black?)
Interesting allotropes, glassifications, and polymorphs.
Experiments with the luminosity of white P
Unusual phosphorus allotropes from red P
Favourite Pnictogen

And there are of course threads on potassium chlorate/phosphorus mixtures, something most of us here know as a more dangerous mixture then we want to mess with, and there are still other threads on accidents, there are better places for this little off shoot of the topic that has budded here.

Edit: Didn't realize this would be on a new page, let's try to make this page more reflective of pages 1-5 rather then page 6, okay :)

[Edited on 9/4/2005 by BromicAcid]

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[*] posted on 5-9-2005 at 00:26


Here's a thread where someone actually managed to make a considerable amount of white phosphorus:
http://www.scienceforums.net/forums/showthread.php?t=3083&am...

The trick is to use metaphosphoric acid (oh how useful this substance turns out to be, it will become one of my most used chems very soon! You can make oleum from it, and white phosphorus!) with charcoal.
The reaction happens at a temperature easily reachable with a bunsen burner and can be conducted in a test tube.
Stuff the mouth of the test tube with glass wool, otherwise the P will burn away as it forms.

A method to actually collect the phosphorus in solid form is to bend the test tube in the middle. The upper part of the test tube iss arranged horizontally for the white P to collect as a puddle and solidify upon cooling.
The reaction mix is contained in the lower, bent part of the test tube.

The necessary metaphosphoric acid can be made by strongly heating ammonium phosphate (available as fertilizer).
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[*] posted on 5-9-2005 at 03:17


I got a different impression from that thread. It seemed like what was being described was a quick-and-dirty synthesis with ordinary phosphoric acid (note the part about dissolving the decomposition product of (NH<sub>4</sub>;)<sub>2</sub>HPO<sub>4</sub> in water), absurdly high temperatures (the burner melted the test tube), and a small yield (.1g).
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[*] posted on 5-9-2005 at 08:12


I also got a different impression then that thread was giving a method for making useable amounts of phosphrous. Just like earlier in this thread with Flayer who also attempted this, some of us were eventually concerned for him due to this method producing phosphine which is quite toxic, in that thread as well it is mentioned that phosphine is produced.

It is a decent method, maybe dehydrating the phosphoric acid to metaphosphate first then grinding and mixing with carbon might help rather then just mixing with phosphoric acid initally and dehydrating them both together. I can personally attest to the sodium hexametaphosphate and aluminum working well for this. Maybe all that individual needed was a better apparatus rather then a test tube, the only problem being that the procedure uses the free acid and it wouldn't be good to do this in anything short of a somewhat inert metal or glass, the iron works that I normally utilize would be out of the question.




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[*] posted on 6-9-2005 at 01:25


Inspired by YT2095's posts, I tried test-tube phosphorus production again with charcoal. I added a couple mL of 75% H3PO4 to a test tube. Initial heating produced some strong bumping so I added a bit of silica powder, and this maintained constant placid bubbling. In order to avoid heating too quickly, I started out with an alcohol lamp. After some minutes of heating the liquid began growing thicker and translucent, and over a time of less than a minute slackened and then ceased to bubble altogether. It thickened to the point of solidification in the tube, and application of the alcohol flame could not make it flow again. Is this metaphosphoric acid? I have been unable to find a melting point reference for metaphosphoric acid. I understand that it may be hard to isolate as a pure substance, but I wish I could find at least a ballpark figure to guess whether I'm seeing metaphosphoric acid or some strange glass/acid reaction product.

I added a small amount of charcoal powder on top of the slug of presumed metaphosphoric acid, wetted it with a couple drops of H3PO4, and fired up the propane torch and began heating the tube again.

The liquid acid seemed to permit the charcoal and plug of presumed metaphosphoric acid to mix. There was bubbling and the glass rapidly softened. Bubbles of gas started forcing their way through the glass. I maintained heating for several minutes, until the bottom of the test tube was thoroughly deformed and pierced by bubbles. I was working in semi-darkness, but never saw the greenish glow of phosphorus appearing in the tube as I did with my reduction experiments using lead. Neither did I ever smell the garlic-like odor I associate with phosphorus production and combustion.

After the glass had melted through, I was able to direct the bright blue cone of the flame against the presumed metaphosphoric acid solidified at the bottom of the tube. This produced a reflected flame tinged light yellow/white and green at the edges, such as I associate with phosphorus, but of course this is no step toward useful production.

Given that I encountered the same difficulties with phosphoric acid/charcoal reaction as I have seen before, that the pyrex tube was destroyed well before there was any noticeable phosphorus production, and that every reference I've ever seen on the topic indicates that carbon reduction of phosphoric acid or phosphates is significant only at temperatures well above the softening point of pyrex, I am very curious how YT2095 managed to produce 100 mg of elemental P from a test tube and propane burner setup.

Thinking perhaps there was some magic to his exact procedure, I combined charcoal and phosphoric acid as he suggested, heating the beaker until I had a just-slightly-damp mixture like moist corn meal. This was loaded into another test tube and again heated ferociously with a propane torch, until the mass was solid, the tube was horribly deformed and glowing bright orange, and I was tired of waiting for results (several minutes). I caught only the barest whiff of what might be the telltale odor, and that only for a short time, and did not see the characteristic glow in the tube that I saw with my experiments where I used metallic lead.

I fear YT2095 is omitting some key details or is talking about things that he hasn't actually done, though I hesitate to challenge the integrity of a man with a postcount of over 8000.

Some details that make me doubtful:

He's asking the forum at large how he can make phosphorus in his first post, but less than 2 weeks later he's claiming success in producing phosphorus. Beginner's luck? An unusually fast and skilled experimenter despite his original unfamiliarity with the topic?

His first instructions are
Quote:
add 25% of (the phosphoric acid you just made) mass with carbon (lumpwood chacoal powdered will do). mix well and allow to got as dry as possible.

step 4: put a little of this mix in a heatproof test tube and heat it over a bunsen burner (in a dark room is best). you will see Phosphorus begin to distill up the tube and maybe catch fire with a green glow when it hits the air

Now anybody who's actually tried this or related attempts at home phosphorus knows that a standard Bunsen burner is insufficient for carbon-reduction phosphorus production. His rather vague description puts me in mind of someone trying to fake his way through a procedure he's only imagined executing.

Later he said he managed to save 100 mg of red phosphorus, produced from a larger stock of WP that mostly went up in flames. He never described how he performed the allotropic transformation, while it's actually worthy of some discussion.

Yet later he said:
Quote:
did you leave the carbon and the conc phos acid to stand a while? I left mine for just over 24 hours ontop of a room heater to make sure it was completely dry and intimately mixed as absorbed into the pores of the carbon, then gently heated it over a flame after to drive off any excess moisture, as soon as there was the garlic type smell I capped the tube with a bleeder pipe, THEN you turn up the heat, the carbon will start to Glow dull red at 1`st then bright orange, leave it like for a good five minutes

It would be quite a feat to begin producing phosphine (the "garlic type smell";) at only a few hundred degrees, below a red heat.

But the #1 fakery tipoff: he says "Sayo I have the pics all leading up to this event, just not on my website yet as I wanted the complete set, you`ll forgive me for not taking pics during the fire I hope!" on 3/13/2004, but he doesn't post after that date until someone bumps the thread in August 2005. Wouldn't everyone here post pictures of their work if they had actually made usable quantities of phosphorus, started a thread crowing about it, and already taken the photographs?

Let's recap: vague descriptions of the processes, no photographic evidence posted though he claimed to have it more than a year ago, and so-far irreproducible results that seemingly contradict the experiences of many others (he wasn't the first to think of charcoal and H3PO4 in a test tube over a burner, but he claims to be the first to get useful results this way).

Now the opposing view, the "maybe he's not bullshitting" view. He said that he actually used a homemade forced air gas burner rather than a Bunsen burner, which could deliver quite a bit more heat. I would expact the test tube glass to lose structural integrity before any usable quantity of phosphorus would be produced, but perhaps a core of carbon and condensed phosphoric acids supported it. He mentioned making his phosphoric acid by double decomposition of fertilizers, followed by heating the produced ammonium hydrogen phosphate until it ceases to smell of ammonia. Is it possible that some impurities were retained that allow his phosphoric acid to be reduced by charcoal with unusual ease? I don't think so, but that's the best I can come up with on short notice.

Given that he started another thread to say he believed himself to be close to a complete theory of the Big Bang and the universe, I'm inclined to believe that he is given to flights of fancy, has never made any macroscopic quantity of phosphorus, and certainly doesn't have 100 mg of self-made red phosphorus in his collection.

I will contritely retract these words if he or anyone else can post instructions for <b>reproducibly</b> duplicating his claimed phosphorus production. Charcoal and acid in a test tube at orange heat do virtually nothing. Where's the key innovation that makes it do something useful?

Edit: garage chemist, where did you get the details about bending the test tube and stuffing its neck with glass wool? I didn't see those details in the thread you linked to. Are those your ideas about successfully implementing the procedure?

[Edited on 9-6-2005 by Polverone]




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[*] posted on 6-9-2005 at 02:34


Bending the test tube is my process for collecting lager quantities of white phosphorus (3 grams), which I make by sublimation of commercially bought red phosphorus (a non-controlled substance in germany, still difficult to get though).
The white P collects as a liquid puddle and solidifies to a slab after complete cooling. It can then be extracted with pliers.

I did not think of the possibility that YT2095 may have faked his success and told of things that he wasn't actually making.
But now that you outlined the flaws in his report, this becomes a possibility.

I have the impression that we need a fundamentally different experimental procedure than "mix a few substances, heat them as high as you can and hope for phosphorus being produced".

Especially the reactor design (glass or metal pipes heated from the outside) doesn't seem that covenient.
We should abandon external heating and try to switch to internal heating, like it's done in industry.
Using an electric arc would be my approach if I would try to make white P without using red P.

A metal reactor, maybe made from a pipe and two endcaps and with a narrow pipe for the P vapor to escape, has a carbon rod inserted from the top, electrically insulated of course. The reaction mix (carbon, phosphate and silica- not too finely powdered, so that not too much dust is produced) is placed in there and the reactor closed.
The pipe is heated from the outside to 300°C in order for the P to stay gaseous.
Then the current is switched on, I'm thinking of a MOT (2000V, 0,5A) as the power source. The gases are filtered from dust by leading them throug a heated glass wool filter. Then the P is condensed by leading the gases through warm water (for the P to stay liquid and not condense to fine flaky material which is hard to melt together- I know what I'm talking about).

Maybe this simulation of the industrial process works better than the ancient process from the times where electricity wasn't available as a heat source.
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[*] posted on 6-9-2005 at 08:05


Garage chemist, I strongly advise against using a MOT transformer. The reason is twofold:

1 - These MOT transformers are not designed to run continuously, even at the given specifications. These transformers (the modern consumer ones) are designed at borderline specifications to save on core dimensions (using less Silicium Iron), and especially expensive Copper wire. They soon run hot, and overheat.

2 - You want to create an Arc with the output power, and the resistance of an Arc is very low. The voltage drop is also very low, and thus will result in excessive power soak requirements in series with the Arc current. Assuming there will be a current of 0.5 ampere running through the Arc at a very low resistance, then the voltage drop (maybe < 20 Volts) will also be very low. This means that if you apply Ohm's law of U = I * R then you can calculate the power (P = I * U) to be P = 0.5 * ~20 = ~ 10 Watts heat input into your reaction mix meanwhile, the rest has to be soaked up (P = 0.5 * <2000 = <1000 Watts). Much less than 1000 watts, because it is a current transformer, and probably more than 10 Watts (the short circuit current may be higher than 0.5 Ampere).

It would be better to use an Arc-welding machine. These are also current transformers, only with the difference that the current is much and much higher (<160 Amps). You then pump P = <160 * ~20 = <~3200 Watts of energy into your Arc. But here again, these welding transformers are not designed to run continuously. The cheap Aluminum wire wound hobby stuff, have a very low turn-on ratio, and even the (semi)professional and Copper wire wound one I have (TICO 160), has a turn-on ratio of only 25 %. But in this case, even if the Arc output power would be far less than 3200 Watts, it will still be a lot more efficient than a MOT transformer out of a Magnetron.

[Edited on 6-9-2005 by Lambda]
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[*] posted on 6-9-2005 at 12:29


Lambda, you're right about a MOT having not enough amperage and not being designed to run continously.

However, an arc welder which might seem ideal at first has an important disadvantage: the arc needs to be started manually because of the low voltage.
Maybe a bridge wire between carbon electrode and metal bottom which burns through when the power is switched on can start the arc.
Or maybe the charcoal powder is conductive enough to allow enough current to flow through the mixture for heating it high enough. If not, an admixture of graphite powder might be the solution.

If the problem of starting the arc inside the chamber can be solved, an arc welder would be perfect for production of phosphorus in a semi-industrial reactor configuration.
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[*] posted on 6-9-2005 at 13:20


Garage chemist, you can simply start the arc with a high voltage burst. You may need to place a third electrode though, and just use a simple Geiser or Heater Igniter (Coil induction or Piezoelectric). Maybe just shortly tipping the two Carbon rods together, and then pulling them apart may work out easier. Wants the arc has started, you can pull them quit a distance apart.

The biggest problem may still be, the good conductivity of fused salts. Excessive heating, vaporization and maybe even explosions may be the result of this. When these salts have molted, they become conductive. If one electrode is placed in the molten salt, then the other electrode may be used to create an arc towards the molten salt surface, not touching it though. This may be done in a ceramic (heat resistant) vessel or maybe even a Steal pipe (with one Ceramic Electrode isolator).

Please check these threads out for castable Ceramics:

Kiln progress:
https://sciencemadness.org/talk/viewthread.php?tid=4381

Reaching higher temperatures:
https://sciencemadness.org/talk/viewthread.php?tid=4376

[Edited on 6-9-2005 by Lambda]
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[*] posted on 7-9-2005 at 00:01
A few more odds and ends


I had a lot of acid-impregnated charcoal left after my last experiments. So I maintained heating all night. Today it was slightly less damp than yesterday, but not much. Anyway, I tried again with the charcoal, this time grinding in some silica powder. There was a little bit of phosphorus production. It wasn't much, but it was steady as long as I kept the base of the tube at a bright orange. I can't imagine how many hours it would take to get 100 mg out of a test tube like this, even if I could collect the phosphorus instead of burning it.

I tried mixing zinc powder and then zinc powder plus silica powder with the acid charcoal. Both of these reactions went very poorly. I didn't notice any increased production of phosphorus; in fact I couldn't see any production at all since the zinc volatilized and left opaque oxide coatings on the inside of the tube, but neither could I see any white smoke in the light, so I don't think much P was being produced. Some zinc phosphide was formed, evidenced by the scent observed upon adding hot water to the cooled tubes.

Aluminum worked much better. In the first attempt, I placed cut-up pieces of a soda can's pull tab in the bottom of a test tube and poured the acid charcoal over it. This showed the most rapid and easy production of phosphorus, giving a healthy green combustion front racing up the tube as soon as the bottom reached red heat. The rate of reaction slackened considerably after that first burst, but it was still considerable compared to my earlier efforts. All of the successful reactions leave a white ring (presumably of phosphorus oxides) at the point in the tube where the combustion front spends most of its time; this one's white ring had some visible thickness by the time I was done. I scraped it with a bamboo skewer and the residue seemed to absorb water from the air. This showed an acid reaction with litmus (unsurprising).

For the final reaction I ground 400 mesh aluminum (the only sort of particulate aluminum I have) with the acid charcoal and loaded it into a test tube. There was some exotherm and funny smells even before I applied heat. I ran a very small batch, less than 1 gram of mixture, because I was wary of what might happen in the event of a violent reaction or accidental tube break. The reaction actually seemed harder to initiate than the one using chopped-up soda can bits. It never got as vigorous either, but it did all right.

I don't think any of these reactions showed marked improvements over the ones I did a few months ago with metallic lead and phosphoric acid.

I will probably continue to try things with my acid charcoal, but this path (and all those using free acid) looks unpromising compared to sodium hexametaphosphate plus aluminum. Now I just need to get some sodium hexametaphosphate.

Of course, even if I can make tongues of flaming phosphorus shoot from a test tube, I can't recover it very easily. But one step at a time, eh?

[Edited on 9-7-2005 by Polverone]




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[*] posted on 9-9-2005 at 20:19


A while back I posted an idea to obtain phosphorus by the basic method of electrorefining copper metal. I.e. putting two electrodes of phosphor-bronze (avalible for welding) into a solution with some H<sub>2</sub>SO<sub>4</sub> and preform electrolysis, the copper going into solution from the anode and plating out on the cathode, leaving the phosphorus particles in solution. Today however when looking up metaphosphoric acid I came across this somewhat relevent entry:
Quote:
Anodic oxidation of copper phosphide yields up to 60% of the dissolved phosphorus as hypophosphate (A. Rosenheim and J. Pinsker, Ber. 1910, 43, 2003).
So maybe this wouldn't be the best method in the world as I didn't anticipate anodic oxidation to be an issue here. Although phosphor-bronze doesn't contain much phosphorus it may be useful, personally I think more hope would lie in the nickel platings that do not require electrolysis to produce and other high-phosphorus nickel alloys (which are fast becoming popular, 8-15% phosphorus in some!) these may prove useful for making phosphorus and again they may not and only be useful for preparing hypophosphoric acid and the like.



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[*] posted on 10-9-2005 at 10:13


pyrex test tubes simply wont do for this i think - all the texts i read use steel or a clay retort of some sort and say 1400 - 1600 degrees C - so i guess an acetylene torch and a small fireclay container might work - maybe even try mixes of thermite - carbon and acid phosphate or maybe use the thermite to heat it in some fashion - set it off with long strip of magnesium - i remember someone making bits of sodium this way somewhere
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[*] posted on 17-9-2005 at 17:49


Bromic scanned a page of Gmelin's earlier, but I decided to make a pdf of the same page anyways, and also the page before (red P) and after (purification). Because I already had the photocopies, so I might as well make them available, FWIW.

Attachment: P.pdf (583kB)
This file has been downloaded 1309 times

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[*] posted on 18-9-2005 at 02:41


Interesting passages from the text:

"Hydrogen, when led over P2O5, HPO3 or alkali- or earthalkaliphosphates at 800 to 900°C, contains phosphorus vapor which can be condensed to white or red P."

"When a melt of NaPO3 is electrolyzed with a nickel cathode, phosphorus is depositing there."

"When an evaporated leachate of bone ash with H2SO4 is heated with charcoal in a porcelain tube, P evolution begins at 740°C, the largest part of P goes over at 960°C and at 1170°C a 92% yield is obtained."

"NaPO3 produced by melting NH4NaHPO4 is mixed with Al powder and heated. Already at red heat, the mass begins to glow and emit P vapors. Other phosphate salts can also be used, even the Ca and Mg salts."
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[*] posted on 27-9-2005 at 22:06


I found something else pretty interesting - it may not be too much use to any of us - unless someone knows jack about ultrasonics

METHOD OF SONOCHEMICAL REDUCTION OF PHOSPHATE SALTS
Valentin V. Oshchapovsky, Serikjan D. Kulbekov
1
, Victoria V. Shylo
2
Lviv State Institute of Fire Safety, P.O.Box 10676, Lvov, 79000, Ukraine
E-mail: asu@franko.lviv.ua and oshchapovsky@yahoo.com
1
Chimkent Corporation “Phosphorus”, Chimkent, 486025, Kazakhstan
2
Lviv National University, 1, Universitetska Str., Lvov, 79000, Ukraine
Reduction of phosphate salts is the high-temperature process. To lower the temperature of process
we have proposed to reduce the phosphates ores in ultrasonic field [1]. The reduction of Vyatsko-
Kamsky phosphorite was carried out in solid-phase with the application of natural gas as reducer.
We have studied the influence of temperature, process duration, frequency of ultrasound oscillations
and other factors on the degree of phosphorus extraction. The experiments were conducted in the
electric furnace with the ultrasound generator. The experiments showed that in the ultrasonic field
the process of phosphate ion reduction and extraction of phosphorus out of phosphates accelerated
considerably. The temperature of the beginning of the process dropped to 300-350°. A marked
extraction of phosphorus (12.5%) was fixed already at 700° C. Depending on the frequency of US-
oscillations at 900° C the degree of phosphorus extraction reached 90 % and more. Thus, the
application of US-oscillations intensifies the process of phosphate salts reduction considerably and
lowers the temperature of the process.
[1] Kulbekov S.D.; Oshchapovsky V.V. et al., Author Svid. of USSR No 1369176, 1987.
Submitted by:
Associate Professor V.V. Oshchapovsky, Department of Fundamental Disciplines, Lviv State
Institute of Fire Safety, P.O.Box 10676, Lvov, 79000, Ukraine
Phone: 38-0322-33-02-02; Fax: 38-0322-33-00-88.
E-mail: asu@franko.lviv.ua and oshchapovsky@yahoo.com and ndr@lipb.lviv.ua
Preferred Scientific Session / Presentation:
7D. Novel phosphorus chemistry / Poster
Signed:
Date: 02 December 2003
Page 2
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[*] posted on 7-10-2005 at 18:09


Hey Bromic,

I've obtained some Iron Phosphide and I am considering performing the reaction that you mentioned earlier on in this topic.

Do you have any further information on this reaction? I'm looking for specifics...

Also, as for the reaction vessel, what do you recommend? What is the latest status on your P production? What is the current vessel you are using?

If I decide to perform this, I'll post pictures and progress.

Thanks all!
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[*] posted on 7-10-2005 at 18:37


I really wish I knew more, I don't know if I posted what I comprehensively know word for word so here it is, from Comprehensive Tretise on Inorganic and Theoretical Chemistry
Quote:
E. Minary and R. Soudry prepared phosphorus from a mixture of iron phosphate and coke; and R. A. Brooman heated a mixture of silica, iron, coal, and calcium phosphate so as to form a fusible slag and iron phosphide. The latter when heated with sulfur, hydrogen sulfide, carbon disulfide, etc., furinshed phosphorus.
Somewhat straight foreward but still, what about the reference?
Quote:
A. Nicolle, Brit. Pat. No. 1693, 1888 ; R. Lammy, ib., 311, 1857 ; J. H. Player, ib., 660, 1866 ; 1064, 1867 ; R. A. Brooman, ib., 2294, 1864 ; J. Townsend, ib., 1862, 1872
And what does that refer to? I don't know, I never learned much about references and when I took the book to my librarian and pointed at the reference they didn't know either (Mind you I was in the 'Reference Help Office' of the library!) I would really like some feedback on where I might find this reference, I was told by a librarian there may be a table that it refers back to but they couldn't find anything, I have a feeling ib means something simple and once that is discerned I will be able to find the reference (though I looked up the meaning online and it was no help.)

Anyway, heat the two reactants together, I don't know if excess S is added to drive the reaction foreward, because excess S would react with phosphorus. Also, I don't know if you need to distill the phosphorus from the mixture or if it pools on top. Finally since H<sub>2</sub>S is listed as a sulfur source it means that it doesn't have to occur in the liquid phase, it may be gaseous sulfur running over iron phosphide. None of these details are given. Given enough time one could calculate the thermodynamic values for the system to see at what temperatures it becomes spontaneous (though we would of course know nothing of the rate). One good idea if distillation seemed probable then you could run it between 280 C (boiling point of phosphorus) and under 444 C (the boiling point of the sulfur) with a stoichiometric or slightly less quantity of sulfur maybe?

Sulfur is corrosive to many metals in the liquid state so thick metal would be preferable, or its still within the relm of glass heating so it could be done in that medium. Hopefully more imput from other members will come and you will be sucessful in your efforts.




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[*] posted on 7-10-2005 at 19:59


It looks like British patent number and year, as in patent number 1693 in the year 1888.

Speaking of: are any of these helpful?

4,204,925 Recovery of phosphorus from sludge
4,689,121 Recovery of phosphorus from sludge
3,113,839 Recovery of phosphorus from sludge
3,442,621 Phosphorus Production
2,050,796 Recovery of Phosphorus
4,462,973 Phosphorus purification
4,608,241 Production of phosphorus and phosphoric acid
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Magpie
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[*] posted on 7-10-2005 at 20:28
ibidem


Bromic Acid says:


Quote:

I have a feeling ib means something simple


I'm guessing this means ibidem, which means "in the same place." In the USA this is usually abreviated "ibid." It is, or was, commonly used to refer to a reference already cited. In your case it is just the reference for the 1st author.




The single most important condition for a successful synthesis is good mixing - Nicodem
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S.C. Wack
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[*] posted on 7-10-2005 at 20:44


Yep.

GB patents up to the 191?'s are found by using the year followed by a 5 digit number. The first would be gb188801693, if only the coverage on espacenet was not so spotty for the older GB patents. Some are there, others like this one aren't. IIRC the earliest GB patent that I've found there was from 1886.

I hate it when there are US patents for the corresponding GB or DE ones, but the US number isn't mentioned - supposedly all US patents are online.
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IrC
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[*] posted on 12-10-2005 at 13:20


BromicAcid, I recently nabbed two check valves on ebay and I wonder if they could be used. They are threaded for standard half inch plumbing pipe at both ends (inside the ID). They would screw perfectly into a section of pipe, are spring loaded and open at a couple PSI. The problem is the big ball inside of each is some type of plastic and I am not sure if they would melt or if there would be some reaction with the material. I do not know what the material is, I am half tempted to take one apart and see if I can find a perfect ball bearing to replace the plastic ball with, around 11 mm or so in diameter.

Going back to Polverone's beginning post on page one:

"Sadly, this reaction requires 1000-1500 C to operate. It's done in an arc furnace. Building a suitably airtight, nonconducting, refractory vessel for an arc furnace is something well beyond my current engineering skills/resources (any brilliant suggestions?)"

Why does the vessel have to be an insulator? If you had say a 9 inch diameter 11 inch tall graphite crucible with one inch thick walls (and bottom) as the grounded electrode (the whole crucible itself), could you not use castable refractory to create a gastight lid which also holds the second termimal (say a one inch diameter graphite rod going down into the crucible stopping an inch or so before the bottom)? The refractory would be the insulation to keep the center electrode from contacting the outer electrode (i.e., the crucible itself). A suitable hole could be cast in the refractory top where the exit pipe came out.

Sitting here looking at this exact crucible I had this idea. If you do not ground the crucible, another cast refractory piece could be made which holds the crucible keeping it insulated from the stand, assuming you are using a floating source of power such as a two bushing pole transformer (also sitting here looking at one of those).

[Edited on 13-10-2005 by IrC]
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leu
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[*] posted on 13-10-2005 at 04:48


Quote:
I really wish I knew more, I don't know if I posted what I comprehensively know word for word so here it is, from Comprehensive Tretise on Inorganic and Theoretical Chemistry

quote:E. Minary and R. Soudry prepared phosphorus from a mixture of iron phosphate and coke; and R. A. Brooman heated a mixture of silica, iron, coal, and calcium phosphate so as to form a fusible slag and iron phosphide. The latter when heated with sulfur, hydrogen sulfide, carbon disulfide, etc., furinshed phosphorus.

Somewhat straight foreward but still, what about the reference?

quote:A. Nicolle, Brit. Pat. No. 1693, 1888 ; R. Lammy, ib., 311, 1857 ; J. H. Player, ib., 660, 1866 ; 1064, 1867 ; R. A. Brooman, ib., 2294, 1864 ; J. Townsend, ib., 1862, 1872

And what does that refer to? I don't know, I never learned much about references and when I took the book to my librarian and pointed at the reference they didn't know either (Mind you I was in the 'Reference Help Office' of the library!) I would really like some feedback on where I might find this reference, I was told by a librarian there may be a table that it refers back to but they couldn't find anything, I have a feeling ib means something simple and once that is discerned I will be able to find the reference (though I looked up the meaning online and it was no help.)


Mellor's citations were written in the ancient style; clearly the reference librarian didn't have enough grey hairs; the citations are on pp 743-4; and are:

Minary & Soudry

Rev Univ Mines, (1), 16. 360, 1864

Brooman

Ann Chim Phys 2294, 1864

The latter article may be available from Gallica; but two citations previously searched for from that publication given in Mellor's were erroneous, whether this is due to errors made by the author, typesetter or proofreader is unknown :(
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[*] posted on 13-10-2005 at 08:19


wp using microwaves.
hey sounds cute
will post patent number as soon as I find it - its somewhere around here I just know it.

WOWWIE - I R A HAZARD TO OTHERS. WHOOPPEEEEE- I was just getting used to being a hazard to my own damn self.

[Edited on 13-10-2005 by jimwig]

well my new title requires that I actually have to think about it some more - seems like an ion exchange resin was involved along with phosphoric acid - kinda vague but will not let my fellow officers and crew down - NOSIREEE!!!

(Jeez give a guy a little fucking title?)

[Edited on 13-10-2005 by jimwig]
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HomeAlchemy
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[*] posted on 26-10-2005 at 12:08
Looking For Phoshorus?


I am amazed that it is so hard to find Phosphorus in the US!

It is very frustrating trying to do neat experiments at home -- it sounds pretty harsh in the US:(

It's not that easy to find in Canada, but at least you are allowed to own some.

If you are looking for a little to play with just e-mail me @ darien88@hotmail.com

I also have many other neat, hard to get exotic chemical elements, metals, and non-metals if you are interested

I have shipped this stuff to the USA without problems. Just a few friends who needed some.:cool:
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[*] posted on 3-12-2005 at 15:43


some general comments about high tem. decomposition of phosphates (also applicable for sulfates, CaSO4 reduction thread), and please correct me if I'm wrong:
I believe that the actual reduction occurs with the oxide (i.e P4O10 or SO3 and C, Al, ...) the very high temp. is needed for the decomposition of the very stable ions: 4[PO4(-3)] -> 4O(-2) + P4O10.
now, as the polarizing power of the cation increase, the thermal stability of the salt decrease and it decomposes at lower temp. i.e AlPO4 should be a better choice then Ca3(PO4)2 and Fe III better then Fe II
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