Author Topic: Red P from Phosphoric acid?  (Read 9497 times)

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UTFSE

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Re: Red P from Phosphoric acid?
« Reply #20 on: October 14, 2001, 09:21:00 PM »
(with hesitation UTFSE said)

i like more control. using an arc between two carbon rods easily gives mucho heat. the whole generation is controled by the old current and voltage regulation (various ways)

the sand in the process is used to convert the calcium to slag so as to remove it BUT ONLY when you are starting out with a phosphate rock.

phosphoric acid to white P still seems like the best route IF the heat is there.

And as someone said just burn off the H and CO thats generated.

Or if your dirigible needs a boost-------------?



always appreciate your time and consideration

UTFSE

  • Guest
Re: Red P from Phosphoric acid?
« Reply #21 on: October 14, 2001, 09:28:00 PM »
but here is to Sir Halfapint - because  your method  certainly wins for simplicity and kitchen caveman chemistry.

I think Thermite easily melts steel rails together so that's about 4000 anyway.

I assume the iodine is the catalyst along with UV?

In situ RP (sorta)- who'd thunk it.

always appreciate your time and consideration

foxy2

  • Guest
Re: Red P from Phosphoric acid?
« Reply #22 on: October 15, 2001, 03:31:00 AM »
Nice Job Halfapint!!!
This is the shit for home phos production.
Here is some info.

Reduction of metallic oxide to metal
Reduction
The conversion of metal oxide into metal (by removal of oxygen) is called reduction. 
Generally the 3 methods used are:
Reduction by heating the oxide
Chemical reduction
Electrolytic reduction.

Chemical Reduction Processes
Under this process the oxides of metals that are in the middle of the reactivity series are reduced to free metals using chemical reducing agents such as carbon, aluminium, sodium or calcium.

1. Reduction by carbon process
Oxides of metals like zinc, iron, copper, nickel, tin and lead are reduced using carbon as the reducing agent.(note: phosphorus is done this way) Carbon can be used only if it has greater affinity for oxygen than the metal. For example, carbon can reduce copper oxide to copper, but it cannot reduce calcium oxide. It can reduce zinc oxide.

ZnO + C -----> Zn +  CO
        Zinc metal   Carbon
monooxide
 
2. Reduction with aluminium by thermite process
Metals which are too active to be obtained by reduction of their oxides with carbon are reduced using aluminium, which is a more powerful reducing agent.(note: It will reduce Phosphorus!!!) Chromium and manganese oxides are reduced using aluminum. This reaction is highly exothermic.

Cr2O3 + 2Al -----> 2Cr +  Al2O3
        Chromium metal    

3MnO2 + 4Al -----> 3Mn +  2Al2O3 
        Manganese metal    
……………………………………………………………………………………………

http://www.compassbox.com/cbse/demo/chemistry/chapter10/3704061004.asp




And More.

Thermite reaction.

            Soon after metallic aluminium was first isolated, both Sainte-Claire Deville and Wöhler noted its property when mixed in the form of powder or granules with the oxides of some of the metals, of reducing them with the evolution of sufficient heat to melt the metal and the alumina produced [1].

            On this was based the process applied by Dr Hans Goldschmidt of Essen, who in 1898 was developing commercially the promising work of Claude Vauntin and Hugh Picard in London, following the change in the economics of aluminium supply which had taken place when production by the Héroult and Hall electric furnace method superseded the expensive sodium reduction process; prior to that time the use of aluminium as a reducing agent was little more than a scientific curiosity [2].  Goldschmidt has obtained either the metal, or an alloy of the metal, with aluminium, from the oxides of chromium, manganese, iron, copper, titanium, boron, tungsten, molybdenum, nickel, cobalt, zirconium, vanadium, niobium, tantalum, cerium, thorium, barium, calcium, sodium, potassium, lead and tin.  He said:

In a thermite reaction, a metallic compound is reduced by one of several metals or metallic alloys in such a way that when the mixture is ignited at one place, the reaction continues of its own accord, so that under complete oxidation of the reducing element, a fluid slag is formed, while the reduced metal is obtained as a homogeneous uniform regulus; if the oxide is used in excess, the reduced metal is free, or practically free, from the element used as a reducing agent.

 

            Goldschmidt’s significant innovations comprised the means of starting the reaction by a fuse, instead of heating the mixture until ignition took place, and the various controlling procedures which made the process practicable on a plant scale.

            This is the first of two solid/solid reactions, see also experiment 18a.  This reaction, uses powdered aluminium metal to reduce metallic oxides and is especially useful for the reduction of those metal oxides which are difficult to reduce such as titanium and molybdenum.  It is also known as the Goldschmidt process, and the Aluminothermic process.  This is a highly exothermic reaction and the metal emerges in its molten state often very much above its melting point.  A mixture of finely divided aluminium with ferric oxide (or the oxide of some other metal), approximating to 2Al+Fe2O3, is sold under the registered name Thermit (no final ‘e’), and is used in joining or welding iron and steel rails, pipes, etc.  Sections of railway lines are usually welded in this way and the reaction is mostly associated with the reduction of iron oxide as in our demonstration.  Like the first part of the next demonstration this reaction takes place between solids and is, consequently, difficult to start.

            Two equivalents of finely divided aluminium and one of iron oxide are mixed together and ignited.  The reaction takes place as follows:

Fe2O3 + 2 Al ==> Al2O3 + 2 Fe + 848.54 kJ                             (17.1)

            Safety.  This is a hazardous procedure, but is a safe demonstration in experienced hands.  However, there must always be a first time, and it is to those persons that we offer the following advice.  Read the safety recommendations of say reference 7 below.

First perform this experiment outdoors a couple of times, preferably use a table as you would indoors.  There are very few demonstrations that can safely be performed for the first time in front of an audience and, in this case, we recommend that you practice at least twice more indoors before regarding yourself as sufficiently experienced and competent.  It is always a good idea to get someone else to work with you as an equal partner, in that you should both be equally familiar with the procedure, and both sense the burden of responsibility.  In these circumstances the partners should assume individual and collective responsibility and so will ‘watch out for each other’.  For example a teacher might involve his technician in this way.

            It is important that the Thermite mixture is perfectly dry otherwise extremely hot material might be violently ejected from the crucible.  Dry the components separately at ca. 125C.  Do not use heat to dry the mixture use a desiccant.

            Metallic iron is produced at a temperature significantly above its melting point at 1535C.  Once the reaction has started it is almost impossible to stop it.  A CO2 fire extinguisher should to hand; water should not be used because potentially explosive hydrogen can be produced.  No one should be closer to the reaction than two metres.

References

1.    Thorpe’s Dictionary of Applied Chemistry, 4th ed., vol. XI, London - New York - Toronto, Longmans, Green and Co., 1954, pp. 562-565.

2.    H. Goldschmidt, German Pat., D.R.P. 96317, 1895; Z. Elektrochem., 1898, 4, 494; Ibid., 1899, 6, 53; Electrochem. Metall. Ind., 1908, 6, 360; Stahl Eisen, 1898, 18, 408; H. Goldschmidt and C. Vautin, J. Soc. Chem. Ind., 1898, 17, 543.

3.    J.W. Mellor, A Comprehensive Treatise on Inorganic and Theoretical Chemistry, vol. 5, new impr., London, Longman, Green and Co., 1956, p. 218.

4.    Tested Demonstrations in Chemistry, ed. G.L. Gilbert, et al., vol. 1, Granville, OH, Denison University, 1994, p. H-9.

5.    P.J. Roebuck, Educ. in Chem.(Britain), 1979, 16, 178.

6.    J.R. Crellin, Educ. in Chem. (Britain), 1980, 17, 93.

7.    B.Z. Shakhashiri, Chemical Demonstrations, A Handbook for Teachers of Chemistry, vol. 1, Madison, The University of Wisconsin Press, 1983, p. 88.

8.    G. Fowles, Lecture Experiments in Chemistry, 3-rd ed., London, G.Bell & Sons, Ltd., 1947, pp. 285-287.


http://www.chem.leeds.ac.uk/delights/texts/Demonstration_17.htm




More References

Microscale thermite reactions.    
J. Chem. Educ.  (1998),  75(12),  1630-1631.

How to get the most from the dichromate volcano demonstration:  aluminothermy.    
J. Chem. Educ.  (1984),  61(10),  908.

The thermite lecture demonstration.    
J. Chem. Educ.  (1979),  56(10),  675-6.

Abstract
A lecture demonstration of the thermite reaction is described.  The mixt. of Al powder and Fe2O3 is ignited by the heat produced on oxidn. of several milliliters of glycerin added to KMnO4 crystals placed in a small depression on the surface of the reaction mixt.  The reaction can be carried out in a small clay flower pot with a sand bath to collect the molten Fe, with the whole setup being surrounded by a proper safety shield to contain sparks and provide protection from this highly exothermic reaction.

A modified thermit lecture demonstration.    
J. Chem. Educ.  (1981),  58(10),  802. 

Abstract
A lecture demonstration using Thermit with a KMnO4-glycerin ignition mixt. is described. 




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halfapint

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Re: Red P from Phosphoric acid?
« Reply #23 on: October 15, 2001, 06:33:00 AM »
Thanks, UTFSE, and thank you, Foxy2. This came on just like a flash, it hits you and you know it's right, can't bee any question.

It's not needful to stress this is a hazardous operation. Anybody who sets up to do this and is not nervous, is in need of some serious help. But we should get specific about the failure mode of this particular operation, for anyone who may not have the imagination to know what we are nervous about.

Thermite reactions are dangerous because they get hot and you can't put them out. This is not just a plain vanilla thermite reaction. It produces a vapor which is spontaneously flammable in air at its formation temperature. It is a deadly poison. A lot of this vapor is produced very fast, and its production is unstoppable.

This reaction fails if this vapor does not all go into the water. In case this reaction fails, you will have a very large fire in the sky above the apparatus. Your neighbors will notice. If you do not run far and fast, you will be injured. A dense and caustic white smoke of phosphorus pentoxide will form. In great volume. You will be notorious.

So have some sense, and get nervous. Make everything sturdier than it has to be. Test things. Make a dry run. Make a small pilot run. This one, you can't fuck up and get away with it. It's dangerous.

I'm thinking I might just run the condenser pipe into loosely packed crushed ice in the receiver tub at the start of the reaction. That will give minimal back pressure to start with. As the reaction progresses, the temperature and pressure of the vapor will both increase, while the ice is melting. The retort head will be held on the reaction vessel with heavy clamps. That's where failure is intolerable, but I want to be able to fasten them down pretty damn quick, before things get hot.


turning science fact into <<science fiction>>

foxy2

  • Guest
Re: Red P from Phosphoric acid?
« Reply #24 on: October 15, 2001, 07:34:00 AM »
Yep
VERY DANGEROUS


I would try very small batches to see how this works.  Possibly multiple small batches would greatly increase the safety margin.  Maybe do it way, way out in the desert where you can't burn anything down.


An external ignition method would bee ideal.  Who knows how vigorous this reaction is?  You could try a model rocket ignitor stuck in a little pile of (gunpowder? or something highly flamable) mixed with some magnesium powder.  Once the magnesium is lit I imagine the whole thing will go, (hopefully not EXPLOSIVELY!!!)



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UTFSE

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Re: Red P from Phosphoric acid?
« Reply #25 on: October 16, 2001, 02:57:00 AM »
post deleted by UTFSE cause it was so dumb.

Oh embarassment - --cringe shudder.

UTFSE

  • Guest
Re: Red P from Phosphoric acid?
« Reply #26 on: October 16, 2001, 03:40:00 AM »
Okay we are on the right track but let me say a couple of things concerning Al.

Powdered and granulated aluminum are used in pyrotechniques

Principally it is THE ingredient in flash powder.

It does go boom when mixed with an oxidizer (i think) it does go boom spontaneously from friction/pressure.....

It is very dangerous. It will take your fingers to see God.
There are several chemicals with which it is entirely uncompatible.
Make it your busienss to know which ones.

I think sulfur is one.

Everyone in the pyro pages says mix no more than 10 grams of this stuff at a time and then with a ten foot pole.

I have about a pound of this stuff in powder form. And about a million in various other forms - foil, extruded, etc. Most are probably alloys.

Several question loom (SP) like how are the various alloys in this readtion?

How does one obtain rather large quantities of powder without large quantities of danger.

Ball milling is used but is it done underwater ?

this is exciting - I am looosinnnngngn it -  dAVE. r u there

always appreciate your time and consideration

UTFSE

  • Guest
Re: Red P from Phosphoric acid?
« Reply #27 on: October 16, 2001, 04:00:00 AM »
I hate it when I have to respond to myself ---however-------

small - tiny vesuvious type eruptions happening in small thick walled ceramic spaces with vast condensing coils of stainless leading to icecubes brimming over in large cast iron club footed bath tubs. Yes bring it on.

Did i fail to mention the ice cold water circulating around and about the shiny stainless steel coils sweating, working hard in the moonlight.

This started with H3PO4 ==> P + et al but the main thing is that RP is easy once the hard thing white P is obtained.

Go go I have got to calm down now.

I truly need a general. but a nurse will do.





Now isn't that better.................

always appreciate your time and consideration

PolytheneSam

  • Guest
Re: Red P from Phosphoric acid?
« Reply #28 on: October 16, 2001, 04:01:00 AM »
I looked through about 25-30 chemistry books in the library to dig up stuff like this.  Its about time you try to make use of it.  Also, I read in two books that terra cotta retorts were used for making and distilling phosphorus.  I recently saw a terra cotta vase in a store.  If a still head could be made for it, maybe some electrodes could be put in it (the vase), ie. screws put through threaded holes.  For the thermite process, maybe metal pipe might be the best.

http://www.geocities.com/dritte123/PSPF.html

UTFSE

  • Guest
Re: Red P from Phosphoric acid?
« Reply #29 on: October 16, 2001, 04:06:00 AM »
Polysam- I too have been searching. I have posted many dumb ass questions trying to stay in touch with anything to do with white phophorous.

I use Mellor's, Lange, anybody, everybody that I can get a lead on in. Duh..

But the vesuvious demos just whizzed by me. I didn't even read them in Shakhashiri, cause I guess after many hours on many nights I was just too tired to pay attention.

Thank you sir(s)- may I have another?

always appreciate your time and consideration

foxy2

  • Guest
Re: Red P from Phosphoric acid?
« Reply #30 on: October 16, 2001, 04:49:00 AM »
This actual form of the thermite reaction is probably not documented or has only been tried by a few due to the obvious hazards involved.

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wandering101

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Re: Red P from Phosphoric acid?
« Reply #31 on: October 16, 2001, 09:56:00 AM »
> I never heard of P exploding.  I thought it just caught
> on fire in the air (above 34-37º C).  I don't think P can > explode unless it is mixed with an oxidizer or is finely > divided.

2 words. Phosphorous grenades. Yes, they're finely divided (and quite possibly mixed with an oxidizer - been a LOOONG time since SWIW was making explosives...) - but it's dangerous stuff.

foxy2

  • Guest
Re: Red P from Phosphoric acid?
« Reply #32 on: October 16, 2001, 04:20:00 PM »
I also don't think phosphorus is explosive, (not sure on this tho)  Those phos. grenades have a regular explosive, the phosphorus is there to burn the shit out of anything in the area.



By explosively I meant that your reaction vessel could explode.  This reaction needs to be in a relatively contained vessel to maintain the inert atmosphere and if the pressure builds up to fast that vessel could go BOOM, which would be like a Phos. grenade, NOT PRETTY. 

Here is one idea.
Maybe a mixture of Aluminum, carbon, SiO2 and phosphate could be used to mediate the reaction.  It would be ideal if you could set it up so the reaction needs moderate heat to proceed but stops when heat is removed.  That MIGHT bee possible with the mix I described, who knows? 


Someone calculate the enthalpy of this reaction for us.
6NaPO3 + 10Al + 3SiO2 --> 3Na2SiO3 + 5Al2O3 + 6P. 

This reaction MAY actually require heat to work, that would bee great because then the reaction is controlable!  It is not the same as those thermite reactions because of the SiO2 which has very STRONG bonds that might eat up much of the energy liberated when Al2O3 is formed.  Someone calculate this, it might be better than we think!! 

I cannot find a heat of formation for sodium hexametaphosphate??  Anyone have access to the PREDICT program?  Their site says it will calculate it.



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UTFSE

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Re: Red P from Phosphoric acid?
« Reply #33 on: October 16, 2001, 08:45:00 PM »
let me reiterate something- with this near explosion happening visa vi the very rapid burning of thermite I am very concerned with the gases produced. The pathway to the condensor for the P vapour will also have to carry H and CO and whatever else is vaporized. All expanding gases and in a rather rapid sequence.

This ain't gonna be know drops per minutes situation. Perhaps an intermediate holding vessel for expanding gas and then into a condensation device.

But then there's that oxygen problem - inert atmosphere problem. Maybe an expanadable bladder- high temp.

And how does one keep the splatters from clogging the tube exiting the reaction vessel?



always appreciate your time and consideration

Rhodium

  • Guest
Re: Red P from Phosphoric acid?
« Reply #34 on: October 16, 2001, 08:51:00 PM »
Required reading for people contemplating the preparation of phosphorous from urine/phosphates/phosphoric acid:

"The 13th Element : The Sordid Tale of Murder, Fire, and Phosphorus" by John Emsley - many free pages are available at

http://www.amazon.com


Agent_Smith

  • Guest
Re: Red P from Phosphoric acid?
« Reply #35 on: October 17, 2001, 01:32:00 AM »
RP in most certainly explosive (when mixed with an oxidizer of course).  Search the web for "Armstrong's Mix" I think it's called.  Thats the formula.  Armstrongs mix is the shit used in those champagne bottle shaped streamer popper things.

blah blah blah something clever blah blah blah

foxy2

  • Guest
Re: Red P from Phosphoric acid?
« Reply #36 on: October 17, 2001, 07:12:00 AM »
well since this reaction is a reduction there are no oxidizers unless the ambient air gets in and i don't think air is sufficient for an actual explosion, however it will burn vigorously.

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UTFSE

  • Guest
Re: Red P from Phosphoric acid?
« Reply #37 on: October 23, 2001, 12:20:00 AM »
Okay I read it. Beside the verbal graphics nothing I ain't aware of.

The poisoning is most scary. Murder by definition came from another being not phosphorous. I suspect a lot of heinous activities came from greed and avirace on the part of SWI-phosphorous.

BUT all our talk is aimed at OTC.

If your objective is to drain the swamp then you gotta put up with a few aligators. Sometimes you win sometimes they win.



UTFSE

  • Guest
Re: Red P from Phosphoric acid?
« Reply #38 on: October 23, 2001, 12:51:00 AM »
Okay where do I send my dues for the HalpAPint fan club?

And one question Oh Diety master sir - do these insights just pop out or are you on drugs?

always appreciate your time and consideration

halfapint

  • Guest
Re: Red P from Phosphoric acid?
« Reply #39 on: November 02, 2001, 03:57:00 PM »
OK this is how to do it. Think vertical. Use a bubble cap still, like those used in the petroleum industry. My early examples of these were made of cat food cans, like a model of the big ones. But here, we can't use soldered cans in the lower stages -- too damn hot for too damn long, under too much pressure.

Build the lower stages sturdy, using bolts. Allow plenty of headroom, and use shallow water, in wide pans, with plenty of bubble caps in these high pressure lower stages. Easiest bubble cap construction is a tube shaped like an upside down J with its open tip immersed in water.

In the upper stages the heat and pressure criteria are relaxed. It can be built in a conical taper, like a ziggurat, smaller toward the top. Leave a vent in the top stage, and just flare off any vapors you can't tame. Not while you're breathing, though. A proper sized reaction for your apparatus should give nearly zero vapors out the top, if you use the pure thermite reaction. Foxy's way using carbon and silica as diluents for the thermite would produce vapors in normal operation. It seems it would be very tricky trying to balance the charge so it would still burn, and if it burned I'm not sure it would slow it down that much. Don't complicate it, until you get the simplest method down.

All right, with a bubble cap still your layers of WP sitting under water will solidify when they're not in the sunlight, so you can't use mine and PolySam's simplified RP conversion scheme. You will have to use the heating method, with exclusion of air, which gives faster conversion to RP. That will bee after you dig every morsel of that rubbery, glowing, toxic solid WP out of every pan of your bubble cap still. At least it won't burst into flame on contact with air any more, after it gets cold, so you can pour the water off from your pan.

turning science fact into <<science fiction>>