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Author: Subject: Phosphorus halides from phosphine
CEY-19
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[*] posted on 20-7-2015 at 08:45
Phosphorus halides from phosphine


Hey guys,

Long time lurker, first time poster. Recently I've been interested in finding a way to prepare PCl3 and PBr3 without having to face the hassle of either preparing elemental phosphorus or of collecting it from matchboxes.

Whilst looking into a few possibilities, I found a patent (US6685904: Process for making phosphorus halides and oxyhalides) which outlines a process of reacting PH3 with Cl2 in the presence of H2 at various temperatures in a quartz tube to produce PCl3 and HCl, the extra hydrogen being present as a diluent possibly, but mostly as a relic of the process of phosphine production the authors of the patent used. In theory, one could use undiluted phosphine if one planned, as I do, to get their phosphine some other way.

I was wondering if anyone had attempted this reaction themselves?

I was planning on using the 1:1:3 mixture of PH3:H2:Cl2, supplying the hydrogen and phosphine separately and mixing them before drying them, and using an old Graham condenser I have lying around as a reaction vessel with hot water running through the "cooling" jacket, with a separatory funnel serving as a collection flask to allow easy transfer to ampoules. Excess unreacted gas would be drawn off and burned through an old bunsen isolated from the gas generators and reaction chamber.

Does anything about that strike anyone as dangerous or ill advised? The system will be flushed out with excess hydrogen to remove any unreacted lingering phosphine and drive it out to the bunsen once the reaction is complete.

Would love to hear your thoughts and get a few sets of fresh eyes on the whole thing, personally.
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[*] posted on 20-7-2015 at 08:55


You can make PCl3 by chlorination of phosphide.
"Small-Scale Synthesis of Laboratory Reagents with Reaction Modeling", Leonid Lerner. Chapter 18. Phosphorus Pentachloride.
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[*] posted on 20-7-2015 at 09:05


Useful to know, and logged for consideration, though I was planning to get my phosphine from sodium phosphinate as I have some of that around from some experiments many moons ago. My only source of phosphide would be either importing mole killer (expensive and only a few percent phosphide) or trying to prepare some myself (unnecessary hassle).
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[*] posted on 20-7-2015 at 09:15


You are planning to generate three gas streams simultaneously, regulating flow of each to obtain the said ratio? When the Cl2 oxidizer comes in contact with the reductants you will produce a controlled (hopefully) combustion process.

This sounds complex and demanding. Do you have experience in such endeavors?




The single most important condition for a successful synthesis is good mixing - Nicodem
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[*] posted on 20-7-2015 at 09:37


Quote: Originally posted by Magpie  
You are planning to generate three gas streams simultaneously, regulating flow of each to obtain the said ratio? When the Cl2 oxidizer comes in contact with the reductants you will produce a controlled (hopefully) combustion process.

This sounds complex and demanding. Do you have experience in such endeavors?


The important ratio to maintain is the ration of phosphine to chlorine, the hydrogen concentration is not as vital. I plan on running the reactor chlorine lean so as to prevent the formation of the pentachloride.

The reaction isn't so much a controlled combustion (which would presumably take place at much higher temperatures) but a more controlled chlorination, taking place at temperatures below 100°C.

Ultimately I plan to control the mixture by controlling the rate of chlorine generation and letting the phosphine/hydrogen mixture flow remain fairly constant.

That said, it is fairly complex and I must admit I have never done anything quite similar. I've used bromine and methane to prepare some bromomethane using a roughly similar method with UV irradiation to a quartz tube, that's about as close as I got, and it wasn't massively successful. More for interest than for proper use.

[Edited on 2015-7-20 by CEY-19]
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[*] posted on 20-7-2015 at 10:44


Hot phosphine self-ignites in atmospheric air producing a loud "pop."- I know this by experience when making phosphorus in a furnace. Have you computed the heat of reaction of phosphine with Cl2?

Do you plan on running this continuous process at a sufficiently slow rate that heat removal will not be a concern? You say that you will be using hot water in the condenser jacket - so I guess you are not worrying about too much heat. The coil of a Graham is a rather restricted space. I guess you are not concerned with surges that would cause small explosions?




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[*] posted on 20-7-2015 at 11:05


Yes, the gas phase heat of reaction is 565.6kJ mol-1, less than half the heat of combustion of phosphine in oxygen (closer to 1200kJ mol-1). The reaction rate is being kept slow, yes, so heat production is not a massive concern. The reaction is apparently not explosive so long as some hydrogen dilutant gas is present.



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[*] posted on 20-7-2015 at 11:10


Hydrogen and chlorine will explode if mixed and ignited. Phosphine and chlorine will almost certainly do so too.
Why would diluting one (probably) explosive mixture with another (known) explosive mixture stop it going bang?
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[*] posted on 20-7-2015 at 11:29


They aren't being ignited: the reaction is more akin to a chlorination than to burning one in the other to my understanding. The reaction takes place at a low enough temperature that chlorine does not even react with the hydrogen present. This, of course, is if the patent is to be believed, which for the initial runs I do not plan to trust. Slow addition of the chlorine to the hydrogen/phosphine will precede any proper runs, in order to test the possibility of explosions. Blast shield at the ready.

As a note, I do not know whether or not the phosphine/chlorine mixture will be explosive: I know that in 2008 woelen posted a page on his site of a reaction between chlorine and phosphine under wet conditions which did give spontaneous combustion. It is thus my speculation that if the patent can be believed, the hydrogen is playing some role in preventing this combustion. However, it could also be the exclusion of moisture which prevents the spontaneous combustion, or it may be that the patent is instead patent nonsense...





"The chemists are a strange class of mortals, impelled by an almost insane impulse to seek their pleasures amid smoke and vapor, soot and flame, poisons and poverty; yet among all these evils I seem to live so sweetly that may I die if I were to change places with the Persian king." - Johann Joachim Becher
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[*] posted on 20-7-2015 at 16:04


It will probably blow up.

Anyhow, you want to avoid blue vis or UV light--the H2 + Cl2-->2HCl rxn is easily initiated photochemically (an old, particularly striking laboratory demo). The reaction is violent.

So, if you must do this, do it in the dark or under filtered red-light.

See: https://www.youtube.com/watch?v=NN82GoBG98s

Cheers,

O3





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[*] posted on 21-7-2015 at 03:56


Quote: Originally posted by Ozone  
It will probably blow up.

Anyhow, you want to avoid blue vis or UV light--the H2 + Cl2-->2HCl rxn is easily initiated photochemically.



Yeah, seems like the chance of an explosion is pretty high on this, planning on doing it outside, night time. Originally, so I could see any signs of more combustion-type behavior, but the additional thought of the possibility of blue light setting off the Cl2/h2 is a good one so you have my thanks.

Blast shields at the ready and cheap glassware means if it does go off I mostly just have to play thousand piece pick up haha




"The chemists are a strange class of mortals, impelled by an almost insane impulse to seek their pleasures amid smoke and vapor, soot and flame, poisons and poverty; yet among all these evils I seem to live so sweetly that may I die if I were to change places with the Persian king." - Johann Joachim Becher
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[*] posted on 21-7-2015 at 04:40


Quote: Originally posted by CEY-19  
Quote: Originally posted by Ozone  
It will probably blow up.

Anyhow, you want to avoid blue vis or UV light--the H2 + Cl2-->2HCl rxn is easily initiated photochemically.



Yeah, seems like the chance of an explosion is pretty high on this, planning on doing it outside, night time. Originally, so I could see any signs of more combustion-type behavior, but the additional thought of the possibility of blue light setting off the Cl2/h2 is a good one so you have my thanks.

Blast shields at the ready and cheap glassware means if it does go off I mostly just have to play thousand piece pick up haha


My research on H2/Cl2/sunlight (especially red light) is that light can indeed initiate an explosive chain reaction. However, a lecture I once read on chain reactions (may still be available somewhere on the web) did also indicate a small amount of O2 interjects a termination step into the otherwise explosive chain reaction sequence.

But unfortunately, oxygen may not be a life saver here because if its interaction with PH3 (Edit: more accurately, the presence of P2H4 impurity may be responsible for spontaneous ignition, see http://phosphorus.atomistry.com/hydrogen_phosphides.html in air, which apparently can also occur with PH3 at reduced pressures). However, PH3 itself may act in the role of a spoiler in place of O2, so no explosion may actually take place. Best to test out on a very small scale a few times to be sure.
--------------------------

A comment from Atomistry.com on PCl3 on its preparation (link: http://phosphorus.atomistry.com/phosphorus_trichloride.html ):

"It is possible to prepare it directly from calcium phosphate by heating this with silica and charcoal and passing over it the vapour of sulphur monochloride:—

4S2Cl2 + Ca(PO3)2 = 2PCl3 + CaCl2 + 3SO2 + 5S "

Note, Atomistry on S2Cl2 (link: http://sulphur.atomistry.com/sulphur_monochloride.html ) to quote:

"Sulphur and chlorine interact slowly at the ordinary temperature but much more readily on warming. The customary procedure is to pass dried chlorine into fused sulphur or over dry " flowers of sulphur " until most of the sulphur has disappeared. The resulting monochloride contains considerable amounts of higher sulphur chlorides in solution, but if the mixture is heated for some time under a reflux condenser the pure monochloride can subsequently be distilled over. "
----------------------------

Also, an interesting path to P suggested also via PCl3 in the same Atomistry link, to quote:

"....antimony, phosphine and arsine, giving phosphorus in each case."

which implies to me the reaction:

PCl3 + PH3 = 2 P + 3 HCl

But the same link also states:

"Heating phosphorus in a sealed tube with HCl:—

2P + 3HCl = PCl3 + PH3 "

so to favor the reaction direction in formation of Phosphorous, cooling may work along with an absence of any water as to quote the same source:

"PCl3 + 3H2O = H3PO3 + 3HCl "

[Edited on 21-7-2015 by AJKOER]
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[*] posted on 21-7-2015 at 05:50


Quote: Originally posted by CEY-19  
Quote: Originally posted by Ozone  
It will probably blow up.

Anyhow, you want to avoid blue vis or UV light--the H2 + Cl2-->2HCl rxn is easily initiated photochemically.



Yeah, seems like the chance of an explosion is pretty high on this, planning on doing it outside, night time. Originally, so I could see any signs of more combustion-type behavior, but the additional thought of the possibility of blue light setting off the Cl2/h2 is a good one so you have my thanks.

Blast shields at the ready and cheap glassware means if it does go off I mostly just have to play thousand piece pick up haha


My research on H2/Cl2/sunlight (especially red light) is that light can indeed initiate an explosive chain reaction. However, a lecture I once read on chain reactions (may still be available somewhere on the web) did also indicate a small amount of O2 interjects a termination step into the otherwise explosive chain reaction sequence.

But unfortunately, oxygen may not be a life saver here because if its interaction with PH3. Edit: More accurately, the presence of P2H4 impurity (which can reportedly be removed by washing the gas mixture with concentrated HCl) may be responsible for spontaneous ignition (please see Atomistry on P2H4 at http://phosphorus.atomistry.com/hydrogen_phosphides.html ) in air, which apparently can also occur with PH3 at reduced pressures. However, PH3 itself may act (speculation) in the role of a spoiler in place of O2, so no explosion may actually take place. Best to test out on a very small scale a few times (after scrubbing the gas mixture with HCl) to be sure.
----------------------------

A comment from Atomistry.com on PCl3 on its preparation (link: http://phosphorus.atomistry.com/phosphorus_trichloride.html ):

"It is possible to prepare it directly from calcium phosphate by heating this with silica and charcoal and passing over it the vapour of sulphur monochloride:—

4S2Cl2 + Ca(PO3)2 = 2PCl3 + CaCl2 + 3SO2 + 5S "

Note, Atomistry on S2Cl2 (link: http://sulphur.atomistry.com/sulphur_monochloride.html ) to quote:

"Sulphur and chlorine interact slowly at the ordinary temperature but much more readily on warming. The customary procedure is to pass dried chlorine into fused sulphur or over dry " flowers of sulphur " until most of the sulphur has disappeared. The resulting monochloride contains considerable amounts of higher sulphur chlorides in solution, but if the mixture is heated for some time under a reflux condenser the pure monochloride can subsequently be distilled over. "

Also, to quote:

"Phosphorus trichloride reacts with sulphur monochloride, iodine acting as a catalyst; the products are phosphorus pentachloride and phosphorus sulphochloride:

3PCl3 + S2Cl2 = PCl5 + 2PSCl3 "

So, absence an Iodine catalyst, excess S2Cl2 should not significantly reduce the yield of PCl3.

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

Also, an interesting path to P suggested also via PCl3 in the same Atomistry link, to quote:

"....antimony, phosphine and arsine, giving phosphorus in each case."

which implies to me the reaction:

PCl3 + PH3 = 2 P + 3 HCl

But the same link also states:

"Heating phosphorus in a sealed tube with HCl:—

2P + 3HCl = PCl3 + PH3 "

so to favor the reaction direction in formation of Phosphorous, cooling may work along with an absence of any water as to quote the same source:

"PCl3 + 3H2O = H3PO3 + 3HCl "

[Edited on 21-7-2015 by AJKOER]
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[*] posted on 21-7-2015 at 09:11


Quote: Originally posted by halogen  

chlorinate a metallic phosphide solid like byko suggested, from which one assumes you'd prepare the phosphine anyways.

[Edited on 21-7-2015 by halogen]


As previously noted, I'd be using sodium phosphinate and not a phosphide as that is what I have access to.




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[*] posted on 28-7-2015 at 12:40


How can sodium phosphinate (sodium hypophosphite) be used to make a steady flow of PH3? That would be interesting on its own. Sodium hypophosphite is cheap for me and I can buy it at kg-quantities without problems. I never considered it really interesting because of its rather sluggish reactions in aqueous solutions.



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[*] posted on 28-7-2015 at 17:11


H2(PHO3) + Zn (H2SO4) => PH3 + 3H2O
The reaction is pretty much a reversal of PH3 + 2 I2 + 2 H2O => H3PO2 + 4 HI.
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[*] posted on 28-7-2015 at 17:14


Per Wikipedia on NaH2PO2 (link: https://en.m.wikipedia.org/wiki/Sodium_hypophosphite ):

"Sodium hypophosphite should be kept in a cool, dry place, isolated from oxidizing materials. It decomposes when heated and produces toxic phosphine gas, causing irritation to the respiratory tract.

2 NaH2PO2 → Na2HPO4 + PH3"

So phosphine gas is but an irritant?!??
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[*] posted on 29-7-2015 at 04:27


AJKOER, phosphine has a definite disagreeable odor, but in case you continue to breath it in for a long period of time - you will be poisoned and maybe even die.
In fact, the odor is tolerable and some people are ignorant enough to ignore it. Natural selection in action.
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