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TheAMchemistry87
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Get Zirconium from Zirconium Tetrachloride
So whats a good metal to use to react with Zirconium Tetrachloride to recieve the Zirconium Metal ?
Aluminum? Magnesium?
AMchemistry
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kristofvagyok
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Magnesium, sodium, potassium, calcium ect.
Aluminum sometimes (mainly home chemist's supply) contains iron and a lot other things what is aint so good for pure reactions.
But also: use the search engine and read the Inorgo chem book by Brauer, as I remember there is a method for this...
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Hexavalent
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This should definitely be in the beginnings section.
I don't know enough about zirconium chemistry to be certain, but as far as reduction potentials go I think magnesium should work. Consult 'plante1999'
- he may be able to say for certain.
Doing the reduction electrolytically may also be an option.
Are you implying that this be done in aqueous solution? Hydrolysis would happen for sure...even if this was possible, then the reaction of Na, K or Ca
with water would be a problem, no? If done in an alcoholic solvent, then the formation of alkoxides could also be problematic.
[Edited on 1-9-2012 by Hexavalent]
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kristofvagyok
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Quote: Originally posted by Hexavalent  |
If this is done in aqueous solution, then the reaction of Na, K or Ca with water would be a problem, no? If done in an alcoholic solvent, then the
formation of alkoxides could also be problematic. |
ZrCl4 is really unstable in presence of water, it hydrolises rapidly as I remember, so just solid state reduction could be done where the sodium with
it's low melting point is one of the best.
[Edited on 1-9-2012 by kristofvagyok]
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barley81
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Brauer says that zirconium can be prepared by heating ZrCl<sub>4</sub> together with Na metal, or by reduction of
ZrCl<sub>4</sub> vapor with Mg in helium atmosphere.
Other methods: reduction of ZrO<sub>2</sub> with Ca metal, or reduction of K<sub>2</sub>ZrF<sub>6</sub> with Na
metal.
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Hexavalent
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kristofvagyok
Ah yes, I see. Would a solid-state reduction be efficient, though? How practical is it? Would it have to be done under an inert gas? No offence,
TheAM, but if you're asking a question like the one here then I don't think you should be handling liquid sodium by yourself.
[Edited on 1-9-2012 by Hexavalent]
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blogfast25
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ZrF4 + Mg is basically the Kroll process (Ti and Zr) applied to zirconium. Don't try that at home! Both obtaining signifcant quantities of ZrCl4 and
the actual reduction reaction aren't exactly child's play! The reduction reaction (with Mg or Na) is seriously exothermic and ZrCl4 is quite volatile.
Volatile + heat = pressure!
Aluminium is generally (bar exceptions) not a great reductant for chlorides: it's HoF isn't very high and it is also very volatile (in some set ups
the latter can be an advantage, of course).
| Quote: Originally posted by Hexavalent | Ah yes, I see. Would a solid-state reduction be efficient, though? How practical is it?
[Edited on 1-9-2012 by Hexavalent] |
About as practical as not possible at all. TiCl4 and ZrCl4 aren't your usual ionic chlorides: they're about as covalent as CCl4.
[Edited on 1-9-2012 by blogfast25]
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kristofvagyok
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The method with liquid sodium is a pity, the only thing what is important that a really strong walled glass is needed for this method (not a test
tube!!!!).
It should be performed as the following: in a large round bottomed flask filled half with paraffin oil, some sodium is melted on a sand bath (10% more
that what will be needed to the reduction) with a PTFE stirring bar (IKA stirrer preferred) and the powdered ZrCl4 is added slowly. A highly exotermic
reaction will take a place at the bottom of the flask and the NaCl what will form will float up the the top of the molten sodium. The produced Zr
metal will remain at the bottom.
At the end of the reaction, the excess sodium is decomposed by methanol, the solids are filtered out and washed with water, dried, pure Zr could be
obtained, easy, the only problem is when shit glassware is used and it breaks... That could hurt.
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Hexavalent
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Any particular reason why?
Also, could you not substitute a well-made crucible for the flask?
Myst32YT has a video on making sodium peroxide where he melts sodium metal into a crucible; http://www.youtube.com/watch?v=ZqEWUw6sgpA
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barley81
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I have heard that stirring molten alkali metals with teflon stir bars can lead to violent explosions. The overhead stirrer's agitator is probably
glass, so it won't pose that risk.
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blogfast25
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kristof, 'easy' really is the understatement of the year, as far as I'm concerned. This is something a hobbyist cannot pull off.
It's even far from certain that the initially solid ZrCl4 will react with liquid but relatively cold sodium. Assuming the reaction needs heat to get
started, the ZrCl4 starts subliming at 331 C! And once reaction does start, huge amounts of enthalpy are generated. This requires a pressure vessel
and some serious temperature controllers to keep in control of things.
[Edited on 1-9-2012 by blogfast25]
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blogfast25
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| Quote: Originally posted by barley81 | | I have heard that stirring molten alkali metals with teflon stir bars can lead to violent explosions. The overhead stirrer's agitator is probably
glass, so it won't pose that risk. |
'explosions' may be an overstatement but molten alkali metals can react violenty with halocarbons, including PTFE (Teflon, essentially).
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kristofvagyok
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| Quote: Originally posted by blogfast25 | kristof, 'easy' really is the understatement of the year
It's even far from certain that the initially solid ZrCl4 will react with liquid but relatively cold sodium. Assuming the reaction needs heat to get
started, the ZrCl4 starts subliming at 331 C! And once reaction does start, huge amounts of enthalpy are generated. This requires a pressure vessel
and some serious temperature controllers to keep in control of things.[Edited on 1-9-2012 by blogfast25] |
This is an easy reaction, no special things are required, no special conditions and no special reagents... I think that it is not a big deal, just
don't break the glass 
The liquid sodium (slightly above 100Celsius) is enough for the reaction and the high excess of paraffin oil, the stirring prevents the higher
temperature and the "problems". Also, it is recommended to add the ZrCl4 in small portions...
I had no problems with PTFE bars and sodium, I have only once burned PTFE shavings with magnesium... But it was at several huderead celsius and it was
boosted with some KClO3.... But safety first, I agree, PTFE is not the best, but I had no problem with it in the past. So, use any else polymer coated
bars.
The IKA is preferred, because it has a stronger magnet compared to most other manufacturers, and to my experiences with most third party stirrers it
often happens that they throw off the magnet at fast stirring and heating what is aint a good thing at this reduction.
[Edited on 1-9-2012 by kristofvagyok]
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blogfast25
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Kristof:
Are you speaking from personal experience here? Or do you have an authorative text you’re quoting from? (In the latter case, please share)
The Standard Enthalpy of Reaction for ZrCl4(s) + 4 Na(s) →Zr(s) + 4 NaCl(s) is a whopping – 663.5 kJ/mol (NIST Webbook data), barely 200 kJ
less negative than Classic Thermite ( -851 kJ/mol)!
Unless the ZrCl4 is added in really small amounts at one time, allowing sufficient cooling between the enthalpy bursts, this is really dangerous stuff
to be carried out in glass, w/o cooling etc etc.
If it were that easy, you’d find Youtubers showing it off.
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kristofvagyok
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This was written in an old inorgo. chem. lecture note according to my memories, but next week I will perform this experiment in the lab if I will find
the ZrCl4 or ZrOCl2...
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Hexavalent
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'Bump' my question... what about the use of ceramic or porcelain crucibles as reaction vessels?
TheAMchemistry87....it looks like you probably won't be performing this synthesis in your lab, after all.
Where did you get your ZrCl4 from anyway?
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plante1999
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Good luck finding ZrCl4, its not OTC, at best you will be able to make it from the easier procedure I developed, old procedure use zirconium dioxide,
carbon, Chlorine and 1000 degree Celsius. Seriously I recommend to use the fluoride instaid of the chloride, and use calcium instead of sodium, don't
try to do it in glass, use at least ceramic. The reaction is manageable for someone with at least some knowledge in IVB column elements.
I never asked for this.
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blogfast25
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| Quote: Originally posted by kristofvagyok | | This was written in an old inorgo. chem. lecture note according to my memories, but next week I will perform this experiment in the lab if I will find
the ZrCl4 or ZrOCl2... |
ZrOCl2 is a completely different animal. I'm not even sure it's possible to obtain it in anhydrous form. I have about 100 g of homemade ZrOCl2.8H2O.
It's likely to convert entirely to ZrO2 on dehydrating. And even if you could make anhydrous ZrOCl2, converting it to ZrCl4 would be difficult.
As plante wrote: ZrCl4 is very difficult to buy and very hard to synthesise at the home lab level.
Still, I look forward to your experimenatl results. I have my own planned route to Zr, hence my interest.
[Edited on 1-9-2012 by blogfast25]
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kristofvagyok
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| Quote: Originally posted by blogfast25 |
ZrOCl2 is a completely different animal.
As plante wrote: ZrCl4 is very difficult to buy and very hard to synthesise at the home lab level.
Still, I look forward to your experimenatl results. I have my own planned route to Zr, hence my interest.[Edited on 1-9-2012 by blogfast25]
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Yes, I know that ZrOCl2 is completely different, but as the topic title says metallic Zr should be obtained from ZrCl4... So ZrOCl2 is also an
alternative....
And the ZrCl4 is also not an impossible task, I won't prepare it from ZrO2, I don't have that much time, but maybe there will be a small ampoulle
somewhere in the lab, who knows...
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blogfast25
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An alternative in what specific way?
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elementcollector1
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Do tell how a home chemist could prepare ZrCl4 from materials around him (cubic zirconium, possibly zircon, etc)...
It would probably involve some very strong acids.
I can attempt the ZrCl4-Na reduction, as fairly soon I will have everything but the ZrCl4.
Elements Collected:52/87
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blogfast25
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| Quote: Originally posted by elementcollector1 | Do tell how a home chemist could prepare ZrCl4 from materials around him (cubic zirconium, possibly zircon, etc)...
It would probably involve some very strong acids.
I can attempt the ZrCl4-Na reduction, as fairly soon I will have everything but the ZrCl4. |
For ZrCl4 look up 'Kroll process zirconium'. Making this chemical at home in any significant quantities is most probably outside the capacity envelope
of most backyarders. It's certainly outside of mine!
ZrOCl2.8H2O home synth has be described on this forum at least twice. Search 'zirconium' by 'blogfast25' and ye shall find. But zircomium
tetrachloride and ziconyl chloride are very different things...
[Edited on 3-9-2012 by blogfast25]
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elementcollector1
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"For a simpler procedure see: Inorg. Syn., 4, 121-126(1953)."
Where do I find this?
Also, I don't think I can do the dioxide + carbon + chlorine thing easily, not without some serious heat and apparatus.
Elements Collected:52/87
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blogfast25
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In a nutshell...
Try Georg Brauer's 'Preparative Inorganic Chemistry' (SM Library) for possible alternative prep.
In any case, here’s Brauer on the reduction of ZrCl4 with sodium (so much for using glass apparatus ):
Page 1173:
III. ZrCl4 + 4Na = Zr + 4 NaCl
233.0 92.0 91.2 233.8
Up to 1 kg. of sublimed ZrCl4, crushed to lumps, and 450 g.
of distilled Na may be reacted in one run in a sealed steel tube
at 850°C. The bottom of the tube is charged with a layer of Na;
this is followed by the reaction mixture (ZrCl4 + Na), topped with
a layer of Na. Since the vapor pressure of ZrCl4 is considerably
lower than that of TiCl4, the processing of larger quantities is
simpler. The heat evolved in the reaction is so large that partial
sintering of the metal occurs.
IV. ZrCl4 + 2Mg = Zr + 2 MgCl2
233.0 48.6 91.2 190.4
As in the magnesium process for Ti, Zr may be prepared by
reduction of ZrCl4 vapor with Mg in a helium atmosphere (see
references below for further details).
V. Zrl4 = Zr + 2I2
598.9 91.2 507.7
The glowing wire temperatures during refining should be
~1400°C in the case of Zr and ~ 1600°C in the case of Hf. The
Pyrex vessel must be kept at 600°C. The crude metal obtained
from the chloride is the most suitable raw material. Recently
Zr has been prepared in large glass vessels in the form of rods
weighing up to 200 g.
[Edited on 4-9-2012 by blogfast25]
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Wizzard
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Crystal Bar technique has my vote!! If one makes it hot enough (real white heat), you can make crystals of Zr!
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