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Author: Subject: Distillation Over Metal Dust
DFliyerz
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[*] posted on 4-6-2015 at 07:02
Distillation Over Metal Dust


A very old (and still fairly useful) method of deoxygenating hydrocarbons is distilling the material with zinc dust, such as in the deoxygenation of phenol to benzene. I am wondering, is zinc the only metal that this process can be performed with? Could copper, nickel, etc. be used instead, or just zinc? Would aluminum explode?
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unionised
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[*] posted on 4-6-2015 at 09:57


Part of the answer may be that zinc was readily obtained as "dust".
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[*] posted on 4-6-2015 at 10:13


Quote: Originally posted by unionised  
Part of the answer may be that zinc was readily obtained as "dust".


Granulometry should only affect kinetics, not actual reductive capacity.

I think Mg powder might work very well here. Perhaps Al shavings or turnings too.




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[*] posted on 4-6-2015 at 10:55


You seem to have missed the point.
Powdered gadolinium probably works too, but you couldn't get it from the smelting works in 1900.
It might be interesting to try it with pyrophoric iron.

Also, three's kinetics and kinetics.
it's plausible that the rapid reaction with the dust happens quicker than, for example, some rearrangement but that if you have to work slowly because the metal is in big lumps, the rearrangement is quicker so you would get a different product.
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DFliyerz
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[*] posted on 4-6-2015 at 11:44


I don't know why it took me so long to realize (even though I have cooled molten zinc in water), but zinc doesn't react with water. Therefore I could probably precipitate a decently fine powder of it by dissolving impure zinc in HCl and displacing it with aluminum metal. I'll be sure to try it when I get home today, and report on my results.
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[*] posted on 4-6-2015 at 12:35


https://en.wikipedia.org/wiki/Rieke_metals
Also, as you may know, zinc is the only metal capable of reducing ketones directly to hydrocarbons in Clemmensen reduction. However, mechanism of the reaction is complicated and for complex compounds can give unexpected product (double bound reduction, cleavage, etc.).
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UC235
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[*] posted on 4-6-2015 at 16:38


Zinc is fairly unique in that it is easy to powder finely without significant oxide formation. Supposedly, it is very brittle above about 210C, but below its melting point at 420C, and beating/pounding it crushes it into dust.

The easiest way to get this temperature range is probably to melt it, cool, and start crushing as soon as it's solid.

Zinc does react with water, though it may not be apparent from quenching the metal in large chunks. The finer the material, the more rapid it's oxidation, such that attempting to displace it from liquid would probably produce a mess containing significant hydroxide content..
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[*] posted on 4-6-2015 at 17:41


Distillation from magnesium turnings is a good way to dry some solvents that react with alkali metals.



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[*] posted on 6-6-2015 at 16:33


Quote: Originally posted by UC235  
Zinc is fairly unique in that it is easy to powder finely without significant oxide formation. Supposedly, it is very brittle above about 210C, but below its melting point at 420C, and beating/pounding it crushes it into dust.

That's very interesting. I have noticed when melting down Aluminium chunks that the aluminium also becomes extremely weak and crumbly a little below its melting point, so perhaps that same method could also be used for Aluminium.
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