Sciencemadness Discussion Board - Making uranium and thorium by electrolysis?

Making uranium and thorium by electrolysis?

nagyepf - 28-1-2020 at 09:29

I wonder if it is possible or not to make uranium and thorium from its soluble compounds by electrolysis?Or will we only get hydrogen gas and never plate out uranium or thorium metal?
I dont have any uranium or thorium minerals neither chemicals to dissolve them,so i cannot try it out

But i'm still curious if it's even possible.

SWIM - 28-1-2020 at 12:14

Uranium reacts readily with water to form the oxide, producing hydrogen gas.

Doesn't sound like a happening deal.

Checking if the thing you're trying to make in aqueous solution is stable in aqueous solution is always a good first step.

Maybe you could find a uranium salt soluble in pyridine or something like that giving an ionized enough solution that you can electrolyze it.

Some poster from Britain a few years back wanted to make cesium that way.

Hey, just a thought. you know those electrolytic cells with mercury on the bottom for one electrode that they used to make chlorine gas and sodium/mercury amalgam in?

They'd take the amalgam and hydrolyze it to get NaOH.

If you ran a the right uranium salt in one of those it might give you uranium/mercury amalgam which you could distill to drive off the mercury.

Anybody up for distilling an amalgam of mercury and uranium at home?

[Edited on 28-1-2020 by SWIM]

j_sum1 - 28-1-2020 at 13:23

I recently acquired a uranium salt and was wondering some if the same things.
It would be great to have a thin coating of U on a strip of copper as an element sample.
Unfortunately an aqueous solution is a no go. I have not gitten to researching other options.

DraconicAcid - 28-1-2020 at 14:58

Cotton and Wilkinson say....

The [actinide] metals may all be prepared by a method applicable on either a [micro]gram scale, as in the first preparation of Cm, or on a multikilogram scale. This is the reductuion of one of the anhydrous fluorides MF3 or MF4 with the vapour of Li, Mg, Ca, or Ba at 1100 to 1400 oC; chlorides or oxides can be reduced similarly. On large scales (e.g., for U) Mg or Ca is normally used.

There are other procedures; thus very pure Th is made from thermal decomposition (de Boer process). Electrolytic methods are not commonly used, but Th can be obtained from a melt of ThF4, KCN, and NaCl. Amarecium has been obtained by a method depending on its volatility, which is greater than that of the other actinides:

2 La + Am2O3 = 2 Am(g) + La2O3 (1200 oC)

Curium has also been made on a gram scale by extraction from a melt of MgCl2, MgF2, and CmO2 with molton Zn-Mg alloy, the excess of which is then distilled off; uranium can also be obtained as an amalgam, from which is can be recovered, bu action of Na/Hg on uranyl acetate.

Abromination - 28-1-2020 at 15:17

I wouldnt think so. F block elements tend to be too reactive towards water and as far as I know can not be plated out of solution.

j_sum1 - 28-1-2020 at 22:36

UCl3 melts at 850°C or thereabouts. Bromide and iodide are probably lower. Lower MP mixtures may also be possible. So, molten salt electrolysis is not out of the question theoretically.

woelen - 28-1-2020 at 23:53

I expect uranium (which normally is in the +6 oxidation state in UO2(2+) ion) to be reduced to U(4+) by electrolysis. When no acid is present the oxygen in the uranyl ions leads to hydroxide formation in solution and you get precipitate around the cathode. If sufficient acid is present, you might get a solution with U(4+).

The above is all an educated guess, not more than that. I cannot test it in real experiments.

12thealchemist - 29-1-2020 at 11:43

Quote: Originally posted by j_sum1

UCl3 melts at 850°C or thereabouts. Bromide and iodide are probably lower. Lower MP mixtures may also be possible. So, molten salt electrolysis is not out of the question theoretically.

Theoretically, yes. But U(III) compounds are highly reducing - similar to Cr(II). They are preparable for the amateur, but preparing and melting a pure dry sample without oxidising it could be... challenging to say the least.

nagyepf - 30-1-2020 at 10:24

Quote: Originally posted by SWIM

Uranium reacts readily with water to form the oxide, producing hydrogen gas.

Doesn't sound like a happening deal.

Checking if the thing you're trying to make in aqueous solution is stable in aqueous solution is always a good first step.

Maybe you could find a uranium salt soluble in pyridine or something like that giving an ionized enough solution that you can electrolyze it.

Some poster from Britain a few years back wanted to make cesium that way.

Hey, just a thought. you know those electrolytic cells with mercury on the bottom for one electrode that they used to make chlorine gas and sodium/mercury amalgam in?

They'd take the amalgam and hydrolyze it to get NaOH.

If you ran a the right uranium salt in one of those it might give you uranium/mercury amalgam which you could distill to drive off the mercury.

Anybody up for distilling an amalgam of mercury and uranium at home?

[Edited on 28-1-2020 by SWIM]

I am not sure if uranium and thorium form amalgams

DraconicAcid - 30-1-2020 at 10:54

Quote: Originally posted by nagyepf

I am not sure if uranium and thorium form amalgams

Are you doubting Cotton and Wilkinson?????????

Tsjerk - 30-1-2020 at 11:26

If you have sodium, mercury and a CCl4 you could try this:

https://sci-hub.tw/https://doi.org/10.1016/0022-1902(69)80145-4

It still needs seperation from the mercury though, but if you get as far as the point described in the article above, that should be doable as well.

SWIM - 30-1-2020 at 14:10

If heat will drive the mercury off, then perhaps it could be 'fire gilded' onto another metal the way they used to put gold on some tremendously ornate french clocks and other sideboard impedimenta back in the 19th century.

You could gild it onto a little statue of Uranus!

Maybe trying thorium first would be a good idea though.

People wouldn't be alarmed at your saying, "I'm going to put a permanent coating of radioactive material on Thor", because that phrase is less likely to lead to misunderstandings.

chornedsnorkack - 30-1-2020 at 22:18

https://www.sciencedirect.com/science/article/abs/pii/002219...

Uranium metal produced by electrolysis into amalgam.
For those who can get into full text, why was the amalgam heated to 1300 degrees to get U? How much Hg was left in at 400 degrees?

Note that U(III) aqueous cation is routinely produced by zinc amalgam, so electrolysis in absence of amalgam should reduce U(IV) to U(III) already.

Tsjerk - 31-1-2020 at 07:01

Quote: Originally posted by chornedsnorkack

https://www.sciencedirect.com/science/article/abs/pii/002219...

Uranium metal produced by electrolysis into amalgam.
For those who can get into full text, why was the amalgam heated to 1300 degrees to get U? How much Hg was left in at 400 degrees?

Note that U(III) aqueous cation is routinely produced by zinc amalgam, so electrolysis in absence of amalgam should reduce U(IV) to U(III) already.

Next time: go to sci-hub.tw and fill out e.g. the DOI. Pass the captcha and Voila!

https://sci-hub.tw/https://doi.org/10.1016/0022-1902(78)80432-1