Sciencemadness Discussion Board

UO2 looking for ways to react it

urenthesage - 4-4-2016 at 00:42

Hey forum! So I have 7 grams of crude, natural uranium dioxide and Im looking for ways to react this to get different uranium compounds. Ive tried HCl and it doesnt do anything at all. Is there any way to get that pesky oxygen off of the uranium so I can do other chemistry with it?

j_sum1 - 4-4-2016 at 01:02

I recall a shocking YT video in the thread on bad youtube videos. From memory it clocks in at about post 40-50. I will look it up for you.

I would not emulate the procedure but it may be that the theory is worth a look.
I am sure that someone more knowledgeable will be here to point you in the right direction. But in the meantime, you may as well be entertained / shocked / informed by someone doing uranium chemistry beside the swimming pool.

Edit
Here is the thread and the relevant post. Thanks blogfast.
http://www.sciencemadness.org/talk/viewthread.php?tid=48892&...

[Edited on 4-4-2016 by j_sum1]

phlogiston - 4-4-2016 at 01:12


Someone named Carl Willis has a very nice page with some practical uranium chemistry:

https://carlwillis.wordpress.com/2008/02/20/uranium-chemistr...

Joe Skulan - 4-4-2016 at 04:16

It will dissolve in nitric acid.

hyfalcon - 4-4-2016 at 08:01

Apparently HCl and an oxidizer, bleach, conc. peroxide will work also.

urenthesage - 4-4-2016 at 09:52

Quote: Originally posted by j_sum1  
I recall a shocking YT video in the thread on bad youtube videos. From memory it clocks in at about post 40-50. I will look it up for you.

I would not emulate the procedure but it may be that the theory is worth a look.
I am sure that someone more knowledgeable will be here to point you in the right direction. But in the meantime, you may as well be entertained / shocked / informed by someone doing uranium chemistry beside the swimming pool.

Edit


Here is the thread and the relevant post. Thanks blogfast.
http://www.sciencemadness.org/talk/viewthread.php?tid=48892&...

[Edited on 4-4-2016 by j_sum1]



Thanks for that video, I dont think that process will work with what I have though. Someone else here is suggesting nitric acid, I think Ill try that before anything else. Thanks so much for the video, it was informative and the next time I find myself in the US southwest Ill try and get some of that ore.

My UO2 is hard and glassy and came from veins of calcite at a road cut.

urenthesage - 4-4-2016 at 09:54

Quote: Originally posted by hyfalcon  
Apparently HCl and an oxidizer, bleach, conc. peroxide will work also.


Its certainly worth a try, Worst case is that it does nothing, best case Ill have uranyl chloride as a building block for more complex arrangements in the future. Thanks.

hyfalcon - 4-4-2016 at 18:31

Read the link phlogiston kindly provided. Very interesting chemistry.

Calcite, carbonates. You really need to read phlogiston's link.

[Edited on 5-4-2016 by hyfalcon]

neptunium - 5-4-2016 at 06:19

Some rust remover contain HF and oxalic acid. It can also be used to obtain the tetrafluoride which precipitate out as a green solid

urenthesage - 17-4-2016 at 11:08

Quote: Originally posted by neptunium  
Some rust remover contain HF and oxalic acid. It can also be used to obtain the tetrafluoride which precipitate out as a green solid


Actually HF is one of the easier acids to make. CaF when treated with 98%H2SO4 releases relatively pure HF. The problem with pure HF is temperature. It has to remain below 19oC or it vopourizes and puts huge stresses on the container it is in. I wasnt really interested in a uranium fluoride as its difficult to do anything with it. I am currently reacting it in a strong solution of NaOH, and its slowly but surely converting to UO2(OH)2. From there Ill see about making organic complexes from the hydroxide.

bur - 24-6-2016 at 07:37

I know the tread is a bit old, but for the record, in my experience no oxidizer is required to dissolve U metal in hot nitric acid. So the same should be true for UO2.

By the way, for purification the PUREX method could be interesting. Tributylphosphate very selectively complexes U, causing it to leave the water layer. It's the commercial way to recover U and Pu from used fuel. I haven't tried it yet but it seems to be easy and efficient.

urenthesage - 4-7-2016 at 10:43

Quote: Originally posted by bur  
I know the tread is a bit old, but for the record, in my experience no oxidizer is required to dissolve U metal in hot nitric acid. So the same should be true for UO2.

By the way, for purification the PUREX method could be interesting. Tributylphosphate very selectively complexes U, causing it to leave the water layer. It's the commercial way to recover U and Pu from used fuel. I haven't tried it yet but it seems to be easy and efficient.



Cold nitric acid (fuming) did the trick, now im just waiting for evaporation to get rid of the water. Thanks for the tip, it worked.

DDTea - 27-11-2016 at 14:00

Maybe not what you're going for, but uranyl nitrate has some potential in photochemical transformations of alkanes (!).

Quote:
One aspect of uranium chemistry that has been well-studied, however, is the photochemistry of the uranyl cation (UO22+).[22-24] Studies by multiple groups have revealed that this cation possesses several intriguing characteristics. Notably, a highly oxidizing excited state, [UO2]2+* (+2.6 V vs. SHE, almost equal to the oxidizing power of elemental fluorine![25]), is accessible under blue light (hν 450–495 nm) irradiation. This excited state is sufficiently reactive to abstract hydrogen atoms from unactivated C−H bonds (BDE >100 kcal mol−1) to generate carbon-centered radicals. Furthermore, pioneering studies by Bakac and co-workers showed that this reactivity could be rendered catalytic for aerobic oxidation of alkanes (Figure 2); with some substrates, the quantum yield approaches unity.[26, 27] Despite this promising reactivity and abundance of desirable characteristics, the applications of the uranyl cation in catalysis remain largely underdeveloped.


http://onlinelibrary.wiley.com/doi/10.1002/anie.201603149/fu...

Yamato71 - 4-2-2017 at 19:41

When prospecting for uranium containing rare earth minerals at night in Texas, I carry an ultraviolet lamp and a spray bottle filled with either a 50% solution of glacial acetic acid or 10% nitric acid in water. Almost all uranium specimens here are oxides, which are not fluorescent. By spraying the diluted acid on a pitchblende or other specimen, the acid converts the outer layer of oxide to either the nitrate or the acetate, both of which are fluorescent because they contain the uranyl (UO2)+2 ion in aqueous solution. After a minute or two, the UV lamp lights them up a nice bright green.

Chlorine - 4-2-2017 at 19:52

It should dissolve in an HCL+HNO3 (3:1) solution.

elementcollector1 - 4-2-2017 at 20:02

Quote: Originally posted by Yamato71  
When prospecting for uranium containing rare earth minerals at night in Texas, I carry an ultraviolet lamp and a spray bottle filled with either a 50% solution of glacial acetic acid or 10% nitric acid in water. Almost all uranium specimens here are oxides, which are not fluorescent. By spraying the diluted acid on a pitchblende or other specimen, the acid converts the outer layer of oxide to either the nitrate or the acetate, both of which are fluorescent because they contain the uranyl (UO2)+2 ion in aqueous solution. After a minute or two, the UV lamp lights them up a nice bright green.


That... is actually pretty clever. Congrats, I'm definitely using that method when I go uranium prospecting.

j_sum1 - 4-2-2017 at 20:23

I was thinking the exact same thing.

Radium212 - 17-9-2017 at 01:49

I also recommend Carl Willis's procedure.

VSEPR_VOID - 25-9-2017 at 19:17

Quote:
Originally posted to Quora, written by Carl Willis

Uranium gets a bad rap, being widely regarded as exotic and dangerous. As a fellow "amateur chemist" (more recently, career nuclear engineer) experienced with uranium, I would like to challenge this unfairly negative reputation and suggest that you CAN study the "household chemistry" of uranium safely and responsibly without resorting to a poor surrogate. A basic working knowledge of inorganic chemistry is a prerequisite to a satisfying experience; that is true of all chemistry. So be comfortable with stoichiometry, balancing equations, measuring mass and volume, etc. Be comfortable with prevailing standards of chemical hygiene and safety, like wearing gloves and eye protection. The big dangers here are the same mundane ones you'd find in high-school intro chemistry: strong acids and bases, hotplates, flammable solvents. Although a toxic heavy metal, uranium is far more approachable than, say, arsenic or mercury or fluorine chemistry in a residential setting. The keys to good hygiene and responsible use lie in working with small quantities (think about containing the mess if a container were to break or fall over) and controlling waste generation. Buy some microscale glassware. Just be aware that if you work with large (~kg) quantities, or plan to sell or transfer things you make to other people, you are no longer an inconsequential "hobbyist" and will find yourself up against the strictures of your jurisdiction's nuclear regulatory framework, which in the USA is the domain of the Nuclear Regulatory Commission. The NRC defines, and subjects to a general license for use, "small quantities of source material" below 1.5 kg; see 10 CFR 40.22. So if you play around with some introductory uranium chemistry, start small (with a couple grams of material) to avoid the prospect of a soul-crushing run-in with regulators.

How to obtain uranium: You have two choices. First choice is to buy uranium on eBay, where there are regular sellers of compounds like uranyl nitrate and oxide. Depending on your focus, you might be interested to know if your uranium source is "depleted" (low in the U-235 isotope) or "natural" (0.72% U-235). Typically, commercial uranium compounds are made from depleted uranium (cheaply available from the nuclear fuel industry), while those prepared from uranium ore directly are natural. Your second choice is to refine uranium from a concentrated ore specimen. This process is not difficult (see my website link below), but it does generate a lot of waste that can't be put down your drain.
Basic chemical overview: Aqueous uranium chemistry is dominated by the uranyl ion (UO2)2+, with U in the U(VI) oxidation state. This is a brightly-colored, greenish-yellow, UV-fluorescent species. Uranyl compounds are generally soluble in acids, and precipitate as marginally-soluble yellow to orange uranate and diuranate salts with alkalis. Uranium in its lower (IV) oxidation state is sometimes encountered in the form of the dioxide UO2 and the green tetrafluoride, UF4. These compounds are not appreciably water-soluble and in order to dissolve uranium in these forms, it must be oxidized to (VI) with an appropriate reagent. Uranium metal is very hard to prepare in small quantities and you will probably not get an opportunity to buy it in metallic form either.
Suggestions for chemistry of interest: Uranium is unusual chemically in a few respects. Consider its nearly-insoluble peroxide: no other naturally-occurring elements have an insoluble peroxide at acid pH. Uranium forms some commercially-interesting complexes, like the uranyltricarbonate anion (which is soluble in basic solutions, in which most transition metals precipitate) and the uranyl nitrate-tributyl phosphate complex (which forms the basis of liquid-liquid solvent extraction of U and Pu in nuclear fuel reprocessing), and a peroxo complex that is vivid blood-red. You can play with this chemistry at home because the other chemicals needed are ordinary. TBP has to be ordered from a chemical supplier, but you shouldn't be given trouble for it. Uranium offers interesting opportunities for radiochemistry. Prepared uranium--depleted or natural--quickly builds up an equilibrium concentration of U-238 decay daughters Th-234 and Pa-234. These are beta- and gamma-emitting nuclides, whereas the parent U-238 only emits alpha particles. Thus, it is fun to see in any given chemical experiment with uranium if the apparent activity (on a common beta-gamma sensitive Geiger counter) follows the uranium itself or not. Freshly-purified uranium compounds will seem minimally radioactive, but after a couple months Th and Pa are back in the uranium! The waste from re-purifying daughter-contaminated uranium compounds may be left around to decay, and will exhibit the easily-measurable half life about about three weeks due to the Th-234.
My own background: see my blog posts about household uranium chemistry here: http://carlwillis.wordpress.com/...
Dabbling in uranium chemistry is fun for the whole family, educational, and it ain't gonna kill you or the neighborhood as long as common sense prevails.

Below: uranium compounds made by safe and responsible household techniques. See website for details.

Posted by Carol Willis on Quora.com


(Edited to make clear that the majority of this post was cut and pasted from elsewhere)

[Edited on 5-12-2017 by Bert]

woelen - 5-12-2017 at 05:31

Maybe in the USA it is possible to obtain uranium compounds fairly easily. Where I live, it is really really difficult to obtain uranium compounds. I was very lucky to get a sample of a few grams of uranyl nitrate in the form of some crystalline lumps. I do not use that for experiments (it is a too small amount), I put it in a vial and use it as nice looking sample. In the Netherlands (and probably in the entire EU) it is not wise to tell that you are doing experiments with uranium at home. I am quite sure that you will have a visit and that a hazmat team will take away all your nice uranium stuff.

A few years ago I was given a few grams of finely ground pitchblende (a dark green ore, insoluble in water, having formula U3O8, I do not know whether it is natural or artificial/depleted). I dissolved a small spatula of this in nitric acid and did a little experimenting with it (I obtained a lime green solution and I made the pale yellow insoluble peroxo complex UO4.2H2O), but this was very small scale. Doing lots of experiments with uranium simply cannot be safely done in the Netherlands.

Bert - 5-12-2017 at 09:31


Quote:

Dabbling in uranium chemistry is fun for the whole family, educational, and it ain't gonna kill you or the neighborhood as long as common sense prevails. 


Sense ain't common.

Carl Willis mentions degrees in both chemistry and nuclear engineering. Apparently, Carl also works in these fields professionally.

I would expect that certain things which appear to be common sense for Carl might not be so obvious to some others without his background?

Carl, if you happen to stop by here?

Could you please describe a safe, effective and responsible amateur scheme for storage and handling of lab wastes and radioactive residues? Also your thoughts on a home experimenter concentrating or releasing other radioactive substances found in natural Uranium ore. The ones Mmme. Currie occasionaly walked around with in her lab coat pocket, you know?

Extra points if the amateur handling scheme for nuclear materials and radioactive waste meets the letter of USA legal requirements, rather than being judged to be all right by yourself as "too small scale to matter".

Believe me, I am all too familiar with the variance possible between being sensible/safe and being legal.




Fig01_U238_decay_chain.png - 34kB

(Edited by Bert on noticing that the post by VSEPR_VOID was a cut & paste of someone else's work, thinking that authorship needed to be stated more obviously)


[Edited on 5-12-2017 by Bert]

[Edited on 5-12-2017 by Bert]

MrHomeScientist - 5-12-2017 at 11:26

VSEPR_VOID, you might want to be more clear next time when you post something that isn't yours. At least enclose it in quote blocks and link to where you copy/pasted it from. The footnote at the end about it being posted on Quora is easily missed and isn't a great way to attribute something.

Here is the original source: https://www.quora.com/I-would-like-to-study-the-chemistry-of...