Sciencemadness Discussion Board - Dissolving niobium metal

Dissolving niobium metal

woelen - 22-11-2005 at 04:45

I purchased some elemental niobium metal of high purity in the form of very thin sheets and I want to do some experiments with salts, containing this metal.
I found, however, that this metal is really inert. Does one of you know a means to dissolve this metal in an aqueous liquid, being acidic, alkaline, oxidizing, whatever? I prefer not to use fused salts or alkalies for dissolving the metal.

[Edited on 22-11-2005 by woelen]

The_Davster - 22-11-2005 at 05:58

I hate it when books do this....
From Patnaik P's Handbook of Inorganic Chemistry
"soluble in HF and fused alkali hydroxides" "insoluble in aquaregia"
From Greemwood Ernshaw's Chemistry of the elements
"vanadium and niobium are attacked by hot concentrated mineral acids, but are resistant to fused alkali"

EDIT: Perhaps an electrolytic dissolution? Or does the form of the metal not allow this?

[Edited on 22-11-2005 by rogue chemist]

chromium - 22-11-2005 at 07:25

Connect it as anode in electrolyte cell with acid as electrolyte (as rogue chemist already pointed out). If this does not work try to reflux it with boiling 70% sulfuric acid. If this too does not work then you probably have to find some HF.

IPN - 22-11-2005 at 07:29

From "A Treatise on Chemistry by H.E. Roscoe (Vol IIb 1880)" :

Quote:

It is hardly attacked by hydrochloric or nitric acid or aqua-regia even when heated, but dissolves in concentrated sulphuric acid, yeilding a colourless liquid.

BromicAcid - 22-11-2005 at 18:22

Electrolysis with a sheet as the anode and another as the cathode using AC in hydrochloric acid. Nothing stands up to that nothing.....

Or as Hawley's says

Quote:

Not attacked by nitric acid up to 100C, but vigorously attacked by a mixture of nitric and hydrofluoric acids. Hot concentrated hydrochloric acid, sulfuric acid, and phosphoric acid attack it, but hot concentrated nitric acid does not. Unaffected at room temperature by most acids and by aqua regia. It is attacked by alkaline soluitons to some extent at all temperatures.

I am a fish - 26-11-2005 at 04:45

Using hydrofluoric acid is a viable and resonably safe option if you generate it in situ.

Place the niobium in dilute hydrochloric acid, and then add a small quantity of sodium fluoride solution. Once the resulting hydrofluoric acid has reacted with the metal, add more sodium fluoride solution, and so on. If done carefully, only a small amount of hydrogen fluoride will be present in the reaction mixture at any one time.

hobbylab - 29-11-2005 at 04:43

Unless niobium fluoride is insoluble I don't see a need for adding more fluoride?

chloric1 - 29-11-2005 at 12:19

isn't niobium more closely related to titanium chemically. I have somewhere patent literature which suggest etching titanium in hot oxalic acid before plating. I also have seen compatability tables that suggest titanium is not recommended for working with oxalic acid. Now the attack may be slow and gradual but a pump recirculating system comes to mind. Constant flowing of a hot solution of oxalic acid over the niobium should facilitate faster dissolution. A peristaltic pump would be idea here.

[Edited on 11/29/2005 by chloric1]

neutrino - 29-11-2005 at 14:44

>Unless niobium fluoride is insoluble I don't see a need for adding more fluoride?

It may form a stable fluoride complex when dissolving the metal. The same thing happens when dissolving titanium by this method, so a fluoride must be continuously added.

woelen - 30-11-2005 at 01:09

I'm still waiting for my niobium metal to arrive with the post, I expected it quite some days ago already

. As soon as it arrives, I'll test all your suggestions and then we will know whether the fluoride method works for niobium as well. It indeed works very well for titanium.

[offtopic]
I have an experiment on that in the riddles section on my website. I do not understand the observations over there, due to very weird results. Any ideas are welcome.
[/offtopic]

@Hobbylab: With adding more and more fluoride, it is meant that fluoride is added in small steps. Each step dissolves just a little of the niobium metal and when all fluoride is used up, a little more is added, until all of the metal is dissolved. That is the idea behind it. The reason for doing it this way is to have as little as necessary of free HF around. That stuff is NASTY.

woelen - 14-12-2005 at 10:42

Finally I received my niobium metal

. I did some experiments with it, trying to dissolve it.

I took a small piece and put this in 10% HCl. That does not do anything, as expected. Next I added a pinch of NaF, which dissolves quickly. Still, this does not do anything at all, while such a solution really works nice for dissolving titanium.

Next, I took a larger part of niobium and did electrolysis, with a carbon cathode and a niobium anode. As electrolyte I used a 10% HCl solution, reagent grade.

At 3V no reaction occurs at all. I raised the voltage to 4 V. Some H2 bubbles from the cathode, no gas is formed at the anode. This lasts for a few seconds, the reaction comes to a halt within a second or three. Next, I pumped up the voltage again, this gives some H2 but only for a few seconds. Finally, I raised the voltage to 30 V (yes, 30 V!!). This results in formation of some H2 at the cathode, but again, the reaction comes to a halt after a few seconds. The anode becomes passivated and non-conductive. It is covered by a beautiful blue, non-conductive layer, which protects the underlying metal REALLY good. This result is so amazing, that I want to share it with you. I made pictures of the piece of niobium, which served as anode. The blue part was under the HCl, the metallic part was above the liquid and there, the copper wire was connected by means of a small clamp. The blue layer is VERY inert. It cannot be removed by applying concentrated HCl and also rubbing it does not remove it.

Here follow two pictures of the piece of niobium metal. This is a piece of 2.7 grams and the size of the piece is approximately 3.5 cm at its longest edge.

http://woelen.scheikunde.net/science/chem/pics/niobium1.jpg
http://woelen.scheikunde.net/science/chem/pics/niobium2.jpg

Does anyone of you have a nice explanation for these observations?

I hoped a little that I would have an anode, which would be very inert, allowing me to do electrolysis without pulverization, such as with graphite anodes. Indeed, it does not pulverize, nor does it dissolve

, but is becomes totally non-conductive due to the blue layer

I like it!

chloric1 - 14-12-2005 at 10:52

Woeler you are becoming one of my favorite members here!

You always provide stunning visuals, especially on your website. Niobium is a valve metal like titanium and tantalum. That means a very inert oxide layer is deposited on the metals surface. The color is a result of the thickness of the oxide and how it bends light. This anodizing process is very popular with metallurgist and jewlers because there is no need for expensive dies and the color is voltage controlled. What you need is a 3 amp variac transformer and a rectifing diode set rated over 100 V. you can create many colors at voltages between 0 up to I think 80 or 90 volts DC.

12AX7 - 14-12-2005 at 13:07

Ah, looks like the colors I've seen on pieces of titanium I've induction-heated to yellow incandescence. Those reactive/refractory metals have wonderful colors, don't they?

I guess you should try AC then, that was suggested. Might have to start with a lot of negative voltage though, depending on the rectification effect of the oxide, its thickness, and if it reduces very well at all...

Could you do an alkali fusion with it?

Tim

IrC - 14-12-2005 at 14:48

Just for fun I started googling niobium and niobium chloride, as I have several sheets of the stuff and was going one day to play with this neat element. In most of the information they state that the chloride is yellow. Finally I found mention of niobium IV chloride as being violet-black:

http://www.webelements.com/webelements/compounds/text/Nb/Cl4...

Below are a few links that are interesting.

Read the chart on this page for corrosion resistance: http://www.rembar.com/niobium.htm

https://fscimage.fishersci.com/msds/58773.htm This page shows the chloride as a yellow solid with real unfriendly toxicology.

[Edited on 14-12-2005 by IrC]

12AX7 - 14-12-2005 at 15:00

Hum, suprised it's that nasty. I'd think it would be relatively harmless besides hydrolysis (as with TiCl4). Isn't Nb inert in the body, or is that just the oxide on the metal?

Tim

Fleaker - 14-12-2005 at 15:28

12AX7, the metal may be inert, but the ion could be a different story. Platinum salts are a good example, you can swallow a nugget of elemental Pt and come to no harm, but look at all of those chemotherapy drugs (cisplatin and the like), they aren't exactly the best for you.

IrC, would you care to trade a few grams of that niobium for some titanium alloy pieces?

Nice job Woelen! That is an interesting blue coating. Have you tried hot aqua regia (won't dissolve titanium, but still worth a try) or other concentrated mineral acids? If they do not work, perhaps an alkali fusion would be in order :-/ Although, (purely speculation here) you could heat some of the plate in a sealed container with bromine or chlorine gas to oxidize the metal.

[Edited on 14-12-2005 by Fleaker]

IrC - 14-12-2005 at 21:02

I think 12AX7 said something about needing some titanium, maybe he has something to trade, only small amounts in any trading however as it took me a long time to find all this stuff and I mostly keep it for strange experiments which I only do after midnight. Seems daylight erases my creativity. Actually have titanium floating out the ying yang, so I don't need that, maybe something else. I was thinking woelen made a chloride of niobium (IV) coating, unless he just invented a cool way to anodize niobium. Is that possible with his setup I wonder. 12AX7 just read the fishersci link I posted as to toxicity. I think woelen should read the table in the rembar link, it clearly gives some chemicals to use for reacting niobium. Fleaker U2U me your email and I will send you my list of what I have, way too big to post and I really don't want it public anyway. Might be something we can work on trading about, possibly sending whatever with the kaowool, I'm not in a super hurry to get it right away anyway as I'm in the middle of another project not involving my high temperature madness right at the moment. I actually was thinking some kaowool I will dedicate to an annealing box for glass tubing and use the rest for the quartz tube furnace.

[Edited on 15-12-2005 by IrC]

woelen - 16-12-2005 at 12:31

I've read the rembar link and I tried some of the combinations from that site. It allows me to dissolve some niobium, but at a VERY low rate. Practically, it still is insoluble.

I did some further experimenting with the electrolysis (not yet AC, I need to make a safe provision for that, I don't want to do that directly off the wall-outlet anymore, after I had a shortcircuit

because the electrodes touched each other under water with a few drops of acid in it).

The blue color is not due to niobium (IV) chloride. Exactly the same blue color is obtained with lab grade nitric acid as electrolyte.
The color indeed depends on the voltage applied. I can get light yellow, bronze, shades of brown/green and blue.

In order to keep this post short, I want to refer to the page I added to my website. I contains all things I did with the niobium metal and its solutions. This is really interesting stuff and I certainly will delve deeper into this. The URL is

http://woelen.scheikunde.net/science/chem/exps/niobium/index...

IrC - 16-12-2005 at 13:39

Cool. You should go to the hardware store and buy one of those light bulb sockets that mounts flat onto wood or a box or whatever. Put the socket in series with your wall current (line side not neutral, thats the smaller blade, the wider blade is the neutral) to your electrodes. Then you have no short circuit worries, and can get an idea of current flow by watching the brightness of the light. You can even control things by choosing the wattage of the bulb, and colored lights such as red ones look neat and are easier on the eyes. Kind of a poor mans current meter and short circuit protection combo. I have used a setup like this for years to test high power audio amps, so that when the biasing is optimal the lamp filament dims down to a null, and of course full brightness equals a bad transistor in the output stage (or in your case shorted electrodes in the cell).

Transformer? Then he would not have the cool light and raw AC on the bench. Where is the danger in this I ask. There must be at least some danger or it is not mad science.

[Edited on 17-12-2005 by IrC]

12AX7 - 16-12-2005 at 14:29

...Or get a fricking transformer...YIKES!

They have those things at RadioShack you know.

The_Davster - 10-6-2007 at 17:15

Finally found my niobium in the lab! I have been wanting to try this for a while, I really wish I had a 30V source, All I got was the brown/bronze colour at 12V

anodized Nb 12V.JPG - 11kB

The_Davster - 10-6-2007 at 17:39

Heh, forgot about the -12V line on the PSU, instant 24V

Jdurg - 10-6-2007 at 17:50

Niobium is one of the coolest transition metals in the periodic table. The sheer number of colors you can get through anodization is remarkable. The best part is that the coloring is consistent and looks almost like paint as opposed to some other anodization where it seems more like tarnish than coloring. (Though I will say that potassium has one of the most beautiful oxidation colors on it when it is JUST starting to oxidize. I almost wish I could ampoule a sample of it right when that faint purple/blue hue first hits).

The_Davster - 10-6-2007 at 20:17

Hmm I wonder if tantalum does anything similar?
I have some tantalum in the same form as the niobium, 1/4" tubes. I will have to try this again with it.

UnintentionalChaos - 10-6-2007 at 20:39

Anyone wanting to play with niobium should check out this source:
http://theringlord.com/cart/shopdisplayproducts.asp?id=126&a...
It helps to have diverse and bizarre hobbies

I'm sure its nowhere near the cheapest out there, but the supply is consistent, the source is well respected within the chainmaille community (shipping is not too fast if you're in the US though), and they sell small quantities to anyone. They also have 99.9% fine silver wire and titanium wire.

The_Davster - 10-6-2007 at 21:38

From that site:

Wow, too bad they do not list voltages to make them.

EDIT: not sure if this image stretches anyone's screes resolution, mine is fine, but on high res. Let me know if it does and I'll remove it.

[Edited on 10-6-2007 by The_Davster]

woelen - 10-6-2007 at 22:48

This really is cool. I now have a DC power supply, which can give any voltage between 0 volts and 400 volts and I'll definitely try with that and see what colors I can get with the different voltages.

Engager - 1-7-2007 at 03:31

Best solvent for niobium and thantalium is HNO3+HF mixture. Blue layer is a film of oxide probably with some oxychloride contamination. Similar things happen with Ti, Zr, and Ta, after the breach oxide film appears almost momentaly and reduces current density on electrode to hardly measurable level. This is why Ta and Ti are ofter used as substrates for anodes. Color of oxide film depends from it's thickness and may vary in big interval.

Below is picture of my niobium metall sample, i can post Ta plates picture if requested.

franklyn - 1-7-2007 at 04:26

Hmm I thought that Aqua Regia dissolved everything ( except it's container )

Common laundry full strength NaClO solution is an extremely corrosive electrolyte
and is easy enough to try. You don't need to go over 12 volts unless you're
trying for cold fusion

DerAlte - 1-7-2007 at 20:38

Slightly OT, but I'm on an elecrolysis kick. Is niobium any good for an anode for anodic oxidation? Seems to resist fairly heroic efforts to oxidize, in the general sense...

Regards,

DerAlte

Fleaker - 1-7-2007 at 20:43

Actually, I recall Woelen mentioning his electrochem experiments being ruined by its blue oxide layer that just won't dissolve.

DerAlte - 1-7-2007 at 21:21

Sorry. stupid of me. It happens to be a main point of the thread. Must be losing my marbles...

The_Davster - 2-7-2007 at 12:19

Yeah, the oxide layer is completly unconductive. The electrolysis runs for a few seconds colouring the anode, then the current drops to zero.

Eclectic - 2-7-2007 at 12:40

You could try the same sort of surface treatments that work on titanium if you just happen to have niobium but no titanium.

12AX7 - 2-7-2007 at 13:52

Incidentially, I have "burned" titanium in ~30% sulfuric acid with more than 20 volts. Up around 100V, it sputters and makes some sort of aerosol, probably acid.

Might be a little too strong... the same pitted and corroded aluminum as well.

I would be interested to know just how high the voltage can go. Eventually, it's going to tunnel through and erode or dissolve (or at least form a sol of oxide crud). I'll be damned if it goes beyond, say, 1000V!

Tim

not_important - 2-7-2007 at 23:23

You can exceed the dielectric strength of the oxide, just as with any film or sheet of insulating material. The breakthrough, in effect discharging a capacitor, tends to vapourise some of the the underling metal and the electrolyte near the breakthough; the vapourised metal generally is going to react with the electrolyte as well.

UnintentionalChaos - 29-7-2007 at 18:46

Time for a thread ressurection! I managed to attack some niobium wire to a visual extent. Who knows how long it would take to fully dissolve. Basically, I plopped the thing in very strong lye with a dash of dilute H2O2 for added flavor. In a few hours, I've gone from polished , shiny metal, to grainy, etched looking metal, although the extent of the dissolution was not measurable with my calipers. If it sat for a week or two, there might be some more significant results, so I'll report back.

[Edited on 7-29-07 by UnintentionalChaos]

Xenoid - 29-7-2007 at 23:15

Quote:

Originally posted by not_important
You can exceed the dielectric strength of the oxide, just as with any film or sheet of insulating material. The breakthrough, in effect discharging a capacitor, tends to vapourise some of the the underling metal and the electrolyte near the breakthough; the vapourised metal generally is going to react with the electrolyte as well.

Actually, an interesting feature of these "valve metal" oxide layers is that they exhibit electroluminescence. I recently stumbled on the following article "Electroluminescent Rectifiers" by Norman Stanley in his "Chemistry Corner"

http://www.sas.org/E-Bulletin/2001-11-16/chem/column.html

Quote:
"At the outset of the formation process, sparking will occur on the surface of the aluminum due to breakdown of the thin oxide layer; this will subside as the layer thickens. However a very interesting residual effect remains: If the plates are observed in a darkened room they will be seen to glow with a uniform soft white luminescence. Presumably this is caused by reverse current leakage, though no individual sparking is seen. Whether it is due to micro-sparking or some more esoteric effect I don't know. Investigating this by making a cell that can be observed microscopically should make an excellent amateur project. "

The effect that he describes, refers to Al plates in borax solution, sort of like an early version of an LED

Lots of scope here for amateur investigation, different metals, electrolytes, voltages, layer thickness etc. etc...

Xenoid

indigofuzzy - 7-7-2009 at 13:48

It doesn't look like anyone else has hit on this yet:
The colors on anodized niobium are caused by interference. (The same was as colors on an oil slick.)
The anodizing voltage affects the thickness of the oxide layer, which is only a few tens of nanometers thick.

An explanation can be found here: http://www.sozra.com/niobium.html
Be forewarned: this was not written for technical folks, and may seem a bit "dumbed down".

I personally own around a dozen pieces of Niobium jewelry. Sadly, this is the only niobium I have on hand, so I'm not too willing to do chemical experiments on it.

For what it's worth, some beautiful anodized niobium pictures:
http://www.sozra.com/Merchant2/merchant.mvc?Screen=PROD&...
http://www.sozra.com/Merchant2/merchant.mvc?Screen=PROD&...

UnintentionalChaos - 7-7-2009 at 14:00

Long past-due update on that Nb. There never was much dissolution beyond a surface etching.

For anodization, also see this guy: http://www.mrtitanium.com

Jewelry supply places sell variable-voltage sources precisely for anodizing titanium and niobium jewelry, although they are very expensive. I know some people who do this, so it is definetly possible if you have a precisely controlled voltage source. The typical recommended electrolyte is trisodium phosphate.

Come to think of it, I never bothered to test HF on the stuff. 1M HF tears titanium a new one in a few minutes, so perhaps Niobium will be similar.

Eclectic - 17-2-2010 at 01:35

Mixed concentrated sulfuric and nitric acid is supposed to dissolve Niobium, and well as sulfuric + H2O2.

Also electrolysis in alcohols made conductive with ammonium chloride or NaOR seems to produce distillable alcoholates.

[Edited on 2-17-2010 by Eclectic]

blogfast25 - 17-2-2010 at 09:54

Only HF solution or anhydrous, IMHO. Oxidising acids should only yield Nb2O5, I feel.

It does quite readily react with O2 and Cl2 with heat applied.

Fusion with a KOH/KClO3 mixture could yield niobate, which should hydrolyse quickly to Nb2O5 on dilution.

Apart from Nb2O5, NbCl5, NbF5 and the complex fluoroniobates, not much springs to mind in terms of Nb compounds.

Eclectic - 17-2-2010 at 10:46

http://www.4shared.com/file/104119863/7da5825b/Niobium.html

Jeeze, I just did 4 hours of googleing....over 100 pages read....

Niobium sulfates, peroxycomplexes, ammonium niobium oxalate....all water stable... and anodic dissolution in conductive anhydrous alcohols....

"It will never fly"

(Quite possibly dissolution of Nb2O5 needs VERY hot 93+% H2SO4 to proceed at useful rate))

[Edited on 2-17-2010 by Eclectic]

blogfast25 - 17-2-2010 at 13:01

But making Niobium metal (from Nb2O5 thermite) is a whole lot more exciting than trying to dissolve it: temperatures in excess of 2,500 Celsius are needed...

Eclectic - 17-2-2010 at 13:07

I can get the metal, but compounds seem a bit scarce....there are some interesting catalyst applications.

blogfast25 - 17-2-2010 at 14:09

That's a very nicely rounded review you're unearthed there nonetheless.

But for backyard scientists it's hard to tell these, say oxychlorides from their chlorides, or oxyfluorides from their fluorides, without precise and extensive quantitative work... The furthest I might go some day is heat some Nb foil in dry Cl2 to get NbCl5. Woelen bought some of that some time ago.