Fleaker
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Things to do with Nickel
Just purchased 500g of very decent quality nickel metal (4N5) 2cm by 2cm by .5cm thick. Having done so on an impulse, I'm now quite puzzled as to
what to do with it. Do any of you think it would be feasible to make Raney nickel catalyst? While I'm melting it I should probably cast some
thin plates for anode duty too.
Do nickel/chromium crucibles have good chemical resistance?
Thanks for any insight/ideas.
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BromicAcid
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Nickel is fun stuff to have around. Nickel crucibles are great for their chemical resistance, noteably to bases. Nickel electrodes are also great to
have around. As to making Raney Nickel, that is just one of my someday fun projects. I precipitated nickel oxylate from nickel chloride and
decomposed it and I intend to heat that with aluminum powder to get the alloy which can then be treated with aqueous base. The reaction betwen nickel
and aluminum powder described as very vigorous by some members of this forum.
Also there are fun chemical experiments to do with it, such as attempting to acheive some of its higher oxidation states, I made a post on this awhile
back and put up the relevent data on some of the information I found on high oxidation state nickel. Of course don't forget its possibilites for
catalysis of other reactions, and also making lab ware with it, I bought mine in the form of rods and dissolved them by using them as anodes in
electrolysis leaving sharp points at the ends, these have become very utilitarian in my lab, their chemical resistance combined with their strength
making them great to use.
I could go on and on about nickel but there really is a lot to do with it, so have fun!
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JohnWW
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Oh yes. I am sure that nickel could be used for many things for which the much more expensive palladium and platinum are used. As well as crucibles
and implements requiring corrosion resistance, it can substitute for Pd and Pt for many applications as an heterogenous catalyst, particularly where
the absorption of hydrogen is required for hydrogenation or catalytic reduction. However, for this application it would not be as efficient as
palladium or platinum.
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Fleaker
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It is true that nickel catalysts (Raney or Urushibara) are not quite as active as palladium on carbon or platinum but when one considers their price
and relative easy of preparation, they become more attractive. I have a friend who is/was doing a college study of the effectiveness of Urushibara
catalysts in hydrogenation and had some interesting results.
After reading Bromic's thread on electrochemical sodium (the one with the NaOH) I might use some of this nickel for making some large electrodes.
I wonder how malleable nickel is? Do you think I could flatten it out on anvil or would it shatter?
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12AX7
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Should be about as ductile as copper. If nothing else it can be annealed or hot forged as copper or (pure) iron, both of which it closely resembles,
chemically and metallurgically.
Tim
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S.C. Wack
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Raney alloy
THE SKIP THIS, ITS OFF-TOPIC PART:
I was having a little discussion with ning at WD some months ago, causing me to separate a pile of precursor to/prep/uses of substituted cinnamic acid
articles from a much larger pile, and look through them again. He posted a couple of oxidation of subs. cinnamic acid articles that I hadn't seen
before, as I was more interested in reduction. I had earlier lost interest in using typical hydrogenation cats. or that much Na to give the saturated
cpd., then using an inorganic chloride to give the amide with NH4OH.
The point is, just after ning wrapped up and there was nothing more to say, and it was a ketone thread anyways, I noticed that one of these
photocopies, JACS 62, 161 (1940) said: "a-Methyl-2,5-dimethoxyhydrocinnamide.-The amide was obtained by heating the corresponding hydrocinnamic
acid (above) in a stream of ammonia at 220-230° for two hours. Recrystallized from benzene it forms a finely crystalline powder melting at
99°." That was one of the more detailed steps in the article. OK, maybe urea could also give the amide. But there is still the hydrogenation, to
get to the a-methylphenylpropionic acid.
THE ON-TOPIC PART:
Then I noticed in JOC 22, 33 (1957): "DL-a-Methylhydrocinnamic acid (I) mas prepared in 95% yield by treating 30 g. of a-methylcinnamic acid and
99.8 g. of sodium hydroxide in 900 ml. of water with 90 g. of Raney nickel-aluminum alloy at 90°. The cooled filtrate and washings were stirred into
720 ml. of concd. hydrochloric acid and about 700 g. of ice and extracted with ether (600 + 300 + 300 ml.). The ether extracts were washed with 2 N
hydrochloric acid and with sodium chloride solution, dried, and evaporated. The distilled acid (b.p. 148-149'/9 mm., 116.5'/0.5 mm.)
solidified on chilling; m.p. 36-37°; yield 28.9 g. (95%). A sample crystallized from pentane in colorless prisms, m.p. 36.6-37.5° (lit. m.p.
37°)"
Nifty. The hydrogen from the dissolving Al (or additional aluminum) provides all you need, without pressure.
This led me to JOC 9, 175 (1944), which led me to 7, 587 (1942), 9, 1 (1944), and IEC Anal 15, 576 (1943). Wow. Following up led me to JOC 10, 233
(1945) and Chem Rev 89, 459 (1989).
In short, in alkali OH it reduces alkenoic acids to alkanoic, reduces or doesn't aryl ethers or unsaturated rings, quantitatively reduces halogen
functions (leaves them alone in organic acid), reduces the usual N-functions to amines like other hydrogenation cats. do (nitriles to aldehydes in
organic acid), ketones to alcohols or alkanes, or to amines when ammonia is used. And much more. There is a lot of unexplored/unpublished territory,
esp. in the reductive amination, nitro-whatever, and co-solvent dept. No doubt much private research has/will be done, there is a host of obvious new
substrates.
axehandle has all of my Chem Revs, BTW. Here are the mentioned alloy articles, as this does not seem to be as widely known as it should be.
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S.C. Wack
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The above reductions by Raney alloy collection of articles was uploaded too soon, I have three more, although no one else gives a shit/was unaware. They are JOC 27, 3873 (1962), Chem. Commun. 514 (2003), and JCS 531, (1966). Some
likely more interesting articles are unavailable to me.
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Fleaker
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Thanks very much for making those available to me, I appreciate it and I'll take a look asap.
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enima
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Raney alloy preparation.
Does anyone have information about making the alloy. I know its suppose to have 50/50 Ni-Al. Would one use the metal powders of each, mix them
together and slowly heat until they both become molten in a crucible?
Will either powder ignite during the heating process? A butane burner could be useful as it reaches a nice temp of 1300C.
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12AX7
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Aren't AlNi intermetallics exothermic? Powder could be quite interesting then, though not particularly useful!
The best way to prepare would be a vacuum or inert gas furnace capable of melting nickel, next to that you need a flux resistant to aluminum which
means no silicate flux like nickel would prefer. Fluorite may be able to do this, as IIRC its melting point is around there. For sure it forms low
eutectics will all sorts of things, but I don't know how many of those are aluminum-compatible. Oh, and use a good solid crucible also resistant
to aluminum and as resistant to fluorospar as possible (now that's a toughie).
Tim
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Fleaker
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I was going to do it in a fused quartz crucible (chemical compatibility there?) which would take the temperature well. I don't mixing the powders
and heating is necessary. I would probably melt the nickel and add the apporpriate mass of Al.
Oh by the way, took one of the nickel pieces to the anvil, and it's remarkably resilient to hammer strokes: no deformation whatsoever. I should
mention that it's very thick. I didn't have time to heat it however.
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BromicAcid
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Yes 12AX7, the reaction is a self-sustaining exotherm between the metals, not only has this been described by other members of this forum, but that is
what I ment by the two powders undergoing an 'very vigorous' reaction together.
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12AX7
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Say, is the powder like thermite, flash or what? 
Fused quartz might do it, but Al + SiO2 ~= Si + Al2O3 so it wouldn't really be preferrable if you want purity. I'd use sintered or fused
alumina or magnesia, whichever's cheaper..
BTW here's some typical data on nickel. Pretty ferric in characteristics, lack of transformation temperature and low curie point aside. http://www.matweb.com/search/SpecificMaterial.asp?bassnum=NL...
Tim
[Edited on 8-4-2005 by 12AX7]
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Fleaker
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I forgot about that (ref: Al+ SiO2). Alumina is cheaper.
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