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Sedit
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Just thought I would upload a couple pictures of the seperation process. I am far from documenting the entire thing which I will produce a very full
writeup and post it over at The Vespiary since we need more serious contributions over there.
Here is what it looks like after the addition of the Chloride salts to (aq)Ammonia Hydroxide. This picture does not show the light greenish blue
precipitate to well since there is only a little bit of the salt in this picture. This was just a preliminary run to test to see if my theory was
right but you can still see a small layer at the bottom of the flask. The deep blue color is from Copperamine complex formed with the ammonia
dissolved in the solution.
The solution is decanted and washed several times with H2O to remove the Cu from the mixture. At first the precipitate is light blue but the more you
wash it the greener it becomes until you have something that looks like this.
Sorry its not the best quality photo but I will work on better versions when I produce the final draft of my writeup which I will hopefully quantify
the entire composition of the coins recovering the metallic Copper as well the Nickle salts.
Once you have got it all washed nicely instead of filtering which is a pain in the ass I think your better to just add HCl at this point until you
have a transparent green solution and filter the NiCl2 and evaporate.
So what do yall think? Easier then dicking around with Selective precipitation using citrate salts or whatever was mentioned dont you think?
Knowledge is useless to useless people...
"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the
fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story
before."~Maynard James Keenan
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not_important
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Well, no, as nickel forms complexes with ammonia as well
From A Text-Book Of Inorganic Chemistry Vol-X Metallic Ammines by J.Newton Friend
http://www.archive.org/details/textbookofinorga025530mbp
an example
and Yes, because I'm sure the copper complex is more stable than the nickel, but I don't know by how much more; I question the completness of
separation.
[Edited on 30-3-2010 by not_important]
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Sedit
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As far as completeness I can reassure you that there is NO Cu left in the precipitated oxide. I know this because I turned it back to Nickel chloride
and precipitated it again showing No! dark blue solution this time. Only the precipitation of a green compound with the properties of NiO. Plus a
flame test and a prism assures me there is trace... if any Copper left.
This does however explain why when I first begin to base it with Ammonia hydroxide it forms alot of precipitate but further addition yeilds less
product and a darker blue solution. Presumably this is due to excess Ni turning into the amine complex as well but I am unsure at the moment.
In all honesty I doubt the validness of this reference after my personal observations. The nickle complex seems to form slightly if at all.
Knowledge is useless to useless people...
"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the
fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story
before."~Maynard James Keenan
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not_important
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`twould be useful to be able to peruse these:
http://openlibrary.org/b/OL186958M/formulas_and_stabilities_...
http://openlibrary.org/b/OL20031085M/Metal_ammine_formation_...
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Eclectic
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I suspect the difference in solubility between Ammonium Nickel Sulfate and any similar copper double salt or complex may be useful for separation, but
am having some trouble locating actual solubities for double salts....Simple enough to try.
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Sedit
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US Patent 4005031 - Nickel peroxide oxidizing agent
http://www.patentstorm.us/patents/4005031/description.html
This is the patent that gave me the idea on how to perform the seperation. They use Ammonia hydroxide to neutralize a solution of Nickle chloride to
precipitate it onto a carbon support as a finely divided oxide. They proceed further into the formation of Nickel peroxide but no where do they make
mention of the Ni forming a complex with the NH3. I have read papers describing such a complex and it confuses me as to why they would make no
mention of it in the patent.
It makes me wounder if the Chloride salt does not form this complex by precipitating the oxide at such a rate that it does not have the will to form
the complex in the Oxide state. I know what im getting is NiO but the qustion is if im losing yeilds while attempting to wash the Copper out.
Knowledge is useless to useless people...
"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the
fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story
before."~Maynard James Keenan
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not_important
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I think the reason there is no mention of the complex lies in They use Ammonia hydroxide to neutralize a solution, meaning they're not using
an excess of NH3. In the same way if you add NH3 (aq) to a solution of a copper salt, watching the pH or calculating the needed amount so as to just
react with all the anions, you get Cu(OH)2 ppt; more NH3 is needed to get the complex. And I'm sure the Cu complex is more stable than the Ni, but I
don't know how much more.
The reference I gave lists several complexes of NiCl2 with NH3. Like copper and cobalt the anhydrous salr reacts with dry ammonia, and hydrated forms
of M[(NH3)6Cl2 can be had from solutions of the halide on treating with ammonia; the Ni compound is obtained in crystals by addition
of NH3 and NH4Cl to reduce its solubility, while the copper one will form crystals by concentration in an atmosphere of ammonia.
And NH3 precipitates Ni(OH)2 at ordinary temperatures, heat converts it to NiO while oxidation, either chemical or electrolytic, converts it to
NiO(OH) or mixed Ni(III)/Ni(IV) hydrated oxides.
Attachment: BB643.pdf (120kB)
This file has been downloaded 696 times
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Sedit
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If it is indeed the case that Nickel forms a complex with Ammonia as well then what would be the reason that after isolation of the NiO and converting
it back to the chloride I once again precipitated it with more Ammonia hydroxide. This time (even after a couple attempts) there was no blue color at
all just more precipitated NiO.
If it does indeed form a complex like stated it should show some signs of a blue solution like what is reported correct?
I am possitive that this is Nickle because I reduced some last night and the powder was attracted to a magnet so theres no doubt at all that Nickle is
what im getting. Do you think theres a possibility that the solubility of the Nickle ammonia complex is very low and the precipitate is the complex
and not the Oxide like im assuming. I highly doubt it myself but just trying to figure this out because observation is going against all the
literature I'v been reading on Nickle salts reactions with ammonia.
I think perhaps next run I am going to wash the precipitate as before and reflux it in H2O for a while and see if I can detect the presence of NH3 in
the off gas.
Knowledge is useless to useless people...
"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the
fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story
before."~Maynard James Keenan
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not_important
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You shouldn't be getting NiO as a precipitate with NH3 unless the NH3 (aq) is dilute and the solution is hot.
The amino complex can be crystallised from aqueous NH3, but it is described as being distinctly blue.
It doesn't take pure Ni for the reduction product to be attracted to a magnet, a number of nickel alloys are magnetic. Magnetism is a good indicator
of having a high content of Fe/Co/Ni and in alloys possibly Mn. The colour of the ppt argues against a high content of anything but Ni, as Fe and Mn
would be sensitive to oxidation by air to give red-brown colours.
What coins were the starting point for this?
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JohnWW
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Quote: Originally posted by not_important  | (cut)
It doesn't take pure Ni for the reduction product to be attracted to a magnet, a number of nickel alloys are magnetic. Magnetism is a good indicator
of having a high content of Fe/Co/Ni and in alloys possibly Mn. The colour of the ppt argues against a high content of anything but Ni, as Fe and Mn
would be sensitive to oxidation by air to give red-brown colours.(cut) |
There is also a composition range of Cu-Mn alloys, containing no Fe or Co or Ni, that is ferromagnetic, although not as strongly as the latter. In
fact, I have what appears to be a bronze lamp-standard made of this ferromagnetic Cu-Mn alloy. However, the reason why V, Cr, Mn, Cu, and in general
nearly all their alloys, are not ferromagnetic, is because the electron spins of their unpaired "3d" electrons align in parallel but opposite
directions so that their magnetic moments cancel out, which is called antiferromagnetism. In Fe, Co, and Ni, these unpaired electrons spins are
aligned parallel in the same directions in magnetic "domains" - ferromagnetism.
Of course, the same also phenomenon occurs with the unpaired 4f and 5f electrons in the lanthanide amd actinide metals, also conferring
ferromagnetism, especially in those about the middle of the two series where the numbers of unpaired electrons are at a maximum.
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Sedit
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| Quote: Originally posted by not_important | You shouldn't be getting NiO as a precipitate with NH3 unless the NH3 (aq) is dilute and the solution is hot.
It doesn't take pure Ni for the reduction product to be attracted to a magnet, a number of nickel alloys are magnetic. Magnetism is a good indicator
of having a high content of Fe/Co/Ni and in alloys possibly Mn. The colour of the ppt argues against a high content of anything but Ni, as Fe and Mn
would be sensitive to oxidation by air to give red-brown colours.
What coins were the starting point for this?
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The coins are common US nickels dissolved sometime ago in HCl+H2O2 since a freind asked how to go about seperation I decided to try. The salt sat
there and turned into the oxides over time since I could never figure a means of seperation. Before this I just added HCl to the oxide powders afford
a deep greenish almost brown(very dark) salt solution.
There is trace amounts of Fe due to the water I was using for the initial test but this can be seen to precipitate out as a fine brown dust on the
Nickel on sitting. There is only trace amounts of Fe in there at best.
If it takes heat to make the oxide from the precipitate why is that not mentioned in the patent (did I over look something)and also why does this
precipitate not show the blue color mentioned but appears to have all the properties of NiO?
Im going to setup a spectroscope that I can take pictures with when I get time to see if I can post the spectrum of a flame test.
I got ALOT more dissolving in H2SO4 right now so I will perform more complete test when thats done but it is going boringly slow.
Knowledge is useless to useless people...
"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the
fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story
before."~Maynard James Keenan
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not_important
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| Quote: Originally posted by Sedit | ...(much snippage)...
If it takes heat to make the oxide from the precipitate why is that not mentioned in the patent (did I over look something)and also why does this
precipitate not show the blue color mentioned but appears to have all the properties of NiO?
Im going to setup a spectroscope that I can take pictures with when I get time to see if I can post the spectrum of a flame test.
... |
Well, possibly because
A) The patent says
| Quote: | | As used throughout this application, the term "nickel oxide" includes nickel hydroxide, nickel monoxide (NiO), nickel
sesquioxide (Ni2O3) and nickelic tetraoxide (Ni3O4) and mixtures of two or more of the foregoing. |
B) The patent is about producing "nickel peroxide" and not nickel oxide or hydroxide, which is mearly an incidental step along the way.
And ever reference I can find from Mellor and Friend to a recent one like the attached PDF all say that you get Ni(OH) from adding alkali hydroxides,
including aqueous NH3, to solutions of nickel salts. They also state that Ni(OH)2 is soluble in excess ammonia, which is why I asked about the coins;
the precipitate just does not sound like pure Ni(OH)2.
Attachment: On the existence of a nickel hydroxide phase which is neither a nor b.pdf (143kB)
This file has been downloaded 665 times
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Sedit
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Any suggestions on how to test between the hydroxide and the oxide when I attempt to perform this on a larger scale once they finish dissolving?
It's all got me a little curious, more so then I thought I would be over it, because it just don't seem to add up to reports. I guess is possible for
the Cu to be pushing it out simular to the common ion effect but I'll wait till I have more material to work with before making any assumptions.
Thanks for your input its been helpful as usual. Feel free to add anything else as you find it.
Various Ni(II) reactions:
http://www.public.asu.edu/~jpbirk/qual/qualanal/nickel.html
These explain a little of what I have been seeing and like you stated before the Ni(OH)2 dissolves in Excess NH3. At first there is a
large amount of precipitate with a faint blue color however more NH3 solution formed the deep blue you see leaving less precipitate. I think that
correct ratio is key to getting useful seperation of the two compounds.
I also will precipitate some of the solution next time time NaOH and use this as a standard in following test knowing that the NaOH should precipitate
both the Ni and Cu alllowing me to know exactly how much I should be recovering in the way of Ni(OH)2
Knowledge is useless to useless people...
"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the
fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story
before."~Maynard James Keenan
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