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Romain
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Metathesis reaction to make copper (II) nitrate?
Hi everybody,
I'm new to the forum and English isn't my mother tongue so if I make any mistakes, please correct me.
I would like to know if the following reaction is viable:
2NH4NO3 + CuCO3 ⇋ (NH4)2CO3 + Cu(NO3)2
You just need to boil off the resulting solution to decompose the ammonium carbonate and you are left with copper (II) nitrate (hopefully).
I believe boilling the solution also drives the equilibrium to the right.
I don't want to try and see by myself because as I live in switzerland, it's extremely complicated to obtain chemicals.
Just to give you an idea, I have access to 13% ammonium nitrate fertilizer which I need to recrystalize multiple times to get a reasonably pure
product.
I don't have a dessicator so it takes several weeks total for 100 grams of ammonium nitrate!
The copper carbonate is difficult to produce too:
I start by electrolyzing a sodium bisulfate solution with copper electrodes to get copper a mixture of copper and sodium sulfate. Then I add some
sodium carbonate to precipitate copper carbonate which I still need to dry...
And I won't talk about NaOH, HCL, H₂SO₄, ...
So please help me with that reaction,
thanks a lot,
R.
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bismuthate
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Nope it won't work. Although using chemicals you have you could:
Option 1 heat sodium bisulfate with NaCl and lead the HCl gas into water. add this to amonium nitrate and distill the HNO3 or put copper in it and
lead the gas into water.
Option 2 mix NaHSO4 with NH4NO3 and distill the HNO3.
Option 1 variant B take the HCl and add H2O2 and copper to it. Then mix the CuCl2 with NH4NO3 anb decompose the NH4Cl.
Option 3 react CuSO4 with NH4NO3 and boil it down. Then separate the Cu(NO3)2 from the mix by dissolving it in ethanol.
I know that some reactions use HCl sorry.
[Edited on 23-12-2013 by bismuthate]
[Edited on 23-12-2013 by bismuthate]
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Romain
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Thanks for the fast reply!
Just wondering: why doesn't it work?
Also I unfortunately don't have a distillation apparatus . And I can't even make the
HCl because I don't have adequate glassware (yet). Your option 3 seems rather easy, so I will try it as soon as I can.
Though since I will need to make copper sulfate, it will take some time.
And I didn't mention H2O2: It costs 50$ a liter here. (for 3%)!
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bismuthate
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The reason is that ammonia is more reactive than copper so it will keep the strong nitrate ion and the copper will keep the less reactive carbonate
ion.
http://en.wikipedia.org/wiki/Reactivity_series
Read this. (ammonia would be much higher up than copper) As you go up the series the metals (ammonia behaves like a metal) want stronger anions and
the nitrate anion is much stronger than carbonate.
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barley81
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Bismuthate, that's false. You cannot say that carbonate is "less reactive" in the context of metathesis reactions. Such reactions are driven by
solubility and other equilibria, not by metals "wanting stronger anions." Ammonia does not behave much like a metal, either. The only setting where
that is true is Isaac Asimov's short story The Magnificent Possession [which is pretty interesting]. In some situations, the ammonium ion does behave
somewhat like alkali metal ions. Its size is close to that of a caesium ion. Wikipedia: "In terms of size, the ammonium cation
(r<sub>ionic</sub> = 175 pm) resembles the caesium cation (r<sub>ionic</sub> = 183 pm)."
I am not sure if the reaction between ammonium nitrate and copper carbonate actually works. Try and see, though the ammonium cation may not be acidic
enough to dissolve the CuCO3 at an acceptable rate. If it does work, it will probably involve boiling the mixture for a long time.
[Edited on 23-12-2013 by barley81]
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Romain
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Thank's for the reactivity series page. I'll read about it, it looks interesting.
And if what Bismuthate said is incorrect, is it still impossible to make copper nitrate via metathesis?
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bismuthate
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Ammonium behaves like a metal my appologies. Geeze I suck at explaining. Also I'm sorry about the mess up so everyone ignore my post as it is wrong.
I'm going to leave the explaining to the people who are much more qualified.
By the way check out this article ammonia could behave like a metal (although
that wasn't what I meant)
http://adsabs.harvard.edu/full/1954MNRAS.114..172B
[Edited on 23-12-2013 by bismuthate]
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blogfast25
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Quote: Originally posted by barley81  | I am not sure if the reaction between ammonium nitrate and copper carbonate actually works. Try and see, though the ammonium cation may not be acidic
enough to dissolve the CuCO3 at an acceptable rate. If it does work, it will probably involve boiling the mixture for a long time.
[Edited on 23-12-2013 by barley81] |
If it had anything to do with acidity of the ammonium ion then ammonium carbonate could never exist, instead it can exist both as a solid and in
solution.
The reason why this can't work is that ammonium carbonate is fairly soluble, much more than copper carbonate. In short, nothing will happen.
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Romain
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Ok thanks, I'll try the copper sulfate + ammonium nitrate method as soon as I can.
So in fact a metathesis reaction works if products are less soluble than reactants?
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TheChemiKid
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How do you plan to separate the copper nitrate and ammonium sulfate?
When the police come
\( * O * )/ ̿̿ ̿̿ ̿'̿'̵͇̿̿з=༼ ▀̿̿Ĺ̯̿̿▀̿ ̿ ༽
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bismuthate
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Copper nitrate is soluble in ethanol and ammonium sulphate is not.
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TheChemiKid
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Ok, that is a good method. I was just wondering if he knew how to separate them.
When the police come
\( * O * )/ ̿̿ ̿̿ ̿'̿'̵͇̿̿з=༼ ▀̿̿Ĺ̯̿̿▀̿ ̿ ༽
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WGTR
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Copper sulfate is not particularly soluble in ethanol either, but I couldn't tell you whether CuSO4 or (NH4)2SO4 is more or less
soluble than the other.
You could try boiling ammonium nitrate solution with quicklime to form calcium nitrate. The ammonia would boil away (watch
the fumes). Filter off the leftover slaked lime (it's caustic, but not very soluble).
2NH4NO3 + Ca(OH)2 --> Ca(NO3)2 + 2NH3 + 2H2O
Then mix the Ca(NO3)2 and CuSO4 together in water, and filter off the insoluble CaSO4:
Ca(NO3)2 + CuSO4 --> CaSO4 + Cu(NO3)2
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Romain
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The quicklime idea looks pretty good too, thanks! The only problem is I don't have quicklime, I don't know where to find some and if it is regulated
somehow.
But so far it's the best method as it also produces calcium sulfate, a useful dessicant.
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WGTR
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I suppose you could buy it from a garden store. I couldn't imagine it being restricted. But why buy it when you could make it?
Plante1999 published a short writeup on how to do this at this link.
I showed briefly how to make CaO in this thread where I built a small homemade electric kiln.
I've even done it in a small charcoal furnace on the front porch. It's best to get a pure CaCO3, but you can get it from seashells,
limestone rocks, some forms of chalk, etc. Of course, you can make CaCO3 from CaCl2 (desiccant) and Na2CO3 (washing
soda), both of which are available here in every grocery store.
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blogfast25
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In essence, yes, one of them:
AX(aq) + BY(s) → AY(aq) + BX(s)
Quicklime is easy to get and not really worth making yourself, IMHO. Get it from eBay. Slaked lime (Ca(OH)2, even easier to get) would work here too.
Bear in mind that CaSO4 is poorly soluble but not completely insoluble. Your Cu(NO3)2 will be slightly contaminated. Better would be to use Ba(NO3)2
but that's much harder to get and much more expensive.
Cu(NO3)2 is also hard to crystallise because it so damn soluble (83.5 g Cu(NO3)2 per 100 g of water @ 0 C, Wiki). The solid is deliquiescent, at least
in my experience.
[Edited on 24-12-2013 by blogfast25]
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Romain
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I may order Ca(OH)2 on ebay but I'll first try to find some at my garden store.
Here in switerland, a lot of chemical are regulated or unavailable so I don't think it's the solution though.
I may also try to make some Ca(OH)2 but I don't want to get too fancy and build a frunace.
And for the solubility porblem of Cu(NO3)2, if I order some Ca(OH)2 on ebay, I will also order some silica gel to dessicate the copper nitrate.
Or maybe a few hours in my oven at 200°C is enough to dry it?
Anyway, thanks a lot to everybody for your answers, I didn't expect to get so many!
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blogfast25
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| Quote: Originally posted by Romain |
And for the solubility porblem of Cu(NO3)2, if I order some Ca(OH)2 on ebay, I will also order some silica gel to dessicate the copper nitrate.
Or maybe a few hours in my oven at 200°C is enough to dry it?
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Neither of these things will work. Silica gel isn't a very strong desiccant (more for keeping things dry than for drying things, there's a
difference).
Heating a hydrate like copper nitrate (there are acc. Wiki three hydrates: tri, hexa and hemipenta) will cause it to melt and dissolve in its own
crystal water. Trust me, I've been there...
Your best bet is probably to start from a quite concentrated solution of Cu(NO3)2 and gently boil this in until there is almost no liquid left. The
solid crystals are probably Cu(NO3)2.3H2O (hard to be sure without a two phase temperature diagram). Remove what liquid is left while still hot. After
cooling try storing in a CaCl2 desiccator.
I am of course assuming it is the hydrate you want, not the anhydrous salt.
[Edited on 24-12-2013 by blogfast25]
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Romain
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The goal of all this is to make copper nitrate flash powder so as to get a green flame and also to have a sample of copper nitrate to add to my
chemicals collection.
At first I thought of making some copper carbonate and add it to existing sodium nitrate flash powder but copper carbonate would slow down the
reaction.
I believe hydrated copper nitrate works for flash powders so I won't need to dehydrate it completly, but it's just a guess.
I also heard that anhydrous copper nitrate is way too reactive to be used in flash powders.
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blogfast25
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Depends what you call a flash powder. Best results would be obtained with an anhydrous nitrate. Cu(NO3)2 dehydrates well. Just keep heating until
steam evolution stops.
Re. reactivity, it depends largely on composition. For example, if you use Mg powder the amount (among other things) will determine how violent it is.
Cu(NO3)2 + 2 Mg === > CuO + N + 2 MgO
But with extra Mg, also:
CuO + Mg === > Cu + MgO, a lot more violent if both happen.
[Edited on 24-12-2013 by blogfast25]
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Marvin
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| Quote: Originally posted by blogfast25 | | Best results would be obtained with an anhydrous nitrate. Cu(NO3)2 dehydrates well. Just keep heating until steam evolution stops.
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My understanding is that the anhydrous salt cannot be made by drying the hydrate, it decomposes.
There are reports of solutions containing ammonium nitrate and copper salts spontaneously detonating during crystallisation. (Mellor). Might be best
to make it a different way.
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Romain
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When I say it's not suitable for flash powder, I mean it would make a very sensitive mixture that may deflagrate (or even detonate) upon impact or
friction.
I sure do not want that, I want a stable mixture that won't ignite spontaneously. I think I read somewhere that it's a very potent oxidized and I
thought it may make very reactive mixtures.
I just read on this thread that dehydrating copper nitrate is extremely difficult.$
And about solutions of ammonium nitrate and copper salts, perhaps it was copper chlorate in the solution? I know ammonium chlorate is extremely
unstable and explosive even in solution according to Wiki..
And now that I think of it, making copper chlorate could be another way of making green flash powder though if copper nitrate is reactive, copper
chlorate may be even more. What do you think?
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blogfast25
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Acc. to my CRC (just got it, best Crimbo present ever!) copper chlorate is highly soluble in water and forms a hexahydrate. Possibly even harder to
dehydrate than the nitrate...
Have you considered anhydrous CuSO4 as oxidiser?
Calcium sulphate (anh.) works very well for oxidising Al powder for instance: CaSO4 + 8/3 Al === > CaS + 4/3 Al2O3. Mixtures like that burn
fiercely hot when lit.
[Edited on 25-12-2013 by blogfast25]
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PHILOU Zrealone
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1°) The reaction you thought about of mixing CuCO3 and NH4NO3 should work but not the way you all think about... because:
a) NH4(+) is mildly acidic and so H2CO3 (H2O and CO2(g)) will be produced in some extend and thanks to heating, the gaseous CO2, will be expelled out
of the system.
b) NH3 is leading to tetraamino complexes with Cu(2+) what is also a driving force for the reaction
So
2CuCO3 + 4NH4NO3 --> Cu(NO3)2 + (NH3)4Cu(NO3)2 + 2CO2(g) + 2H2O
The same holds true for Cu(OH)2 and CuO...
2Cu(OH)2 + 4NH4NO3 --> Cu(NO3)2 + (NH3)4Cu(NO3)2 +4H2O
2CuO + 4NH4NO3 --> Cu(NO3)2 + (NH3)4Cu(NO3)2 +2H2O
The reactivity of the oxydation layer of Cu (CuCO3, Cu(OH)2 and CuO) towards NH4NO3 is the main reason for the uncompatibility of Cu and NH4NO3.
Tetraamino copper nitrate being a sensitizer of decomposition of NH4NO3.
2°) A flash powder with NaNO3 would be extremely detrimental to the integrity of the blue color from copper because Na produces a strongly remanent
yellow colour that will hide any blue or green shade. Better use KNO3!
Blue color can be obtained only at low temperature and flash powder would produce a very hot and bright flame inducing a shift to the white side of
the emission spectra (silvery light) this will hide the blue expression. Better find a colder flame!
Usually the blue color of copper is enhanced by the presence of chloride in the powder mix (PVC, CuCl2, Cu(OH)Cl, Cu(ClO4)2, K chlorate - perchlorate
or chloride, ...). Use sodium free ingredients in your powder (suggar and natural charcoal contains a lot of Na...)!
[Edited on 25-12-2013 by PHILOU Zrealone]
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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blogfast25
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PH Z:
I doubts if the acidity of ammonium is really enough. As stated above, it that was the case, (NH4)2CO3 solutions would 'self destruct'. Yet only on
heating do they lose CO2.
[Edited on 25-12-2013 by blogfast25]
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