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Author: Subject: Dehydrating Copper Nitrate
GhostofUnintentionalChaos
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[*] posted on 11-2-2007 at 20:17
Dehydrating Copper Nitrate


This is UnintentionalChaos. I tried to log on with a different computer and I couldn't remember the password, so I requested it to my e-mail, but I'm impatient and its taking a while, so I made another name temporarily.

Is it possible to dehydrate Cu(NO3)2 *2.5H2O (or *3H2O) without it decomposing or subliming, both of which occur at very low temperatures. Also, info on the compound seems to be scarce. Does anyone know just how soluble it is in alcohol? I may have to rethink my synth if it's not as soluble as I'd hoped.

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[*] posted on 11-2-2007 at 22:38


The only possibility that I know of is to react it with N2O5, which reacts with the water forming nitric acid.

The hydrated forms of cupric nitrate are reasonably soluble in alcohol, no idea on the anhydrous.
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[*] posted on 12-2-2007 at 01:33


Making anhydrous copper (II) nitrate is very difficult. This has eluded chemists till the sixties of the past century. It finally succeeded by dissolving copper in liquid NO2, in which some N2O5 was dissolved. The NO2 was diluted with some solvent (IIRC it was CH2Cl2) in order to make the reaction less vigorous. On evaporation of the solvent, the NO2 and N2O5 at reduced pressure, a solvated solid remains, Cu(NO3)2.xNO2 (I don't remember x anymore, I think it is 2). On careful heating of this solid (at 80 C or so), the NO2 slowly is given off and anhydrous copper (II) nitrate remains.

Anhydrous copper (II) nitrate is not a salt, but a volatile covalent compound.

Careful heating of Cu(NO3)2.3H2O leads to loss of both water and nitric acid and at best a basic copper nitrate is formed, something like Cu(OH)(NO3), but the ratio of OH(-) and NO3(-) may be different than I suggest with this formula. Stronger heating of Cu(NO3)2.3H2O leads to loss of all nitric acid in the form of acid, NO2 and O2. What remains is CuO.




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[*] posted on 12-2-2007 at 18:42


And superstrong dehydrating agents won't do the job? I wonder what will happen in i.e. the presence of absolute ethanol/acetone etc, or an active scavenger such as acetanhydride or trifluoro acetanhydride...
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[*] posted on 13-2-2007 at 10:28


Probably it will loose (some of) the water, but then you don't have it isolated. Probably that has been the lergest problem for preparing the anhydrous compound. Isolation probably leads to decomposition.



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[*] posted on 18-2-2007 at 23:39


I wonder if the water of hydration become remotely dissociated in alcohol solution. An insoluble dehydrating agent (MgSO4) could be stirred in, filtered out, and the alcohol evaporated off, leaving *hopefully* drier copper nitrate. To go ina completely different direction, does anyone know if tetraammine copper nitrate is alcohol soluble? I was thinking bubble dry ammonia gas through the alcohol solution to ppt the now explosive compound.

This is heading quickly toward energetics...I'd rather not break up the thread though.

[Edited on 19-2-2007 by GhostofUnintentionalChaos]
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AndersHoveland
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[*] posted on 28-9-2012 at 06:17


If you are trying to make real anhydrous Cu(NO3)2, you can probably forget ethanol. Anhydrous Cu(NO3)2 is a reactive nitrating agent. I think the anhydrous form is difficult to prepare, and cannot be made by simply heating the hydrate, as the thermal decomposition results in other products.

"at temperatures below –5°, the reaction of diethyl ether with copper(II) nitrate yields exclusively gaseous ethyl nitrite and complexed acetaldehyde. At higher temperatures, the acetaldehyde is further oxidised to acetate, with liberation of gaseous NO and NO2"
Anhydrous copper(II) nitrate as an oxidising agent. L. C. Coard and R. E. Powell

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[*] posted on 28-9-2012 at 10:20


I believe that tetraaminecopper (II) nitrate is insoluble in alcohols. The sulfate monohydrate is, and I believe that I recall a mention that while most tetraaminecopper (II) salts are mostly insoluble in alcohols, Schweizer's reagent reacts with alcohols. There is also this thread.
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[*] posted on 28-9-2012 at 15:34


Quote: Originally posted by Vargouille  
I believe that tetraaminecopper (II) nitrate is insoluble in alcohols.

I really do not think this is correct. If you read the synthesis for TACC, it shows that both copper(II) chlorate, and TACC are soluble in methanol. The TACC does not begin crystallizing out until the methanol begins to evaporate. Nitrates tend to be more solube than chlorate salts, btw.
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