Sciencemadness Discussion Board

TetraAmmineCopper(ii)Hydroxide double displacement reaction?

Fantasma4500 - 12-3-2018 at 03:39

theres quite little information out there about reactions of copper complexes with ammonia, but i got this idea that maybe the rather easily prepared TACH could be used to produce the nitrate variant, possibly with something like calcium nitrate, where the hydroxide would then form insoluble calcium hydroxide? if this type of reaction could work out, using other ions than nitrate could serve as an easy way to make tetraamines quickly, most interesting the more exotic, permanganate mayhabs?
of what i understand copper sulfate should react with calcium nitrate to form calcium sulfate and copper nitrate, so hydroxide version should also, except for if the ammonia complex would get in the way for the reaction

Akhil jain - 12-3-2018 at 12:45

I can't understand what you want to do?

symboom - 12-3-2018 at 22:14

I think i understand he is wondering if tetramine copper hydroxide solution to produce a nitrate variant if calcium nitrate is used will it form calcium hydroxide precipitate and tetramine copper nitrate i dont see why that would not form both start out as being very souble and the end copper hydroxide is insoluble.

This could be applied to make tetramine copper chlorate although with calcium hypochlorite that i would not know tge outcome

Fantasma4500 - 13-3-2018 at 08:17

may also be doable with other metals such as nickel complex, although i recall that is really only phosphide and hydrazine salts that has explosive potential, stoichiometry would probably be a problem in case youre aiming for nitrate complex, getting right ratios of calcium nitrate and copper hydroxide complex, supposing the copper hydroxide complexes solubility varies with ammonia concentration (which doesnt tend to be very constant as ammonia is quite volatile)

if the double displacement reaction would work it could make for quite doable production of tetraamminecopper(ii) bromate, where you wouldnt need to use ammonium bromate, which as per woelens demonstrations has very nasty properties, explodes when wet below 100*C iirc
the chlorate salt is also pretty annoying to form, i recall it was made using NaClO3 and CuSO4, long reaction time to shift equillibrium, poor yields, where calcium chlorate shouldnt be too hectic to produce
2NaClO3 + CaCl2 = Ca(ClO3)2 + 2NaCl to be followed by fractional crystallization

symboom - 13-3-2018 at 13:30

The more insouble tge better tetramine nickel perchlorate comes to mind it forms very easily and precipitates out it is formed by desolving nickel sulfate in ammonia and adding ammonium perchlorate other variations should be possible as long as the salt is soluble. Tetramine nickel perchlorate
Some reactions could possible avoid using water at all and solvate compounds using various amine based complexes

Fantasma4500 - 14-3-2018 at 04:31

what about nickel chlorate complex? could be more sensitive, depending on oxygen balance which i'd suppose would be positive, this could be used together with oxygen negative copper acetylide which already performs well with potassium chlorate 50:50 by weight as primary

if one were to start from NaClO4, CaCl2 could produce Ca(ClO4)2, again using NaCl's solubility "curve", should also be doable with more commercially available KClO4, ammonium variant is more difficult and usually a lot more expensive, maybe ammonium salt could be made from Ca(ClO4)2 with ammonium sulfate?

Ca(ClO4)2 + NiSO4[NH4] = Ni(ClO4)2[NH4] + CaSO4

i should maybe do a collection of calcium salts solubilities in solvents

edit:
it appears Ca(ClO4)2 is very soluble in acetone, EtOH and MeOH, while NaCl is sparingly

MeOH - 166 EtOH, 61.8 acetone, 237 MeOH
where NaCl is 1.5g for MeOH

[Edited on 14-3-2018 by Antiswat]

symboom - 14-3-2018 at 14:23

Antiswat dont worry about percipitating out calcium
The nickel complex is already insouble.

Im looking at soubility of ammonia gas in
Is soluble in chloroform, ether, ethanol, methanol

So other thing is look for a chlorate salt that is soluble in
Chloroform ether ethanol or methanol the same as the ammonia


Hexaaquacopper(II) chlorate Cu(ClO3)2•6H2O has a molecular weight of 338.54 and melts at 65 °C. Its solubility in water in g/100ml at different temperatures: 141 (0 °C) 164.4 (18 °C) 195.6 (45 °C) 332 (70 °C) g/100ml. It also dissolves in acetone and ethanol

Fantasma4500 - 18-3-2018 at 06:19

in that scenario you would be using tetraamminecopper ii acetate forming soluble calcium acetate, dealing with anhydrous ammonia sounds too technical for tetraammine salts, the whole idea is practicality where i would say ammonium hydroxide is a lot easier to get hands on or even make compared to anhydrous ammonia

AJKOER - 18-3-2018 at 11:35

Quote: Originally posted by Antiswat  
theres quite little information out there about reactions of copper complexes with ammonia, but i got this idea that maybe the rather easily prepared TACH could be used to produce the nitrate variant, possibly with something like calcium nitrate, where the hydroxide would then form insoluble calcium hydroxide? if this type of reaction could work out, using other ions than nitrate could serve as an easy way to make tetraamines quickly, most interesting the more exotic, permanganate mayhabs?
of what i understand copper sulfate should react with calcium nitrate to form calcium sulfate and copper nitrate, so hydroxide version should also, except for if the ammonia complex would get in the way for the reaction


I have examined a similar reaction, see my thread in the Energetic materials section: http://www.sciencemadness.org/talk/viewthread.php?tid=26053#...

I also recall looking at the action of [Cu(NH3)4](OH)2 on Mg(NO3)2 which clearly forms Mg(OH)2. The magnesium nitrate was prepared from freezing out K2SO4 from the reaction MgSO4 + 2 KNO3.
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Note: More correctly, I am citing the compound [Cu(NH3)4(H2O)2](OH)2 or tetramminediaquacopper(II) hydroxide. But, apparently, there is actually nothing sacred about the tetraamminediaquacopper cation as depending on the ammonia concentration in solution, one could have anywhere from [Cu(NH3)(H2O)5]2+ to [Cu(NH3)5(H2O)]2+, with the latter occurring in very concentrated ammonia solutions. There can also be cuprous, Cu(+), versions of these compounds created in the presence of excess copper.
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Some of the underlying chemistry, which is, in part, electrochemical in nature so adding a good electrolyte may promote the reaction:

2 Cu + 4 NH3 + 1/2 O2 (or H2O2) + H2O --> 2 [Cu(NH3)2]OH (see https://onlinelibrary.wiley.com/doi/abs/10.1002/bbpc.1963067... and reference below for half cell reactions)

2 [Cu(NH3)2]OH + 4 NH3 (aq) + 1/2 O2 + H2O --> 2 [Cu(NH3)4](OH)2

Cu + [Cu(NH3)4](OH)2 <---> 2 [Cu(NH3)2]OH

So, upon adding Mg(NO3)2 or MgSO4:

[Cu(NH3)4](OH)2 + MgSO4 --> Cu(NH3)4SO4 + Mg(OH)2 (s)

Note, some HNO2/NH4NO2 can apparently also be formed as, however, a side product. Please review my cited reference "Kinetics and Mechanism of Copper Dissolution In Aqueous Ammonia" fully available after signing on to ones Facebook account at http://www.academia.edu/292096/Kinetics_and_Mechanism_of_Cop...

If, as a consequence of a standard chemical side reaction, some NH4NO2/HNO2 is also be formed (per the cited reference) usually within the first 1O minutes of the reaction (per my observation), you can personally observed the decomposition of any formed HNO2/NH4NO2 (well, at least if one uses cheap household ammonia that foams owing to the presence of surfactants, which can actually create a column of foam as the decomposition takes place). Caution, in a sealed vessel, eruption/spillage can occur.

[Edited on 19-3-2018 by AJKOER]

symboom - 18-3-2018 at 14:08

Not liquid ammonia ammonia disolved in a solven other than water i know its not common normally ammonia gas is desolved in water

Copper nitrite ive never been able to get that to work even when hydrogen peroxide is added to a solution of amine copper complex copper peroxide is formed

Complexes with permanganate is difficult and they are very unstable diamine zinc permanganate is tge only one i have see form and that decomposes in hours

[Edited on 18-3-2018 by symboom]

[Edited on 18-3-2018 by symboom]

Fantasma4500 - 3-4-2018 at 00:22

we consider glass to be a boring reagent or chemical to handle because its very unreactive
"if it doesnt come with warning labels on it, then its simply not worth buying" -NurdRage ~2008??
the goal is a reactive chemical

very interesting with the magnesium, although magnesium hydroxide has low density so it would be tedious to remove by filtration, anyhow its proof of concept that the thing works, i wonder if there could be some catalytic processes going on to produce HNO2/NH4NO2?

aqeous ammonia is to be understood as NH4OH / NH3*H2O

about magnesium nitrate this is the solubility in 100g solvent
http://puu.sh/zVfWA.png
where K2SO4 is insoluble in both acetone and ethanol, most likely in methanol as well. you could probably precipitate it from solution like that

i think easiest for copper would be to get a piece of copper and run electrolysis with NaCl then ppt the copper with carbonate, the basic copper carbonate is much more stable then Cu(OH)2, where the hydroxide would decompose in solution below 100*C into copper oxide
knowing CuO dissolves in HCl within seconds i wonder how CuO works with ammonia? likely it would work fast. i guess adding ammonia to basic copper carbonate (mix of hydroxide and carbonate) as precipitated with sodium carbonate or likewise would react to form a mix of copper carbonate and hydroxide tetraammine complex
which wouldnt really stand against any of the reactions with calcium, but it should be kept in mind still

for making ionic copper readily available NaHSO4 would work, 150g NaHSO4 producing 100g CuSO4, along with some Na2SO4 which is easily fractionally crystallized off with a solubility of about 5g/100mL @0*C, i dont think going straight to copper hydroxide is a friendly method for anyone else others than an experienced monk. i did try with Ca(OH)2 and NaOH and it seemed super slow, the NH4OH would dissolve the formed copper hydroxide which could make reaction work a lot faster, but as AJKROER listed its adviced to add air or oxygen some other way which just makes the whole thing more tedious and not suitable to run in a closed vessel which you would usually want with something as volatile as ammonia