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Author: Subject: anyway to make [Ag(NH3)2]Cl? (having trouble)
Armus_
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[*] posted on 6-1-2020 at 20:07
anyway to make [Ag(NH3)2]Cl? (having trouble)


so im researching on this subject and im thinking to add silver chloride to an ammonium chloride solution to get this silver complex but for some reason it didnt work. why and how could i make [Ag(NH3)2]Cl using AgCl? (the AgCl was supposed to dissolve but it didnt)




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[*] posted on 6-1-2020 at 22:28


You need ammonia, not ammonium chloride.



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[*] posted on 6-1-2020 at 23:39


DraconicAcid is right.

I want to add something to this. Silver ions and ammonia can react to form highly explosive fulminating silver. Sometimes this can form a thin crust on the surface of the liquid, or some crystalline solid at the bottom. This stuff is very very sensitive to mechanical agitation. If the crust on the surface breaks (e.g. the liquid is sloshed around a little and has surface waves) or crystals move/scratch along each other, then the stuff explodes and your beaker is shattered. This material can be formed if the silver ions can interact with the ammonia for a longer time (e.g. when standing overnight).




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[*] posted on 7-1-2020 at 12:39


Quote: Originally posted by woelen  
Silver ions and ammonia can react to form highly explosive fulminating silver.

woelen do you mean silver nitride Ag3N ? There is no HNO3 either C2H5OH to forme silver fulminate AgCNO, but AgCNO could be formed from Ag2CO3 + NH3 too.
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[*] posted on 7-1-2020 at 12:52


To quote wikipedia:

"Silver nitride was formerly referred to as fulminating silver, but this can cause confusion with silver fulminate or silver azide, other compounds which have also been referred to by this name. The fulminate and azide compounds do not form from ammoniacal solutions of Ag2O.[3] Fulminating silver was first prepared in 1788 by the French chemist Claude Louis Berthollet.[4]"




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[*] posted on 7-1-2020 at 15:46


Quote: Originally posted by woelen  
Silver ions and ammonia can react to form highly explosive fulminating silver.


well is there a way i can dissolve the silver chloride safely because im trying to make a solution of soluble silver with silver, HCl and whatever else i need. would sodium thiosulfate work in these conditions?

[Edited on 1/7/2020 by Armus_]




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[*] posted on 7-1-2020 at 23:19


You can safely have an ammoniacal silver solution, but you should not store it overnight. Prepare what you need and use it up completely.

If you don't use up all of it, destroy the remaining part by adding an excess amount of strong acid, so that the liquid becomes acidic. In that way you are sure that no explosive material is formed.

[Edited on 8-1-20 by woelen]




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[*] posted on 13-1-2020 at 05:12


For the home chemist, one can prepare [Ag(NH3)2]Cl, by first dissolving Ag in a combination of vinegar, dilute H2O2 (or pumped in air/O2) with a small amount of KNO3 as an electrolyte. The electrochemistry can be jumped started (to avoid the inception period) by 30 seconds of microwaving (the vigorous nature of the microwave-assisted electrochemical dissolution may be surprising from such dilute reagents, 5% vinegar, 3% H2O2 and a bit of KNO3).

Upon dissolving all or part of the silver metal, add aqueous NH3 forming a precipitate of AgOH/Ag2O. Separate out the Silver oxide and treat with aqueous NH3 creating [Ag(NH3)2]OH (aq). To quote a source (https://pilgaardelements.com/Silver/Reactions.htm):

"Ammonia precipitates Ag+ as brown/black oxide.

2 Ag+(aq) + 2 NH3(aq) + H2O(l) --> Ag2O(s) [brown/black] + 2 NH4+(aq)

In excess, ammonia dissolves the precipitate, forming a diamine silver complex.

Ag2O(s) + 4 NH3(aq) + H2O(l) --> 2 [Ag(NH3)2]+(aq) + 2 OH−(aq) "

Finally, add aqueous MgCl2 (from say mixing Epsom salt with NaCl and freezing out the Na2SO4 hydrate). The reaction:

2 [Ag(NH3)2]OH (aq) + MgCl2 (aq) --> 2 [Ag(NH3)2]Cl (aq) + Mg(OH)2 (s)

The white precipitate formed is Mg(OH)2. In general, one can add say Mg(NO3)2 (from MgSO4+KNO3+cooling) to create a corresponding nitrate salt (per my experience).
--------------------------------------------------

Here is my prior thread at SM http://www.sciencemadness.org/talk/viewthread.php?tid=89458#... suggesting a theoretically improved path to account for Silver nitride (Ag3N) formation. I claim it should also provide paths for Silver amide (AgNH2) and also the imide (Ag2NH), which are known reported secondary products.

The short version, a reverse reaction occurring in time involving the loss of water and ammonia, resulting in some Ag2O formation, which further acted upon by sunlight or lab light, may have a role.

Here is a selective extract of the referenced thread:

Quote: Originally posted by AJKOER  

.........
A very important new point is that once any Ag2O is formed (by say moving the equilibrium to the left from a possible loss of water on standing in an open vessel or upon addition of dry alcohol), light can further accelerate the process. See, as a source, "Ag2O as a New Visible-Light Photocatalyst: Self-Stability and High Photocatalytic Activity", by Xuefei Wang, link: http://onlinelibrary.wiley.com/doi/10.1002/chem.201101032/ab... . To quote from the abstract:

"Ag2O is unstable under visible-light irradiation and decomposes into metallic Ag during the photocatalytic decomposition of organic substances. However, after partial in situ formation of Ag on the surface of Ag2O, the Ag2O-Ag composite can work as a stable and efficient visible-light photocatalyst"

The use of photolysis and also other irradiation paths (like X-rays) are commonly associated with radical formation. Here is an interesting radiation study, ‘The X-ray activated reduction of silver (I) solutions as a method for nanoparticles manufacturing' by M. Staszewski, et al., published in Journal of Achievements in Materials and Manufacturing Engineering, Volume 28, Issue 1, May 2008, link: https://pdfs.semanticscholar.org/3877/7e9bee7cee0fba5e9bf41b... . To quote a passage discussing radiation treatment:

“The next step was aimed at eliminating glucose-containing ammonia solutions. The reactions taking place in these solutions resulted sometimes in the formation of precipitates with unstable composition. These precipitates contained considerable amounts of silver nitride Ag3N, which formed in some ammonia solutions of the silver salts and exhibited explosive properties in a dry state [15]. The results from analysis of the deposits obtained for three selected types of solutions are presented in Table 1. “

As the irradiation of glucose is a path to radicals, my proposed mechanics incorporates an ostensible radical pathway......

Note, my suggested pathway is largely promoted from the recognition of Ag2O as a new (article was 2011) visible-light photocatalyst with the possible introduction of contributing radical based reactions.

[Edited on 25-8-2018 by AJKOER]


[Edited on 13-1-2020 by AJKOER]
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[*] posted on 14-1-2020 at 09:34


Quote: Originally posted by AJKOER  

Finally, add aqueous MgCl2 (from say mixing Epsom salt with NaCl and freezing out the Na2SO4 hydrate). The reaction:

2 [Ag(NH3)2]OH (aq) + MgCl2 (aq) --> 2 [Ag(NH3)2]Cl (aq) + Mg(OH)2 (s)

The white precipitate formed is Mg(OH)2. In general, one can add say Mg(NO3)2 (from MgSO4+KNO3+cooling) to create a corresponding nitrate salt (per my experience).
[Edited on 13-1-2020 by AJKOER]


i thought [Ag(NH3)2]Cl was the most efficient and easiest option but if [Ag(NH3)2]2SO4 is soluble? if so, then it would be better to just use magnesium sulfate and then filter the magnesium hydroxide off for whatever else.
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[*] posted on 14-1-2020 at 11:23


Almost any silver compound will be soluble in ammonia, apart from the really insoluble ones such as silver iodide, silver sulphide, silver cyanide, and possibly the bromide and thiocyanate (depending on the concentration of the ammonia). Sulphate, acetate, nitrate, etc. will all dissolve easily in ammonia.

If you want to store this solution long-term (as a display?), you don't want to use ammonia. You can dissolve these compounds in cyanide, pyridine, or another amine for more stable solutions. Not that I recommend using cyanide.




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[*] posted on 14-1-2020 at 13:54


it wont be for long term storage, but thank you for the advice. dont worry, the most practical way is to purify silver the electrochemical way and also to get some silver compounds i could just add the [Ag(NH3)2]2S04 to a hcl solution to get silver chloride for storage (in a bottle with no light to shine in) which will be perfect for what i need to do. im trying to get stable bulk silver compounds to use later



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[*] posted on 16-1-2020 at 11:06


so i was actually able to do the experiment and i made [Ag(NH3)2]Cl and i was delighted with the light blue color and the same with [Ag(NH3)2]2SO4 so it seems to work and im ecstatic. ima try AJOKER's method to see if it works and if it does then i will update you guys.



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[*] posted on 16-1-2020 at 11:45


Light blue colour? That would indicate a copper impurity- silver ions have a full d subshell (rather than the partially-filled d subshell of most transition metal ions), and will give colourless compounds in the absence of charge-transfers (just like zinc, cadmium, aluminum and potassium).



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[*] posted on 16-1-2020 at 13:03


it probably is a copper impurity because for only a test i didnt filter the silver sulfate precipitate and i just went straight to seeing if the precipitate would dissolve with the presence of ammonia. it was just assumption on my end, that was probably why i was surprised all of a sudden



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