Sciencemadness Discussion Board

Quick silver sulfide

silvergrahm - 6-4-2013 at 09:08

So, we all know the old trick for removing silver sulfide tarnish from old silverware: fill a sink with hot water, add baking soda, and place foil of aluminum over the silver ware.

But how would you do this in reverse? I guess fuming silver with hydrogen sulfide would do the trick, if you want to die. But is there an aqueous solution of some sulfide that does not hydrolize into hydrogen sulfide?

I'd also love a detailed explanation of what is going on to remove the silver sulfide w/ aluminum and baking soda. The bicarbonate is an electrolyte?

DutchChemistryBox - 6-4-2013 at 11:24

Maybe you could make a solution of K2S or Na2S.
And then electrolyse it with the silver in the solution.

Na2S(s) > 2Na+(aq) + S2-(aq)


2Ag(s) > 2Ag+(aq) + 2e
2H2O(l) + 2E > H2(g) + 2 OH(aq)
----------------------------------------
2Ag(s) + 2H2O(l) >2Ag+(aq) + H2(g) + 2 OH(aq)


Then you'll have a solution with Ag+,S2-,Na+,OH

The Ag+ and the S2- aren't soluble in water together:
2Ag+(aq) + S2-(aq) > Ag2S(s)

Then you can filter it and you'll have your silversulfide.

At least, that is what i'm thinking:P


[Edited on 7-4-2013 by DutchChemistryBox]

Metacelsus - 6-4-2013 at 12:01

First, S2- (pKa > 14) doesn't exist in aqueous solution, even at pH 15. The active ion would be HS-.

Na2S(s) + H2O(l) -> 2 Na+(aq) + OH-(aq) + HS-(aq)

Second, the Ag+ reacts both with HS- AND OH-. Four reactions are possible (I think).

2 Ag+(aq) + 2 OH-(aq) -> Ag2O(s) + H2O(l)

2 Ag+(aq) + OH-(aq) + HS-(aq) -> Ag2S(s) + H2O(l)

2 Ag+(aq) + OH-(aq) + HS-(aq) ->Ag2O(s) + H2S(g)

2 Ag+(aq) + 2 HS-(aq) -> Ag2S(s) + H2S(g)

I'm not sure which one(s) take place. For better results, try sodium hydrosulfide (NaHS) instead of sodium sulfide.

Finally, silver suldife is Ag2S, not Ag2Cl. :D

[Edited on 6-4-2013 by Cheddite Cheese]

silvergrahm - 6-4-2013 at 18:41

Aqueous HS. Is that hydrosulfuric acid? Trying to keep the HS down. Even under the hood I'm scared.

Are their sulfurous compounds that will produce a sulfide with Ag, but not with other metals, namely copper? Zinc? Iron?

elementcollector1 - 6-4-2013 at 19:54

H2S is the compound you're looking for, and it's not a problem under a hood.

DutchChemistryBox - 7-4-2013 at 10:27

@Cheddite Cheese:
I didn't thought about the fact that S2- is such a strong base.

@Silvergrahm
Are you going to try it with NaHS? I'm curious about the results.


silvergrahm - 7-4-2013 at 18:01

Quote: Originally posted by DutchChemistryBox  

@Silvergrahm
Are you going to try it with NaHS? I'm curious about the results.



I think I might whip up something that yields H2S on hydrolysis, after all. I'm doing this on silver plated copper, really no need to submerge it I guess, can just add MgS or something of that nature and fume the plate over the gas that wafts off.

Is MgS the best choice? Maybe not...

[Edited on 8-4-2013 by silvergrahm]

MrHomeScientist - 8-4-2013 at 05:49

Tarnishing silver is very simple, since it happens so readily. Just place your silver object in a ziploc bag along with a rotten egg, or some sulfur powder. You might want to do this outside anyway, as I've found that the sulfur smell seeps through the bag, no matter how many bags you use!

From the abstract of an article I can't access the full text for:
"Contact with materials that contain sulfur compounds, such as hardboiled eggs, mayonnaise, mustard, and rubber bands can cause tarnish. In air, a silver object can tarnish owing to the reaction of silver with hydrogen sulfide (H2S). This is a gas found in the air as a result of some industrial processes and the decomposition of dead plants and animals."

chemrox - 22-4-2016 at 12:55

I want to tarnish some silver jewelry to get a nice patina. I did this in the past using a cutting oil with S in it. In this, these cases, there are silver "ropes" and other crevice types involved so cleanup is an issue. I'm thinking of burning some S in the hod and holding the objects in the smoke (vapor).

[Edited on 22-4-2016 by chemrox]

Metacelsus - 22-4-2016 at 13:33

I would think that SO2 wouldn't tarnish silver like H2S would. However, there might be enough unburned S in the smoke to cause the silver to tarnish.

Instead of burning the S, you could try heating it in a closed container along with the silver item. It should sublime onto the silver and cause it to tarnish.

JJay - 22-4-2016 at 19:38

I would think the heating silver powder with flowers of sulfur in a crucible would do the trick.

violet sin - 22-4-2016 at 20:48

Liver of sulfur anyone? Made specifically to blacken/age/patina jewelery. Like the black shadows in the crevices of a class ring. It is submerged to color the piece, then buffed on the surface highspots, leaving the dark inbetween the nooks
Wiki page
https://en.m.wikipedia.org/wiki/Liver_of_sulfur
Being used
https://m.youtube.com/watch?v=gCiKs60kXJ4
Being made
https://m.youtube.com/watch?v=30hEhFJ8Ejc

unionised - 23-4-2016 at 04:49

Some sort of polysulphide seems like a god choice.

BromicAcid - 23-4-2016 at 05:22

Liver of sulfur is incredibly easy to make, I have used it several times for art projects. A few pellets of NaOH, some water, and a few pinches of sulfur, not much to it. Attached is a photo of the marquee of my arcade cabinet, I electroplated the dark parts on the brass plate with copper and then treated with 'liver of sulfur' to achieve the dark appearance.

Edit: Am I the only one that read this and registered quicksilver sulfide? I.e., mercury sulfide?

marquee.JPG - 369kB

[Edited on 4/23/2016 by BromicAcid]