...Maybe I should say that my purpose would be to get a good metallic silver plate on the cathode. If you're more interested in investigating things, or want to produce silver sulfide, that's fine too, refiners can work with that. But I don't think anyone would do that commercially, anymore. A well-controlled electroplating system can give you a known quantity, in the form of high-purity flake, so at least you have a very good idea of what's supposed to be there.
Fabricating a constant current source is pretty simple with a couple of op amps. I was figuring 5 ma as a starting place for the current, and allow the terminal voltage to float up to 24VDC as the conductivity of the solution goes down. I can get up to about 60VDC with stuff from my junk box if 24VDC is too low. And I suppose you could just straight rectify the 120VAC into a VDC bus if I really need higher potential, but finding op amps that won't fry at 160 volts may be harder. I'd probably have to buy something.
My plan for circulating the fluid was to put a stir bar in the jar and put the whole thing on a cheap stirrer plate from fleaBay.
My plan for the electrodes was to use silver jewelry wire for collection, and I haven't figured out what yet for the anode. Maybe a stainless rod?
So, although I'm not the one who posted, how's my scheming? OK? Out to lunch?
The theoretically correct solution involves a potentiostat and a reference electrode, but I haven't been able to figure out how to do that for less than about $100.
Michael,
As you read the following, please bear in mind that I am a physicist and not an electrochemist, so the fact that I can't explain it in simple terms doesn't mean that I don't understand it
A "reference electrode" in this context is a device which establishes an absolute potential reference.... There are various forms of more practical electrodes, and the one of interest here allows silver ions to come into equilibrium with silver metal: there will be a particular potential developed at any given temperature if the silver ion concentration is fixed (say, by the presence of solid silver chloride, which will dissolve and dissociate to a thermodynamically determined extent.
The way that this comes into play is by means of a "potentiostat", which is essentially a variable-voltage supply that regulates its output with respect to the reference electrode. Since the reference electrode potential is fixed, the potentiostat can regulate the "working electrode" (in this case the cathode where silver is being deposited) to any desired potential, compensating for things like lead resistance, current, stirring, and voltage drop across the electrolyte. In this way, the chemistry of the cathode reaction can be controlled to deposit metallic silver, but not silver sulfide, even when the silver concentration has become very low.
There are a couple of decent illustrations of reference electrodes on Wikipedia, except that the means of connecting them to the working electrolyte isn't very clear. This is sometimes done with a capillary opening at the bottom of the electrode, but more often with a porous glass plug or a thin membrane which will allow ions to migrate through while preventing gross mixing of the electrode contents with the working electrolyte. Since the potentiostat has an arbitrarily high input resistance, essentially no current flows and there doesn't have to be a low-resistance connection between the reference electrode and the solution.
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