Quote Originally Posted by skahde
(I'll use X_n for subscript and X^n for superscript like in TeX)

This is *very* interesting! So we have an equlibrium between S_n (eg. S_1 to S_8) and Na_2S_(n) in the solution, the white deposit probably being the stable (and rather inactive) S_8.

So if you lower the concentration of the polysulfide you will end up with less sulfur in the solution and S_8 is less likely to form. Does it sound reasonable that there is more reactive S_(n<8) in the solution at lower polysulfide-concentration and that this may be the reason for polysulifde-toners to speed up at higher dilutions?

best

Stefan
Ah! I haven't written T_E\ X in many years!

Trying to guess hat happens in such a solution is something I would leave to my University techer - professor Foss. He was nominated to the Nobel price for his work on sulfur chemistry!

The S_n^2- ion is very soluble, unlike S_8 (which, to the uninitiated, means solid sulfur). The "n" is not limited to 1-8, there are chains as long as 14 (although they are a lot less stable than shorter chains)!

Since a polysulfide chain can "drop" a sulfur atom without changing oxidation state, the reaction with silver is 2Ag + S_n^2- -> Ag_2 S + S_(n-1)^2-.

Then since the silver is a solid, and the sulfur reacts "dirctly" with the metallic silver, the only influence of higher concentration would be to increase the amount of sulfur available for the reaction - so it should speed up with higher concentration.

Since this doesn't happen, there must be some other reaction involved. My initial idea is that the lower concentration gives a proportionally higher concentration of thiosulfate (which will form in any aqueous sulfide solution). As we know the thiosulfate is a strong complexing agent for silver - that's why it's so good for fixing. So a relatively higher concentration of thiosulfate could "mobilise" the silver, causing it to react more easily with hte sulfide?
A similar effect is the "development" of van Dyke prints in the fixer - the dissolving silver reacts with the Fe^2+ to form more solid silver. The darkening in the fixer is abrupt and very obvious; a case of fixer working as developer.