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Why are developers so unstable?

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37th Exposure

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I always thought that if a developer's chemicals could be packed in glycol, like HC-110 is, it will last for years even in a partially filled bottle. If I am not mistaken this is exactly the reason Sandy King made a version of Pyrocat packed in glycol, because the usual mix had a short shelf life. I've not tried it, but Pyrocat in glycol is supposed to keep for years. I don't know what makes Rodinal last so long.
 
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RattyMouse

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I always thought that if a developer's chemicals could be packed in glycol, like HC-110 is, it will last for years even in a partially filled bottle. If I am not mistaken this is exactly the reason Sandy King made a version of Pyrocat packed in glycol, because the usual mix had a short shelf life. I've not tried it, but Pyrocat in glycol is supposed to keep for years. I don't know what makes Rodinal last so long.

As mentioned in some posts above, hydrolysis is a pathway that developers can degrade. Replacing water with a highly hindered glycol is one way to prevent this from occurring.
 

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You're still missing the point of my question. I was concerned with the scientific reasons behind the instability of developers. By *any* measure, most are very unstable materials. I formulate highly oxidizable products that can sit in an oxygen environment for years sometimes without degradation.
Are these compounds stored in aqueous solution? You know that powder developers can last for decades ...
 

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I always thought that if a developer's chemicals could be packed in glycol, like HC-110 is, it will last for years even in a partially filled bottle. If I am not mistaken this is exactly the reason Sandy King made a version of Pyrocat packed in glycol, because the usual mix had a short shelf life. I've not tried it, but Pyrocat in glycol is supposed to keep for years. I don't know what makes Rodinal last so long.
If a liquid is very concentrated, it will take up less oxygen, and such a developer concentrate will tend to last longer. For some reason p-Aminophenol is also less prone to aerial oxidation, and as a result Rodinal lasts forever.
 

Rudeofus

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Yes, the products I formulate are typically 90% water, 10% organics at the end user stage.

A developer with 10% organic reducing agent would be outrageously expensive and waaay too active ...
 
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You're still missing the point of my question. I was concerned with the scientific reasons behind the instability of developers. By *any* measure, most are very unstable materials. I formulate highly oxidizable products that can sit in an oxygen environment for years sometimes without degradation. Because of my background I wanted to learn why a photographic developer cannot do the same. I learned that from this thread, regarding why only weak anti-oxidants can be used otherwise you get no development activity. The developers get diverted towards reacting with the anti-oxidants, not the silver halide.

Cost to the end user had nothing to do with my question. I was thinking and asking from the point of view of a formulation scientist. I make products for customers and they *demand* a long shelf life. Any product that I formulated that went bad in 6 months would be a complete failure. Replenishment is simply replacement of key additives. That is not stability, that is replacement. Would you consider your transmission fluid in your car highly stable if every 3 months you had to go to the shop, pull out 25% of the volume and "replenish" it? No, I don't think you would.

As I already said, I know all about methods to improve stability from a hobbyist point of view. That has nothing to do with my scientific query.

Cool. Good luck in finding an answer.
 

Rudeofus

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Here is mentioned sodium benzenesulfonate and some antioxidants patented long ago by Ilford:
(there was a url link here which no longer exists)

Are you sure, that Sodium Benzenesulfonate works as anti oxidant? Is there a chance the Fuji patents refer to the very similar sounding Benzenesulfinates? It would surprise me a great deal if 0.3 g Sodium Benzenesulfinate could effectively protect 50 g p-Aminophenol ...
 

Alan Johnson

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Reading the subsequent pages in the link, even the experts were not able to clearly resolve this question.
It seems unlikely to me that the additive could inhibit oxygen diffusion, as was suggested in the link, and it being a surfactant seems to me probably not important in this application.
I prefer that -sulfinate is a reducing agent and -sulfonate may slow the oxidation by inhibiting production of quinone sulfonate from the developing agent aminophenol or hydroquinone.
Your guess is probably better than mine.
 

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Patent US 2618558 A claims Sodium Benzene Sulfonate as compound which enables higher solubility of p-Phenylenediamine compounds. Maybe it acts in a similar fashion with p-Aminophenol ...

AFAIK the "production of the quinone sulfonate" is quite important and beneficial, because the semiquinones accelerate developer composition, see lith developers.
 

Alan Johnson

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Photography Theory and Practice Vol 4 Monochrome Processing LP Clerc & RE Jacobson Revised Ed 1971 p486:
"Other substances have been suggested for use instead of sulphite to protect the developing agents from being oxidized by atmospheric oxygen.Greater protection is afforded by substances containing an -SH (thiol) group, such as cysteine and thioglycolic acid (TH James and A Weissberger 1939).The protection appears to be due, as with sulphite, to the destruction of quinonoid oxidation products which catalyse the oxidation of hydroquinone."
That seems to be a good explanation of the mechanism of action of antioxidants with hydroquinone, IDK if it can be applied to aminophenols also.
I have not been through the patents to check claims for specific antioxidants.
 
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