Murray Kelly
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If you are trying to make a special purpose low contrast developer, you are better off without ascorbate. The reason why POTA works the way it does is because Phenidone is the sole developing agent and there is no superadditive agent.
Now, if you want a Phenidone developer that is similar to D-23 but without sulfite, that can be arranged.
It is not the ascorbate that activates the Phenidone,
but the other way round, according to some experts.
Thanks Ryuji. My understanding was that the ascorbate/AA didn't actually 'add' at pHs associated with borax or lower? All it did was to regenerate the phenidone or metol and not contribute any developing effect itself.
Is this not true? They are superadditive at pH9 or lower?
Murray
I think that likely the case. Most PC formulas specify
phenidone levels on the order of 0.00x %. In my view
such a low level would not even qualify such a developer
as being of the compensating type.
Take Beutler's for example; a classic developer of
the compensating type. The level of metol is 0.1 %.
It would have to be diluted 1:24 to equal the
phenidone levels of at least a few PC
developers. Dan
The real trouble is that theories diverge from each other. I'm not as well studied as I sometimes pretend, but I have seen mention of superadditivities between certain developing agents that do not seem to show that the experimenters even considered omitting the sulfite, without which there is no superadditivity. Does anyone ever state that, eg., Metol and hydroquinone are superadditive in the presence of sulfite ion? Most often it seems that ascorbate is considered as a substitute for hydroquinone. In fact, it can be a substitute for both hydroquinone and sulfite in the same developer. In the Pyrocat developers, when they are put up (as we say in the country) in glycol, a very small portion of ascorbic acid, which is soluble in glycol, does the job of sulfite, which is not very soluble. Any superadditivity that may occur is not obvious.
I recommend you to read GIP Levenson's (Kodak Harrow lab) series of beautiful work on superadditivity. Also recommended is work by Umberger (E. I. du Pont de Nemours) on surfactant model, and another series of beautiful work by Pontius (Kodak Rochester lab).
Effect of sulfite on both single developers and superadditive developers is well studied and well documented.
James had such a simple and appealing charge barrier theory, and while it is probably very true, in reality, the work of those three named above explains the development mechanism better, and the latter also offers much more insight into the developer.
You must realize that the rate of development is only one aspect of developer, and distinguish this from a range of factors that must be considered in formulating practical developers. For the latter purpose, there are other requirements, such as photographic speed, compatibility with a wide range of emulsion types, tonality, granularity and keeping properties.The graph showing the effect of relative proportions of Phenidone and hydroquinone does not give a clue as to the need for sulfite. The earlier graph in the same chapter showing the effect of sulfite, ascorbic acid or hydroquinone on development by Metol shows that there was no increase in rate of development by Metol as hydroquinone was added. Even if the PQ mixture was synergistic without sulfite while the MQ mixture was not, the two sets of experiments show that we cannot conclude that sulfite is not needed for PQ synergism because the other ingredients of the PQ developer were not mentioned.
Now, the MQ and the MA developers tested without sulfite were vastly different one from the other. We cannot tell from the graph whether the ascorbate was regenerating the Metol, or deactivating the oxidation products of the Metol. The author supposes that the sulfite deactivates while the ascorbate regenerates. Apparently, the hydroquinone does neither without sulfite, which means that the MQ mixture is not synergistic. I don't see the error in my logic. I see the lack of data other than what I get from my own experiments, and so would really like to do more reading. I'm sure the original reports had more detail.
Isn't it odd how one uses a very strong concentrated developer or a very! dilute one for a long time to achieve low contrast?
Murray
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