The Darkroom
When Good Chemicals Go Bad; Tips For Maintaining Freshness And Best Image Quality

Many people seem to believe that darkroom chemicals have a fixed capacity, beyond which they stop working. This is quite a long way from the truth. The life of most chemical baths used in the darkroom can be divided into four stages. First, there is the fresh bath, with full vigor. Second, there is the partially exhausted bath, which still works but takes longer. Third, there is the bath that appears to work but has a concealed and sometimes fatal flaw. Fourth, there is the bath that is so exhausted it will not work at all, or at least not within a realistic length of time.

Knowing how and why the various chemicals die is very useful if you want to get the maximum quality and value out of your darkroom chemicals, so here is a basic guide. Of course you can simply rely on the manufacturers' stated guidelines, but if you do, there are two things worth knowing.

Aircraft graveyard, Slovakia. For maximum quality in a print like this, with a long tonal range, you need the full density range of which the paper is capable. A print developed in dying developer or one that was "snatched" (overexposed and underdeveloped) could differentiate the light tones easily enough but the darkest areas would be gray instead of black and there would not be enough contrast in the shadows. As it is, the maximum print density (on the wheel, white light densitometer) is 2.35--a print brightness range of 1:223--and the darkest area with texture is around 2.00. Photo specs: Leica MP, 90mm f/4 Macro-Elmar-M, Ilford HP5 Plus at 500 in Ilford DD-X, Ilford Multigrade Warmtone RC glossy lightly selenium toned with Maco toner.
© 2004, Roger W. Hicks, All Rights Reserved

First, the manufacturers assume "average" conditions of use and storage. A film developer, for example, will exhaust faster if the images are overexposed or if the pictures are of very light subjects, because there is more silver to develop. Also, more air means faster oxidation. Make up solutions with water that has been boiled and allowed to go cold for minimum air content, and decant concentrates and stock solutions into smaller bottles with no airspace or otherwise exclude air. Warm weather speeds oxidation, too. Some people refrigerate their developers, though this can be risky with some formulations if crystals form and fail to re-dissolve.

Second, some manufacturers' guidelines are considerably more relaxed than others: some quote capacities that reflect no visible change (e.g., the bath is always in its first, vigorous phase) while others assume a small degree of deterioration will be acceptable and can be compensated for by extended processing. Also, the degree of deterioration that is acceptable will depend on the photographer.

Developers die in five ways: through hydrolysis, oxidation, bromide build-up, pH change (loss of alkalinity), and actual exhaustion of the developing agent(s). With print developers, the collapse is fast enough that if you are looking for it, you will see it in the course of a print or two. Contrast falls, and maximum black weakens. If you are developing film, of course, you do not want to take this risk. Stay inside the manufacturers' guidelines, subject to the qualifications given earlier.

Hydrolysis, as its name suggests, is the breaking down of developer components (usually the developing agent itself) in water. Plain phenidone is particularly prone to this but later pyrazolidones, as used in most modern developers, are much more resistant to hydrolysis. The byproducts of hydrolyzed developing agents may be colorless, which explains how sometimes even a brand-new unopened bottle of developer can be water-clear but inexplicably inactive. This is where use-by dates are invaluable.

Castle, Hungary. This is a fairly "average" subject, a broad mixture of light, dark, and middle tones: exactly the kind of negative (and print) on which manufacturers' predictions of chemical life are predicated. Photo specs: Bessa-T, 28mm f/1.9 Ultron, 2x yellow B+W filter, Kodak Tri-X at 500 in Ilford DD-X, Ilford Multigrade Warmtone RC glossy selenium toned with Maco toner.
© 2004, Frances E. Schultz, All Rights Reserved

Oxidation is much more familiar. This is caused by the reaction of the developing agent with oxygen, and the byproducts are usually brown. Color alone is not a reliable guide to developer exhaustion, however. You also need to know the concentration of developing agent(s). If there is very little developing agent, even a weak tea color may indicate that the developer is oxidized beyond use. If there is a lot of it (or them), the developer concentrate may still work perfectly even when it is opaque.