D-76 (pH) Activity Changes

Widely held belief: D-76 changes differently than other developers; sometimes changing activity without warning. This makes it a developer of doubtful performance among many camera counter experts, who direct the new darkroom photographer to a different developer. [needlessly]

photographic chemistry

Is it true? How true? What happens when mixing the developer? Do you have to wait a week before using? What makes the developer last?

All HQ containing developers have a small pH shift in the first few hours of mixing. The pH goes up, then down, due to oxidation of HQ, formation of the sulfonate salt of the quinone, and release of Sodium Hydroxide.

The chemical that causes the changes is a main player in most developer formulations before 1970; this includes Dektol (D-72). HQ (hydroquinone) reacts with oxygen producing quinone, which in turn reacts with sodium sulfite (in the developer) making HQ-mono sulfonate and hydroxide; this is the cause of the slight pH raise. This very slight pH increase results in a slight increase in activity of the developer (it develops more). However, there is also a loss in HQ which lowers the effect.

Where does the oxygen come from: initially, from the mixing water. Later, it comes from storage, and from tray or tank agitation.

How long does the ‘stabilizing’ of pH take? Depends upon your water and mixing vigor, but not longer than 4 hours before the pH stops changing. Definitely not weeks. Mix in the morning, use in the evening. HQ developers, as they age(ripen) in a replenished (re-use) system also produce sulfonate, and release Sodium Hydroxide. That action is what makes these type of developers “non self-replenishing” — you must use a Replenisher formula. Unless you are souping hundreds of rolls, sheets of film, one-shot is a real world solution.

Once again take care of oft heard advice, even from established workshop instructors: “As D-76 ages a chemical compound, hydroquinone monosulfonate, is formed. This chemical compound will INCREASE the activity of the developer and the contrast of your negatives in a big way with T-MAX. ” — Sexton.

From another vantage point: storage of D-76 type developers affects ‘graininess’ of Tri-X (from 1968) Rarely did this alter the contrast or speed of the venerable old lady, much to the chagrin of labs hunting magic bullets. They did, however, alter D-76 packaged developers with an additive: for each liter of D-76, add 8 grams Sodium Carbonate (anhy) and 3.6 grams of Sodium Bisulfite. pH will be 8.6 at 70F.

Kodak’s 2003 • CIS-61 gives the pH as 8.5 +/1 0.05 at 77F, which is the same pH as T-MAX RS. XTOL should be 8.2.

Mix from the bottom: this reduces aeration of the chems.

chemistry propellers… as an idea. Magnetic mixers mix from the bottom. They should be a first choice for the small volume (under a gallon) user.

Better advice:

 comment is technically incorrect. HQMS is lower in activity, but it produces a byproduct of Sodium Hydroxide as it is formed. This causes the rise in pH.

One way to check D-76 is to measure the pH 1 day after mixing. Prior to use, re-measure the pH. If it is higher or lower by more than say 0.2 units, do not use it, discard.


Refs:

Kodak D-76 replenisher
If using a replenished line, or processing large volumes of film, consider using DK-50. It lasts.

control of agitation is essential.

— the initial agitation being the most important contrast control .

read the highlighted passage

Kodak Kodalk Developers — the “K” in DK

Divided Developers

Turn D-76 into a divided, two-step, developer. Solution B is borax. This is a good procedure for other developers even off the shelf ones. Kodak’s Kodalk was sodium metaborate which has higher alkalinity than borax. This form of bath ‘B’ is a great benefit in controlling (compensating) for hard (high contrast) subject lighting. See the above page copies for specific formulas.

How bout Pyro: it was used for years in emulsion research labs until results couldn’t be reproduced among labs. Enter a Capstaff answer. (along with a summary)

Lustrum Press Darkroom Books

Lustrum Press published many of the most influential books during the Silver Age of photography.

Two of them were based upon the darkroom practices of some of the established photographers — those first period producers. Ralph Gibson published 2 such volumes. Each edited by a different person.

scan_darkrooms

Darkroom & Darkroom 2

Darkroom & Darkroom 2

Contents:

Darkroom

INTRODUCTION ELEANOR LEWIS
WYNN BULLOCK PHOTOGRAPH AS SYMBOL
JERRY BURCHARD NIGHT PHOTOGRAPHY
LARRY CLARK MIXING YOUR OWN CHEMICALS
LINDA CONNOR PRINTING-OUT PAPER
RALPH GIBSON HIGH CONTRAST PRINTING
BETTY HAHN GUM PRINTING
EIKOH HOSOE SHADOW DETAIL
GEORGE KRAUSE INTENSIFICATION
ELAINE MAYES LONG TONAL RANGE
DUANE MICHALS CAMERA AS DARKROOM
W. EUGENE SMITH FORTY YEARS OF EXPERIENCE
GEORGE TICE PLATINUM PRINTING
JERRY UELSMANN MULTIPLE PRINTING

Darkroom 2

This book’s chapter titles are the name of the photographer. Each person gets an extended time to explain their work. In the Web Age, this would be called BTS – behind the scene.

JUDY DATER – My work is rooted in 19th-century portraiture. I like very formal pictures. I began with self-portraits, but they were unsatisfactory because I could not see what I was doing. So I started to use other women as stand-ins.

FRANK GOHLKE – My attitude toward the world is shaped by my response to its abundance, richness and generosity. In some ways, I have a similar response to the materials used in photography.

EMMET GOWIN – Let me just talk to you from my feelings, first about my beginnings, then about technique. (provides specifics of his contour printing control – mask)

CHARLES HARBUTT – I work in sort of an off-the-wall manner. I shoot by whim; I don’t really go out with specific ideas. After I develop the negatives, I decide if I like a picture, and if I want to print it.

LISETTE MODEL
HANS NAMUTH
DOUG PRINCE
AARON SISKIND
NEAL SLAVIN
COLE WESTON

EDITED BYJAIN KELLY

Darkroom Bullets from the age of the stampede
print developer modifications of note