Replenished D23 and development times

[Xícara]

Hello,

I've started using D23 recently and I will shortly begin replenishing my litre bottle with DK-25R. On John Finch's Pictorial Planet website, and if I'm not misunderstanding anything, he writes that once the cycle of replenishment is initiated, development times should be increased by 10% for most films, and in his experience, 30% with HP5+ (a film that I use regularly). Why would this be? I would have thought that the replenishment with a solution containing more metol would speed up development, but there must be more to it. Is it to do with a change in alkalinity?

This is the page that I'm referring to:

D23

Photo

www.pictorialplanet.com

Cheers,

 

[Alex Benjamin]

I don't know the scientific explanation for his recommendation, although I think it has to do with the fact the the replenisher doesn't fully compensate for the exhaustion the developer has experienced. More experienced and chemically proficient members can answer this question better than I can.

I also read Finch's comment when I started to use replenished D-23, but decided to keep the same time as the one that I had adopted for stock solution D-23, which, for me, is about 15% more than the time for D-76.

I'm no expert on the matter and haven't done extensive tests, but from what I understand, slight overdevelopment with D-23 will not affect the highlights — i.e., risk of blown highlights — as with other developers such as D-76 or Xtol. It will, however, affect contrast. D-23 not being a high-contrast developer, it is possible that, to John Finch's taste, the extended time becomes preferable. I prefer to control constrast through agitation.

Then there is the matter of how you rate you film. For me, HP5+ works in D-23 at ISO 250.

That said, I have realized that with D-23 times, you do have to apply the "better safe than sorry" principle. There is loss of speed with this developer, and with underdevelopment there is a strong chance of ruining your film. I found that to be true the few times I used it with Tri-X (rated at 400, though), which needed a higher percentage of added time than HP5+.

 

[MattKing]

I don't know the scientific explanation for his recommendation, although I think it has to do with the fact the the replenisher doesn't fully compensate for the exhaustion the developer has experienced

The other very real possibility is that the amount one loses to carry-over or discards as a part of the replenishment regime isn't sufficient to remove enough of the development byproducts to compensate for the effects of byproduct build-up.
Replenishment is a two part process - replace lost activity, and remove byproduct build-up. It is relatively difficult to design a replenishment regime that compensates for both issues with a single replenishment action.

 

[Donald Qualls]

Bromide picked up from the film into the developer is what I understand to be the main cause. Replenisher replaced the oxidized metol and increases alklinity to compensate for the loss of pH due to that oxidation -- but the steady state reached by replenishing seasoned developer isn't the same as using fresh developer as a one-shot, and that's mainly due to bromide in solution acting as a restrainer. This is also the main reason for adding time when you reuse stock solution without replenishment (along with oxidation of developing agents and loss of pH, of course).

 

[Xícara]

Bromide picked up from the film into the developer is what I understand to be the main cause. Replenisher replaced the oxidized metol and increases alklinity to compensate for the loss of pH due to that oxidation -- but the steady state reached by replenishing seasoned developer isn't the same as using fresh developer as a one-shot, and that's mainly due to bromide in solution acting as a restrainer. This is also the main reason for adding time when you reuse stock solution without replenishment (along with oxidation of developing agents and loss of pH, of course).

I see, thanks a lot, that makes a lot of sense

 

[Mr Bill]

The other very real possibility is that the amount one loses to carry-over or discards as a part of the replenishment regime isn't sufficient to remove enough of the development byproducts to compensate for the effects of byproduct build-up.

Replenisher replaced the oxidized metol and increases alklinity to compensate for the loss of pH due to that oxidation -- but the steady state reached by replenishing seasoned developer isn't the same as using fresh developer as a one-shot, and that's mainly due to bromide in solution acting as a restrainer.

Yep, with film the main development byproduct of concern is probably bromide ion. I don't personally have too much experience with B&W materials in this respect, but my understanding, via literature, is that Metol is only moderately affected by bromide ion. So I would guess that this is a main reason why D-23 replenishment works as well as it does.

The ideal developer, if designed for replenishment, would already include a significant amount of bromide in the formula. This would allow a special replenisher - one with essentially NO bromide in it - to dilute the used developer (with additional bromide added as a development byproduct) back down to the original bromide concentration. This is, in fact, how the C-41 (color negative) process works.

FWIW many modern films also include a small amount of silver iodide, releasing iodide ion as a development byproduct. Iodide seems to be a much stronger restrainer than bromide, so perhaps this could explain why some films seem to need even more added development time. Just a wild guess on my part.

 

[Donald Qualls]

Tabular grain films have iodide; its lower reaction rate with thiosulfate is responsible for fixing being very slow and sometimes incomplete if these films (Delta, T-Max, Acros, possibly Foma 200) are fixed with sodium thiosulfate vs. ammonium thiosulfate (no, I don't know the chemistry behind why one works better than the other). The effect of iodide in developers is already accounted for in the one-shot development times for these films, and phenidone seems less prone to this effect even than metol.

I don't hear about a lot of folks developing tabular films in D-23, but I'd guess you'll see more loss of activity over a period of replenishment with these films. For myself, I've only used D-23 on conventional grain films -- mostly Fomapan, come to that.

 

[doctorpepe]

I read some of this and other content on replenishing D23. I have used d23 for a long time e and always replenished with d25r formula. After more thought, I had a few ideas.

First, wouldn’t just adding 1g of KBr to the initial fresh formula be the equivalent of running 3 rolls of film through it at the outset? I calculated that, with an average silver content of 0,25g silver per 8x10 sheet, development releases about 0.36g of free bromine. This gets picked up by the Sodium Sulfite, coverts to Sodium Bromide and releases a small amount of SO2. 1g of KBr in a fresh mix of D-23 gets you there right out of the gate and is probably the equivalent of adding “starter” to C41 developer so it acts like already seasoned developer.

Next, I wonder if using Kodalk (Sodium Metaborate) over time makes the D-23 overly alkaline and affects development times or contrast? I guess its purpose is to neutralize the released SO2, but this amount is probably negligible, since there is such a huge amount of Sodium Sulfite already present and that keeps the pH relatively constant over time.

Anyway, I think I wil try adding 1g of KBr to the initial D-23 fresh and then replenish (top off) with plain D-23 ((NO bromide!) and see how t goes over time.

Please don’t wait for test negs as I work very slowly now and don’t produce a lot of 8x10 films, but as I try this, I may report back with some scans at a later date.

 

[Raghu Kuvempunagar]

Adding Bromide is what I also did when working with replenised Adox MQ Borax. But ripening probably means the formation of some HQMS in Adox MQ Borax that could be contributing to the behaviour of the ripened developer. But D-23 does not have any Hydroquinone anyway.

 

[dokko]

The ideal developer, if designed for replenishment, would already include a significant amount of bromide in the formula. This would allow a special replenisher - one with essentially NO bromide in it - to dilute the used developer (with additional bromide added as a development byproduct) back down to the original bromide concentration. This is, in fact, how the C-41 (color negative) process works.

yep, that's exactly how D-96 and D-96R for b/w cine film processing works: