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Thread: What is ruining my Tri-X 320?

  1. #41

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    Re: What is ruining my Tri-X 320?

    This could be related to differences in "Rodinal"-type formulations, specifically with respect to whether or not there is any free hydroxide - which could have a significant affect on both pH and keeping properties.

    Agfa Rodinal changed from time to time, and then there are formulas such as R09, Adonal, Blazinal etc. which may or may not correspond exactly to whichever Rodinal formula. It is a complicated history. Ian Grant might know whether or not Adonal is a variant which contains free hydroxide or not.

  2. #42
    Kyle M.'s Avatar
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    Re: What is ruining my Tri-X 320?

    I am by no means an expert on the matter, but I have some experience with Adonal/Rodinal. I currently have two bottles of Rodinal at home, one was purchased in April 2014 from freestyle, and the other about 3 months ago locally. Both bottles are labeled as "Adox Rodinal", though I previously had a bottle labeled as "Adox Adonal" I have read that they are the same formula and the name was changed due to a copyright issue. But I have no proof of this. The first bottle of Rodinal is now a dark brown almost black color but as of last week was working just fine, the second bottle is still very near clear with only a slight tint to it.

    While the first bottle has no such thing, the top of the second bottle has a plastic insert to decrease the size of the opening, there is a small plastic stopper in the cap which goes into that opening when the cap is screwed on thereby limiting the amount of air that can enter the bottle. The older bottle simply has a screw on plastic cap. Therefore I am able to keep air out of the new bottle but not the older bottle. I have also heard from several sources both online and real world that there was a bad batch of Rodinal at the time that it was labeled as "Adonal" again I have no proof that this information is true. So I suppose the OP's bottle could be from this so called "bad batch."

  3. #43

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    Re: What is ruining my Tri-X 320?

    I'm not at all sure what someone means by free hydroxide. The Rodinal formulas I've seen have extremely high pH until diluted for use. There's going to be quite a bit of hydroxide in there.

    The stuff I made from scratch does not last forever regardless of recipe. That said, the oxidation of p-amino-phenol creates intensely colored compounds, so dark color is not proof it's bad. Fresh made it is light tan/straw colored depending on the purity of the p-amino phenol. Ditto if you start from acetaminophen. It gets dark on exposure to air even in glass bottles. One 450 ml batch I've had sealed for going on two years is still pale colored.

    Sometimes I think we would be well served to get a bottle of argon and purge the oxygen out of our developers. It's routine in organic chemistry labs to purge out the air before sealing up a bottle of chemicals and with some chemicals you handle them with positive pressure to keep air out completely. But that "cure"'costs more than the solution: ditch the suspect Rodinal and get fresh.

  4. #44

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    Re: What is ruining my Tri-X 320?

    Some versions of "classic" Agfa Rodinal did not contain free hydroxide. The hydroxide and p-aminophenol were reacted to produce the alkaline phenolate salt of p-aminophenol. There was no excess hydroxide (evidenced by the presence of a few remaining crystals of p-aminophenol free base). The pH of these formulas would still be higher than those of most general purpose developers, but significantly lower than versions of Rodinal containing excess hydroxide.

    When it comes to figuring out which (if any) current Rodinal formulas (Adonal, R09, Blazinal etc.) contain free hydroxide, measuring the pH of the concentrate would be an indicator. Someone more knowledgeable regarding the long history of all these Rodinal formulas and current versions might be able to shed some light. Ian Grant could probably help on this.

  5. #45

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    Re: What is ruining my Tri-X 320?

    I will bow to other people's experience here, but from the formulae I've seen there's always excess hydroxide and quite a bit of it or there would not be enough basicity to activate the developer when diluted. But, like I said, I'm just an organic chemist, long out of the lab, and my speciality back then was NOT in developers.

    They made Rodinal from the free base? That's less stable and harder to purify than the HCl or other salt. Why would they do that? Hydroxide for free-basing the salt is cheap compared the junk and problems you'd carry along by starting with the free base. And you are sure the xtls were the free base?

    BTW, there's free hydroxide in normal, pH 7 water, though the concentration is quite small, which is, again, why I'm questioning terms like "free hydroxide,"

    Most pH meters won't measure pH terribly accurately once you get out of certain range and you might damage the electrode by putting it in strong base (Rodinal concentrate) so I'm not sure that's such a great idea. And don't believe anyone who quotes pH to more than one decimal place unless things have changed in pH measurement in recent times.

    One of the reasons I gave up on Rodinal is the "mysticism" surrounding it and the lack of definitive recipe. And, it involved making extremely strong solutions of either sodium or potassium hydroxide which are reasonably dangerous (you should wear goggles not just glasses) and some recipes from places I thought I could trust did not reliably work. At this stage in the history of chemical photography, I'm not willing to invest my time in developers of unknown composition. I will mix known recipes on my own from individual chemicals. One less variable.

    The point I was trying to make with earlier posts is that p-amino-phenol ought to be susceptible to making the N-oxide which ought to be highly colored, meaning tiny amounts make dramatic colors. But once you get dark purple, telling that apart from extremely dark purple with no or insufficient remaining developer may be difficult. I can't do it terribly reliably. Hence, I split my home brewed Rodinal into smallish batches and when results got odd, went to a new bottle. This sort of thing was more common in the early days. The early days of science many measurements were made by telling the difference between something and nothing not between two quantities for which you needed a calibration curve like how dark is your rodinal?.

    I think we've all heard of 40 year old bottles of Rodinal being good, but it doesn't square with my experience with home brewed stuff. It's inexpensive to make, make or buy more and see if that fixes the problem. Or try D-23 or Pyrocat-HD or a VitC based developer or HC110 or Tmax or something else you know to work.

  6. #46

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    Re: What is ruining my Tri-X 320?

    To be clear, I meant bottles that've been open for 40 years. Sealed, I bet it will keep indefinitely.

  7. #47

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    Re: What is ruining my Tri-X 320?

    Rather than "free hydroxide" I suppose a better term would be "excess". My understanding of the history of Rodinal is that most of the earlier versions were made with only enough hydroxide to convert the p-aminophenol to the alkaline phenolate salt. One way to do this would be to slowly add potassium hydroxide until nearly all the p-aminophenol free base is dissolved, or add hydroxide to entirely dissolve the p-aminophenol and then add potassium metabisulfite until a small amount of p-aminophenol free base is formed again.

    Apparently p-aminophenol HCL was never used "directly" by Agfa. In early publications it appears the first step was precipitation of the free base from p-aminophenol HCL using carbonate and sulfite. It seems later as higher purity p-aminophenol free base became available this is what was used rather than precipitation from p-aminophenol HCL.

    Again, Ian Grant could probably shed more light on the historical aspect since the evolution is rather confusing. I agree with you - it is difficult to know what/when/if any particular recipe corresponds to Rodinal.

    I agree depending on the quality of the pH meter, number of calibration points etc. it can be difficult to measure highly alkaline or acidic pH values with good repeatability/accuracy, but normally these high/low values are only rarely encountered in photographic processing. My meter does ok, but it is important to care properly for the instrument and calibrate frequently. Photographic solutions can be hard on electrodes. I also agree with you on the issue of pH value precision and accuracy. With most instruments I would not bother with anything more than 1 decimal place, and with many meters even that is suspect. Fortunately when it comes to photographic processing, if one is formulating a developer there is no need for precision greater than 0.1 pH.

  8. #48

    Re: What is ruining my Tri-X 320?

    Quote Originally Posted by deej View Post
    I have been having trouble with my developing routine. The film comes out clear.

    The routine is a 1 minute prewash at 68-degrees F. Rodinal 1+50 for 17 minutes at 68-degrees F., normal agitation. 1-minute tap water stop at 68-degrees F. TF-5 archival fix for four minutes, room temperature. 10-minutes wash at 68-degrees F. My 4x5 Tri-X 320 film comes out clear:

    Attachment 144503

    My hypotheses are 1) the Rodinal is at fault, somehow bleaching off the emulsion; 2) the fixer does not agree with 4x5 Tri-X, although it works fine on my 120 and 35mm film; 3) the batch of Tri-X is faulty; or, just maybe, 4) the shutter has failed and never actually exposed the film (unlikely because I have used the same shutter with other film and not had exposure problems).

    Anybody had this quandary? Any ideas what's up? Should I just experiment with a different developer and/or fixer?

    (The first time it happened I was sure I had mis-labeled the holder as Tri-X when it actually had Portra.... But check out those notches.)
    How old is this MIXED batch of Rodinal, and have you used any of it successfully with other films?

  9. #49

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    Re: What is ruining my Tri-X 320?

    The developer is technically Adanol. The bottle was opened less than a year ago. (I did not date the bottle; thought that unnecessary with this developer!)

    I do not pre-mix rodinal or Adanol. So the batch was about one minute old from mix to pour-into-tank. I did not develop any other films with the batch I mixed that day. I only mix for what I need in the immediate situation, even if I plan to do another tank right after--I mix and use immediately every time.

  10. #50

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    Re: What is ruining my Tri-X 320?

    Very useful post, Neal! Thanks!

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