Rodinal exhaustion?

The last batch of negatives developed in Rodinal 1:50 are extremely grainy and low contrast. I've used Rodinal for the last ten years as my primary low/medium B&W developer, and always found it pretty good. Developer exhaustion is only one of the variables, but I'm erring towards developer as the culprit.

Rodinal has a reputation for being immune from the effects of time. My current bottle is about 6 years old and 3/4 empty. I abandoned a previous bottle at a similar point because I became doubtful of its effectiveness.

Am I looking in the wrong place, or has the Rodinal succumbed to the effects of old age?

As I understand, the longevity of rodinal concentrate greatly depends on which version of the soup you're using, with several derivatives/variants being available. Some of them will be good for years, some of them may last only a few months. I can't say off the top of my head what the keeping properties of the different variants are. But it is certainly possible that the one you're using happens to be dying.

My Rodinal (500mL) is only 3 and a bit years old, down to perhaps 10-20% of its volume and I can hear quite a bit of precipitate scratching around at the bottom of the bottle. It's working fine.

But if you had an extreme amount of precipitate that might be a sign of its EOL. Some precipitate seems to be normal but unusually much could mean that what makes it stable has been removed from solution. This, apparently, can be forced by refrigerating it.

I have recently ordered a fresh bottle and put into storage in my basement chemical cabinet, just in case whats left in the old one dies on me. I guess I should do the occasional clip test to monitor it.

I had a roll of Ilford come out completely blank out of a 2 year old bottle of Rodinal, i was not amused

You don't say what film you used. Rodinal contains free Hydroxide that can lead to issues with some emulsions if temperature control is lax. Acros & Rodinal is the common cause of issues with emulsion lifting from the base, excessive graininess caused by reticulation and yet used carefully Acros and Rodinal can produce superb results.

Ian

Ian Grant said:

You don't say what film you used. Rodinal contains free Hydroxide that can lead to issues with some emulsions if temperature control is lax. Acros & Rodinal is the common cause of issues with emulsion lifting from the base, excessive graininess caused by reticulation and yet used carefully Acros and Rodinal can produce superb results.

Ian

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Film is Fomapan 100. I've used this without problems, except for a period when I used stand development which gave a similar appearance to the recent issue. Your temperature control point is interesting, as I suspect the recent film developed at 23 degrees rather than 20 (68F). Not sure if 3 degrees would promote reticulation, but the film is slightly over-developed as you would expect. Stand development temperature is also difficult to control in domestic conditions, and there's usually a few degrees drift over a hour, which makes me think you may be onto something.

I have a short roll in a stand solution at the moment (1:85) to see whether that shows any improvement or otherwise.

koraks said:

As I understand, the longevity of rodinal concentrate greatly depends on which version of the soup you're using, with several derivatives/variants being available.

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I've heard that to be the case. My current bottle is the original formula made by Adox, the previous one I abandoned was RO9. No idea how the chemistry varies.

blockend said:

Film is Fomapan 100. I've used this without problems, except for a period when I used stand development which gave a similar appearance to the recent issue. Your temperature control point is interesting, as I suspect the recent film developed at 23 degrees rather than 20 (68F). Not sure if 3 degrees would promote reticulation, but the film is slightly over-developed as you would expect. Stand development temperature is also difficult to control in domestic conditions, and there's usually a few degrees drift over a hour, which makes me think you may be onto something.

I have a short roll in a stand solution at the moment (1:85) to see whether that shows any improvement or otherwise.

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Foma films have a slightly softer emulsion compared to Ilford and Kodak. While in Turkey I process my films at 27ºC most of the year, that's the tap water temperature and I can keep the whole process cycle to +/- 0.1º of that 27ºC without having to do anything, here in the UK it's much harder keeping to 20ºC

I've developed maybe a 100+ rolls of 120 Fomapan 100200 at 27ºC while living abroad and never had an issue. A friend developed a roll of 120 Tmax 400 in Xtol at my house some years ago, the results were excessively grainy and lower contrast, now I developed a roll of 35mm Tmax 400 in the same developer (replenished), stop bath and fixer and had excellent results, the only difference was my friend hadn't checked the temperature of the stop, fixer or wash water - the film wasn't at fault it was a batch I'd bought.

It doesn't need much temperature variation to cause issues, and a softer emulsion with Rodinal is far more prone to problems.

Ian

blockend said:

Your temperature control point is interesting, as I suspect the recent film developed at 23 degrees rather than 20 (68F). Not sure if 3 degrees would promote reticulation, but the film is slightly over-developed as you would expect.

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This is strange, as earlier, you said the following:

blockend said:

The last batch of negatives developed in Rodinal 1:50 are extremely grainy and low contrast.

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Combining these statements, you are saying that the film is overdeveloped, but the negatives lack contrast. That is odd.

Can you post a photograph of the negatives (not a scan of the negatives)?

Btw, 23C will not result in reticulation assuming that consecutive baths after the development weren't absurdly cold, like 10C or lower. And even then, you'd be hard pressed to get reticulation from any modern film.

koraks said:

Combining these statements, you are saying that the film is overdeveloped, but the negatives lack contrast. That is odd.

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I suspected the camera of underexposing, which is why I wasn't too concerned about developing at a higher temperature. It was a test of an old (new to me) camera, and I wanted to discern how far out the shutter speeds were, if at all. The appearance of the film isn't an effect of the exposure, but of the development. The images lack contrast when deliberately over and under exposed, and grain is very intrusive. Reticulation was a possibility as the fix had been stored in a cold garage, but it wasn't cooler than dev or stop by a degree that I would expect reticulation to occur, though that was one possibility. The negative doesn't look reticulated, but lacking in contrast on thin and dense negatives. The lens isn't the problem, I've used it a lot recently. No fixing fog either. Which leaves the developer.

A lack of contrast denotes reduced development. Simplifying: exposure determines shadow detail, development determines contrast. Hence:
Lack of shadow detail but high contrast = underexposed and overdevelopment.
Lack of shadow detail and low contrast = underexposed and underdeveloped.
Sufficient shadow detail but low contrast = sufficiently exposed bit underdeveloped
Sufficient shadow detail and high contrast = sufficiently exposed and overdeveloped
Reduced contrast as a result of overexposure only starts to become a problem at gross overexposure as you push the image onto the film shoulder. With films like Foma100, this means in excess of 3 stops overexposure.

Your last posts clearly suggests underdevelopment, so I think you're right in questioning the status of your rodinal bottle.

koraks said:

Your last posts clearly suggests underdevelopment, so I think you're right in questioning the status of your rodinal bottle.

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I think you're correct. I just stand developed an 8 exposure roll, exposure was metered, development, stop and fix and was were all within 1 degree C. When semi-stand developing in Rodinal previously I diluted 1:100 and gave it 1 hour. This time I used 1:85 for an hour and the negatives were almost devoid of image. The Rodinal is kaput. Thanks everyone for the input!

Rodinal concentrate contains a mixture of sulfite and aminophenolate. The sulfite is oxidized by air in the bottle, at an ever increasing rate as the volume of air compared to that of the liquid increases.
When the sulfite is all gone the aminophenolate will oxidize rapidly resulting in loss of activity.
Sometimes developing agents and sulfite protect each other from oxidation, as is the case with metol and sulfite (Mees & James 3rd ed p293).It may be that the long life of Rodinal results from an effect of this type.

OK, I am not a chemist but I will say this to even out the informal output.

A few years ago, in a deal, I got some VERY, VERY old (I would say about 40 years old) Rodinal that had turned as black as black coffee. There was considerable sediment at the bottom of the bottle. I saw this as a stellar opportunity to see just how 'good' old Rodinal was. First, I carefully filtered out all the sediment and was left with black liquid. Carefully, I tested its potency with a bit of exposed Pan F + and, simultaneously, compared another bit of similarly exposed Pan F + with 'new' Rodinal.

Here is what I found: with multiple attempts to get the old to perform as well as the new, I found that precisely one third more of the old was needed to achieve the same contrast as the new. That is not bad at all for something that looks defunct.

So, that means that if I want to make 240mL of a working solution developer I would dilute the new Rodinal at 80X (1 + 79). This equates to diluting the old Rodinal only 60x (1 + 59) to achieve the same result. (This is the same as saying 1.33mL of the old Rodinal is needed for each 80mL of working solution. (i.e., 1.33 + 78.67.)

Thus, I would need 3mL of new Rodinal to make a viable working solution of 240mL (3 X 80mL). I would need 4mL of old Rodinal to make an equally viable working solution of 240mL of the same potency and performance as the new.

David Lyga is very frugal and does not wish to waste developer when doing his 'clip tests'. His remedy to measure the tiny quantities needed for tiny working solution quantities for development (as little as 0.1mL Rodinal concentrate could, theoretically, be needed!) force him to ponder, seriously, just how bad would it be to store mildly diluted Rodinal (despite the severe warnings not to do that!!!). Not wanting to avoid yet another 'experiment' in order to educate myself, I did just that and now REGULARLY store this mildly diluted Rodinal (filled up in PET plastic or glass bottles: 1 + 9). I have found that this 'minor' dilution has no deleterious effect with ongoing performance; it is still strong enough to withstand oxidation, but, as a precaution, again, is stored air-tight. No, I take no chances and store this diluted Rodinal in airtight containers with glass marbles taking up the slack. Now I can to all my clip tests without having to mix larger, more serious quantities of the stuff. (Of course, the dilutions for working solution now need ten times more "Rodinal" than before.) - David Lyga

David Lyga said:

I found that precisely one third more of the old was needed to achieve the same contrast as the new.

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Thinking on similar lines, I strengthened my normal semi-stand developer ratio, sadly to no avail. There's an image, albeit next to clear film base. I'd guess a +/- 500% time increase in conventional developers to achieve a fully tonal negative. With an acutance high dilution developer like Rodinal, activity would cease long before 5 hours arrived, and probably before my single hour was up. However I admire your economy, and aim to emulate it to the successful side of complete failure. Barely. Not sure I'd be brave enough to keep stock diluted Rodinal, however. My Tetenal C41 kit earns its keep way beyond common sense, or my ability to count films processed therein. Keep brim full in concertina bottles, obviously.

If time allows a clip test, I might see if there's life in the old Rod yet at much smaller dilutions.

Alan Johnson said:

Rodinal concentrate contains a mixture of sulfite and aminophenolate. The sulfite is oxidized by air in the bottle, at an ever increasing rate as the volume of air compared to that of the liquid increases.
When the sulfite is all gone the aminophenolate will oxidize rapidly resulting in loss of activity.
Sometimes developing agents and sulfite protect each other from oxidation, as is the case with metol and sulfite (Mees & James 3rd ed p293).It may be that the long life of Rodinal results from an effect of this type.

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There's no lack of air in my Rodinal bottle. The developer isn't quite as opaque as the RO9 remnant, which is the exact colour of a Victorian cough remedy in this part of the world, but it's still pretty dark so I'm guessing the Rodinal died from a surfeit of air.

blockend:
Well, I do not mix the whole bottle of Rodinal; just about 50mL (to make 500mL of the mildly diluted Rodinal). That quantity allows me to experiment to my heart's desire. Sometimes one must act out of proportion to the written word. I have all my life and it usually has served me well. Your five hour stand development probably caused the Rodinal to go bad through oxidation, given the intense dilution. It is true: Rodinal goes bad rather quickly with much dilution, but my 10X I think serves me well, given that it is protected from air. - David Lyga

David Lyga said:

blockend:
Well, I do not mix the whole bottle of Rodinal; just about 50mL (to make 500mL of the mildly diluted Rodinal). That quantity allows me to experiment to my heart's desire. Sometimes one must act out of proportion to the written word. I have all my life and it usually has served me well. Your five hour stand development probably caused the Rodinal to go bad through oxidation, given the intense dilution. It is true: Rodinal goes bad rather quickly with much dilution, but my 10X I think serves me well, given that it is protected from air. - David Lyga

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The 5 hour approximation was purely theoretical, I don't think there's much to be gained beyond 90 minutes as Rodinal gives up the ghost even at homeopathic dilutions of 1:200+. I can see how a modest addition of water to your stock wouldn't go amiss, the chemistry is largely water anyway (presumably?)

In truth I fancy a change from Rodinal, so if anyone can recommend a suitable black and white developer for 100 ASA film that doesn't cost the earth, I'd be most grateful. There's a 30 metre tin of FP4 waiting in the fridge when the Fomapan runs out.

David, the old rodinal you tried is different from most/all of the stuff sold today. The formulation has changed and varies across brands.

I've noticed that the last 100 ml or so can be dead. I just toss as this point.

Sorry to hear of your problem,blockend. What I have always wondered about is: Is there any reliable(as in scientifically tested) info source that compares the "new" Rodinal with the original one in terms of longevity and how many versions are there now?

As far as a new developer goes, I have been very happy with Xtol. I feel sure I had seen it under £10 for the 5L powder recently but now it is nearly £15 even at Sharif Photographic, a small retailer in Dumfries which is about as competitive as any U.K retailer. So it's good stuff but it seems Kodak prices for both film and chemicals have become a joke of late in terms of price. A real pity

Anyway if you decant the stock liquid into old winebags in boxes then my experience is that its longevity is OK and it is easy to dispense that way

pentaxuser

pentaxuser said:

Sorry to hear of your problem,blockend. What I have always wondered about is: Is there any reliable(as in scientifically tested) info source that compares the "new" Rodinal with the original one in terms of longevity and how many versions are there now?

As far as a new developer goes, I have been very happy with Xtol. I feel sure I had seen it under £10 for the 5L powder recently but now it is nearly £15 even at Sharif Photographic, a small retailer in Dumfries which is about as competitive as any U.K retailer. So it's good stuff but it seems Kodak prices for both film and chemicals have become a joke of late in terms of price. A real pity

Anyway if you decant the stock liquid into old winebags in boxes then my experience is that its longevity is OK and it is easy to dispense that way

pentaxuser

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I'd like to use Xtol again but $20 here is crazy. I liked using at 1+1.

Andrew O'Neill said:

I'd like to use Xtol again but $20 here is crazy. I liked using at 1+1.

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For me, because I use X-Tol replenished, that means 70 rolls at less than 30 cents per roll.
Not as cheap as it once was, but not too bad.
If I am being extraordinarily productive, and shooting 3 rolls a week, that is just over $40.00 per year for developer.

MattKing said:

For me, because I use X-Tol replenished, that means 70 rolls at less than 30 cents per roll.
Not as cheap as it once was, but not too bad.
If I am being extraordinarily productive, and shooting 3 rolls a week, that is just over $40.00 per year for developer.

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I guess I would have to get into replenishing, then. I'll consider it when I've depleted my Pyrocat-HD chemicals...which won't be for a few years!

Andrew O'Neill said:

I'd like to use Xtol again but $20 here is crazy. I liked using at 1+1.

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There are some X-Tol equivalents in Darkroom Cookbook the you brew yourself. I would think they might be cheap alternatives.