Concerned about how old your Rodinal is?
Old 01-02-2018   #1
x-ray
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Concerned about how old your Rodinal is?

I see a lot of questions on the forums as to whether a partially used bottle of Rodinal that's been sitting around for a few years is still good. I've always stated from personal experience that I've never had a bottle go bad even one that's 10 or more years old. For those that have reservations, check this out.

https://petapixel.com/2018/01/02/guy...veloper-tried/

The author of the article came into a partially used bottle of Rodinal that turned out to be 100 years old. Curiosity got the best of him so he ran a test roll and found it was still good. Now you can put your mind at ease when you revisit that 10 year old bottle of Rodinal.
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Old 01-02-2018   #2
valdas
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Surely not 100years old, but still very old... The bottle says Deutsche Demokratische Republik which was not created until 1949...


P.S. oh, I see there is a comment about DDR at th bottom of the article...
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What about the clones?
Old 01-02-2018   #3
ChrisPlatt
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What about the clones?

I'm curious to know the keeping properties of the various Rodinal clones available.
If they use the original formula as claimed shouldn't they last as long as the AGFA original?
However in another forum an R09 user reports his properly-stored bottle was ineffective after just 18 months!

Chris
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Old 01-02-2018   #4
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Quote:
Originally Posted by ChrisPlatt View Post
I'm curious to know the keeping properties of the various Rodinal clones available.
If they use the original formula as claimed shouldn't they last as long as the AGFA original?
However in another forum an R09 user reports his properly-stored bottle was ineffective after just 18 months!

Chris
I'm not putting anyone down but I read so many comments that I'm skeptical of and you never know the level of expertise of that individual and whether they knew what they were doing in the first place. Ive read the formulas for most of the Rodinal variations since the 1st version and they're all closely related. I have no reason to believe R09 is any different than earlier versions as to keeping properties.

It's always a good policy if in doubt to do a clip test.
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Old 01-02-2018   #5
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I had 2 year old R09 go bad, just last month. The bottle had sediment rocks in the bottom that rattled when I shook the bottle. The bottle was about 1/4 full. I followed the exact same development procedure that had worked with the developer before, and the negatives came out about 2 stops underdeveloped. I tossed the rest of the bottle.
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Old 01-02-2018   #6
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Quote:
Originally Posted by sreed2006 View Post
I had 2 year old R09 go bad, just last month. The bottle had sediment rocks in the bottom that rattled when I shook the bottle. The bottle was about 1/4 full. I followed the exact same development procedure that had worked with the developer before, and the negatives came out about 2 stops underdeveloped. I tossed the rest of the bottle.
That sediment is actually a part of Rodinal and shouldn't be filtered. It's something I've seen since I started using it 50 years ago and has never been an issue. There's a den quite a bit written on it.
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Old 01-02-2018   #7
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Here's a link to the Rodinal formulas.

https://www.digitaltruth.com/article...ic-rodinal.php

It's my understanding there are two R09 variations but the difference is negligible with one being the original formula. At one point ratios of some components changed to bring the standard dilution from 1:49 down to 1:50. Essentially though they're all basically the same.
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Old 01-02-2018   #8
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I looked over the various formulas. At one point there was a change from sodium hydroxide to lithium hydroxide. The only reason I could think of to do this is the Lithium hydroxide would be more active than sodium hydroxide. Possibly it was cheaper at the time but would essentially do the same thing. They're both strong alkaline agents which raise the ph of the solution.

Also sodium Sulfite was used. This often is used as a silver silver to reduce grain and help retard oxidation.

Potassium carbonate was added at one point and may have been to accelerate development and partially buffer the ph. Potassium metabisulfate also appeared for a while. This is purely to buffer the alkali in the solution.

Citric acid also came and went. I'm not sure why this was added. Possibly it was part of the buffer or as an anti oxidant.

Really though the changes have been more in an attempt to buffer the solution than changes in the active components.
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Old 01-02-2018   #9
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My R09 also went off within a few months too, so I doubt it's the old formula exactly. That particular formulation does not like air or light for sure.
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Old 01-02-2018   #10
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Drop clear glass marbles into the container to minimize air/oxygen exposure. It's possible that the oxygen is reverting 4-Aminophenol back to what is essentially Tylenol.
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Old 01-02-2018   #11
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I have a 1L bottle of Rodinal, unopened. It was bought for $2 at a Goodwill then lived for almost a year in the trunk of my car. Through the hot and the cold. I'm not sure what to do with it now.

Phil Forrest
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Old 01-02-2018   #12
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Quote:
Originally Posted by valdas View Post
Surely not 100years old, but still very old... The bottle says Deutsche Demokratische Republik which was not created until 1949...


P.S. oh, I see there is a comment about DDR at th bottom of the article...
Maybe, but I remember a report of a Rodinal bottle being found in the 60s in a bombed building in Germany and it was still good. I keep my Rodinal at indoor temperatures (in the California Democratic Republic) without A/C at times close to 85 degrees F. It is 12 years old and I use it very rarely, I developed a roll 4 weeks ago and the negatives were perfect without adding time.


This is the dust magnet expired Kodak Technical Pan in Rodinal:

Technical Pan Rodinal by John Carter, on Flickr
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Old 01-02-2018   #13
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I have a bottle I've used about half of and it's been open I know for 4 year and maybe 5 that's still good. I did several runs of Pan F in it this past summer. I've been given partial bottles that were many years old that were still good. They were the old amber glass with the rubber stopper that you used a hypodermic syringe and needle to extract the liquid.

If you're concerned about oxidation there's a product you can buy called Bloxygen. Bloxygen is pure Argon gas which is completely inert. When you use your Rodinal just put the aerosol can nozzle up to the mouth of the Rodinal bottle and release some of the Argon for about four seconds and then cap the Rodinal. It drives out the oxygen and prevents oxidation. It works with open wine and oil based paint and varnish also. I use it with wine if I only want a glass.
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Old 01-03-2018   #14
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A glass bottle and Bloxygen will extend the life of every developer. I’ve stored partial bottles of DD-X, Sprint Quicksilver, Microphen, Perceptol, Studionol and yes, R09 without any noticeable change in activity. If DD-X or Microphen can last years stored this way then RO9 will last forever plus.
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Old 01-03-2018   #15
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Now is the right time to start a rumour about the mythical properties of 100 year half-empty bottles of Rodinal. No one should accept using anything less.

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Old 01-03-2018   #16
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My R09 was opened in 2009 when I bought it and I used it a couple of weeks ago. It is fine. Here is a picture.

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Old 01-03-2018   #17
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Somewhat off topic, but I have two bottles of Rodinal bought in 2000 that have never been opened and have been stored on a shelf in the basement. One day I'm going to have the time to do a test strip.
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Old 01-03-2018   #18
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Quote:
Originally Posted by p.giannakis View Post
My R09 was opened in 2009 when I bought it and I used it a couple of weeks ago. It is fine. Here is a picture.

None of the Rodinal formulas that I've seen have deviated from the original formula enough to be concerned about longevity of the concentrate. I seriously doubt R09 is any different.

I'd like to know more about the circumstances where it's claimed the developer went bad. What was used to measure the concentrate? Was it mixed and let sit for a period of time before use? We're these folks using extreme dilutions like for stand development or we're they using standard dilutions like 1:25 or 1:50? What film? Was there enough Rodinal for the film area being processed. Due to the concentration of Rodinal it's quite easy to make errors.
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Old 01-03-2018   #19
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Quote:
Originally Posted by x-ray View Post
None of the Rodinal formulas that I've seen have deviated from the original formula enough to be concerned about longevity of the concentrate. I seriously doubt R09 is any different.

I'd like to know more about the circumstances where it's claimed the developer went bad. What was used to measure the concentrate? Was it mixed and let sit for a period of time before use? We're these folks using extreme dilutions like for stand development or we're they using standard dilutions like 1:25 or 1:50? What film? Was there enough Rodinal for the film area being processed. Due to the concentration of Rodinal it's quite easy to make errors.
If you're asking me, my dilution was 1:50 (6ml in 300ml tank), 12.30 mins on 18 degrees for T-MAX 400 film. My R09 is so oxidised that is very dark brown and there are flakes of developer floating but small enough to be sucked into a syringe (still goes inside the tank).
Stand and semi-stand development was always problematic for me so I avoid using them.
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Old 01-03-2018   #20
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6 ml in a 300ml tank: Do you mix the Rodinal and distilled water together first in a graduated cylinder and let them sit for a bit to thoroughly mix?
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Old 01-03-2018   #21
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Why anyone would take a chance on their negatives and use potentially old chemicals to try to develop them is just beyond me. It's not that the chemicals do cost an arm and leg. But oh well SD cards don't go old anyway.
Have fun in your darkroom adventures.
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Old 01-03-2018   #22
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I would never ever use marbles or buy compressed gas to squirt into my developer.
Too much trouble! I choose Rodinal (and HC110) for simplicity, ease of use and longevity.

I have no way to authenticate these reports, but they are there nonetheless.
I suppose I'll just have to wait 100 years to see which Rodinal clone is best...

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Old 01-03-2018   #23
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Quote:
Originally Posted by x-ray View Post
I looked over the various formulas. At one point there was a change from sodium hydroxide to lithium hydroxide. The only reason I could think of to do this is the Lithium hydroxide would be more active than sodium hydroxide. Possibly it was cheaper at the time but would essentially do the same thing. They're both strong alkaline agents which raise the ph of the solution.
The alkali has no effect on Rodinal's keeping properties.

I described some of the chemistry associated with the para-aminophenol in Rodinal here: https://www.rangefinderforum.com/for...5&postcount=22

Quote:
Originally Posted by x-ray View Post
Also sodium Sulfite was used. This often is used as a silver silver to reduce grain and help retard oxidation.
Modern Rodinal has metabisulfite and hydroxide in the formula. At the alkaline pH that the hydroxide creates, the metabisulfite is reduced to sulfite. A litre of 1:25 strength Rodinal has about as many sulfite ions as 10 grams of sodium sulfite. This is a fifth as much sulfite as a litre of D76 1+1 or half as much as a litre of Xtol 1+3. This sulfite and the carbonates and citrates buffer the pH and aid in preventing autoxidation. These are very important for storage but how substantially they change between formulae is unclear. The different formulae all are adequately buffered and protected from oxidation at the factory but that is not always a good predictor of their behaviour over time.

Even more important than the formula is the packaging. The bottles or containers need to prevent diffusion of oxygen for the developer to last. The capacity of containers to do this is certain to vary between manufacturers.

My store of Rodinal is from 1998 and works fine with no change in development time. I bought some R09 One Shot in 2011 but haven't opened it yet. Hopefully it will be okay when I get to it.

Marty

Last edited by Freakscene : 01-10-2018 at 16:56. Reason: Added detail
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Old 01-03-2018   #24
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Quote:
Originally Posted by Daryl J. View Post
6 ml in a 300ml tank: Do you mix the Rodinal and distilled water together first in a graduated cylinder and let them sit for a bit to thoroughly mix?
I don't use distilled water, just tap water. I pour the 6 ml in a cylinder and I give it a stir with the thermometer. Then pour in the tank.
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Old 01-06-2018   #25
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Transferring the concentrate into a well-stoppered glass bottle
might be a good idea, but I'd rather not go to the trouble.

Like the clones IIRC later AGFA Rodinal did come in a plastic bottle.
Maybe current manufacturers failed to copy that formula as well.

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Old 01-06-2018   #26
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Quote:
Originally Posted by ChrisPlatt View Post
Transferring the concentrate into a well-stoppered glass bottle
might be a good idea, but I'd rather not go to the trouble.

Like the clones IIRC later AGFA Rodinal did come in a plastic bottle.
Maybe current manufacturers failed to copy that formula as well.

Chris
Chris I have a print on my desk that I think you'll like. I matted it and need to find a box to ship it.

If you're concerned about oxidation of anybliquid developer get yourself son Bloxygen. It's available reasonably off Amazon.
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Old 01-07-2018   #27
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I still have two unopened bottles still in the orange box. almost 20 years old. Stored in a dark closet. This is good to know.
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