When will Rodinal go bad?

Usagi · Oct 20, 2010

I have two partially used bottle of Rodinal. One is perhaps bought 5-6 years ago, the another one.. I can't remember.

I just run a test batch with a Rodinal mixed from the older bottle (in the attachment, the left bottle). The results were really uneven. Actually I haven't never seen so bad results before. My luck that I used Rodinal for sheet film developing test, not for a real photograph.

As I have always read that rodinal lasts for decades, even century I wonder that how and when will rodinal actually go bad?
When rodinal is badly expired/exhausted, does it give uneven results or only thinner negatives?

Relayer · Oct 20, 2010

My question is also related to the persistence of Rodinal.
In an old book I found the following recommendations: add 0.2gr/l of Sodium benzenesulfinate (C6H5NaO2S) to Rodinal concentrate as antioxidant. Can someone comment this? Possible to use Hydroxylamine hydrochloride as an antioxidant?

mcgrattan · Oct 20, 2010

I have some R09 that I've had for about 3 years, and which is completely black and has a load of crystals floating in it. I tested it out last week and the results were fine. About what I'd expect. A bit grainier than the Ilford and Paterson developers I use more regularly, but still OK.

Ronald Moravec · Oct 20, 2010

I keep mine in GLASS bottles, small ones 2 oz. Get rid of the plastic.

Rodinal used to come in 8 oz glass bottles ( as late as 1970) with a rubber stopper I punctured with a hypodermic.
I would actually have to introduce air to draw more out after a few draws. Don`t you just love the government looking out for us?

Now I just decant to small glass bottles when I first buy it and use a tranfer pipette to measure it out to a grad cylinder.

How long being the question. My test is still in progress. I rebottled it in 1998 and periodically I test it.
Would 12 years make you happy? That is the results so far in 2010.

The bottles are from Agfa Viradon toner and they have very good sealing caps, best I have seen.

Gerald C Koch · Oct 20, 2010

Relayer said:
My question is also related to the persistence of Rodinal.
In an old book I found the following recommendations: add 0.2gr/l of Sodium benzenesulfinate (C6H5NaO2S) to Rodinal concentrate as antioxidant. Can someone comment this? Possible to use Hydroxylamine hydrochloride as an antioxidant?

You don't need to add an anti-oxidant because Rodinal already contains one. It would be hard to dissolve anything in the syrupy concentrate. You can always decant the Rodinal into several smaller glass bottles to prevent oxidation.

Relayer · Oct 20, 2010

Gerald C Koch said:
You don't need to add an anti-oxidant because Rodinal already contains one.

I ask about home-made Rodinal

Gerald C Koch · Oct 20, 2010

Relayer said:
I ask about home-made Rodinal

Sorry, I was confused by the use of a capital "R" which implies the commercial developer.

Yes, you can add the 0.2 g/l of sodium benzenesulfinate.

Relayer · Oct 20, 2010

Gerald C Koch said:
Sorry, I was confused by the use of a capital "R" which implies the commercial developer.
Yes, you can add the 0.2 g/l of sodium benzenesulfinate.

problem that I haven't it. is the Hydroxylamine hydrochloride in 1-2g/l will be good substitution?

A49 · Oct 20, 2010

Usagi said:
I have two partially used bottle of Rodinal. One is perhaps bought 5-6 years ago, the another one.. I can't remember.

As I have always read that rodinal lasts for decades, even century I wonder that how and when will rodinal actually go bad?
When rodinal is badly expired/exhausted, does it give uneven results or only thinner negatives?

My experiences are: At first that the stuff keeps over 20 years if stored in well closed bottles.

At second that a half full bottle of Rodinal that I kept for about three years brought the same results as fresh Rodinal twice as much diluted. The old 1+100 is nearly the same as the new 1+200. That means in my case it became weaker but the results were still fine if I took that into consideration and diluted it only half as much as the fresh Rodinal.

For 5-6 years of storing Rodinal in half full bottles I have no experience. If your Rodinal was mixed well without crystals or other unevenesses in the working solution so I wonder that it brought you uneven negatives. But maybe at some point even Rodinal goes really bad.

Andreas

Gerald C Koch · Oct 20, 2010

Relayer said:
problem that I haven't it. is the Hydroxylamine hydrochloride in 1-2g/l will be good substitution?

Sorry, I have no idea if hydroxylamine hydrochloride would work. The highly basic nature of the concentrate can "chew" up some chemicals. Certainly hydroxylamine hydrochloride would be converted to the free base. I think the best idea is to use small glass bottles for the concentrate.

dynachrome · Oct 20, 2010

When I was 14 I went to a local pharmacy to buy a hypodermic needle. The pharmacist asked what I wanted it for. I explained that Rodinal came with a rubber stopper and that it would keep better of I drew it out through the rubber stopper with the needle. He gave me a bad look and told me that of I didn't get out of the store right away he'd call the police.

erikg · Oct 20, 2010

And rightly so, you crazy hippy.
sorry, i couldn't resist. i've found that Rodinal in the plastic bottles to last 2-3 years, maybe more, but it does loose some activity, i'll up the time a bit as i finish off a bottle.

piu58 · Oct 21, 2010

Usagi said:
I just run a test batch with a Rodinal mixed from the older bottle (in the attachment, the left bottle). The results were really uneven.

The reason for uneven development ist not old developer, but too less agitation. Weak developer leads to weak density in the highlights.

Rodinal is cheap. I would not bother with an 6 year old bottle.

Athiril · Oct 21, 2010

Usagi said:
I have two partially used bottle of Rodinal. One is perhaps bought 5-6 years ago, the another one.. I can't remember.

I just run a test batch with a Rodinal mixed from the older bottle (in the attachment, the left bottle). The results were really uneven. Actually I haven't never seen so bad results before. My luck that I used Rodinal for sheet film developing test, not for a real photograph.

As I have always read that rodinal lasts for decades, even century I wonder that how and when will rodinal actually go bad?
When rodinal is badly expired/exhausted, does it give uneven results or only thinner negatives?

You didn't develop in a aluminium bbq tray did you? was it face up? face down for the sheet? Initial agitation?

john_s · Oct 21, 2010

Rodinal (in the Agfa days) was changed by the accountants. Although the developing agent p-aminophenol is quite a cheap chemical, potassium hydroxide is cheaper, so they used more of the latter and less of the developing agent. The consequence was similar activity when new and probably less long term life. I don't know about the Rodinal currently made.

The Agfa accountants also changed Viradon direct brown toner, removing the only expensive ingredient (selenium).

Alan Johnson · Oct 21, 2010

There is a lot of evidence for the long life of Rodinal in absence of air.
When air is present it may be that this first reacts with the sulfite preservative and not until this is all gone does the p-aminophenol oxidation occur.It's just a theory,but it is based on the observation that when making PaRodinal from tylenol(paracetamol) the mix of tylenol and sodium hydroxide goes black very quickly if sodium sulfite is not present.

Relayer · Oct 21, 2010

Gerald C Koch said:
Sorry, I have no idea if hydroxylamine hydrochloride would work. The highly basic nature of the concentrate can "chew" up some chemicals. Certainly hydroxylamine hydrochloride would be converted to the free base. I think the best idea is to use small glass bottles for the concentrate.

hydroxylamine hydrochloride used as antioxidant in old color developers (based on CD-1). ascorbic acid also well known as antioxidant component.
ok. I starting some experiment - mix different antioxidants with my homebrew ez-rodinal, place it in open bottles and will testing it activity after 2-3 week

Usagi · Oct 21, 2010

Athiril said:
You didn't develop in a aluminium bbq tray did you? was it face up? face down for the sheet? Initial agitation?

I developed face up. Plastic trays.
Four kind of methods: Slosher tray (just testing the idea), Paterson Orbital agitated like slosher, tray and one sheet, agitation by lifting corners and jobo drum.

As I got much better results with D76 (same agitation, same trays, ..) so I suspected Rodinal.
But I have to do some tests to ensure that it is really rodinal that plays some role in very uneven development. It could be also film + developer combination that just don't work well.

Usagi · Oct 22, 2010

Did another test, now with D-76 and Rodinal using again Efke 25 sheet film.
Now I took Rodinal from the another bottle (the right one bottle on the attachment picture of the first message).

Really even result! Perhaps best I have ever got from Efke 25 and Efke 50!
The D-76 and Rodinal 1+50 gave similar results so fault was not caused by the film or my tank.

So I guess that the another bottle of Rodinal is somehow gone bad. Ofcourse another test would make this assumption clear.

Richard S. (rich815) · Apr 27, 2011

I've used old Rodinal and have never seen any problem or changes needed. Before recently though I think the oldest bottle I used was about 6 years old. Few months ago I won an auction on eBay for a 1/2 full bottle of Agfa Rodinal. It's been opened but the cap wrapped shut with masking tape. It has "Made in West Germany" printed on the bottle. Have used it to develop 35mm and 120 of Tmax400, Acros, Neopan 400, Shantou ERA 100, Shanghai GP3, Plus-X and APX400 using normal times with great results for all.

German reunification was 1990. So this bottle of jet black ink I have is at least 20 years old.

Examples of two results here:

http://www.flickr.com/photos/rich8155/5508112717

http://www.flickr.com/photos/rich8155/5622048507

Thomas Bertilsson · Apr 27, 2011

A good friend of mine recently developed some film in Rodinal that was from the 1970s, still in its original glass bottle. Results were just fine.

Decanting to glass amber bottles is definitely a good idea.

- Thomas

Роберт · Apr 27, 2011

The showed bottles: Agfa (before 2004) and Agfa Photo 2004-2006. Silar plastic bottles, almost no diffusion like glas.

I did a densiometric test for Rodinal 1+25 with APX 100.

Rodinal 4 years old:

Rodinal new:

The differences are very small if not neglectible.

michaelbsc · Apr 27, 2011

Thomas Bertilsson said:
A good friend of mine recently developed some film in Rodinal that was from the 1970s, still in its original glass bottle. Results were just fine.

Decanting to glass amber bottles is definitely a good idea.

- Thomas

I have an unopened bottle of more recent vintage that is in the plastic containers.

Is it worthwhile to decant this. I have been assuming it could sit unopened for several years, if not decades, and be fine.

Thomas Bertilsson · Apr 27, 2011

michaelbsc said:
I have an unopened bottle of more recent vintage that is in the plastic containers.

Is it worthwhile to decant this. I have been assuming it could sit unopened for several years, if not decades, and be fine.

Test it first. If the developer is still good, do it.

All developers eventually oxidize and go bad. Rodinal just happens to be tremendously resistant to it. It's a good idea to keep all developers stored with as little exposure to air as possible.

Of course, if you use it up quickly, you may not have to.

- Thomas

wogster · Apr 27, 2011

michaelbsc said:
I have an unopened bottle of more recent vintage that is in the plastic containers.

Is it worthwhile to decant this. I have been assuming it could sit unopened for several years, if not decades, and be fine.

The issue with plastics is that many of them are solid enough to keep relatively large liquid molecules in place, but are porous enough that much smaller oxygen atoms can pass right through. Plastics that are oxygen proof would be very expensive and may not be chemical proof, so you would need a bottle that has a chemical proof layer, then a oxygen proof layer and then you might need another layer to stiffen it. Wine box liners are mylar with an aluminum layer to make the bag air tight.

Most developer bottles are designed so that they are resistant enough to get the developer through the supply chain, so putting it into a glass bottle is a good idea if you want it to last.

When will Rodinal go bad?

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