Rodinal gets better with age?

StoneNYC · Nov 15, 2013

I just cracked a new bottle of Rodinal.

I developed a bunch of films the same as I always do, no variation, and I noticed that the grain structure in all of the images seems to be a little fuzzier and less sharp then I remembered so I compare them to all the other images that I shot and souped in the older bottle of Rodinal, and it seems like the ones that were at the end of the old bottle were much sharper than the new images.

The old bottle had gone and become crystallized and they were chunks of crystals in the bottle, as I understand it you're supposed to shake those up and they sort of break up and then you can use it and develop as normal.

Is it possible that through not shaking enough each time I used some of the chemistry, the concentration of whatever is in those crystals ended up higher towards the end of the bottle therefore giving me a sharper images?

And if so, does anyone know what the chemical is in those crystals, and if it's possible to add it to a mixture of Rodinal to give it a sharper look at the beginning of the bottle?

I'm not a chemist, so a lot of this is sort of abstract to me, but if that's the case with the crystals then I'd like to be able to replicate that look earlier on when the bottle is new and the crystals haven't become concentrated.

Thanks.

Gerald C Koch · Nov 15, 2013

In rordinal type developers the developing agent p-aminophenol is present as a phenolate formed from sodium or potassium hydroxide. Such a phenolate can absorb carbon dioxide which reduces the developers activity. The phenolate is converted back to the developing agent and sodium or potassium carbonate. Both compounds are insoluble in the developer and crystalize out. There is also a reduction in the alkalinity of the concentrate. For samples with a lot of precipitate, if you cannot get it to redissolve by shaking and heat it really should be discarded.

Steve Smith · Nov 15, 2013

Rodinal is well known for staying the same with age!

Steve.

Gerald C Koch · Nov 15, 2013

Steve Smith said:
Rodinal is well known for staying the same with age!

Staying perhaps usable but certainly not the same as fresh. The useful life can be extended by transferring the concentrate to small glass bottles.

StoneNYC · Nov 15, 2013

Gerald C Koch said:
In rordinal type developers the developing agent p-aminophenol is present as a phenolate formed from sodium or potassium hydroxide. Such a phenolate can absorb carbon dioxide which reduces the developers activity. The phenolate is converted back to the developing agent and sodium or potassium carbonate. Both compounds are insoluble in the developer and crystalize out. There is also a reduction in the alkalinity of the concentrate. For samples with a lot of precipitate, if you cannot get it to redissolve by shaking and heat it really should be discarded.

Doesn't this kind of contradictory but my experience has been?

One of the things that happened was that like someone mentioned above, I transfer my Rodinal from the original plastic bottle to glass bottles. I have one larger storage bottle, and then a mini smaller bottle that goes with the rest of my kit that has a dropper. So periodically I refill the smaller bottle from the larger one.

About two months ago, I went to refill from the larger bottle and noticed that the plastic cap on the larger bottle had cracked and that the developer inside had gone very much more crystallized than I had ever seen it. But when looking at the negatives I didn't notice any issues, the exposure was correct, and the image seemed very sharp, it didn't seem sharper than before, but I was more concerned about it looking unsharp and so I wasn't really thinking about it. It was only with this new bottle that I went to look and noticed that it seemed as if the older contaminated with oxygen bottle of Rodinal seem to produce sharper images. Does this mean if I leave the container open for a couple days and sort of allow that process to happen, that I might be able to cause the effect of the "aged" Rodinal?

You said to throw it out, but in fact I was able to use it and get seemingly better results...

Alan Johnson · Nov 15, 2013

StoneNYC said:
Doesn't this kind of contradictory but my experience has been?

One of the things that happened was that like someone mentioned above, I transfer my Rodinal from the original plastic bottle to glass bottles. I have one larger storage bottle, and then a mini smaller bottle that goes with the rest of my kit that has a dropper. So periodically I refill the smaller bottle from the larger one.

About two months ago, I went to refill from the larger bottle and noticed that the plastic cap on the larger bottle had cracked and that the developer inside had gone very much more crystallized than I had ever seen it. But when looking at the negatives I didn't notice any issues, the exposure was correct, and the image seemed very sharp, it didn't seem sharper than before, but I was more concerned about it looking unsharp and so I wasn't really thinking about it. It was only with this new bottle that I went to look and noticed that it seemed as if the older contaminated with oxygen bottle of Rodinal seem to produce sharper images. Does this mean if I leave the container open for a couple days and sort of allow that process to happen, that I might be able to cause the effect of the "aged" Rodinal?

You said to throw it out, but in fact I was able to use it and get seemingly better results...

It may be that air in the large container causes oxidation of sulphite to sulphate, which lowers the pH. Some p-aminophenol may then crystallise out.
From 1910, "small quantities of white salt are deposited....formed by the action of the air on the sulphite used.."
But "In no way is the energy of the developer affected thereby"
See p26-7:
http://www.archive.org/stream/agfabookofphotog00barrrich/agfabookofphotog00barrrich_djvu.txt

StoneNYC · Nov 15, 2013

Alan Johnson said:
It may be that air in the large container causes oxidation of sulphite to sulphate, which lowers the pH. Some p-aminophenol may then crystallise out.
From 1910, "small quantities of white salt are deposited....formed by the action of the air on the sulphite used.."
But "In no way is the energy of the developer affected thereby"
See p26-7:
http://www.archive.org/stream/agfabookofphotog00barrrich/agfabookofphotog00barrrich_djvu.txt

Hmmm, well they speak of "energy" I assume they mean it's ability to properly develop the film, but does that specifically mean that the characteristic of the grain structure's look (acutence vs sharpness etc) stays the same? Might that change somehow? If the chemicals inside the developer are changing because of oxidation, SOMETHING must be affected, if the ability to develop the film to normal isn't affected, perhaps the look of it is altered somehow?

Shawn Dougherty · Nov 15, 2013

Nothing to add, just want to make sure that this thread shows up in 'My Posts'.

markbarendt · Nov 15, 2013

StoneNYC said:
You said to throw it out, but in fact I was able to use it and get seemingly better results...

Better is a relative concept. Beauty is in the eye of the beholder and all that jazz.

More dilute developers will some times create slightly sharper images. If your Rodinol is less active it's kinda like being more dilute so... maybe IDK?

Silly questions;

First, made any changes in the camera lenses you regularly use over the time you noticed the difference? Different lenses "see" differently, they each have a personality if you will.

Second, knowing you scan, have there been any updates/changes to your software or your hardware?

cliveh · Nov 15, 2013

Rodinal is an excellent developer and if you stick with this for many years to come, at the same dilution it will allow you to fine tune other aspects of your photographic processing.

Gerald C Koch · Nov 15, 2013

As the developer absorbs oxygen and carbon dioxide from the air its activity is reduced. This change is small enough in most cases to cause any visible change in the negatives. For severe cases developing times may need to be extended a bit. My main point was that activity will not increase with age but rather decrease.

StoneNYC · Nov 15, 2013

Gerald C Koch said:
As the developer absorbs oxygen and carbon dioxide from the air its activity is reduced. This change is small enough in most cases to cause any visible change in the negatives. For severe cases developing times may need to be extended a bit. My main point was that activity will not increase with age but rather decrease.

So then how do you explain the difference in Acutance?

And note nothing absolutely nothing has changed, I literally developed the same rolls from the same camera, same water same scanner same film holders same everything the only thing that was different was the new versus old batch of Rodinal. Even the rolls (of Acros100) were from the same pro pack... Haha

It's too bad that I don't have anymore of that old bottle to do a serious comparison, however I could always throw a mini bottle of it open and leave that there for a couple of days and then see what happens as the stuff crystallizes and darkens, and if that in fact makes a sharper image if I do a direct comparison on the same roll of film or something.

Gerald C Koch · Nov 15, 2013

StoneNYC said:
So then how do you explain the difference in Acutance?

Once you add a scanner to the process you add another variable. Do you see any difference in actual silver prints from the two sets of negatives? Even so any perception of grain or acutance differences is highly subjective.

StoneNYC · Nov 15, 2013

Gerald C Koch said:
Once you add a scanner to the process you add another variable. Do you see any difference in actual silver prints from the two sets of negatives? Even so any perception of grain or acutance differences is highly subjective.

Sadly I don't make optical prints, not even contact prints yet...yet....

But my process is fine tuned as far as scanning goes, and the height of the two images scanned hadn't changed, and I did compare OTHER films, I shoot Acros100, TMX, and EastmanXX, obviously the XX isn't going to be a good judge of grain anyway, but even the TMX was fuzzy although finer grained than the Acros, still not defined.

I'll be processing some FP4+ tonight so we shall see...

RalphLambrecht · Nov 15, 2013

+1' subcribed posts' that is.

Tom1956 · Nov 15, 2013

Jaclyn Smith gets better with age. I doubt developer does.

StoneNYC · Nov 15, 2013

Michael R 1974 said:
Fairly easy to explain. You have no way of objectively evaluating acutance, nor have you conducted controlled, side by side tests. So you don't know there is a difference in acutance.

But maybe I'm using the wrong word, but when the edges of the dots are fuzzy instead of looking sharp, I assume that Acutance is the level at which the edges of the dots appear sharp.

Xmas · Nov 15, 2013

if you had been using a bottle of Rodinal from 1995 and just bought NOS Agfa Rodinal 2005 or R09 then they are not the same exactly.

I've used a 1/4 full bottle that was 25 years old until last drop and solid particle and not noticed a different with next bottle.

We need a real organic chemist cause I thought Rodinal kept well cause of an excess of preservative and if you filtered it and rebottled it would not last long?

StoneNYC · Nov 15, 2013

Xmas said:
if you had been using a bottle of Rodinal from 1995 and just bought NOS Agfa Rodinal 2005 or R09 then they are not the same exactly.

I've used a 1/4 full bottle that was 25 years old until last drop and solid particle and not noticed a different with next bottle.

We need a real organic chemist cause I thought Rodinal kept well cause of an excess of preservative and if you filtered it and rebottled it would not last long?

No I checked with Adox directly, the stuff I have is the original Rodinal formula made by / labeled Adox Adonal (about a year or two ago adox attained the rights to fully make the original version with no alteration separating them from those that make the R09 version, The Adox representative told me that they actually had also finally purchased the name and that on future productions they would actually be able to label the bottles "Rodinal" , so this is not the R09 version ... But original.

Yea, we need Ron to get in here and comment

markbarendt · Nov 15, 2013

StoneNYC said:
But maybe I'm using the wrong word, but when the edges of the dots are fuzzy instead of looking sharp, I assume that Acutance is the level at which the edges of the dots appear sharp.

Is the grain affected the same way as the subject?

StoneNYC · Nov 15, 2013

markbarendt said:
Is the grain affected the same way as the subject?

I'm not sure exactly what you mean by that? The role that I have lots of comparison shots for Acros100 was shot in studio with strobes, so there is no motion blur if that's what you mean?

markbarendt · Nov 15, 2013

StoneNYC said:
I'm not sure exactly what you mean by that? The role that I have lots of comparison shots for Acros100 was shot in studio with strobes, so there is no motion blur if that's what you mean?

Just eliminating possibilities.

Grain should be visible at some magnification somewhere in the shots. Is the grain affected the same way the content of the shot is?

Gerald C Koch · Nov 15, 2013

Grain cannot be evaluated from a positive image because what is mistaken for grain is actually the space between the grains. Remember everything is reversed in a positive image. Grain can only be evaluated by looking a the actual negatives with a microscope. This is a very common misconception.

StoneNYC · Nov 15, 2013

Gerald C Koch said:
Grain cannot be evaluated from a positive image because what is mistaken for grain is actually the space between the grains. Remember everything is reversed in a positive image. Grain can only be evaluated by looking a the actual negatives with a microscope. This is a very common misconception.

Alright, I'll dig out my microscope and compare the two different pieces of film and let you know what I think

MattKing · Nov 15, 2013

I'd be very surprised if there hasn't been some change in Rodinal, considering what it has gone through in the last decade or so.

Rodinal gets better with age?

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