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deej
4-Jan-2016, 19:21
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:

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.)

Daniel Stone
4-Jan-2016, 19:44
Rule out developer: try different developer, same fixer
Rule out fixer: Use same developer, different fixer

How old is this MIXED batch of Rodinal, and have you used any of it successfully with other films?

Is the factory-exposed film marks (320TXP) present, or are they not there either? If they're there, something is the matter with your camera/lens. If they are not there, you have either a chemical problem(most likely the case), or the film is bad(unlikely, but Kodak has made mistakes before).

Try this, in addition:
Take an unexposed, undeveloped sheet of film, and in the light, check your fixer. The film should clear completely if the fixer is of proper strength, and not too old.

Kevin Crisp
4-Jan-2016, 20:31
There are lots of threads that claim Rodinal lasts forever. But I have twice had refrigerated bottle go bad and produce essentially clear film. If it goes from purple-ish to brown it is suspect.

If you aren't using Rodinal as a one-shot developer that could be part of it.

Jim Noel
4-Jan-2016, 20:44
Rule out developer: try different developer, same fixer
Rule out fixer: Use same developer, different fixer

How old is this MIXED batch of Rodinal, and have you used any of it successfully with other films?

Is the factory-exposed film marks (320TXP) present, or are they not there either? If they're there, something is the matter with your camera/lens. If they are not there, you have either a chemical problem(most likely the case), or the film is bad(unlikely, but Kodak has made mistakes before).

Try this, in addition:
Take an unexposed, undeveloped sheet of film, and in the light, check your fixer. The film should clear completely if the fixer is of proper strength, and not too old.

A very good answer. My suspicion is that the poster is trying to keep diluted developer, never a good idea.

peter schrager
5-Jan-2016, 02:00
try xtol 1+2 much better and holds film speed

LabRat
5-Jan-2016, 02:42
I have seen where Rodinal (stock) has gone bad, and not develop at all... One clue is if it pours out after the development deep, dark blue colored... (with no/low image...)

The pink color is from silver still remaining on the film from after fixing... If you fog/fix a piece of film, there is still excess silver that has not been reduced/removed, and will oxidize to the pink (very finely divided silver) state...

Steve K

Huub
5-Jan-2016, 06:27
The colour of the film is indeed very pink, which makes me wonder of your fix is working properly. But even then: when the film would have been exposed and developed properly, at least some image should be visible and refixing asap should cure the problem.

As Daniel has asked already: is the factory exposed film mark visible? If not: most likely there is a problem in film development and a good guess is that either your Rodinal has gone bad or you have mixed up the fix and development baths. Rodinal should only be used as a one shot developer, mixed directly before use and the concentrate should be stored at room temperature. Putting in the freezer will make it go bad as some of the chemicals will percipitate and won't go into solution again when it warms to room temperature.

If the film mark is visible, you probably have made an exposure error. The shutter may not have fired, you might have forgotten to pull the darkslide or one of those other user errors that are possible in large format. We all have been through those... ;-)

Tobias Key
5-Jan-2016, 06:34
The colour of the film is indeed very pink, which makes me wonder of your fix is working properly. But even then: when the film would have been exposed and developed properly, at least some image should be visible and refixing asap should cure the problem.

As Daniel has asked already: is the factory exposed film mark visible? If not: most likely there is a problem in film development and a good guess is that either your Rodinal has gone bad or you have mixed up the fix and development baths. Rodinal should only be used as a one shot developer, mixed directly before use and the concentrate should be stored at room temperature. Putting in the freezer will make it go bad as some of the chemicals will percipitate and won't go into solution again when it warms to room temperature.

If the film mark is visible, you probably have made an exposure error. The shutter may not have fired, you might have forgotten to pull the darkslide or one of those other user errors that are possible in large format. We all have been through those... ;-)

I agree with this. Blank film is either no exposure or no development, if the fix was no good the film would look 'milky' when you took it out of the tank. The pink colour in the film base just means you need to fix for a bit longer, I don't think it's anything to do with the film being blank.

deej
5-Jan-2016, 07:45
Thanks, Kevin. This bottle (Adox version) is less than a year old, and has successfully done other film, but maybe not since I started having this problem. I will inspect the color. (I always use it as one-shot.)

deej
5-Jan-2016, 07:58
Rule out developer: try different developer, same fixer
Rule out fixer: Use same developer, different fixer

How old is this MIXED batch of Rodinal, and have you used any of it successfully with other films?

Is the factory-exposed film marks (320TXP) present, or are they not there either? If they're there, something is the matter with your camera/lens. If they are not there, you have either a chemical problem(most likely the case), or the film is bad(unlikely, but Kodak has made mistakes before).

Try this, in addition:
Take an unexposed, undeveloped sheet of film, and in the light, check your fixer. The film should clear completely if the fixer is of proper strength, and not too old.

A very thorough response, Daniel! Thanks! I will work through your instructions and find out what went wrong. I certainly don't want to have this persist.

The Rodinal itself is under a year old; I mixed it immediately before use; it has done other films, I think, but I don't have good ready notes on that (can deduct with a thorough search of my scans, which are tagged with developer). Pretty sure the "320TXP marks are not there; they would be black, correct? I so, they are not there; I'm pretty sure the film is uniformly pinkish-clear edge-to-edge (I am at work now, but will look closer this evening).

Please make sure my procedure to check the fixer is correct: 1) In the dark, remove a sheet from the box, and close the box. 2) Turn on the light and expose the film. 3) Put the film in the tank (I use a MOD54); 4) Fix the film as usual, and rinse. 5) Inspect: the film will be completely clear (except for the 320TXP mark).

Is that right? I think I should try this before moving on to your two-step "rule out" instructions, correct?

Thanks, Daniel!

deej
5-Jan-2016, 08:08
I agree with this. Blank film is either no exposure or no development, if the fix was no good the film would look 'milky' when you took it out of the tank. The pink colour in the film base just means you need to fix for a bit longer, I don't think it's anything to do with the film being blank.


Thanks, Tobias! Your post makes me a bit less inclined to test the fixer I am using, but to run a test with a fresh fixer of a different brand. The brand I have been using for everything for a while is "TF-5 ARCHIVAL FIX" from Photographer's Formulary; they say its for both paper and film, but all the details in the item description are about paper; it has worked well for all my other work, but I wonder if it just doesn't agree with 320TXP?

deej
5-Jan-2016, 08:12
The colour of the film is indeed very pink, which makes me wonder of your fix is working properly. But even then: when the film would have been exposed and developed properly, at least some image should be visible and refixing asap should cure the problem.

As Daniel has asked already: is the factory exposed film mark visible? If not: most likely there is a problem in film development and a good guess is that either your Rodinal has gone bad or you have mixed up the fix and development baths. Rodinal should only be used as a one shot developer, mixed directly before use and the concentrate should be stored at room temperature. Putting in the freezer will make it go bad as some of the chemicals will percipitate and won't go into solution again when it warms to room temperature.

If the film mark is visible, you probably have made an exposure error. The shutter may not have fired, you might have forgotten to pull the darkslide or one of those other user errors that are possible in large format. We all have been through those... ;-)

Thanks for the response! I keep all my chemicals (including Rodinal) at room temperature. (Tobias took up your thread, so I am considering most of your great suggestions in my response to him.)

What would "refixing" mean in my case?

deej
5-Jan-2016, 08:13
Thanks, Peter! I will give xtol a try!

deej
5-Jan-2016, 08:16
I have seen where Rodinal (stock) has gone bad, and not develop at all... One clue is if it pours out after the development deep, dark blue colored... (with no/low image...)

The pink color is from silver still remaining on the film from after fixing... If you fog/fix a piece of film, there is still excess silver that has not been reduced/removed, and will oxidize to the pink (very finely divided silver) state...

Steve K

Thanks, Steve! The prewash poured out deep blue, but the developer came out with just a slight blue tint.

Good info about what causes the pink color.

Kevin Crisp
5-Jan-2016, 08:26
"New" tri-x has a TMAX like ability to hold the pink. Even in film strength rapid fixer it is going to take 6 or 7 minutes with agitation plus a decent wash time to get rid of it. Old tri-x was a piece of cake. Your looks considerably under fixed. Maybe you are using the diluted paper strength mix?

Tri-X works well with HC110, Xtol and D76. It can certainly work fine with Rodinal too. And a number of others.

Kevin Crisp
5-Jan-2016, 08:27
I meant to ask, using Rodinal 1:50 but with what volume of developer and how many sheets at once?

deej
5-Jan-2016, 08:34
I meant to ask, using Rodinal 1:50 but with what volume of developer and how many sheets at once?

I have a tall Patterson tank that holds the Mod54 sheet holder; a liter of fluid covers it nicely. I use a liter of water and 20 ml of Rodinal. I am usually so anxious to see my results that I develop even if I only have two sheets; this bad result has happened once with two sheets, and once with four.

(I am very new at large format, but have been developing 35mm and 120 for three years with nothing quite like this kind of failure. This thread is teaching me a lot.)

Kevin Crisp
5-Jan-2016, 09:11
I haven't used that tank but it looks like it could hold many sheets of film. How many sheets are you doing one shot with that liter of 1:50 solution? With high dilutions, what looks like plenty of developer may not be since the amount of actual developer in the tank isn't sufficient for the film volume. I would think anything over 4 4x5 sheets per quart would be exceeding the capacity of the developer.

Randy Moe
5-Jan-2016, 11:08
WE assume you are mixing fresh Rodinal every time? It goes bad once mixed with water very quickly. I use it up in 10 minutes. ymmv

Some use a minimum of 10 ml per 80 sq inches. 10 ml stock from bottle mixed with 1 liter distilled water is 1/100 and works great for me, every time. 40ml and 1 gallon Chicago water also works fine for 4 sheets of 8x10 any film.

As you have been told change each variable one at a time. Maybe it's your water...

Michael R
5-Jan-2016, 13:30
The brand I have been using for everything for a while is "TF-5 ARCHIVAL FIX" from Photographer's Formulary; they say its for both paper and film, but all the details in the item description are about paper; it has worked well for all my other work, but I wonder if it just doesn't agree with 320TXP?

TF-5 agrees with TXP and all other general purpose films. You can rule that out.

Huub
5-Jan-2016, 14:43
What comes out of the prewash is the anti-halation layer and is nothing to worry about.

I think with 10 ml of Rodinal and 4 sheets you are pretty much in the ball park and should be ok, just like your fixer should work pretty fine as it is. How strong have you diluted your fix and how long did you fix? And how many films ran you through the diluted fix? Try to fix the film a second time in freshly diluted fixer. This can be done in a tray in daylight and see if it clears. This is what i meant with 'refixing the film'.

Then there is still the question about the film marks - do you see the TXP320 mark somewhere along the top or bottom edge of the film? It is an indication of what might have caused the problem.

Fred L
5-Jan-2016, 16:18
I use this same process (Rodinal and TF-5) with no issues at all. As well, when I dump the spent developer from the Jobo tank, the liquid is a dark blue so I'm not sure that should be taken as any indication of developer activity. Oddly enough, Rodinal comes out clear when I develop Acros.

Neal Chaves
5-Jan-2016, 16:40
Kodak HC110 is an excellent developer and very economical at Dilution B (1:31) that I find no need to dilute it further except for a contraction while keeping the development time constant. I posted the following last week in answer to another film development question and have rewritten it bit to correct some errors make it clearer.

Years ago I learned the method to find the correct developing time and EI for any film. I think the source was William Mortensen. Mortensen wrote some excellent books and articles about basic sensitometry. The last time I did this test was when I abandoned Tri-X and switched to HP5+ due to cost about five years ago. I proceed as follows.

I set up my trays with my favorite developer HC110B (1:31). I pull out a sheet from the package in the dark. and then when the package is sealed again I turn on the room lights. This part of the test is done under the lights. I cut the sheet into five strips and mark them 1-5 by punching holes with a paper punch. Lets say the recommended time is 5:00. I want to see 3:00, 4:00, 5:00, 6:00 and 7:00, so I throw all the strips into the developer and agitate as usual until 3:00 when I move the No.1 strip over to the stop bath. Then I pull No.2 at 4:00, No.3 at 5:00, etc. I fix, wash and dry the strips as usual. What we are looking for is the best usable film DMax value. Obviously the film has been fully exposed! When strips dry lay down a page of news print on a table in good light. Find the strip through which the news print is barely visible. That's your developing time. Now to find the film speed.

Go outside in unchanging light conditions and expose five sheets and expose one at the manufacturers rating and then the other four at one half a stop and one stop less and one half a stop and one stop more. In the dark, develop them all together for your newly derived time. Contact print them together exposing and developing the paper for maximum usable paper DMax value. Pick out the best-looking contact print and you have your film speed.

Because my 7:00 negative looked the best on the first test, I did the test again with 7:00 as the central developing time and found that 8:00 was indeed too dense. This HP5+ time was the same as the as the developing time I had been using for Tri-X and film speed was also the same, EI400.

Many of the last generation of B&W gurus favored a development time of 5:00 for Tri-X and suggested an EI of 64-100. You can do the above test backwards, developing for 5:00 minutes and finding the film speed. I like 100. The difference between negatives exposed at 100 and developed for 5:00 and those rated at 400 and developed for 7:00 is quite subtle. Both could be considered "normal" or N negatives. The 100 negative has slightly greater shadow and highlight detail that only a careful, knowledgeable printer and viewer could detect. This slight improvement might not be worthwhile trading for two stops in the field.

From here, if you are still with me, you can derive expansion and contraction schemes for both the 100 and 400 "normal negs". I do this by changing dilution rather than time. Make sure you have at least 1 oz. of the concentrated sauce for each 8X10 sheet or equivalent. For contractions I found that 3/4 oz. concentrate to 31 1/4 ozs. H20 yields an N-1 neg at a one stop loss in film speed and 1/2 oz. concentrate to 31 1/2 ozs. H20 yields an N-2 neg at a two stop loss in film speed. For expansions, 1 1/4 oz. of concentrate to 30 3/4 ozs. H20 yields an N+1 neg at a one stop gain in speed and 1 1/2 ozs. concentrate to 30 1/2 ozs. H20 produces an N+2 negative with a two stop gain in speed.

If you look at the chart of Tri-X film speed in Phil Davis' BTZS book you can easily pick out the film speed in HC110B 5:00 as EI 64.

Harold_4074
5-Jan-2016, 18:13
You might consider a "clip test". Take all or part of a sheet of film into room light, immerse it in developer, and see what happens. If the developer solution really is developer, the film will (eventually) turn black. If it turns clear, you have put it into fixer, and if anything else happens, the liquid is something other than developer or fixer. For an unknown film and/or developer, the time to turn black is a good starting point for real image development.

deej
5-Jan-2016, 21:18
Try to fix the film a second time in freshly diluted fixer. This can be done in a tray in daylight and see if it clears. This is what i meant with 'refixing the film'.

I will definitely try that. I am away from home for a couple days so I can't try until tomorrow evening--and I will check for the TXP320 market then, but I truly doubt it's there.

deej
5-Jan-2016, 21:22
...the method to find the correct developing time and EI for any film....

Wow, Neal! That's so logical! Very useful stuff, thanks!

deej
5-Jan-2016, 21:24
You might consider a "clip test".

As I make my way through all this great advice, I might have to try this. Very useful, deductive advice. Thanks, Harold!

deej
5-Jan-2016, 21:29
TF-5 agrees with TXP and all other general purpose films. You can rule that out.

Thanks, Michael! I really love TF-5!! Glad to hear I don't have to change brands. I think I will mix up a fresh batch, though, after I get through with all these tests.

Four minutes in TF-5 is all I do, and per instructions you don't need hypo clearing agent, which saves a step. I wonder if the standard dilution and/or time even with fresh TF-5 is not enough to do the job with TXP?

Michael R
5-Jan-2016, 21:54
2-3 times the clearing time for any film is a good rule of thumb, and 4 minutes with intermittent agitation in a fresh, film strength solution of a rapid fixer such as TF-5 should be enough for TXP. If you wish you can go a few minutes longer in TF-5.

All that said, your photo in the original post points to a development or exposure problem. I can't tell from the picture if there is any base fog, but either way fixation is not the problem. Something else is going wrong.

deej
6-Jan-2016, 18:24
Just a quick update: The negatives do not have the "Kodak 320TXP" mark, or anything else--uniformly clear. Also, something changed since November, because I have a couple good results from then. As the investigation continues, the idea that the developer is at fault is most plausible at this point.

ronald moravec
7-Jan-2016, 08:29
I HAD A BOTTLE of Ordinal last 10 years, used only for tests. 1998 to 2008. Then it slowly gave less contrast,

If there are particles in the bottom, it may be normal but do not allow them to go into developer.

Huub
7-Jan-2016, 08:32
Could be a developer issue, but you might have mixed up developer and fixing baths too. That mistake also gives very nice, clear negatives. And don't ask how i know.... ;-)

I would try to shoot a few sheets again and develop them in fresh developer and the new fix and see if it works out now. When the new negatives come out alright it will have been some problem in the development process that you have solved by now.

John Olsen
7-Jan-2016, 15:03
Earlier you ruled out shutter problems because you had no failures with a different film, only TriX. If your other film was using a greatly different shutter speed, there could still be the potential for problems at the TriX speed. (At least my lens-rebuilder would periodically find some speeds fine and some others defective, maybe as a way to make his work even more mysterious and expensive.) Good luck with your testing of the many great ideas offered by others.

Bill Burk
7-Jan-2016, 18:15
My favorite "can't believe I did that" mistake was when I once rinsed out a beaker, carefully measured out a small amount of chemical and added it to the beaker, rinsed it out again and added water to the brim...

To make up what was now, 32 ounces of water.

I caught the mistake before any damage was done... But it was really funny. And makes me think switching to Rodinal would mean trouble for me.

Fr. Mark
7-Jan-2016, 22:54
I've had Rodinal go bad in 6 months or less. Admittedly, I made it myself and it was quite dark before it quit. Maybe I did not have the "magic" recipe: I only found about 6 of these recipes on the net not counting the ones starting from headache tablets... Mine was stored in a warm basement (no AC down there) and in a glass bottle so I could not get the air out.

I'm not a real expert like some of you, but it looks like either fixer and developer were switched or the developer didn't work. Esp. w/o film's maker's labels on it.

One sheet of film cut into pieces could yield a lot of data: is developer still working, is fixer working and labelled correctly and is camera working?

deej
23-Jan-2016, 11:05
Here is an update: This morning I finally got around to testing the Tri-X I have been using--this time shot with a different lens (I have tested the previous lens's shutter and it is working perfectly), a fresh batch of fixer, and a different developer (D-76 Stock, one-shot). The results were good.

So I went to the shelf to look at the Adonol I had been using. I happened to have ordered a new bottle roughly at the same time as the bottle I have been using, so I could compare them. Here is what I saw:

http://uploads.tapatalk-cdn.com/20160123/2f777788958d17340880d7413a7502ac.jpg

You can see how dark and opaque the opened bottle on the right is. So, my conclusion is the developer was most likely the problem here. (It may have been the old fixer, but that fixer was working for all other films throughout the era of the problem I was having with Tri-X and this dark bottle of Adonol.)

Michael W
25-Jan-2016, 04:10
That Rodinal colour is quite normal, even darker works OK.

Fred L
25-Jan-2016, 05:59
My opened bottle of Rodinal is way darker than that. I'd run another test with the *suspect* bottle of Rodinal. With no film markings, I'm inclined to think it was a process error and was fixed, not developed. I have never seen Rodinal do this through all the bottles I've emptied but that's just my experience. ymmv

Huub
25-Jan-2016, 07:27
I am not sure if Adonal is completely the same product as Rodinal. What might be the cause of your problems is that the keeping properties of both differ and where as the old Rodinal keeps forever, that possibly could not apply to Adonal. If you really want to be sure, you can do another test with the Adonal but personally i would bring the bottle to a chemical waste station.

deej
25-Jan-2016, 08:47
My opened bottle of Rodinal is way darker than that. I'd run another test with the *suspect* bottle of Rodinal. With no film markings, I'm inclined to think it was a process error and was fixed, not developed. I have never seen Rodinal do this through all the bottles I've emptied but that's just my experience. ymmv

Before I dispose of the rest of this bottle, I will run a test with some 35mm film. If it passes the test, I might keep the bottle for smaller films. I might even research whether developing 320TXP with Adonal using Rodinal times should work. (Last year I used up a whole bottle of Adonal on medium format and smaller films and got great results taking the Rodinal times from the Massive Dev Chart.)

Michael R
25-Jan-2016, 11:49
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.

Kyle M.
25-Jan-2016, 12:05
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."

Fr. Mark
25-Jan-2016, 18:12
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.

Michael R
26-Jan-2016, 05:40
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.

Fr. Mark
26-Jan-2016, 21:19
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.

Fr. Mark
26-Jan-2016, 21:21
To be clear, I meant bottles that've been open for 40 years. Sealed, I bet it will keep indefinitely.

Michael R
27-Jan-2016, 08:07
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.

wallacerichard
27-Jan-2016, 08:52
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:

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?
http://hautavis.net/117/o.png

deej
27-Jan-2016, 09:12
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.

deej
13-Oct-2016, 18:06
Very useful post, Neal! Thanks!