As to Pyro and stop baths, I do not use one, water only.
The reason being, I spent a fair bit of time experimenting to find the true film ratings and, developing times for my favourite films in Pyro 510.
The information available to me at the time was No Acid Stop Bath.
I know my parameters for my films developed in 510 and a homebrewed Kodak fixer. I don't want to go over the same ground again using an acid stop bath.
On working out the appropriate concentration of acetic acid and indicator? Is it really more than a high school chemistry problem? Ah well, I’ve no reason to dispute it if it is documented.
What would you see? Sometimes I can’t tell if you are joking.
I realise I need to reply to this with personal experience.
I used to use Tetenal Emofin as my standard (it is no longer made). With the thin Delta emulsions I started to notice lots of tiny blemishes. I read somewhere that the reason might have been the use of a stop bath, because Bath 2 of that product was strongly alkali and could cause a physically violent reaction (it was said). So I stopped using stop bath on my films. After a while, I realised that my blemishes were white in the positive, so they couldn’t have been missing bits of emulsion blown away by micro-explosions. I improved the filtration on my water supply and all chemicals, and the problem vanished. That’s why I said ‘may’ in my post above. It’s a widespread notion, but I’ve seen no definite proof.
Nevertheless, I realised that the amount of unused developer in bath 2 of my Emofin must have been very small, so a stop bath was probably not doing much anyway. That reasoning applies equally to the Barry Thornton 2 bath developer that I now use. I'm sure I could use a stop bath because I use metaborate in bath 2; but if I used a stronger alkali (there are several options mentioned by Thornton) I might wonder about that acid-alkali theory until I’d done a few films.
If I use a mainstream developer like ID-11, I use a stop bath.
The number of developer molecules carried over to the fixer will be essentially the same, regardless of whether one uses an acid-based stop bath of just plain water. It will only depend on the volume of liquid used in the stop bath, so if you use the same amount of liquid for the stop bath you will transfer the same number of molecules to the fixer, regardless of whether the stop bath is acidic or roughly pH neutral.
This analysis assumes that the developer carryover comes from the film of solution adhering to the surface of the film and the developer tank and reel. It does not include developer molecules that might be trapped inside the emulsion. There might be some subtle effect with regard to how many developer molecules might be removed from the actual film emulsion itself, but given the small volume occupied by the emulsion there must be very few developer molecules trapped in the emulsion, and even then one would have to propose that they are more easily removed under mild acidic conditions than under roughly pH neutral conditions.
Stop bath changes the pH, and the carried over developer is therefore effectively neutralized before it gets into the fixer, where neutralized developer has little or no deleterious effect.
Here's a quick sample calculation to more fully explain what I meant in my last post. In this sample calculation I will not be discussing developer molecules that are in the emulsion itself, only those that are in the liquid residue clinging to the reels and walls of the development tank.
Suppose you are using 500 ml of developer and that in that 500 ml there are 10,000 developer molecules. Yes, I know there are more than that. I'm just using that number to make the calculations easy for illustration purposes.
Assume that after the development stage is completed you pour out 495ml of the developer solution, leaving 5ml clinging to the reels and walls of the tank. That's 1% of the original volume. In that 1% there will be 100 molecules of developer. (1% of 10,000 molecules is 100 molecules.) At this point I will split the analysis into two scenarios.
In scenario one we add 495ml of water to the tank and agitate to mix it with the 5ml of residue from the previous step. There will be 100 molecules of developer in the 500ml of resulting solution. We pour out that solution, leaving 5ml of residue in the tank. In that 5ml there will be an average of 1 molecule of developer. That's the number of developer molecules carried over into the fixer.
In scenario two we add 495ml of acid stop bath into the tank and agitate to mix it with the 5ml of residue from the previous step. There will be 100 molecules of developer in the 500ml of resulting solution. We pour out that solution, leaving 5ml of residue left in the tank. In that 5ml there will be 1 molecule of developer. That's the number of molecules carried over into the fixer. That's exactly the same number of developer molecules carried over as in scenario 1.
If you started with the a different number of developer molecules the carryover ratios will be the same as those described above. For example, if you started with a 100 trillion molecules in 500ml of developer you end up with 10 billion developer molecules carried over into the fixer, regardless of whether you were using a water stop bath or an acid stop bath. The carryover ratio is 0.01% of the original number of molecules.
Suppose there was 10ml instead of 5ml of solution carryover for each step. That would change the fraction of molecules carried over into fixer from 0.01% to 0.04%, independent of whether you use an acid stop bath or a water stop bath.
Conclusion: the number of molecules carried over into the fixer is independent of whether one uses an acid stop bath or a water stop bath.
As noted above, this analysis does not include a discussion of developer molecules that are actually trapped in the gelatin at the beginning of the stop-bath step. However, to argue that an acid stop bath produces less carryover into the fixer one would somehow have to say that, first of all, there are enough developer molecules trapped in the gelatin to matter (which I think it unlikely), and second of all, that an acid stop bath is more efficient in extracting those molecules into solution than a water stop bath, which as far as I am aware has never even been discussed, let alone been proven.
Let's assume for the sake of argument that your analysis is absolutely correct in every respect. I will ask the same questions I asked in post 1161 which no one has yet seen fit to address:
Why has Kodak included using stop bath in its film processing instructions since time immemorial? Did they have any scientific evidence for doing so or did they just make it up out of thin air so they could sell stop bath and make more money? Have materials changed over time eliminating the need for stop bath, and Kodak never got around to updating its directions? Did Kodak pay PE to recommend using stop bath on this forum? He seemed like a pretty knowledgeable guy. How else did he lead us astray? Do any books on film processing say stop bath is unnecessary, or is it just people on photo forums?
Here are two bonus questions:
What purposes, if any, does using stop bath serve, other than stopping development? Are there any benefits to using stop bath?
If you would care to address those, I would be most appreciative.
Here's a quick sample calculation to more fully explain what I meant in my last post. In this sample calculation I will not be discussing developer molecules that are in the emulsion itself, only those that are in the liquid residue clinging to the reels and walls of the development tank.
Suppose you are using 500 ml of developer and that in that 500 ml there are 10,000 developer molecules. Yes, I know there are more than that. I'm just using that number to make the calculations easy for illustration purposes.
Assume that after the development stage is completed you pour out 495ml of the developer solution, leaving 5ml clinging to the reels and walls of the tank. That's 1% of the original volume. In that 1% there will be 100 molecules of developer. (1% of 10,000 molecules is 100 molecules.) At this point I will split the analysis into two scenarios.
In scenario one we add 495ml of water to the tank and agitate to mix it with the 5ml of residue from the previous step. There will be 100 molecules of developer in the 500ml of resulting solution. We pour out that solution, leaving 5ml of residue in the tank. In that 5ml there will be an average of 1 molecule of developer. That's the number of developer molecules carried over into the fixer.
In scenario two we add 495ml of acid stop bath into the tank and agitate to mix it with the 5ml of residue from the previous step. There will be 100 molecules of developer in the 500ml of resulting solution. We pour out that solution, leaving 5ml of residue left in the tank. In that 5ml there will be 1 molecule of developer. That's the number of molecules carried over into the fixer. That's exactly the same number of developer molecules carried over as in scenario 1.
If you started with the a different number of developer molecules the carryover ratios will be the same as those described above. For example, if you started with a 100 trillion molecules in 500ml of developer you end up with 10 billion developer molecules carried over into the fixer, regardless of whether you were using a water stop bath or an acid stop bath. The carryover ratio is 0.01% of the original number of molecules.
Suppose there was 10ml instead of 5ml of solution carryover for each step. That would change the fraction of molecules carried over into fixer from 0.01% to 0.04%, independent of whether you use an acid stop bath or a water stop bath.
Conclusion: the number of molecules carried over into the fixer is independent of whether one uses an acid stop bath or a water stop bath.
As noted above, this analysis does not include a discussion of developer molecules that are actually trapped in the gelatin at the beginning of the stop-bath step. However, to argue that an acid stop bath produces less carryover into the fixer one would somehow have to say that, first of all, there are enough developer molecules trapped in the gelatin to matter (which I think it unlikely), and second of all, that an acid stop bath is more efficient in extracting those molecules into solution than a water stop bath, which as far as I am aware has never even been discussed, let alone been proven.
A neutral pH is plenty good enough to do that
But since plain water isn't buffered, a water "stop" bath won't yield a neutral pH. It'll be decidedly alkaline due to developer carryover the moment it's swirled around in the tank.
Your reasoning does however illustrate why a stop bath that's buffered around a neutral pH does indeed work like an acidic stop bath.
In the end, it's still splitting hairs of course. Legions of people have used a water rinse instead of a stop bath in film development. If there were any structural problems with this, we would have known by now.
Until we instate a stop bath police, that is. They'll patrol your darkroom equipped with pH meters and titration equipment. Punishments will be harsh, and very acidic.
Does developer carryover into fixer harm the fixer because of the developer molecules that are transferred to the fixer or because it tends to raise the pH of the fixer?
Thanks for the clarification. All of my comments pertain to film, not prints.PS & NB: in the above, with staining, I'm referring primarily to prints, not film!
Yes I have the instructions (below). No stop bath stage is listed in the developing/fixing procedure, but under 'Special Comments' they say "The use of a stop bath (INDICET or 2 to 3% acetic acid) before fixing raises the yield of the fixer." One can reasonably conclude that in Tetenal's view a stop bath was optional with this developer.I was unable to locate the manufacturer's directions for Emofin film developer. Did you have them and read them? What did they say? Other two bath developers, like Diafine and Barry Thornton two bath developer, say not to use stop bath, so I would be surprised if the directions for Emofin said to use stop bath. If the directions didn't say to use a stop bath and you used it anyway, then the use of stop bath would be on my troubleshooting checklist. I would also consider that, since Emofin film developer is a powder, perhaps the developer was not fully dissolved, and that particles of developer may have gotten stuck in the emulsion. The same consideration would apply if you mixed your fixer from powder.
Nor mine - see post #1082. Still, the emulsion pin-hole theory was plausible enough for me to experiment with leaving out the (optional) stop bath.Some random guy on the internet telling me that it is not necessary to use stop bath when developing film and I can save a nickle, without more, does not meet my threshold for credibility.
In his article 'Fine negatives automatically', BT mentions stop bath only when warning not to use a rinse or stop bath between Bath A and Bath B. Are there other directions somewhere?The directions for Barry Thornton two bath developer say not to use stop bath. Case closed.
all you will learn by seeing prints is that the photographer at least sometimes gets a printable negative and makes a decent job of printing it. I don’t see how you’d be able to tell whether they used stop bath on the film or not?
For sure the print is - as Ilford expressed it in their Manual - the consummation of the photographer's journey. But what could anyone see in the molecular structure of a print that would cast any light on the role of a stop bath in processing the film?You would have to look at the molecular level.
For sure the print is - as Ilford expressed it in their Manual - the consummation of the photographer's journey. But what could anyone see in the molecular structure of a print that would cast any light on the role of a stop bath in processing the film?
With all love and respect, all you will learn by seeing prints is that the photographer at least sometimes gets a printable negative and makes a decent job of printing it. I don’t see how you’d be able to tell whether they used stop bath on the film or not? Prolific output with consistent quality might be a different matter, I grant you.
For sure the print is - as Ilford expressed it in their Manual - the consummation of the photographer's journey. But what could anyone see in the molecular structure of a print that would cast any light on the role of a stop bath in processing the film?
Nope, sorry, never seen it. I guess it must be the same idea as The proof of the pudding is in the eating? (Who thought that one up?) But I don't know: I don't look at photos by Irving Penn or Sebastaio Salgado and think "There's someone who is sound on stop baths."The last sentence in not meant to be read literally. Are you familiar with the quote "Show me the money." from the movie Jerry McGuire?
But I don't know: I don't look at photos by Irving Penn or Sebastaio Salgado and think "There's someone who is sound on stop baths."
Nearly 1200 posts! I bet if we did a poll, we'd find that folk were equally content with their negatives whether they use stop bath or not.
Nor mine - see post #1082. Still, the emulsion pin-hole theory was plausible enough for me to experiment with leaving out the (optional) stop bath.
Nope, sorry, never seen it. I guess it must be the same idea as The proof of the pudding is in the eating? (Who thought that one up?) But I don't know: I don't look at photos by Irving Penn or Sebastaio Salgado and think "There's someone who is sound on stop baths."
Nearly 1200 posts! I bet if we did a poll, we'd find that folk were equally content with their negatives whether they use stop bath or not.
Do you have a reference for that, please?Pin holes arise in poorer films and/or when the stop bath solution is not properly mixed, that is too strong.
Do you have a reference for that, please?
Here's a quick sample calculation to more fully explain what I meant in my last post. In this sample calculation I will not be discussing developer molecules that are in the emulsion itself, only those that are in the liquid residue clinging to the reels and walls of the development tank.
Suppose you are using 500 ml of developer and that in that 500 ml there are 10,000 developer molecules. Yes, I know there are more than that. I'm just using that number to make the calculations easy for illustration purposes.
Assume that after the development stage is completed you pour out 495ml of the developer solution, leaving 5ml clinging to the reels and walls of the tank. That's 1% of the original volume. In that 1% there will be 100 molecules of developer. (1% of 10,000 molecules is 100 molecules.) At this point I will split the analysis into two scenarios.
In scenario one we add 495ml of water to the tank and agitate to mix it with the 5ml of residue from the previous step. There will be 100 molecules of developer in the 500ml of resulting solution. We pour out that solution, leaving 5ml of residue in the tank. In that 5ml there will be an average of 1 molecule of developer. That's the number of developer molecules carried over into the fixer.
In scenario two we add 495ml of acid stop bath into the tank and agitate to mix it with the 5ml of residue from the previous step. There will be 100 molecules of developer in the 500ml of resulting solution. We pour out that solution, leaving 5ml of residue left in the tank. In that 5ml there will be 1 molecule of developer. That's the number of molecules carried over into the fixer. That's exactly the same number of developer molecules carried over as in scenario 1.
If you started with the a different number of developer molecules the carryover ratios will be the same as those described above. For example, if you started with a 100 trillion molecules in 500ml of developer you end up with 10 billion developer molecules carried over into the fixer, regardless of whether you were using a water stop bath or an acid stop bath. The carryover ratio is 0.01% of the original number of molecules.
Suppose there was 10ml instead of 5ml of solution carryover for each step. That would change the fraction of molecules carried over into fixer from 0.01% to 0.04%, independent of whether you use an acid stop bath or a water stop bath.
Conclusion: the number of molecules carried over into the fixer is independent of whether one uses an acid stop bath or a water stop bath.
As noted above, this analysis does not include a discussion of developer molecules that are actually trapped in the gelatin at the beginning of the stop-bath step. However, to argue that an acid stop bath produces less carryover into the fixer one would somehow have to say that, first of all, there are enough developer molecules trapped in the gelatin to matter (which I think it unlikely), and second of all, that an acid stop bath is more efficient in extracting those molecules into solution than a water stop bath, which as far as I am aware has never even been discussed, let alone been proven.
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