Pyrocat-HD Sudden Death!

[Alan Johnson]

Ian,
Thanks for the clarification, but I was trying to answer the question as to how Pyrocat in Glycol might fail as mentioned by the OP and suggested oxidation.
If not oxidation, what is the explanation?

 

[John Wiegerink]

There's a variant of Pyrocat called Pyrocat HDC which could be of interest to those who want a long lasting variant of Pyrocat. It doesn't use metabisulphite+bromide and hence completely avoids water. I believe ascorbic acid which dissolves nicely in warm glycol provides the necessary acidic environment to prevent the oxidation of catechol. Developing time and results are supposed to be very similar to HD.

I started out using the nbPyrocat-HD version, I then went to Pyrocat-MC and really was happy with it, but when I heard about Pyrocat-HDC I thought I'd give it a go and see how it compared. Well, I'm still using the HDC version and like it just as well as the MC version, but I could easily use either the MC or HDC and be happy for life. These Pyrocat formulas are the best thing since sliced bread. Of course for much of what I do Xtol-R does the job just fine.

 

[Ian Grant]

There's a variant of Pyrocat called Pyrocat HDC which could be of interest to those who want a long lasting variant of Pyrocat. It doesn't use metabisulphite+bromide and hence completely avoids water. I believe ascorbic acid which dissolves nicely in warm glycol provides the necessary acidic environment to prevent the oxidation of catechol. Developing time and results are supposed to be very similar to HD.

I'm aware of the HDC version but it wasn't around when I mixed my Pyrocat HD in Glycol. I've no interest in using Glycol which isn't necessary because the developer keeps well made up in De-ionised water. But for the developer to keep well the Metabisulphite must be fresh and the right bottles used, high density plastic (which I use) or glass and attention paid to the seal as well that can cause issues.

Ian

 

[ParkerSmithPhoto]

YES, Pyrocat-HD can experience sudden death significantly before you expect it and without warning.

I have a 15 month old batch, mixed in glycol, stored in amber glass bottles with a spurt of Protectan after each use, and kept at about 50-55F in the dark.

Alan, this is exactly what happened to me recently. In fact, it happened overnight!

I was using some PF Pyrocat-HD in glycol that was over three years old BUT it had been stored in brown glass bottles which were always pumped and sealed with the vacuum wine corks. I ran six rolls on Saturday and they were all perfect.

Sunday's four roll tank came out poorly, with slightly thin highlights, weak edge markings, and almost no shadow detail. (The rolls were from two shoots and were intermixed between developer sessions, meaning that there was no possibility of camera malfunction.)

This was what I found puzzling, as I've always understood that the shadows develop first, then the highlights. Could it be that the Phenidone is really what dies, causing a complete loss of film speed? In "The Book of Pyro" Hutchings says that pyro by itself gives very low film speeds, usually half. Just trying to explain the complete lack of shadows. Bob Carnie also commented at LFP that someone he knew had some sudden Pyrocat-HD failures and ended up with negatives with zero shadows.

 

[Bob Carnie]

Yes I watched a dude in my darkrooms process thousands of Acros 4 x 5 film in Pyrocat . He was no dummy , but at the time he was having this complete shadow low end failure consistently, and to my knowledge never sorted out exactly what happened, I think the experience really turned him off film and process as he has not done any since and at the time he was indeed a real keener.
I never in my whole career witnessed or seen this type of problem and like I said he was no slouch and he called every expert on Pyrocat and suppliers and during this time processed dozens of runs of test film that he specifically shot in my back alley to figure out the problem .. I stayed out of it as this project was his work , his financial commitment on film , chemicals and of course renting my space, but he was having these really unexplainable errors that everyone attributed to operator error .

 

[Raghu Kuvempunagar]

In "The Book of Pyro" Hutchings says that pyro by itself gives very low film speeds, usually half. Just trying to explain the complete lack of shadows.

Was Hutchings referring to Pyrogallol or Pyrocatechine (Catechol) or both?

 

[Ian Grant]

Yes I watched a dude in my darkrooms process thousands of Acros 4 x 5 film in Pyrocat . He was no dummy , but at the time he was having this complete shadow low end failure consistently, and to my knowledge never sorted out exactly what happened, I think the experience really turned him off film and process as he has not done any since and at the time he was indeed a real keener.
I never in my whole career witnessed or seen this type of problem and like I said he was no slouch and he called every expert on Pyrocat and suppliers and during this time processed dozens of runs of test film that he specifically shot in my back alley to figure out the problem .. I stayed out of it as this project was his work , his financial commitment on film , chemicals and of course renting my space, but he was having these really unexplainable errors that everyone attributed to operator error .

Interesting Bob, it appears that Glycol itself can break down and oxidise with certain reagents (not due to dissolved Oxygen) so there may be something much more complex going on here. And then we find that there can be Catechol grafted Glycols, so perhaps glycol is not as benign as was first thought.

I've assumed my 9+ year old Pyrocat HD made up in Glycol is OK because there's no apparent Pyrocatechin (Catechol) oxidation colour, but what if some or all of the Pyrocatechin has converted to something less or even inactive over time. When I get a chance I'll test some.

Made up with de-ionised water it's very easy to see if it's on the turn and oxidising. Nothing over the years has convinced me using Glycol is worthwhile as Part A keeps longer than most commercial developers made up in water, and that;s after a lot of batches with no issues.

Ian

 

[destroya]

since I switched from glycol to water based mixes, I have never had any issues with my pyro going belly up. the only reason I came up with is that the water from rinsing my syringe was somehow ruining the A solution. I use 2 syringes, one for each solution so as to not contaminate them. Most of my sudden death came after major shooting trips. I would come home and develop 10-30 rolls of 120 film in a day. so between each batch I would wash and towel dry the syringe. it would get used again for the next batch and so on. like I said above, when I switched to using distilled water for the A solution, I never had the issue. I guess the water cant screw the water solution, so to speak. B is always mixed with distilled water. the nice thing is I can mix up 300ml and use it on 6 months or less and if not, I can dispose of it and not worry.

 

[ParkerSmithPhoto]

Was Hutchings referring to Pyrogallol or Pyrocatechine (Catechol) or both?

I believe he was referring to Pyrogallol, although I would assume the info to be applicable to Catechol as well.

 

[ParkerSmithPhoto]

since I switched from glycol to water based mixes, I have never had any issues with my pyro going belly up. the only reason I came up with is that the water from rinsing my syringe was somehow ruining the A solution. I use 2 syringes, one for each solution so as to not contaminate them...I guess the water cant screw the water solution, so to speak..

According to the directions, you have to add a little water to the glycol anyway, so I'm not sure how a few drops more would make a big difference.

Thinking back, I was using a syringe to measure it into a small graduate. After getting my volume correct, I squirted the extra concentrate back into the bottle. I've done that for years with other devs. Maybe not such a great idea with P-HD.

 

[Alan9940]

since I switched from glycol to water based mixes, I have never had any issues with my pyro going belly up. the only reason I came up with is that the water from rinsing my syringe was somehow ruining the A solution. I use 2 syringes, one for each solution so as to not contaminate them. Most of my sudden death came after major shooting trips. I would come home and develop 10-30 rolls of 120 film in a day. so between each batch I would wash and towel dry the syringe. it would get used again for the next batch and so on. like I said above, when I switched to using distilled water for the A solution, I never had the issue. I guess the water cant screw the water solution, so to speak. B is always mixed with distilled water. the nice thing is I can mix up 300ml and use it on 6 months or less and if not, I can dispose of it and not worry.

For all the years I've used Pyrocat-HD, I always use dry, clean syringes or graduates to measure out A and B using marked containers for each part. As IanG suggests, I think there is something much more complex going on with those of us who have experienced sudden death. Time will tell the tale, if my mix small batch and toss every 6 months works out. Pyrocat is cheap enough to mix that I'm concerned with "wasting" chemicals.

 

[Tom Taylor]

"...Xtol-like sudden death..."

About 25 years ago when I first started developing film a camera store clerk told me that Xtol was initially available in 1L/Qt packaging and they theorized that a lot of people were not mixing in the part B which I got the impression came in a smaller package that was attached to the part A. So Kodak discontinued the smaller packaging and thereafter only the 5L size was available. I don't know whether that is true or not but I have been an Xtol user for many years now mixing with distiller water and storing in a floating lid tank. I have noticed that as the developer ages it returns to the light amber color of part A before part B is added. Upon adding only a small amount of part B part A completely clears to a transparent water-like liquid. Thus I suspect that it is part B that over time goes bad in Xtol and is responsible for the change in color back to the original amber of part A. But in a floating lid tank this process takes months and Kodak's estimate of 6 months shelf life is conservative and at $2/L ($1/L if using 1:1) it's dirt cheap!

Thomas

 

[ParkerSmithPhoto]

As IanG suggests, I think there is something much more complex going on with those of us who have experienced sudden death.

Alan, was your experience with sudden death a total loss of shadow detail, or something else?

 

[Steve Goldstein]

A related question - what color are people seeing for their catechol, and for solution A?

A couple of weeks ago I used the last few ml (literally!) of a batch of Pyrocat-HDC I mixed in February 2018. It worked just fine right up to the end, and solution A was light yellowish. It was always stored in a 500ml brown glass bottle.

I mixed up a new batch of solution A and it’s almost colorless even though the catechol (stored in the freezer) was a light yellow-brown. The developer seemed to work fine on a test roll.

I don’t remember if the catechol was the same color 18 months ago. Nor do I recall the color of my last batch of solution A, which was mixed using the same containers of all chemicals. What colors are others seeing?

 

[ParkerSmithPhoto]

If, instead of mixing the Pyrocat-HD "B" solution, you wanted to just add Potassium Carbonate DRY to the working solution and then add the A, how many grams per liter would you need? I do the math and get 0.75g/mL of stock, which would be enough for 100mL working solution. So, 0.75 x 10 = 7.5g/L of working solution. Did I do that correctly?

I was thinking that this way, there is no chance of accidentally mixing up syringes, etc and contaminating the A solution.

 

[Alan9940]

Alan, was your experience with sudden death a total loss of shadow detail, or something else?

Basically, a total loss of the entire image. I could see just a faint trace of parts of the image. I believe what was there was, in fact, the higher values of the image, but to call it loss is shadow detail would be a severe understatement!

 

[Alan9940]

@Steve Goldstein, my catechol is off white (egg shell) in color and my Part A was totally clear. Still died, though...

 

[ParkerSmithPhoto]

I don’t remember if the catechol was the same color 18 months ago. Nor do I recall the color of my last batch of solution A, which was mixed using the same containers of all chemicals. What colors are others seeing?

When I mix my working solution, it's clear as water. Now, this is the glycol stock that I no longer trust, but I don't remember it ever being any other color.

 

[mpirie]

Basically, a total loss of the entire image. I could see just a faint trace of parts of the image.

These are the results i was having earlier this year. When processing in my 2500 tanks, the first batch would come out perfectly, the second tank-load would fail completely, with only the faintest detail visible.

I put this down to contamination or oxidation....but, when i use the same PHD batch in trays, it works perfectly.

I now do all my sheet processing in PHD in trays and (apart from the odd scratch) have been very pleased with the results.

Alan - If you still have the old batch, it might be worth trying it in trays?

Mike

 

[Alan9940]

Alan - If you still have the old batch, it might be worth trying it in trays?

I tossed it and mixed fresh just to verify for myself that one or more of my raw chemicals had not gone off. They're fine. I mixed a small batch in distilled water and the next neg processed was as expected. All that said, I've had enough failures over the years that I'm now experimenting with PMK. Haven't printed anything, yet, but I'll make a decision over time.

 

[ParkerSmithPhoto]

I tossed it and mixed fresh just to verify for myself that one or more of my raw chemicals had not gone off.

Alan, I was about to toss my early 2016 Pyrocat-HD in glycol but decided to run a test roll, thinking that I may have made a dilution error when I experienced "sudden death." My guess was correct. The test roll came out perfectly. I ran part of the same roll through some fresh Pyrocat-HDC in glycol as well. The HDC looked a little denser, which was most likely the result of a slight variation in the B mix concentration. That is, my mix may have ended up stronger than the standard 75% solution of PC from Photo Formulary.

I also ran a test with the old A and the new B which very closely matched the HDC negative, further confirming my belief that my B mix might be a little stronger than standard.

One thing I did before making these tests was to create a dilution workflow checklist so that I marked off and confirmed volumes as I added each solution to the water. Sounds silly, but it's so easy to get working and kind of go on auto-pilot, and clearly I made that mistake last week (ruining four rolls), so this should help.

Good news is, this batch of Photo Formulary Pyrocat-HD in glycol has been in brown bottles with vacuum stoppers for coming up on four years, and seems to be working just fine. It was nice to discover that the "sudden death" was really just me making a mistake. I will post some pics of the negatives after they dry.

 

[Raghu Kuvempunagar]

It was nice to discover that the "sudden death" was really just me making a mistake.

All is well that ends well.

 

[Alan9940]

@ParkerSmithPhoto, glad to hear you worked it out. Personally, I'll never know because I tossed the "old" stuff. I've had a few issues over the years, but Pyrocat-HD is such a nice developer I keep using it. Based on discussion in this thread, though, I may give HDC a try.

 

[ParkerSmithPhoto]

@ParkerSmithPhotoPyrocat-HD is such a nice developer I keep using it. Based on discussion in this thread, though, I may give HDC a try.

I figured if Sandy had settled on the HDC then I might as well make the switch and never think about it again.

I was apprehensive about handling pyrocatechin for the first time, but it was in nice little chunks and didn't really kick up dust the way phenidone does, which was my main worry. If I take a sniff of the PF pyro, I can definitely smell it through the plastic jar so I will be storing that in glass with a vacuum stopper.

Everything I have in stock now should take me through years of film developing.

 

[Sirius Glass]

Alan, I was about to toss my early 2016 Pyrocat-HD in glycol but decided to run a test roll, thinking that I may have made a dilution error when I experienced "sudden death." My guess was correct. The test roll came out perfectly. I ran part of the same roll through some fresh Pyrocat-HDC in glycol as well. The HDC looked a little denser, which was most likely the result of a slight variation in the B mix concentration. That is, my mix may have ended up stronger than the standard 75% solution of PC from Photo Formulary.

I also ran a test with the old A and the new B which very closely matched the HDC negative, further confirming my belief that my B mix might be a little stronger than standard.

One thing I did before making these tests was to create a dilution workflow checklist so that I marked off and confirmed volumes as I added each solution to the water. Sounds silly, but it's so easy to get working and kind of go on auto-pilot, and clearly I made that mistake last week (ruining four rolls), so this should help.

Good news is, this batch of Photo Formulary Pyrocat-HD in glycol has been in brown bottles with vacuum stoppers for coming up on four years, and seems to be working just fine. It was nice to discover that the "sudden death" was really just me making a mistake. I will post some pics of the negatives after they dry.

How about changing the title to "Pyrocat-HD Sudden Death! RESURRECTION! It rose again and is alive!"?