A loooong lasting paper developer.

Paul Verizzo · Jan 7, 2013

Freeze it.

I wouldn't expect any used, working dilution developer to last very long after some use. It's not just the oxygen that may be in the bottle.

Freeze it.

(You'll also get very cold tones.........)

removed account4 · Jan 7, 2013

Photo Engineer said:
John, if Ansco 130 gets better with age, it is nice to hear but that means that it is changing!

PE

hey ron

aged / dilute it gets better, in stock it stays normal ...
when it ages and turns black ( after it has been dilute and had prints run through it ) it is perfect for film and or paper negatives
sorry for my confused post !

john

Paul Verizzo · Jan 8, 2013

K.I.S.S Freeze it.

Take any developer or photo chemical you like that degrades whilst on the shelf and just freeze it.

There seem to be very few of us in the photo-universe that have grasped this super-simple solution, no pun intended. It works.

LPD is essentially a phenidone (instead of Metol) based developer that is otherwise essentially Dektol. Ilford was a big proponent of phenidone back when, and had a number of formulas that were Metol replacements. I took a cursory look in my papers and couldn't quickly find the Ilford "LPD", but if someone wants it, I'll look further. Like LPD, I found it almost inexhaustible. Energizer bunny in the first tray.

Paul Verizzo · Jan 8, 2013

Massive brain awakening. I think it's ID-67:

PHENIDONE-HYDROQUINONE DEVELOPER, Ilford ID-67
For Films and Plates

STOCK SOLUTION
Warm Water (l25 F or 52 C) - 750.0 ml
Sodium Sulfite (anhydrous) - 75.0 grams
Hydroquinone - 8.0 grams
Sodium Carbonate (desiccated) - 37.5 grams
Phenidone - 0.25 grams
Potassium Bromide - 2.0 grams
Benzotriazole - 0.15 grams
Add cold water to make - 1.0 liter

hoffy · Jan 8, 2013

I am not sure if this is typical or not, but just before Christmas, I used up my last bit of Bromphen Stock solution. It had been sitting in my cupboard in PET bottles for around 18 months and seemed to work OK.

Rudeofus · Jan 8, 2013

Paul, Phenidone is known to be unstable in alkaline environment so your ID-67 formula would be quite unsuitable for long shelf life. Replace the Phenidone with twice the amount of Dimezone S if you want longer shelf life.

Richard Jepsen · Jan 8, 2013

sepiareverb said:
Moersch ECO 4812 is my choice. Lasts a startlingly long time as a working solution in a bottle.

Liquidol and ECO 4812 meet your criteria.

Paul Verizzo · Jan 8, 2013

Rudeofus said:
Paul, Phenidone is known to be unstable in alkaline environment so your ID-67 formula would be quite unsuitable for long shelf life. Replace the Phenidone with twice the amount of Dimezone S if you want longer shelf life.

I rather doubt that phenidone is unstable in the alkaline developer environment. Maybe less stable than Dimezone, but not unstable. I rather doubt Ilford and other companies would have spent years making and marketing phenidone/HQ developers if this matter was of concern. Nor has this been any kind of problem in my own mixes and use.

Ian Grant · Jan 8, 2013

Rudeofus said:
Paul, Phenidone is known to be unstable in alkaline environment so your ID-67 formula would be quite unsuitable for long shelf life. Replace the Phenidone with twice the amount of Dimezone S if you want longer shelf life.

Much of that seems to be hype from a US competitor because in practice the form of phenidone used in Ilford commercial developers is/was stable, some now use Dimezone since manufacture was sub-contracted.

Some books claim Phenidone has a poor shelf life (as a raw chemical) but I was using Phenidone made in 1962 until my supply ran out 4-5 years ago and it was just as good as my newer supplies. It's often forgotten that Phenidone is a Trade name and there's a number of variants, there were issues with the original form of Phenidone but by the time Ilford marketd Phenidone based devlopers these had been overcome.

In practice the ID-78 I make up lasts well over 2 years in a good plastic bottle, it's the warm tone variant of ID-62, but shelf lifes no different to ID-67.

Ian

Paul Verizzo · Jan 8, 2013

Michael R 1974 said:
It may depend on the composition of the complete formula, concentrations, how much preservative etc but on its own yes Phenidone is apparently unstable. POTA is just Phenidone and Sodium Sulfite and is quite short lived.

Probably because POTA has no hydroquinone which is regenerative of either metol or phenidone.

I think Ian Grant, below, explains it all well.

Regardless, as to the situation of the OP, FREEZE IT!

Richard Jepsen · Jan 8, 2013

130 is a nice developer but it changes in tray with usage, is expensive, and dislikes temps below 21c.

Thomas Bertilsson · Jan 8, 2013

Actual keeping properties of Ethol LPD I don't know about, but I've had it last for 6+ months, (when I had no darkroom access), at 2+1 dilution in a partially filled brown amber glass bottle. I doubt it would last two years even as a concentrate.
Ethol themselves claim that LPD lasts for six months. I normally use it up before six months passes by so I have no way of verifying working solution or stock solution, only 2:1 mix with water.

Photo Engineer · Jan 8, 2013

Phenidone is a chemical called a hydrazone. Hydrazones in general will hydrolyze in alkali back into their parts. Since phenidone is a ring compound it merely ring opens and becomes inactive. Dimezone and Dimezone-S have blocking groups at the site of hydrolysis and are therefore far more stable in alkali than the parent phenidone.

I know, I know, you all hate organic chemistry. Go ahead and use phenidone developers. They will last - a while, and then organic chemistry will bite you on the butt just when you least expect it.

PE

Ian Grant · Jan 8, 2013

Michael R 1974 said:
I for one do not hate organic chemistry, and appreciate the explanation. I think this is quite important as I doubt many are fully aware of the differences between Phenidone and its Dimezone derivatives. We sort of know Dimezone is "better" than Phenidone, but specifics are helpful. I think there was some good discussion about this in Mark Overton's XTOL clone thread.

There's stable Phenidone derivatives, something that all Kodak chemists were well aware of, particularly as one senior research scientist helped edit LFA Mason's book "Photographic Processing Chemistry, and that included the section on Phenidone & the derivatives.

Sure some developing agents in the Phenidone class are slightly better than others, the Dimezonnes are placed in this class as are other Phenidone derivatives. There's a deliberate attempt in these threads to deride Phenidone when it's been in use commercially for about 60 years with none of the issues.

In terms of shelf life between the Phenidone derivatives and thei Dimezones, is not huge difference like a few weeks or months instead of 2 or 3 years and that's being overlooked.

Interesting that PQ developers have a far better shelf life than MQ developers and in fact was why many manufacturers switched to them, that put's things into a better perspective.

There's a lot of references to old data and books which refer to the original Phenidone which was unstable in highly alkali solutions and so never went int commercial production. Mason of Ilford refers to this instability so it's not something Ilford didn't address

Ian

Photo Engineer · Jan 8, 2013

I refer you all to Haist, page 185, Volume #1

PE

zsas · Jan 8, 2013

Well PE, I tried to request said book from my alma mater, who can get within a week or so any book from almost any university in Illinois, well, problem is that not one school has Vol I, I can find Vol II easily but Vol I is illusive. Can you paraphrase what Haist said?

Ian - If you concede that there can be a difference of possibly weeks/months between A and B, is it not appropriate for one to suggest A is longer lasting than B if that is the question the OP posed? When each 1L of chemistry might cost a dollar or so, a month can matter and be akin to tossing $1 down the drain. If one can prevent wasting a dollar, a dollar saved is....

Fwiw OP, I am a Liquidol user, I don't print frequently, I mixed up 1L this summer and printed maybe 3 sheets in it, then bottled it up and have not been able to print till yesterday, it worked just perfect.

Ian Grant · Jan 9, 2013

zsas said:
Ian - If you concede that there can be a difference of possibly weeks/months between A and B, is it not appropriate for one to suggest A is longer lasting than B if that is the question the OP posed? When each 1L of chemistry might cost a dollar or so, a month can matter and be akin to tossing $1 down the drain. If one can prevent wasting a dollar, a dollar saved is....

Fwiw OP, I am a Liquidol user, I don't print frequently, I mixed up 1L this summer and printed maybe 3 sheets in it, then bottled it up and have not been able to print till yesterday, it worked just perfect.

waynecrider said:
I need something that will last in the cupboard for quite awhile, say 2 years since I develop infrequently. I'd prefer not to mix anything as the scale is shot and that's that and I'd prefer a bottle of liquid developer. Thanks.

Andy, my point is that all the PQ developers I've used have had a shelf life in exceess of the OP's 2 years, there's little point in the deliberate posts by some that deride formulae that have beenin use for around 60 years.

You also have to discount comments from people with a commercial interest in their own product.

Ian

Ian Grant · Jan 9, 2013

Thank you Michael, that's the point I've always made, and people trying to claim otherwise go against Haist, Mason and the senoir research chemists at Kodak, Ilford, Champion, Agfa etc. I did post Mason's comments in a previous thread which were probably more important as he was part of the team who worked on PQ developers.

Ian

Photo Engineer · Jan 9, 2013

Basically, Phenidone is less stable than its chemical cousins, and that is stated in Haist. It goes bad in the concentrated form more rapidly.

It also oxidizes more rapidly in alkali if O2 is present. The same protective groups that help the others in alkali, help them in oxygen.

If you want a good concentrate with long shelf life, use Dimezone or Dimezone-S. If you want it to last long in the tray, same advice.

PS. For those who have not guessed, I've done that experiment!. I can also add that Phenidone lasts a long time dry in coatings! It can be used as an incorporated developer. Done that too!

PE

zsas · Jan 9, 2013

Ian Grant said:
Andy, my point is that all the PQ developers I've used have had a shelf life in exceess of the OP's 2 years, there's little point in the deliberate posts by some that deride formulae that have beenin use for around 60 years.

You also have to discount comments from people with a commercial interest in their own product.

Ian

Hi Ian -
I didnt realize that those who use science to support their option are supposed to be discounted should he/she have a commercial interest too. I guess I should thusly discount anything that Bill Gates has ever said too considering I use Windows. I also attended a professional convention that was led by a person who also wrote a book on the subject of the convention, I guess I should discount his opinion too?
Now suppose one mixed up 1L of working solution of PQ based paper developer and 1L of lets say Liquidol. If the person then let them both sit on the shelf capped for 2 months, would they work equally well? I get the feeling that the PQ will not last as long, and therefore, might be consider longer lasting once mixed?
Just because a bottle of developer can sit in concentrate a while is a good virtue, but shouldnt one also consider the mixed solution in his/her decision? I think so and want the OP to consider that. I dont print frequently and have no desire to put photochemistry in my freezer, and therefore, think that if I print a couple of prints in a 1L working solution and bottle it up and print again in say 2 months a couple more prints, I believe, could be wrong, that something like Liquidol (which mind you ships for FREE in the US) might just meet the OPs needs. Price, free shipping (from Amazon), are also in the algorithm.

Ian Grant · Jan 9, 2013

Andy, they aren't using science, what they are doing is deliberately muddling the trade name Phenidone for the early version that never went into commercial production because it was unstable.

So the scientists from Ilford & Kodak say Phenidone B and Dimezone are stable, and there are other stable versions of Phenidone and Dimezone, that's the science not the misleading comments.

Ian

Photo Engineer · Jan 9, 2013

Interestingly enough, I tried to avoid my own interests and thus tried to "solve" the issue by referring to Haist, and then I tried letting someone else quote him. It seems that people will not even believe this venerable author's comments. And, outside of my interests, I spoke directly to Grant and others at EK in the time frame from about 1970 - 1985, before I started emulsion work, and the entire trend of developer design was towards Dimezone or Dimzone-S.

Ian Grant · Jan 9, 2013

Michael R 1974 said:
From Haist regarding Phenidone B and Dimezone: "Both of these methylated Phenidone derivatives are more stable than Phenidone in concentrated liquid developing compositions that may be maintained at high temperatures or may be stored for long periods of time."

Haist, Mason and others state Phenidone B and Dimezone plus other Phenidone derivatives are stable (Mason & GIP Levenson of Kodak list them) in alkali solutions. So I wouldn't disagreeing with Haist even remotely.

Phenidone and Ilford's derivatives were Patented developing agent and so Kodak preferred to use Dimezones their own equivalent to avoid paying licensing/royalty fees, that side is being deliberately overlooked.

It's simple Ilford used Phenidone and much later Kodak used Dimezone. Also Phenidone is a Trade name rather like Ektachrome or Tmax and there's different versions.

Ian

zsas · Jan 9, 2013

Ian - Let's suppose one mixes 1L of Ilford PQ Universal and 1L of Liquidol. If the person made 10 prints then bottled up the working solution and then 6 weeks later decided to print again, would they have to mix another batch of Ilford PQ Universal? My experience suggests, that Liquidol would be fine, can that be said for the Ilford PQ Universal? The fact sheet for Ilford PQ Universal says mixed working solution bottled lasts 24 hours. If our OP is a small potatoes printer like me, the difference between Liquidol and the others is noteworthy in this regard. Lasting on the shelf is one metric, lasting mixed on the shelf another. If we assume that both PQ and say Liquidol might last undiluted the same amount of time (based on your experience with PQ), then the consumer might want to consider the longevity of mixed developer as a possible advantage of Liquidol....

Why is this bit something the consumer should consider? Print developer is not one shot like say film dev (eg Rodinal).

waynecrider · Jan 9, 2013

Thanks for the education.

I might go back to drawing. Please don't recommend a pencil. ( ^:

A loooong lasting paper developer.

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