Modern Rodinal Substitutes

[Photo Engineer]

Attacks diminish us all!

Back to the OP Ian. In it, you mention the Agfa antifoggant which is unidentified. In my readings of the BIOS reports, I found that all ingredients were completely identified in the appendices unless marked "Hier ist unbekannt" in parenthetical note next to each use of the compound or mixture ID #.

So, I assume that either of these were / are present in your copy of the BIOS reports. If the compound is not identified in either manner, then this is actually a truly glaring first for the reports. And, the "Hier is unbekannt" is a grave copout on the part of the interviewer. If I were interviewing a major plant manager and he said that to me, I would march him to the safe for the key to the chemical names. All Kodak names are cross indexed that way and I could find them. In fact, some BIOS reports did admit to finding the complete names of all of the emulsion chemicals but one. That one was the famous tank car that was filled with an unknown organic on a siding at the Agfa plant and no one would talk about it.

So, can you identify it for us or let us know what the BIOS report said about it in detail?

PE

 

[Ian Grant]

Ron it's rather a long time since I read most of the data, I'd guess 1977 most of which was in Glafkides, I haven't seen the owner of the books or documents for at least 10 years and then only in passing and briefly. He worked for me as a consultant for a year or so and had a lot of material which had come from his mother, she was French & a member of the Lumiere family. At that point I was really mainly interested in the emulsions.

The only data I have to hand here is in the first post in this thread andwas taken from the British RAF report, this was separate and done after the US team had left the factory, I have been trying to get hold of a copy again, ironically of the two APUG members I know who have copies one has disappeared, like Tom Hoskinson, & the other lent his copy to an Agfa salesman, but is trying to get it back. It should of course be in the major UK reference libraries as it was a Government publication.

I have some Agfa Wolfen material waiting for me on my next trip back to the UK, so I'll see what antifoggants they were using, I also have copies of some of the data on film, shot back in 77, I'll try and find a way of scanning it, so it is possible I have more than I think here in Turkey. I'll look at the emulsions too because there maybe a reference to antifoggant there.

Ian

 

[Photo Engineer]

There was only one reference to antifoggants in the emulsion section IIRC. It was so insoluable in water that I have had trouble with it duplicating Agfa results. It recrystallizes in the emulsion when diluted from the alcohol solvent to the water based emulsion. Therefore, I doubt if it was the one. I don't have my data cards here right now to give the name, but it is so inexpensive, I tried it before I went on to the rarer ones that I used at EK.

PE

 

[Ian Grant]

Ron, the RAF formula is almost exactly the same proportions of p-Aminophenol to sulphite & hydroxide as the Andresen 1900's version allowing for the conversion of the metabisulphite with the hydroxide.

It's essentially the same formula so it's unlikely the organic anti-foggant is particularly special, and the bromide level's only around 0.77%, So the only significant difference is the free base rather than the hydrochloride.

I have had correspondence now with Dr Schneour but he's unable to comment on whether he thinks the free base or hydrochloride form is correct.

Interestingly in the Agfa officially published formulae of 1903-1910 that I've looked at Rodinal is always referred to as a Paramidophenol developer (of an alkali salt) and their others as Paramidophenol Hydrochloride-Hydroquinone Developer and the 3 or 4 sources I have all say the same.

Ian

 

[Kirk Keyes]

Ian - do you have the Agfa Factory Wolfen Reports in your pdf collection? Could I get a copy of them. I've been looking all over trying to find copies of them. I think we've emailed in the past so you should have my email, if not PM me.

 

[Photo Engineer]

Ian;

I don't take this quote as being negative:

"Bill Troop has been very well connected to a lot of people in photography over the years and was heavily engaged with developers at Kodak in Rochester. He accumulated a significant amount of subjective information and has pretty much pushed it all right into this book. It's prefect for the darkroom enthusiast who is intrigued with historic processes and how they might effect ones creative options. Note that this is not an instructional book for beginners but something more targeted at the advanced enthusiast whose interest has grown beyond the use of commonly available processes."


And, having talked with Grant Haist, I find that he feels that Bill has captured their interviews quite well. So, I feel comfortable with the rest of the information myself. I am probably the only person here on APUG that has talked to Haist, James, Dickerson, Zawadski, Glafkides, Henn, Lee, Gilman, Pontius, Willis and a host of others in person about some of these topics.

I would add that seeing two historians battle it out over history is rather stressful, and to me it is, from my perspective, like seeing two modern physicians arguing over a copy of a papyrus contemporary with Ipuwer which gives methods of trepanning. Modern formulas are of more import to me. And, to add to this, I might say that I find that the variations in the Windisch, Crawley and Rodinal formulas that we have seen here may be explained or made necessary by the evolution of film emulsions. I have speculated here that Crawley HA developers may fail with some modern emulsions and I have developed a rather extensive theory as to the reasons. From this, I can reason out improved versions and also may even reason out and try an improved Rodinal.

And this is all while you all fuss over formulas that are 50+ years old. I know you are an archaeologist but there is still much to look to the future and work towards.

PE

 

[Ian Grant]

Kirk, no problem as soon as I'm back in the UK I'll try and sort you out a copy. all I ask is please don't pass it on.

Ian

 

[Kirk Keyes]

I don't take this quote as being negative:

"Bill Troop has been very well connected to a lot of people in photography over the years and was heavily engaged with developers at Kodak in Rochester. "

To shorten the sentence a bit, it says that "Bill was heavily engaged with developers at Kodak in Rochester".

If I didn't know the history of how Bill put the book together, I would read that sentence as saying that Bill worked on film developers at Kodak in Rochester.

The use of the word "developers" is confusing. The book is about film developers, so it's only natural for the reader to think that the word "developer" in that sentence is referring to film developers. And, appearantly, not the people that actually designed the developers. That is, the developers of the developers. Is that less confusing?

But most importantly, isn't that quote from a "independant" reviewer of the FDC on Amazon? See the comment by John Douglas (Nashville, TN USA). Isn't he's the J&C Photo guy? He's an upstanding member of the photo community, right? I think we need to blame John for that ambiguous statement.

Anyway, we can't fault Bill for that quote.

 

[Kirk Keyes]

Kirk, no problem as soon as I'm back in the UK I'll try and sort you out a copy. all I ask is please don't pass it on.

Ian

No problem with those terms, and thanks!
;^)

 

[gainer]

Pretty stiff solution. In Nov/Dec Issue of Darkroom & Creative Camera Techniques, I published this formula.
Metol-------------0.2 g
Ascorbic acid------2.0 g
Borax-------------6.1 g
Sodium hydroxide--1.7 g
Water to 1 qt.
The combination of borax abd NaOH is close to the standard ratio for simulating Kodalk.

I forgot to say that was the 1994 Nov/Dec issue.

 

[Kirk Keyes]

Add to that the fact that Agfa themselves say Rodinal (1910) "contains only traces of carbonic alkalies," which can only have come from the preparation of the free base.

Ian - going back a bit - you seem to be hung up on this quote above.

I read that as when Agfa used hydroxide in the preparation, they were able to use high quality hydroxide. Poorer quality hydroxides would certainly contain carbonate. And hydroxide that sits around with exposure to air will sequester carbonate. So it could be both a manufacturing and storage issue when compared to earlier sources of hydroxide.

So I take their statement as one that means they were able to manufacture the hydroxide with very little carbonate content - not that carbonate was used at any point in the process or from any other ingredients. I don't think that statement has anything to do with preparation from free base.

Perhaps they were using sealed reaction vessels and perhaps they had nitrogen atmospheres to protect the hydroxide solution from atmospheric carbon dioxide. It would denote a couple steps up in manufacturing technology from years previous.

 

[Kirk Keyes]

Nothing in this thread accounts for the statement, on Rodinal packages, going back several decades, that hydroxide is only 3%.

A 1998 MSDS confirms this; in its entirety it gives

potassium hydroxide, 3%
potassium sulfite, 30-40%
potassium bromide, 1-5%
p-Aminophenol, 1-5%

and the pH is 14 (!!!) - - which is massively higher than other figures, published by Agfa, that we have all seen.

Bill - are you saying you are suprised that a 3% solution of potassium hydroxide has a pH of 14? If so, here's the way to calculate it.

A 3% solution is about 0.53M KOH.
Calculate pOH first:
pOH = -log10[OH-]
pOH = -log10[0.53M]
pOH = 0.276
Then calculate pH:
pH = 14 - pOH
pH = 14 - 0.276
pH = 13.72

A 0.53M KOH solution should have a pH of about 13.7. That's close enough to pH 14 for my book.

If that's not what you are saying, then don't worry, it's my mistake...

 

[Ian Grant]

Ian - going back a bit - you seem to be hung up on this quote above.

I read that as when Agfa used hydroxide in the preparation, they were able to use high quality hydroxide. Poorer quality hydroxides would certainly contain carbonate. And hydroxide that sits around with exposure to air will sequester carbonate. So it could be both a manufacturing and storage issue when compared to earlier sources of hydroxide.

So I take their statement as one that means they were able to manufacture the hydroxide with very little carbonate content - not that carbonate was used at any point in the process or from any other ingredients. I don't think that statement has anything to do with preparation from free base.

Perhaps they were using sealed reaction vessels and perhaps they had nitrogen atmospheres to protect the hydroxide solution from atmospheric carbon dioxide. It would denote a couple steps up in manufacturing technology from years previous.

We have to remember that Agfa's parent company was already a highly sophisticated chemical manufacturer by 1897 so it's likely that they had a high degree of control over the purity of chemicals like hydroxides used in developers.

Reading work by contemporaries of Andresen working with similar developing agents they were aware of the differences between the free base & different salts of compounds like p-Aminophenol.

Mees & Sheppard did work with p-Aminophenol back in their days at Wratten & Wainwright, how much I don't know without trying to find copies of the book and papers they wrote (while at Wratten). This work is held somewhere along with the work of J.Desaume in Kodak archives.

Kodak also researched p-Aminophenol, Sheppard's name crops up again and their choice of salt was p-Aminophenol Oxalate (Kodelon) which presumably what they used in Kodinol.

George Brown, the Editor of the BJP from 1904 until 1934 would also have been well aware of the differences between the free base & the hydrochloride, (he was himself a Chemistry Scholar) he would have known Mees & Sheppard, he lists their Wratten Formulae in the 1910 BJP Almanac and makes a point of listing a concentrated p-Aminophenol developer, alongside a p-Aminophenol Hydrochloride developer.

What's perhaps more important is we know that by the 40's and through to today Agfa/A&O and Calbe have definitely used the free base, so any attempt at making our own needs to do the same.

Ian

 

[Ian Grant]

Bill - are you saying you are suprised that a 3% solution of potassium hydroxide has a pH of 14? If so, here's the way to calculate it.

A 3% solution is about 0.53M KOH.
Calculate pOH first:
pOH = -log10[OH-]
pOH = -log10[0.53M]
pOH = 0.276
Then calculate pH:
pH = 14 - pOH
pH = 14 - 0.276
pH = 13.72

A 0.53M KOH solution should have a pH of about 13.7. That's close enough to pH 14 for my book.

If that's not what you are saying, then don't worry, it's my mistake...

Shows how much chemistry (& Biochemistry) I've forgotten, I'd just use a pH meter these days

Ian

 

[AgX]

As a historical side note: there was no `parent company´. Rather Agfa was a chemical company mainly producing dyes, that gave a try on producing a photochemical product (a film developer by Andresen) in 1889. That date given by Ian, 1897, was the introduction as brand name of their abbreviated company name.
Even when Agfa started to build their film manufacturing plant in Wolfen the sales of their photochemical products was about 9%. Even in 1923 it was only 36%. The photochemical branch (department from 1891 on) was not independant.

Agfa as a whole ended their independance when they opted to become a part of IG Farben.

 

[Ian Grant]

Good point, but it would have been a division, and it's the Agfa brand name that we all know. In the US the company was the Berlin Aniline Works.

Ian

 

[AgX]

AGFA was the brand name for all products by "Actien-Gesellschaft für Anillin-Fabrikation". Though the consumer only new it at through their photographic products.

 

[cmo]

Would you be able to design an environmentally friendly Rodinal substitute? Paramidophenol is a verifiable water pollutant and injurious to health.

 

[Ian Grant]

p-Aminophenol is far more widely used in hair dyes and in far larger quantities than the volumes of Rodinal used.

The actual amount of p-Aminophenol, sulphite and hydroxide used per film is likely to be far less polluting than most more concentrated developers (at working strength), somewhere I have the Toxicology figures for Colour processing because I had to deal with the regulatory authorities, in the UK there it is the water boards, because they have to treat the water and make it fit for human consumption.

In an average household there are far worse pollutants disposed of in a normal week.

Even a developer like Xtol used 1+1 is far worse than dilute Rodinal, so coming up with something more environmentally friendly is going to be difficult.

Ian

 

[Sean]

fyi- I've had to edit some bickering out of this thread and get it back on topic.

Sean

 

[Kirk Keyes]

A pinch? I thought that was against your religion. How many milligrams in a pinch?

I take the pinch out of the rest of the sulfite that I measured with my precise balance. ;^)

 

[Kirk Keyes]

If I add anything before the metol, it will be a little ascorbic acid. That is to assure that any oxidized Metol that might be in my supply will be regenerated before I add the sulfite.

I suspect that you can add ascorbate to water to remove dissolved oxygen just like you can sulfite. Ascorbate is often used in the lab setting to remove other stronger oxidizers like chlorine.

 

[Kirk Keyes]

fyi- I've had to edit some bickering out of this thread and get it back on topic.

Sean

WOW - I made it without any deletions this time!

 

[gainer]

Bill - are you saying you are suprised that a 3% solution of potassium hydroxide has a pH of 14? If so, here's the way to calculate it.

A 3% solution is about 0.53M KOH.
Calculate pOH first:
pOH = -log10[OH-]
pOH = -log10[0.53M]
pOH = 0.276
Then calculate pH:
pH = 14 - pOH
pH = 14 - 0.276
pH = 13.72

A 0.53M KOH solution should have a pH of about 13.7. That's close enough to pH 14 for my book.

If that's not what you are saying, then don't worry, it's my mistake...

The MSDS, of course, only mentions what you will find by analysis of the product, not what is put into the product. A considerable amount of KOH goes into the formation of the potassium aminophenolate. I do not know the pH of a solution that originally contained only enough KOH to make the p-aminophenol base soluble as the phenolate, but my attempts to make such a solution have measured in the 12-13 region. The 3% spec is surely an excess, not the total amount put in.

One can make a solution of KOH from K2CO3 and Ca(OH)2 in water. A slight excess of Ca(OH)2 would assure no carbonate in the solution, but perhaps a little of the calcium hydroxide. Any comment?

 

[Kirk Keyes]

Shows how much chemistry (& Biochemistry) I've forgotten, I'd just use a pH meter these days

Ian

Well, there's a problem there, as it's really hard to measure pH accurately when it gets much above 12.5 or so. You have to start getting special electrodes and the like.

But for MSDS work, it doesn't have to be too precise.