Modern Rodinal Substitutes
The formula for Rodinal R09 has never been officially published by Agfa. In the "Agfa" Book of Photographic Formulae, published by the Berlin Aniline Company in 1910, the company tells us:
As "AgfA"-Rodinal contains only traces of carbonic alkalies, the use of distilled water for dilution is not necessary. In connection with the use of "Agfa"-Rodinal the following remarks should be carefully noted:
In addition to neutral sulphite and water "Agfa"-Rodinal contains only an alkaline salt of Paramidophenol, but no excess of caustic alkali.
PDF Rodinal 1910
However it's possible to make formulae that's close to the current versions.
Original Rodinal contained p-Aminophenol (once called Paramidophenol by Agfa) and this was formed by precipitation of the free base from p-Aminophenol hydrochloride using sulphite and carbonate (hence Agfa's comment "contains only traces of carbonic alkalies".
The formula for Rodinal has changed and evolved presumably as high grade p-Aminophenol free base became commercially available, allowing Rodinal to be completely free of carbonates.
J. Desalme published a " Concentrated Paraminophenol Developer of the Rodinal Type" in 1913, this was later included in L.P. Clerc's book "Photographic Theory and Practice".
Sodium Carbonate & Sodium Sulphite are added to a solution of p-Aminophenol Hydrochloride which precipitates the free base, which is filtered and collected.
The paste of p-Aminophenol free base is then added to a solution of Sodium Metabisulphite and Sodium Hydroxide added until all the free base is dissolved, finally a small amount of Metabisulphite is added until the first crystals of p-Aminophenol free base begin to form again.
This mirrors Agfa's own description of early Rodinal, and accounts for the traces of carbonates, and the "no excess of caustic alkali". (J. Desalme was a photographic chemist specialising in aminophenols and other developing agents particularly for colour processing).
Now we reach a point of contention "Free base" or "Hydrochloride", genuine Rodinal has always been made using the Free base of p-Aminophenol . (50g of p-Aminophenol is equivalent to 66.2 g p-Aminol hydrochloride). There is no evidence to suggest that Rodinal of any form has ever contained p-Aminophenol Hydrochloride.
The MSDS sheets for both Rodinal and Calbe R09 show clearly that both developers contain p-Aminophenol free base (CAS 123-30-8) and not p-Aminophenol hydrochloride (CAS 51-78-5).
Making a Rodinal substitute with p-Aminophenol Hydrochoride will leave free chlorides in the solution, and neutralise more Hydroxide, the amount of developing agent would need to be increased along by a factor of 1.33 and also more KOH added.
Data on early Rodinal is hard to find but in a thread on Photo.Net "Edward Zimmermann" wrote:
The formulas for Rodinal, resp. R09 (1964 to present), have never been published. The patent is for Paramidophenol developers and there are many recipes making the rounds since the late 1800s. One of the most famous is attributed to Eder. From my copy of Spörl and Neumann, "Fotografisches Rezeptbuch" 1943 edition, p.50):
- Paramidophenol 50g
- Kaliummetabisulfit [Potasium Metabisulfite] 150g
- Wasser 625ccm (ml)
Then a solution of
- Ätznatron [Sodium Hydroxide] 215g
- Water 500ccm (ml)
is slowly added untill the cloudyness breaks. According to the book it says this is typically around 350ml.
Then the solution is diluted with water to make 1 liter.
My note: 350ml of the Sodium Hydroxide solution contains 150.5 gms Sodium Hydroxide.
The same formula was published in the British Journal Photographic Almanac (1910 & earlier) as:
Potassium metabisulphite 300g
Distilled water 1 litre
Dissolve in the above order and add gradually:
Caustic soda or potash to dissolve the precipitate first formed.
For use, dilute 1 part. with 10-20 parts of water.
No final volume of solution is given but it's likely to be 2 litres if you want the equivalent of early Rodinal.
It's important to note that these sources clearly indicate the use of the free base, as they go on to also include p-Aminophenol Hydrochloride film developers. These are in the 1910 "Agfa" Book of Photographic Formulas, the 1910 BJP Almanac and Ed Zimmermann's book all from quite different sources & countries.
However other versions of this formula appear in various books from the early 1900's onwards, but using p-Aminophenol Hydrochloride, because of the difference in Molecular Weight and the effects of the additional Hydrochloride they won't be quite the same. Dr M. Andresen, of Agfa, who discovered & patented p-Amaninopheol and designed Rodinal published it himself in the "AGFA Photo-Handbook" he did not claim it was similar to Rodinal, listing it as - Formula 21: Concentrated single solution. (As above proportions but using p-Aminophenol Hydrochloride).
L.P.Clerc and others indicate that Potassium Metabisulphite was the preferred source for the Sulphite in Rodinal, Potassium salts are used in preference to Sodium because of their greater solubility in water which becomes far more important in concentrated developer solutions. Metabisulphite and Hydroxide form Sulphite in solution.
At some point before or during WWII Agfa began using Potassium Sulphite and also adding Potassium Bromide and an anti-foggant to Rodinal. It's entirely possible that Agfa modified Rodinal so that it was more suitable for roll & particularly 35mm films which became cfommon in the 1930's.
Some have made the assumption that this formula might be "Classic Rodinal" but if we compare it to a modern MSDS's it's only close s to Calbe's R09 MSDS for the p-Aminophnol.
P-Aminophenol 50g - 5%
Potassium Metabisulphite 150g - 15%
Sodium Hydroxide - very approx 150g - 15%
Water to 1 litre
Calbe R09 MSDS
Potassium Sulphite 30%
Potassium Hydroxide 4%
However Potassium Metabisulphite is quite acidic in solution and will neutralize a considerable proportion of the Hydroxide. Replacing it with Potassium Sulphite cut's the amount of Hydroxide needed very substantially. Potassium Metabisulphite 5% solution has a pH of 3.8 - 4.6, while a similar Potassium Sulphite solution has a pH of 9 - 10
Only one parameter seems to stay constant from early published alternatives through to Orwo/Calbe R09 - the fact that Rodinal is a 5% solution of p-Aminophenol free base in a sulphite solution, with no excess of alkali. It's reported that the Calbe product usually has a few crystals of the free base in the bottom of the bottle, which indicates no excess of Hydroxide.
The British RAF report into the "Agfa Film Factory - Wolfen" reported by G.C. Brock, London : H.M.S.O. gives a formula for Rodinal as:
Dissolve 34 kg of para-aminophenol in 340 litres of water. Add 558 kg of a 30% solution of potassium sulphite at 55C followed by 50 kg of a 34% potassium hydroxide solution, then 5.52 kg of potassium bromide in a little water. Add 42 g P.1347 (an Agfa-specific anti-foggant). Filter and allow to stand for 14 days.
Knowing the Specific Gravities etc this seems to be around:
Potassium Sulphite 128.08kg
Potassium Hydroxide 12.57 kg
Potassium Bromide 3.75 kg
We aren't given a final volume, but if we relate this to the 5% p-Aminophenol of the Calbe MSDS this works out as:
Potassium Sulphite 19%
Potassium Hydroxide 1.85%
Potassium Bromide 0.77%
But the Calbe/Orwo version of R09 is the pre-WWII formula and it's MSDS is
Potassium Sulphite 30%
Potassium Hydroxide 4%
Potassium Bromide - not included (below 1%)
Unfortunately we can't really completely trust the RAF report, none of the Allied F.I.A.T. reports about Agfa products is entirely accurate, after all some Agfa employees were former members of the National Socialist Party (Nazi's). There is insufficient Potassium Hydroxide to react with the p-Aminophenol free base, and it is possible the resulting solution was then adjusted until the free base had just fully dissolved.
Patrick "Gadget" Gainer has published "EZ Rodinal" which in terms of its ratio of p-Aminophenol to Potassium Hydroxide is probably close to Calbe R09 as there will be no excess of Hydroxide, the weights in brackets have been scaled to give a concentration of 5% p-Aminophenol.
To 400 ml water, add:
Sodium sulfite (anhyd) 85 g (106.3)
p-Aminophenol base 40 g (50 g)
Stir well. Add
Sodium hydroxide 13.8 g or Potassium hydroxide 19.2 g (24g)
Add water to make 500 ml. (1 litre)
If EZ Rodinal; is adjusted a little further by adding 300 g of Potassium Sulphite in place of the Sodium Sulphite, some Potassium Bromide added plus some Benzotriazole and Potassium Hydroxide added slowly until the free base just dissolves
EZ Rodinal New (Calbe R09 substitute)
To 800 ml water, add:
p-Aminophenol base 50 g
Potassium sulphite (anhyd) 300 g
Potassium hydroxide 24 g
Potassium Bromide 0.8 g
Benzotriazole 1% 10 ml
Water to make 1 litre)
This would be a lot close to the pre War formula and Calbe RO9, although this is itself now being made in a more concentrated form so that the dilutions & dev times are more comparable to Agfa /A&O Rodinal (post 1964)
Patrick's second Rodinal substitute formulae is close to the Bayer/Agfa/A&O MSDS data-sheets for modern Rodinal:
p-Aminophenol 4.1% (A&O)
Potassium Sulphite 30-40%
Potassium Hydroxide 2.7% (A&0)
Potassium Bromide 1-5%
Anti-foggant - not specified
Gainer Rodinal Substitute
To about 750 ml of water at room temperature, add
p-Aminophenol 38 g
Sodium sulfite (anh) 160 grams
Sodium hydroxide 23 grams
Water to 1 liter.
This is on the right track, you need to use the free base and an excess of Hydroxide unlike the older R09 formula which has nearly 20% more p-Aminophenol and also requires using at a higher concentration to get equivalent results.
In a post about Patrick's version a comment was made about the pH at 1:50 being roughly 11.6, Agfa Rodinal has a stock concentrate pH of 14 and a dilute pH of 11.55 so if this is the case Patrick's formula is about right, except too little Sulphite and there's no Bromide or anti-foggant.
Agfa's modern Rodinal 1964 onwards uses an excess of Hydroxide and as a consequence is more active despite the lower level of p-Aminophenol than the previous formulae. Calbe R09 concentrate has a pH of 11.8.
This is what I would use as a starting point for a good modern substitute:
p-Aminophenol.(free base) ................... 41 g
Potassium sulphite (anh) ..................... 348 g
Potassium Hydroxide ........................... 27 g
Potassium Bromide ............................. 10 g
Benzotriazole 1% ............................... 10 ml
EDTA Na4 (optional) ........................... 6 g
Water to make .................................. 1 litre.
If necessary adjust to pH 14
The balance of the Bromide & Benzotriazole may need adjusting upwards..
The mixed developer should be left a couple of weeks before use.
Contrary to what has been written in some books Rodinal has always used the free base of p-Aminophenol although in the early days this was prepared from the Hydrochloride first.
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?
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.
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.
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.
Last edited by Ian Grant; 08-28-2009 at 01:05 PM. Click to view previous post history.
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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.
For up from the ashes, up from the ashes, grow the roses of success!
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.
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.
Last edited by Ian Grant; 08-28-2009 at 04:06 PM. Click to view previous post history.
To shorten the sentence a bit, it says that "Bill was heavily engaged with developers at Kodak in Rochester".
Originally Posted by Photo Engineer
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.
Last edited by Kirk Keyes; 08-28-2009 at 07:14 PM. Click to view previous post history.
For up from the ashes, up from the ashes, grow the roses of success!
No problem with those terms, and thanks!
Originally Posted by Ian Grant
For up from the ashes, up from the ashes, grow the roses of success!
I forgot to say that was the 1994 Nov/Dec issue.
Originally Posted by gainer