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  1. #1
    Ian Grant's Avatar
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    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):

    N16:

    • 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:

    Paramidophenol.
    ONE-SOLUTION

    Potassium metabisulphite 300g
    Distilled water 1 litre
    Paramidophenol 100g

    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

    P-Amininophenol 5%
    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:

    p-Aminophenol 34kg
    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:

    p-Aminophenol 5%
    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

    p-Aminophenol 5%
    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.

    EZ Rodinal

    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
    pH 14

    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:

    Rodinal 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

    Some notes:
    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.

    Ian

  2. #141
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    I would hate to condemn a book that has done a great service to our community, because one reference has changed his goals and work area in the years since the book was published.

    I must admit to knowing both authors to some extent, but I used the book for quite a while before I met either of them and I found it useful but not perfect. Nothing is!

    PE

  3. #142
    Ian Grant's Avatar
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    I'd add something here not directly related to this thread or any book mentioned in it.

    I worked with someone once who told me how he wrote his Degree Thesis/Dissertation (History of Art) about a painter, he totally fabricated the quotes and references he attributed to one particular source. When I last visited the US I was told by a very senior Company Vice President (ex Kodak) to tell the same person how he to was about to get his MBA. I'm afraid at that point I told the truth, my work colleague had no MBA, he wasn't actually bright enough to get on a course.

    A quote or reference has to be totally verifiable or it's completely worthless. In our own fields of higher academic research many of us did/do follow up references made.

    We have quite a large number of people on APUG with post Graduate Degree's and a significant number of Professors, so quotes & citations etc need to be accurate.

    Ian

  4. #143
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    Ian;

    This could go on forever. Just because, 10 years or so later, a particular reference refuses to comment on old work does not mean much to me. Many of my friends are the same. They refuse to comment here or to me when I ask them things that are vague in my memory. So, your entire premise to me is faulty.

    In addition, I have verification that these conversations did take place. Grant Haist confirmed not only the nature of the conversations but the content and time period. So, I have to say that you are not being fair in this situation.

    In addition, if two authors are involved, the senior author is responsible for the veracity (or for verifying) the data as well as the other author. So, this whole thing appears to be an unfair attack to me. I have used the book and found it was a worthwhile investment.

    There is absolutely no evidence that the quote in question is inaccurate, merely that the person quoted is no longer interested in responding.

    PE

  5. #144

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    Quote Originally Posted by Ian Grant View Post
    A quote or reference has to be totally verifiable or it's completely worthless. In our own fields of higher academic research many of us did/do follow up references made.

    We have quite a large number of people on APUG with post Graduate Degree's and a significant number of Professors, so quotes & citations etc need to be accurate.

    Ian
    I agree that a verifiable quote or reference is most desirable, but unfortunately not every last one can always be confirmed. That - in and of it self - does not invalidate their intrinsic value. There are many references one cannot locate due to any number of reasons. Cost, typing errors, rarity/ limited distribution, total destruction due to wars... and what about pc... "personal communication"? People die as well as forget.

    I am not taking sides here, I think everyone has truth by the tail, hand or foot....

    Ray
    Last edited by Ray Rogers; 10-16-2009 at 06:48 PM. Click to view previous post history.
    Be free of all deception, Be safe from bodily harm
    Love without exception, Be a saint in any form
    (Patti Smith)

  6. #145
    Ian Grant's Avatar
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    Can we come back on topic.

    My contact with Dr Dr Shneour was to try and find out more about Rodinal, and to hopefully tie up what I've found in 1930's Agfa Patents relating to additives to a p-Aminophenol developers and the mystery additive mentioned in the FIAT reports.

    None of this information has been published in any books or articles, and I had hoped that Dr Shneour might have been able to shed some further light on this in view of any analysis he's done of Rodinal.

    Ian

  7. #146

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    Quote Originally Posted by Ian Grant View Post
    My contact with Dr Dr Shneour was... to hopefully tie up what I've found in 1930's Agfa Patents relating to additives to a p-Aminophenol developers and the mystery additive mentioned in the FIAT reports.

    None of this information has been published in any books or articles, and I had hoped that Dr Shneour might have been able to shed some further light on this in view of any analysis he's done of Rodinal.

    Ian
    Other than a CAS # and synthesis for the desensitizer,
    I am not so sure there is that much mystery.

    I wouldn't expect the Professor Dr. to know those things from a simple study.

    More interesting is the question of how the developer behaves without it...
    Is there any evidence of problems with the simple rodinal formulas?

    I don't see the sense of trying to duplicate one particular formula if other,
    similar formulas work just as well.

    Ray

  8. #147
    Ian Grant's Avatar
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    You make a good point Ray.

    Rodinal is unique in that no other developing agent keeps as well in such a high alkali concentrate. Sometimes understanding how a particular developer functions triggers/sparks ideas for others.

    As the Agfa Patents are cited in even quite recent Patents, or cross linked through others to Ilford, Fuji and Kodak it appears that the anti-oxidant used is quite important.

    The simple Rodinal type formula has been reported to cause Dichroic fog with some emulsions. This may have become a problem as emulsion speeds were improved, there are quite a number of Patent's many not so easy to access, and some would need translation.

    The problem with Dichroic fogging reared it's head again when Kodak released Tmax Developer, which isn't recommended for sheet film use for this reason.

    Ian

  9. #148
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    On the strength of Ian's advice in this article I have prepared a substitute using the last formula he listed. 45% solution of potassium sulfite is easy to get so I adjusted for a 1 liter bottle and adjusted the hydroxide to provide a pH of 13. It appears to work exactly the same as the Agfa Rodinal I have, whether it's their exact formula or not, it's really good and I am happy with it.

    Thanks to Ian Grant

    Ianol makes 1.3 L

    p-Aminophenol (free base) ................... 53 g
    Potassium sulfite 45% sol...................... 1L
    Potassium Hydroxide ........................... 54 g
    Potassium Bromide ............................. 13 g
    Benzotriazole 1% ............................... 13 ml
    Water to make .................................. 1.3 L

    Stock pH 13

    I like this for stand development in a Jobo drum, use 20g stock in 2 Liters of water, agitate briefly and develop for one hour..good with TMY, TriX, Delta, FP4 and nice with Rollei Retro 100,

  10. #149
    Leigh B's Avatar
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    Quote Originally Posted by eclarke View Post
    Ianol makes 1.3 L
    Why do you make 1.3L of stock (that won't fit in any standard commercial container) rather than 1L?

    Quote Originally Posted by eclarke View Post
    use 20g stock in 2 Liters of water
    Why do you specify the amount of stock solution by weight rather than by volume?

    - Leigh
    “Wise men talk because they have something to say; fools, because they have to say something.” - Plato

  11. #150
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    Quote Originally Posted by Leigh B View Post
    Why do you make 1.3L of stock (that won't fit in any standard commercial container) rather than 1L?


    Why do you specify the amount of stock solution by weight rather than by volume?

    - Leigh
    Because I can buy liter bottles of 45% potassium sulfite solution and the dry ingredient, which I can't get calls for 348g. I recalculated to just dump a liter of 45% as opposed to having 102 cc left over. I have all kinds of containers..no problems with storing it.

    I weigh extremely dilute working strength developer because it's just accurate..14cc in a graduate is pretty fickle..If you want to measure, it's 14 cc in 2 liters of water.



 

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