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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. #51
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    Kodak found that early PPD developers were affected by the acid used to make the salt, and converted to either the Sulfate or the p-Tosyl salt which you see in use today. This is true to the present time in CD-6 and CD-3 for example. The chloride had varying adverse effects on early Cl/Br emulsions used in print films and papers. I don't know what all was affected, as the change was complete when I joined EK.

    As for a standard sensitometric test, the pAP developers were not in use by the end of the war, and at Kodak they used an Elon + Ascorbic Acid developer called internally EAA. I do not remember the formula.

    My military manuals from the 50s do not describe any developer such as the one above nor does any Kodak manual. They basically describe Metol + HQ developers with 50 g/l or so of Sodium Sulfate, and that is the reason I asked the question.

    PE

  3. #52
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    Quote Originally Posted by Photo Engineer View Post
    Charon was the proposed use of H2 and F2 as fuels for a new rocket with high specific impulse. The reaction is the highest energy chemical reaction possible, but would have contaminated the east coast from Georgia to Cuba.

    Fortunately, an astute engineer pointed this out to NASA. One of their oversights I guess.

    PE
    In the days before NASA, NACA managers came up from the engineering ranks. That was the only way you could advance above GS-14. So, the better you were as an engineer, the more likely you were to become a manager, where you could no longer do what you loved doing. If anyone had asked me, I would have asked what they planned to do with the hot hydrofluoric acid exhaust besides kill people.

    We tend to forget that NASA means National Aeronautics and Space Administration. Human factors apply to both, but my theories and experiments applied mostly to pilots of aircraft.
    Gadget Gainer

  4. #53
    Ian Grant's Avatar
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    Quote Originally Posted by Photo Engineer View Post
    Kodak found that early PPD developers were affected by the acid used to make the salt, and converted to either the Sulfate or the p-Tosyl salt which you see in use today. This is true to the present time in CD-6 and CD-3 for example. The chloride had varying adverse effects on early Cl/Br emulsions used in print films and papers. I don't know what all was affected, as the change was complete when I joined EK.
    PE

    Kodak also did a lot of work on p-Aminophenol and it's derivatives in the 30's & 40's, there are various Patents etc, Sheppard was involved and must have moved from Wratten to Rochester with Mees.

    Your comments about the PPD acid salts are matched by Kodak's use of p-Aminophenol Oxalate, and Edmund Lowe's Gradol the sulphate form and confirm what I'm thinking about the importance of the free base in Rodinal.

    On the point of ascorbic, here's the second to last paragraph from Edmund Lowe's 1939 book on Developers:

    As for developers, it is probable that the next few years will see the introduction of a series of developing agents that that can actually be eaten if desired. Some, chemically related to Vitamin C, are available now though at enormous cost. One call almost see the advertisement of the new Zero-Grane 999 (1960 A.D.) ----- "Try Zero-Grane 999. Non-poisonous. Enlargement to 999 diameters, miraculously discovered by George Gizzlewski after 84 years of painstaking research. If it won't develop your negative, take two teaspoonsful after each meal. It puts spring in your step and a light in your eye. $10 per 2 oz. bottle sufficient for 89 rolls of film."

    It's Lowe's nice way of saying there's no magic bullets.

    Ian

  5. #54
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    Quote Originally Posted by Photo Engineer View Post
    My military manuals from the 50s do not describe any developer such as the one above nor does any Kodak manual. They basically describe Metol + HQ developers with 50 g/l or so of Sodium Sulfate, and that is the reason I asked the question.

    PE
    The manual I have,TM 1-219, was written under the direction of the Chief of the Air Corps. There was no separate Air Force at the time, so the front cover only mentions the War Department. It is truly basic photography. I suspect that most of the formulas were designed to be capable of high contrast for aerial photography.
    Gadget Gainer

  6. #55
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    Here is Kodak's DK-15 Tropical Developer from 1941

    Water-------------------750 cc
    Elon---------------------5.7 g
    Sodium Sulfite (anh)-----90 g
    Kodalk------------------22.5 g
    Potassium Bromide--------1.9 g
    Sodium Sulfate----------45.0 g
    Water to 1 L

    Use up to 90 F but at temperatures up to 75 F the Sodium Sulfate may be omitted for some films.

    This formula or derivatives of it were in use through the 50s for tropical processing of films. The USAF manuals for photography are 95- series, and the AFIT (Air Force Institute of Technology) also issues a set of books for the course in photo science. I have copies of both. They are rather hefty 8x10 size books and take up quite a bit of shelf space.

    PE

  7. #56
    Ian Grant's Avatar
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    Kodak also published D13 which is a Kodelon (p-Amininophenolol / Hydroquinone) Tropical developer:

    D13 Tropical Developer

    p-Aminophenol Hydrochloride 5,2 g
    Sodium Sulphite (anh) 52.5 g
    Sodium Carbonate (anh) 50 g
    Hydroquinone 10.5
    Sodium Sulphate 45 g (105 cryst)
    Potassium Iodide 2.1 g
    Water to 1 litre

    Dev times 6-7 mins @ 29°C

    (Both p-Aminophenol Hydrochloride and the Oxalate have been sold as Kodelon)

    Ian
    Last edited by Ian Grant; 08-26-2009 at 10:06 AM. Click to view previous post history. Reason: missed the Hydroquinone

  8. #57
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    And, I have found absolutely no reference in US publications of that approximate era to Kodelon, pAP or D-13. Your formula does include the Sulfate I see, even though the earlier formulas do not. I would have to say that the use of the Sulfate is necessary with most films or about 75 F just as with my formula.

    I have found references here to similar developers with Sulfate by Tom Hoskinson and also a reference to Kodelon by Mees in his 1921 textbook on photography.

    PE
    Last edited by Photo Engineer; 08-26-2009 at 10:13 AM. Click to view previous post history. Reason: Add information

  9. #58
    Ian Grant's Avatar
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    There are rather a lot of official Kodak formulae not in the Formulary etc, but Kodak published them none the less.

    It's exactly the same with Ilford, Agfa & Agfa Ansco, etc none of their books contain all the officially published formulae

    In the case of D13 my source differs from Tom Hoskinson's source (posted previously on APUG) because his says Kodelon, mine says p-Aminophenol Hydrochloride and had UK spelling, all UK formulae use Hydrochloride, US usually Oxalate.

    Ian
    Last edited by Ian Grant; 08-26-2009 at 10:24 AM. Click to view previous post history. Reason: add

  10. #59
    Ian Grant's Avatar
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    We cross posted

    But there is this gap of knowledge where it's hard to find the original Kodak references etc.

    Presumably Mees book is a continuation of what he began at Wratten with Sheppard, I'd guess the pair worked od Kodelon there.

    Ian

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    And, the correct formulas for some of these is either lost or in peril of being lost.

    That is why I believe that we should develop a new formulary with some sort of accuracy, to weed out and verify the best of the best. There are just too many dissenting "votes" on Rodinal type developers just to pick one, and high temperature developers to pick another.

    PE



 

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