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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. #71
    Ian Grant's Avatar
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    Who is Dr Elie Scheour "of Agfa", (or rather who your readers assume is from Agfa, as he's not) ?

    I quote "According to Bill Troop, Agfa's Elie Shneour provided the following mixing instructions for what is generally agreed to be, for all intents and purposes, Rodinal." and another "According to Elie Shneour of Agfa, the original Rodinal". I have to admit that I assumed he was probably from Agfa when I first read the FDC.

    Agfa, Bayer & A&O have published far more accurate MSDS's than the one you quote.

    Even the original Agfa Rodinal could be used at 1+100 it's in the 1910 Agfa books etc used for papers at that dilution, and the modern version while it contains approx 20% less p-Aminophenol will work well at 1+ 100 because of the higher pH. The increased Sulphite helps with the stability of the modern developer.

    Edward Zimmermann is particularly authoritative about Rodinal, and knows his facts, and I tend to agre with all he's written on the subject.

    Ian

  3. #72

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    Ian, where are you quoting from? You don't say. Certainly not from my book. Can I suggest you buy a copy and keep it in your overnight luggage? It would save a lot of trouble when you're 'quoting' from it. Alternatively, you could learn to use Google Books. Like I've said before, think before you post. I do! You're not, I must say, displaying the signs of a good researcher. By the way, have you -- or anyone you know -- done any spectrographic analysis of Rodinal? Shneour, a well-known biochemist, has, and has shared his results with me.

    Regarding something Ed Zimmerman wrote about me and Rodinal on the Net in 2003

    http://www.photo.net/bboard/q-and-a-...?msg_id=006fc5

    which is practically indistinguishable from this thread, but go ahead and read it to prove Nietzsche's doctrine of the Eternal Recurrence of the Same -- and while away some more time not taking good photos, I asked Dr Schneour to comment, and he did as follows:

    'I have read the exchanges about "Rodinal". These consist mainly of flailings about its formula (actually a whole bunch of them) which in the last analysis mean nothing in today's world. There are at least two outstanding issues regarding "Rodinal". One of them is the variations in the actual early formula which were made almost continuously and thus it is today difficult to discern which of these variants was the actual "original" formula. The other issue is that one of the remarkable properties of "Rodinal" was its long life before dilution for use. The caveat to this long life was (and is) that its developing properties change importantly but subtly as a function of time and storage conditions, to say nothing about the quality of the water used in the dilution for use. The formula I have settled on and which is listed in the now classic Anchell & Troop "The Film Deevloping Cookbook" is stored at about 15 degrees Celsius after compounding and is "marinated" for six months before first use. When compared to an old version (about 1936) it is undistinguishable for my uses. The conclusion must be that the arguments about "Rodinal" and its successor(s) will remain controversial because there are so many versions and so many usage and storage variations as to make any emotional discussion about that developer unproductive and a total waste of time. Instead, if you work with monochrome photography, make or buy the stuff, work out your best combination of variables and be productive rather than engage in idle chatter signifying nothing.'

    I've seen it all before. I actually like Ed Zimmerman, who is very intelligent if irascible, but he and Ian both belong to that class of pestiferous readers who submerge themselves in the exquisite frustration of not having written a book that someone else has written. They then spend a substantial part of their lives making that author's life as miserable as possible, instead of letting him get on with his work, much less getting on with their own. I have noticed before that the impulse to create one's own work is not really compatible with the impulse to criticize other people's work. That's probably one reason why Ian hasn't written a book about photochem.

  4. #73
    Ian Grant's Avatar
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    Bill, I have the FDC beside me. On pages 57 & 117 the mention of Schneour is very ambiguous because you don't say who he is and his name only ever crops up in relation to you & Rodinal. Gerald Koch, who's opinions I respect is the source of the second quote which is here on APUG.

    If Elie Schneour has definitive data on Rodinal where is it ? I could have done spectrographic analysis on Rodinal & other developers lf but in fact it's quite difficult to determine what's in a compouded developer. I had two Varian AA Spectrometers in the lab I ran, and access to other instruments as we worked closely with 2 or 3 other labs specialising in different testing methods, however as Ron (PE) could confirm some elements or salts are difficult to detect and measure. Getting a full analysis done is extremely expensive.

    I'd request you don't turn threads like this on APUG into the ill tempered and bitter threads that you've taken part in so many times before on various forums.

    I don't doubt that the formula published by Agfa themselves in Andresen's book is the closest formula to Rodinal that Agfa has ever published. (Which is the formula in the FDC). Other people may have been closer to the mark.

    Ian
    Last edited by Ian Grant; 08-27-2009 at 09:05 AM. Click to view previous post history. Reason: add

  5. #74
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    Ian, you are correct about cost to an extent and correct about difficulty to an extent. At EK, analysis of any processing solution or emulsion (or coating for that matter) was routine and a snap. I got back analyses on all of my processing solutions before and after use if they were experimental. In fact, such analyses are essential for determining how to work out seasoning and balance (see my post on steady state).

    As an additional factor here, analysis is essential for patent infringement work and thus all competitor products are analyzed in great detail. This extensive work reduces the cost to being minimal.

    PE

  6. #75
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    Another factor with Rodinal would be the tests show what's in the developer once matured, rather than the chemistry used to make it.

    So the early Andresen published formula and both R09 & modern Rodinal would show Sulphite while in fact the first uses Metabisulphite and wouldn't test for the full hydroxide content that would need to be added.

    Again it would be almost impossible to determine what form the p-Aminophenol was in when added.

    Ian

  7. #76

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    Sorry, Gerald has got it wrong - - and anyone who wants to know who Dr Shneour is has only to look him up on Google. Ian, are you looking for facts in Internet posts? You'll find they're few and far between, because few people will actually spend an hour or two thinking, researching, and drafting before they post. At that point, you have to wonder - - for what? As you'll see from the previous thread cited, on which Dr Shneour permitted me to quote him, it's all been said and done before! Why repeat it every five years? In any case, whatever he may have learned when he analyzed the developer would only have been true for that iteration of it. He remains the only person I know who actually has done the work. You can talk all you like about the difficulty, ambiguity, expense etc. and how much equipment you may once have had and no longer do, but Shneour is the only guy I know who actually did it. HE DID IT !!! I wish you people would actually do things!!! Patrick comes in for a lot of flak, but I so admire that he actually keeps his hand in.

    For the record, I suggested to Ed Zim back in 2003 and in an email this morning, that these questions can be answered once for all - - by him - - by the simple expedient of his looking up the right people and talking to them. Six years have elapsed, and no action. I also suggested that what attracts people to these cyclical discussions of Rodinal is precisely that they don't know. That's the allure. In the meantime, were anyone from Agfa reading this - - I'm sure they aren't - - they'd be dying of laughter. I don't think you guys really want to know about Rodinal. It's the not knowing, the 'cloud of unknowing' - - that gets you. I can sympathize - - I can empathize - - up to a point. I feel your pain!

  8. #77
    Ian Grant's Avatar
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    Then where is Dr Elie Sheours data ? There's nothing inthe thread you quoted. You never answer question.

    Ian

  9. #78
    Ian Grant's Avatar
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    Something smells very fishy here

    If Dr Elie Shneour is THE expert on Rodinal (which for all we known he might well be) then surely he would have known & told Troop that the formula in the FDC was actually one published by Andresen & Agfa themselves at the start of the 20th C.

    It's rather like the "Authentic" formula for Edwal Super 20, and a few others.

    Ian

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    >Then where is Dr Elie Sheours data ?

    You'll have to ask him for that, Ian. Nicely. And don't show him this thread, or he won't talk to you. Also fyi, he doesn't like people who can't spell his name.

    You know folks, what gets me through a day of having to deal with the Ian Grants of this world is that I remember the civility and respect that I was accorded by people like Henn, Haist, TH James, Crawley, HD Russell, Mason, Dickerson, Zawadzki, etc. What a contrast! Such nice people! And what a lot of work they did! It's the wannabes, or I guess, really, the woulda-coulda-beens, that give you all the trouble in this world.

    >Something smells very fishy here

    If I've told you once, I've told you a hundred times, Ian, not to eat herring for breakfast!

  11. #80
    Ian Grant's Avatar
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    Hey Kirk, what did you predict even more name dropping

    We've got you sussed Bill you attack as a means of defence .

    Ian

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