Rodinal formula from Wolfen via British post-WWII intelligence

Discussion in 'B&W: Film, Paper, Chemistry' started by Lee L, Jan 11, 2006.

  1. Lee L

    Lee L Member

    Messages:
    3,247
    Joined:
    Nov 17, 2004
    Shooter:
    Multi Format
    Silverprint has an ad/info in the December 2006 B&W Magazine with a version of Rodinal taken from post WWII military intelligence, modified to use the currently more commonly avaliable sodium salts. That page is available online:

    http://www.silverprint.co.uk/PDF/Rodinal-4.pdf

    Lee
     
  2. Gerald Koch

    Gerald Koch Member

    Messages:
    1,670
    Joined:
    Dec 14, 2004
    Shooter:
    Multi Format
    The Wolfen recipe is difficult to convert for modern use. The solutions are measured by weight and not by volume.

    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.

    One must know the density of the solutions used (potassium sulfite and potassium hydroxide) and account for them in determining the total amount of water. I would like to see the calculations used to arrive at the formula given in the Silverprint article.

    The use of sodium salts rather than potassium ones results in a softer working developer. This can be seen by comparing the two negatives in the article.
     
  3. Kevin Caulfield

    Kevin Caulfield Subscriber

    Messages:
    3,386
    Joined:
    Aug 3, 2004
    Location:
    Melbourne, A
    Shooter:
    Multi Format
    The example of the neg they show in the Silverprint ad looks to me completely different from the true Rodinal one.
     
  4. Harry Lime

    Harry Lime Member

    Messages:
    476
    Joined:
    Dec 10, 2005
    Shooter:
    35mm RF
    Isn't this no longer an issue, since Rodinal is back in production, or did I missread that post from a few days ago?

    Harry Lime
     
  5. Lee L

    Lee L Member

    Messages:
    3,247
    Joined:
    Nov 17, 2004
    Shooter:
    Multi Format
    It looks softer working to me as well, but it's difficult to judge as the pattern of the brighter sky (denser part of the neg) and clouds, and presumably the pattern of sunlight on the foreground objects, has changed a lot between exposures.

    You read the earlier post about A&O putting the current Rodinal back into production correctly Harry, although I don't see why it would necessarily lessen curiosity about the topic.

    Lee
     
  6. gainer

    gainer Subscriber

    Messages:
    3,725
    Joined:
    Sep 20, 2002
    If the original solution strengths are in grams/gram of solution, it's easy enough at least to get the weights. I then calculate:

    34 grams p-aminophenol
    167 grams K2SO3 or 133 grams Na2SO3
    17 grams KOH or 12 grams NaOH

    and I'm assuming that the total volume at the factory will be 500 liters, but my calculated weights would work for 500 ml. These are close to the proportions I have been using in my homebrew. I'll bet there would have been much less difference between the illustrating photos if these proportions had been used. The 12 grams of NaOH with 34 grams of p-aminophenol will leave a little precipitate. If you leave it for 2 weeks, most of that may be used up by aerial oxidation as all the air in the original mixture takes a while to work. The oxidation of the aminophenol in the presence of sulfite makes a monosulfonate and the hydroxide, which make some of the precipitate soluble and active as developer. The solution will also darken somewhat over time as a little oxidized aminophenol makes a lot of dark.
     
  7. gainer

    gainer Subscriber

    Messages:
    3,725
    Joined:
    Sep 20, 2002
    Note: if you use p-aminophenol hydrochloride, you will need about twice as much NaOH. For every mole of p-aminophenol.HCl you will need one mole of NaOH to neutralize the HCl and a little less than one more mole to make the sodium aminophenolate salt, leaving some aminphenol base precipitated. This solution will contain some sodium chloride, but I doubt it will make much difference in performance or grain size.
     
  8. gainer

    gainer Subscriber

    Messages:
    3,725
    Joined:
    Sep 20, 2002
    I shouldn't do these things late at night. I think the weights are right, but I should have calculated the volume of water. It starts with 340 liters. 167.4 kg of K2SO3 comes in 30% of 558 kg od solution, leaving 390.6 kg of water, or 390.6 liters. 17 kg of KOH comes in 34% of 50 kg of solution leaving 33 kg of water. Thus, the total water in the mixture is 763.6 liters. What are the odds that the final volume was topped off at 1000 liters? Pretty good I think. If that is the case, the solution would be about half the strength I have been using in my homebrew. Sorry about that. I'll stick with mine, though, for my use.
     
  9. Gerald Koch

    Gerald Koch Member

    Messages:
    1,670
    Joined:
    Dec 14, 2004
    Shooter:
    Multi Format
    The Wolfen recipe does not indicate that the final solution should be diluted to a set volume. Rather I get the impression that the amounts were arrived at by the size of the reaction vessel.
     
  10. gainer

    gainer Subscriber

    Messages:
    3,725
    Joined:
    Sep 20, 2002
    When I get some more p-aminophenol I shall see what the volume is without adding any more water. It may be that the volume of solids added to the 763 or so liters comes out to be about 1000 liters. It is difficult to tell because some solids seem to fit between water molecules with practically no change in volume. It is true that the conversion to sodium makes it tricky, and perhaps an excercise in futility. Would converting to moles of the potassium salts/ gram of solution before attempting the conversion help?

    My opinion is that the sulfite content is not critical but should probably be sufficient to make the monosulfonate from the available aminophenol; that the developing agent ends up being the sodium or potassium aminophenolate, and that the presence of some precipitated aminophenol, at least initially, is important. The ratio of hydroxide to aminophenol seems to be such as to provide more aminophenol than can be converted to the phenolate by the amount of hydroxide provided. Anyway, it's fun to think about and play with.
     
  11. Photo Engineer

    Photo Engineer Subscriber

    Messages:
    25,779
    Joined:
    Apr 19, 2005
    Location:
    Rochester, NY
    Shooter:
    Multi Format
    The fundamental problem with Rodinal is that the pH is critical no matter what you do to mix it or how you mix it.

    At the correct pH (which was also rather hard to do back then) there should be a small amount of undissolved PAP remaining in the bottle. If it dissolves, then the solution is too acid and if too much precipitates (more than 1 or 2 crystals) then it is too alkaline.

    This will be critical if the concentration is wrong as the pH will then be off as well.

    This information in complete form was published elsewhere in another thread with complete instructions.

    PE
     
  12. gainer

    gainer Subscriber

    Messages:
    3,725
    Joined:
    Sep 20, 2002
    And you know this by experiment or by theory or by some inside knowledge of how it was done most recently by AGFA? There are three sources of contamination in Rodinal: the sulfite or metabisulfite, the p-aminophenol, whether the hydrochloride or not, and the hydroxide. I'm assuming that the purest possible water is used. Will leaving a few crystals in a vat of, say, 1000 liters, guarantee always the same pH, or only within some tolerance? How far off would the pH be if there were 1 gram of precipitate per liter instead of, say, 0.1 or 0.01? How does precipitate affect the pH of what is in solution?

    The implication in the quoted recipe is that all the amounts are dumped in the vat, probably stirred or otherwise agitated, and left for 2 weeks to age. A minimum of stirring is guaranteed when the components are in solution to begin with, but it is not likely that there is such a thing as a 34% solution of p-aminophenol in water unless it is extremely hot water. That is why the aminophenol is dry. There was no indication of any sort of titration to produce only a few crystals. In point of fact, I have made Rodinal Expedients all the ways I could think of and some that others thought of, and the only difference I could find in operation was due to concentration.

    There is something to be said for adding the p-aminophenol last. The solution is less colored, indicating less initial oxidation. However, no one has to my knowledge successfully correlated the color of Rodinal from the factory with its activity in the developing tank. If you add it last, the solution may be at room temperature.
     
  13. Photo Engineer

    Photo Engineer Subscriber

    Messages:
    25,779
    Joined:
    Apr 19, 2005
    Location:
    Rochester, NY
    Shooter:
    Multi Format
    Patrick;

    I know a lot about Rodinol from all three; experiment, theory and reading reports.

    I didn't mention contamination or pH effects from water due to the fact that pH and buffer capacity are two different things. A water source at pH 5 and another at 8 if 'pure' water do not have sufficient buffer capacity per se to have significant effect on the other ingredients. Also, a 1% or so impurity in any of the other ingredients is not likely to have much buffer capacity, but may affect pH which is quickly overcome during proper mixing.

    The discussion of buffer capacity vs pH has come up enough times in various posts to indicate to me that most non-chemists don't understand the difference.

    The use of PAP or PAP.HCl does affect final results for a number of reasons. Most tend to ignore this as well, but it is a not insignificant change. The presence of oxidized products also influences final solution strength to some small degree, but has a bigger effect during mixing of large batches. This is often ignored by non-chemists as well. On the small scale, oxygen entrainment in probably unimportant, but on the 100L or so size batch you can introduce problems. Having mixed developers at both scales, I can tell you that there is a significant difference as a function of batch size.

    Read the other thread on Rodinol mixing and formulations.

    PE
     
  14. Sponsored Ad
  15. gainer

    gainer Subscriber

    Messages:
    3,725
    Joined:
    Sep 20, 2002
    You didn't explain how precipitated anything can affect the pH of what is in solution. If pH is the principal concern, should we use a pH meter to decide when we have reached Rodinal, or will a development test suffice? pH meters are less reliable in the hands of amateurs than teaspoon measurements. What are the prime characteristics of Rodinal that would be affected by variation in pH? Most users of it are looking for a certain grain-gradation-sharpness character that they consider unique to Rodinal. If pH is a critical variable in determining those characteristics, then pH of the working solution should be critical as well. Is it?

    A saturated solution of potassium paraminophenolate should have a certain pH. The concentration of sulfite may have some effect on how concentrated a saturated solution can be, but I cannot see how precipitated p-aminophenol can affect pH. It is not ionized, is it?

    If using p-aminophenol or the hydrochloride makes a difference, why did not the recipe discovered during WWII use the hydrochloride? The amount of hydroxide is in fact almost but not quite enough to convert all the specified amount of aminophenol to the phenolate.

    If someone can show by experiment, and not by fanciful imaginings of what goes on in the mixing tank, that the order of mixing makes a noticeable difference I would appreciate it. You can refuse to listen to anyone who does not have a degree in chemistry. I can refuse to listen to anyone who does not have a degree in common sense, but I do not. In all my years at NASA, I engaged in many different research projects requiring many different fields of expertise. What I needed to know, I crammed into my brain both during working hours and at home. I found that having a degree in anything was a license to learn aout everything.

    Did I tell you I grew up in Missouri? Show me.
     
  16. Photo Engineer

    Photo Engineer Subscriber

    Messages:
    25,779
    Joined:
    Apr 19, 2005
    Location:
    Rochester, NY
    Shooter:
    Multi Format
    Please read the other thread. I don't intend to rehash what others have posted.

    PE
     
  17. gainer

    gainer Subscriber

    Messages:
    3,725
    Joined:
    Sep 20, 2002
    I read and reread the other thread long ago. Nowhere in it was there an indication that, let alone an explanation of how, precipitated p-aminophenol could affect the pH of a solution. Neither was there any prediction of exactly what would be the practical effects of mixing the ingredients in a different order. Furthermore, the fact that the Wolfen formula specifies p-aminophenol, not the hydrochloride, indicates that if the lacking potassium or sodium chloride is important, it did not seem so to AGFA. These are your theories that you could test in short order and perhaps explain in even shorter order.
     
  18. Gerald Koch

    Gerald Koch Member

    Messages:
    1,670
    Joined:
    Dec 14, 2004
    Shooter:
    Multi Format
    The presence of a small amount of unreacted paraminophenol indicates that the solution is at the lowest pH where the phenolate can exist. There is nothing mystical about its presence.
     
  19. Kirk Keyes

    Kirk Keyes Member

    Messages:
    3,267
    Joined:
    Jun 17, 2004
    Location:
    Portland, OR
    Shooter:
    4x5 Format
    Patrick - if something is dropping out of solution, it will be removing ions from the solution. This can affect the pH of that solution (or the buffering capacity) depending on what it is that has dropped out.

    So it is not the unionized material sitting on the bottom of the vat that affects the solution pH, but it is the ions that were removed from solution that can affect the pH.

    Kirk - www.keyesphoto.com
     
  20. gainer

    gainer Subscriber

    Messages:
    3,725
    Joined:
    Sep 20, 2002
    That is not the point in this case. P-aminophenol does not drop out of solution. It is practically insoluble. It never gets into solution. Only that part that is combined with sodium from the hydroxide to form the phenolate gets into solution. If you start with a solution of p-aminophenol.HCl, the first hydroxide that hits the solution makes salt out of the HCl and precipitates the p-aminophenol. When that has been done, if there is more hydroxide available, the phenolate is formed. Whichever starting point you use, if there is not enough hydroxide to make phenolate out of all the p-aminophenol, some of it will remain undissolved. However, in the presence of sulfite, aerial oxidation will make monosulfonate and hydroxide which can act on precipitated p-aminophenol to make phenolate. But that is not the precipitated aminophenol changing the pH. That is a change in pH due to aerial oxidation unprecipitating some of the amnophenol.
     
  21. Gerald Koch

    Gerald Koch Member

    Messages:
    1,670
    Joined:
    Dec 14, 2004
    Shooter:
    Multi Format
    I think that it is significant that the Wolfen recipe calls for the potassium sufite solution to be at 55C. This increases the solubility of the p-aminophenol and helps the formation of the phenolate when the hydroxide is added. As more phenolate is formed more pap will dissolve. I would assume that the reaction takes place in a closed vessel to prevent oxidation.

    BTW, there is a recipe in the Focal Encyclopedia of Photography that starts with p-aminophenol rather than the hydrochloride.
     
  22. gainer

    gainer Subscriber

    Messages:
    3,725
    Joined:
    Sep 20, 2002
    Gerald, did I miss something? The recipe you gave near the beginning of this thread had 34 kg of paraminophenol and 50 kg of 34% KOH. I calculated 34 kg of the base to be 0.312 kmoles and 34% of 50 kg of KOH solution to be 17 kg or 0.304 kmoles of KOH. That is 0.008 kmoles less than enough to make all possible phenolate out of paraminophenol. If we assumed that the HCl was intended, 34 kg would be 0.234 kmoles and 0.468 kmoles of KOH would be required to make phenolate out of all of it. That would be 26.2 kg, which doesn't compute to be 34% of 50 kg of solution. In other words, I think the equation balances better when the paraminophenol is interpreted to mean the base and the percent solutions are taken to be grams/100 grams of solution rather than grams/100 ml.

    I don't have ready access to the Focal Encyclopedia. Could you quote that recipe, please?
     
  23. gainer

    gainer Subscriber

    Messages:
    3,725
    Joined:
    Sep 20, 2002
    Gerald, did I miss something? The recipe you gave near the beginning of this thread had 34 kg of paraminophenol and 50 kg of 34% KOH. I calculated 34 kg of the base to be 0.312 kmoles and 34% of 50 kg of KOH solution to be 17 kg or 0.304 kmoles of KOH. That is 0.008 kmoles less than enough to make all possible phenolate out of paraminophenol. If we assumed that the HCl was intended, 34 kg would be 0.234 kmoles and 0.468 kmoles of KOH would be required to make phenolate out of all of it. That would be 26.2 kg, which doesn't compute to be 34% of 50 kg of solution. In other words, I think the equation balances better when the paraminophenol is interpreted to mean the base and the percent solutions are taken to be grams/100 grams of solution rather than grams/100 ml.

    I don't have ready access to the Focal Encyclopedia. Could you quote that recipe, please?
     
  24. gainer

    gainer Subscriber

    Messages:
    3,725
    Joined:
    Sep 20, 2002
    I forgot to mention that 55 C is only 131 F. The water I wash my hands in is hotter than that. What happens when it cools? Will we have a supercooled solution with just the right amount of precipitate? There was no provision in the quoted recipe for adding more hydroxide or more paraminophenol to get the famous, or perhaps fabled, few crystals.
     
  25. Gerald Koch

    Gerald Koch Member

    Messages:
    1,670
    Joined:
    Dec 14, 2004
    Shooter:
    Multi Format
    I guess I wasn't clear, what I meant is that the Focal formula used the free base like the Wolfen recipe. Most formulas for a concentrate pap developer start with the hydrochloride salt.

    Distilled water (55°C) .................. 500 ml
    Paraminophenol .......................... 100.0 g
    Potassium metabisulfite ................. 300.0 g

    These ingredients are brought into solution with the least amount of concentrated potassium hydroxide solution and then made up to a final volume of 1 liter.

    For normal tank development the solution is diluted about 40 times.

    Encyclopedia of Photography, Focal Press (London:1962), p 319.
     
  26. gainer

    gainer Subscriber

    Messages:
    3,725
    Joined:
    Sep 20, 2002
    Now I get it. Thanks.