Disappointing results (i.e. nothing happened !)

Discussion in 'B&W: Film, Paper, Chemistry' started by slm, Nov 11, 2005.

  1. slm

    slm Member

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    Hello Everyone, I just tried mixing (first time mixing anything from raw chemicals) the D-85 found on unblinkingeye.com. I followed the formula in the order shown, mixing each chemical in until fully dissolved. I also substituted the Paraformaldehyde for acetone.
    Nothing happened ! I left a test strip in the developer for 20mins, and nothing. I tried Ilford Multi FB paper (wasn't expecting it to work from what I read, but tried anyways) and Forte Poly warm tone FB (supposed to be lithable). I then left the test strips out (of the tray that is), with any developer left in it, over night. There has been a change in paper color (Forte is copper looking). Any ideas where I went wrong, and if I can add to or save the batch ?

    thanks
    steven


    D-85 Two Solution Lith Developer

    Solution A
    Water at 125° F 500 ml
    Sodium sulphite 36.5 g
    Boric acid crystals 9.4 g
    Hydroquinone 28 g
    Potassium bromide 2 g
    Water to make 1 litre

    Solution B

    Water at 90 ° F 500 ml
    Sodium bisulphite 11 g
    Sodium sulphite 1 g
    Paraformaldehyde 37.5 g
    Water to make 1 litre

    Mix solutions with good ventilation. Mix 4 parts A + 1 part B for use.
    You may substitute 82.5 millilitres of acetone for the paraformaldehyde.
     
  2. psvensson

    psvensson Member

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    The formula seems to be missing an alkali! Very strange. I checked unblinkingeye and digitaltruth, and they have the same formula. Try adding 10g sodium hydroxide or 30g sodium carbonate.
     
  3. Gerald Koch

    Gerald Koch Member

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    The paraformaldehyde reacts with the sodium sulfite to generate sodium hydroxide and the formaldehyde sulfur dioxide addition product.

    Na2SO3 + H2O + HCHO --> 2NaOH + HCHO.SO2
     
  4. psvensson

    psvensson Member

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    ... but if you're using acetone instead of formaldehyde, does the same thing happen?

    Edit: Indeed, it seems it should.
     
  5. Gerald Koch

    Gerald Koch Member

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    Yes. It is the carbonyl (-CO-) group in both acetone and formaldehyde which reacts.
     
  6. psvensson

    psvensson Member

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    It's great to have real chemists on the board! I'd still add some alkali to the mix to see what happens. When I've tried Ilford papers in my homemade lith developers, it's not that they don't develop, they pretty much turn grey-black all over, immediately. See the Dr. Jekyll formulas in the paper developer formulas section.
     
  7. Photo Engineer

    Photo Engineer Subscriber

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    While I agree with this statement, I question the rate at which it proceeds and the yield that it gives.

    If either rate or yield is off, you don't get the amount of base that you are entitled to.

    My question is this... Was part "B" cloudy? This is a characteristic of the reaction when the paraformaldehyde reaction does not take place or is slow or is incomplete. In that case, there was not enough base formed. If acetone was used, remaining acetone odor is the clue that things didn't work as expected.

    This is a neat way to get base, but I wouldn't do it myself for any reason other than avoiding handling sodium hydroxide. But then you are substituting formalin. Nice tradeoff.

    PE
     
  8. Gerald Koch

    Gerald Koch Member

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    The portraitist G. Paul Bishop used the following for all his negatives. Here the acetone serves only to create an alkaline solution by reacting with the sulfite.

    Water .................................. 28 oz
    Acetone ................................ 1 oz
    Sodium sulfite (anhy) .................. 30 gr
    Metol .................................. 20 gr

    http://www.gpaulbishop.com
     
  9. slm

    slm Member

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    Hi, yes part B is cloudy, and still has a strong acetone odor. Working solution is clearer, maybe just a tint of cloudiness, and has a much less pronouced acetone odor.
    Can I fix this, or is it just no good ? Also, was considering trying Ansco 81, but I can't find dilutions to use with paper developing.

    Many thanks for all the replies !
    Steven
     
  10. Gerald Koch

    Gerald Koch Member

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    The reaction between acetone or formaldehyde does not go to completion but is in equilibrium. The intent is to reduce the amount of sulfite ion in solution to a low level to encourage infectious development. As sulfite is used up more is released from the addition product. In other words the adduct is a reservoir for sulfite ion.
     
  11. Donald Qualls

    Donald Qualls Member

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    From my reading on this, I understand lith printing requires a HUGE amount of exposure -- that is, many minutes for paper that would require a minute or less for development in Dektol; it then takes a relatively long time for the image to begin to appear in the lith developer. Is it possible your paper either simply didn't get enough light for the lith developer to bring up an image, or wasn't left in the developer long enough (like fifteen minutes, if I recall correctly)?
     
  12. Photo Engineer

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    Steven, residual acetone odor indicates that the formation of the sulfite adduct was incomplete. Less alkali was formed than desired, but by how much is hard to determine. Also, acetone reacts itself with alkali, forming polymeric compounds IIRC, and can further tie up the alkali.

    To my way of thinking, this is a very qualitative way of making a developer and I would not use it myself personally. By all means, try other lith developers, and Donald has a very good point above about exposure.

    PE
     
  13. psvensson

    psvensson Member

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    Looking at the formula, I would guess that acetone is in excess in B, so that it can absorb the sulfite in A when the solutions are mixed together. So it would make sense that even as designed, part B would have an acetone smell.
     
  14. Photo Engineer

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    Quite possibly true (I didn't do a molar calculation), but the excess acetone, if present, would begin reacting with the sodium hydroxide in an aldol condensation creating polymers and reducing the amount of acetone available for producing further base thereby possibly reducing the alkalinity. The point is that this is a qualitative method for generating base in situ.

    It can be used, but I wouldn't.

    It is so much easier to add X grams of NaOH. One ingredient instead of 2 and having to hope that things turn out for the best. The relative concentration of NaOH and the rate of appearance in soltuion would depend on room temperature as well.

    PE
     
  15. dancqu

    dancqu Member

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  16. slm

    slm Member

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    Thanks everyone for the info.

    I did add 2 stops more exposure than what was required for development in a normal developer, but it was not in the order of minutes, and the test strip was left in the developer for ~20mins.

    Not sure how I will proceed yet, but I'll probably try another formula.
     
  17. dancqu

    dancqu Member

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    Your first Home Brew, D-85. That's jumping in the deep end.
    I suspect you committed a lot of chemistry; a live and
    learn experience.

    I'm a little amused at the fixes suggested for Kodak's D-85.
    AFAIK, that formula has been producing a sold dependable lith
    developer for 60, 70, maybe 80 years. I did not take note but
    in the 50s when doing process camera work and half-tone
    production D-85 may have been there.

    D-85 is just one of many lith developers. I'm very sure it's
    intended use was and is publishing and newspaper plants. One
    of many developers intended for that purpose. I can just about
    guarantee that EVERY lith formula you look at is intended for
    film and LOTS of it.

    Your advantage in compounding your own chemistry is one of
    batch size. I've a .01 gram Acculab scale. I weigh no amounts
    less than 1 gram. Where smaller amounts are called for, stock
    or concentrates are used. Perhaps only a few drops of this or
    that from a bottle is all that is needed.

    Give a one gram HQ Ansco 81 a try. Leave out the citric acid
    and the bromide. The citric I think is a many years ago Calgon;
    the bromide, to counter the high activity of the developer
    and for the films of days gone by.

    Tweak the carbonate level and see what happens. If the
    developer turns any more than a little yellow while developing,
    up the sulfite a bit. I've a very well lighted Graded paper
    darkroom. No problem watching the action. Dan
     
  18. Photo Engineer

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    I would like to point out that the last use by EK of Paraformaldehyde was in the E1 stabilizer bath. The results were so variable that it was never used again or recommended in any product.

    PE