PC-Sulfite: A simple developer giving XTOL-quality

Discussion in 'B&W: Film, Paper, Chemistry' started by albada, Dec 29, 2011.

  1. albada

    albada Subscriber

    Messages:
    741
    Joined:
    Apr 10, 2008
    Location:
    Escondido, C
    Shooter:
    35mm RF
    Here's a developer I discovered that gives XTOL-quality with D-23 simplicity. Well, almost as simple as D-23. But before I spend any more time testing this, could somebody tell me if this developer is already known? My searches didn't find this formula. It's so simple that I'm thinking that somebody must have already discovered it. Anyway, if your motto is "simple is beautiful", you'll like PC-Sulfite. Here's the 1-liter formula:

    Sodium sulfite ................ 90 g
    Phenidone ..................... 0.15 g
    Ascorbic acid ................. 2.8 g

    Target pH = 8.2 (same as XTOL).
    Add 15% to XTOL's time as a starting-point.

    I've only tested this with Tmax-400 (TMY) using distilled water at 20C. I shot all identical frames on a roll, and developed test-strips at 20C using XTOL and PC-Sulfite. Carefully examining the neg's through 22x loupes, I could scarcely see any difference between them. Same grain and shadow-detail.

    PC-Sulfite contains no chelation agents and is not buffered, so its shelf-life will probably be short, even if you use distilled water. So use it shortly after mixing.
    I use a 1% solution of phenidone in propylene glycol (PG) because phenidone is slow to dissolve in water.
    The chemistry of PC-Sulfite is sufficiently different from XTOL that times might vary significantly from the "add 15%" time-rule above. Test first.
    I haven't tried diluting it, but the pH of a sample of diluted PC-Sulfite matches that of diluted XTOL, so I'd expect it'll deliver similar results.

    An interesting fact: You can be sloppy about measuring the ascorbic acid. For example, boosting the ascorbic acid will help the phenidone, increasing activity, but will also drop the pH, reducing activity. These effects roughly cancel out. My first test had 3.5g ascorbic acid, and the correct time was about the same as this 2.8g version. I haven't tried reducing ascorbic below 2.8g, but I'd say that being .1 or .2g off in measurement will have negligible effect.

    In the DS-10 thread here and here, Photo Engineer (PE) was encouraging me to remove borate from a formula I'm working on due to environmental restrictions, and after doing so, and removing the PG-carrier as well, this is all that was left. It's so simple that I didn't think it could work, but it works great.

    Well, did I just re-invent the wheel here? OTOH, if this really is new, then I'll test it some more.

    Mark Overton
     
  2. RidingWaves

    RidingWaves Member

    Messages:
    808
    Joined:
    Feb 22, 2006
    Location:
    Hawaii
    Shooter:
    35mm RF
    Great! Any idea what the conversion to Dimezone-S would be since I have that on hand....
     
  3. Ryuji

    Ryuji Member

    Messages:
    1,416
    Joined:
    Jan 15, 2005
    Location:
    Boston, MA
    Shooter:
    Multi Format
    Mark, I would strongly recommend against this formula as a practical formula. Despite your observation, formula like this is very intolerant of small errors and performance will be very much variable in practical situations. You are getting into roads that careful chemists avoid.

    Borates are very useful buffering agents. There are some known downsides, and I wouldn't use it unless there is a good reason to do so. But any chemical ingredient that has any useful property has good and bad aspects. If you remove the buffering capacity and alkaline agent (borates) from your formula, you must balance with something else. You have to weigh risks and benefits of using each and all ingredients that go into formula and make a rational judgment.
     
  4. albada

    albada Subscriber

    Messages:
    741
    Joined:
    Apr 10, 2008
    Location:
    Escondido, C
    Shooter:
    35mm RF
    Yes, an error of just a few hundreths of a gram of the phenidone will cause a substantial change. But an error of a gram of sulfite will make no perceivable difference, and I've verified robustness in the ascorbic acid. Further testing is needed to gauge sensitivity to type of water (if distilled/DI isn't used), temperature, dilution, and film-type.

    And I forgot to mention this recommendation: Dissolve the sulfite first, so it'll scavenge the dissolved oxygen.

    I suggest 0.2 g of dimezone-S, because that's what XTOL uses. Others have changed this to 0.15 g of phenidone in XTOL-like formulae, so 0.2 g dimezone-s should be very close.

    Mark Overton
     
  5. Ryuji

    Ryuji Member

    Messages:
    1,416
    Joined:
    Jan 15, 2005
    Location:
    Boston, MA
    Shooter:
    Multi Format
    This formula is not robust against the errors made in the quantity of ascorbic acid. If you don't accept my knowledge on this topic, you should at least run somewhat decent sensitometric test, and report pH of each solution with varying amounts of ascorbic acid used.
     
  6. albada

    albada Subscriber

    Messages:
    741
    Joined:
    Apr 10, 2008
    Location:
    Escondido, C
    Shooter:
    35mm RF
    Yes. Changing the ascorbic acid will change pH. Yet I just re-examined my negatives developed with 3.5g and 2.8g of AA. Their densities are practically identical. But 3.5 vs 2.8 would be a 25% measurement-error. With the virtually the same results. That's robustness.

    Here are the pH's I measured:
    3.5 g of AA: pH 8.21
    2.8 g of AA: pH 8.33
    XTOL: 8.37

    Notice that XTOL is well above 8.20. I thought my meter was reading high, but I did a two-point calibration, and it passes the Borax-test. Methinks that Kodak boosted the pH a little after filing the patent.

    Ryuji, when testing DS-10, you noticed that some 100-speed films develop poorly below pH 8.2. I suspect that Kodak observed the same thing late in the game, and boosted pH to give themselves more pH-headroom. Either that or my meter's defective. :confused:

    Mark Overton
     
  7. RidingWaves

    RidingWaves Member

    Messages:
    808
    Joined:
    Feb 22, 2006
    Location:
    Hawaii
    Shooter:
    35mm RF
    Yes, I think Kodak boosted it when they shifted the packaging way back when it first came out, I never could get a decent neg from Tmax 100. Now its not the case....
     
  8. analog what is that?

    analog what is that? Member

    Messages:
    172
    Joined:
    Nov 26, 2011
    Shooter:
    Multi Format
    Just wanted to ask about Phenidone, since more and more esoteric names for this has started to fly:

    I have phenidone from Photograpic Formulary
    Cat no 10-0870
    CAS no 92-43-3

    I have done some searching:

    - Dimezone (4,4 Dimethyl 1 Phenyl 3 Pyrazolidone)
    - Dimezone S (4 HydroxyMethyl 4 Methyl 1 Phenyl 3 Pyrazolidone)


    - Phenidone A (1 Phenyl 3 Pyrazolidone)
    - Phenidone B (4 Methyl 1 Phenyl Pyrazolidone)

    Dimezone S is almost as active as the original
    Phenidone but with lower level of fog.



    ?Name? Dimezone, Phenidone D


    4,4-Dimethyl-1-phenyl-3-pyrazolidone
    ?CAS?

    2654-58-2
    ?Synonyms?

    4,4-DIMETHYL-1-PHENYL-3-PYRAZOLIDINONE
    4,4'-DIMETHYL-1-PHENYL-3-PYRAZOLIDONE
    4,4-DIMETHYL-1-PHENYL-3-PYRAZOLIDONE
    DIMEZONE
    DIMEZORE
    LABOTEST-BB LT00440816
    TIMTEC-BB SBB003657
    4,4-dimethyl-1-phenyl-3-pyrazolidinon
    4,4-dimethylphenidone
    nsc215239
    4,4-Dimethyl-1-phenyl-3-pyrozolidinone
    4,4-Dimethyl-1-phenyl-3-pyrazolidione
    3-Pyrazolidinone, 4,4-dimethyl-1-phenyl-
    4,4-Dimethyl-1-phenyl-3-pyrazolidone (Dimezone)
    4,4-Dimethyl-1-phenyl-3-pyrazolidon
    4,4-DIMETHYL-1-PHENYL-3-PYRAZOLIDONE DIMESON
    Phenidone D
    DIMEZONE (4,4-DIMETHYL-1-PHENYL-3-PYRAZOLIDINONE)
    dimethyl-phenylpyrazolidine DPP
    4,4-Dimethyl-1-phenylpyrazolidin-3-one


    Mol-weight.
    Phenidone-A : 162.19
    Dimezone, or phenidone-D : 190.24
    Dimezone-S : 206.24

    *****************************

    To me it seems obvious it is very important to know what type of Phenidone one has, and adjust the recipes for this, if comparing notes shall serve any meaningful purpose at all.
     
  9. albada

    albada Subscriber

    Messages:
    741
    Joined:
    Apr 10, 2008
    Location:
    Escondido, C
    Shooter:
    35mm RF
    I just checked the CAS-number on my packet of phenidone from PhotoFormulary. It's the same as yours, 92-43-3. So that's what was used in PC-Sulfite.

    Mark Overton
     
  10. analog what is that?

    analog what is that? Member

    Messages:
    172
    Joined:
    Nov 26, 2011
    Shooter:
    Multi Format
    Thank you Mark.

    I have also another type of Phenidone here, or rather Dimenzione, but don't have the CAS number handy, will get back with that.
    Hopefully the others here will also submit their CAS numbers, so we are sure we don't talk past each other and comparing apples with oranges......

    PS looking at my notes, could this be the CAS number for Dimezione, and if thats the case, WHAT type Dimenzione exactly :

    2654-58-2
     
    Last edited by a moderator: Dec 30, 2011
  11. oldfaithful58

    oldfaithful58 Member

    Messages:
    21
    Joined:
    Apr 6, 2008
    Location:
    Hull, UK
    Shooter:
    Multi Format
    http://www.chemblink.com/products/2654-58-2.htm
    This suggests its Phenidone D

    Dave
     
  12. analog what is that?

    analog what is that? Member

    Messages:
    172
    Joined:
    Nov 26, 2011
    Shooter:
    Multi Format
    Name 4,4-Dimethyl-1-phenyl-3-pyrazolidone
    Synonyms Phenidone D

    Molecular Structure

    Molecular Formula C11H14N2O
    Molecular Weight 190.24
    CAS Registry Number 2654-58-2
    EINECS 220-181-1

    *****************************

    Name Phenidone
    Synonyms 1-Phenyl-3-pyrazolidone; 1-Phenyl-3-pyrazolidinone; Graphidone

    Molecular Structure

    Molecular Formula C9H10N2O
    Molecular Weight 162.19
    CAS Registry Number 92-43-3
    EINECS 202-155-1
     
  13. Tronds

    Tronds Member

    Messages:
    122
    Joined:
    Sep 26, 2011
    Shooter:
    35mm
    Name Dimezone S
    Synonyms 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone
    copyRight
    Molecular Structure Dimezone S, 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone, CAS #: 13047-13-7
    Molecular Formula C11H14N2O2
    Molecular Weight 206.24
    CAS Registry Number 13047-13-7
    EINECS 235-920-3

    Properties
    Melting point 122-126 ºC
    Water solubility 7.1 g/L (20 ºC)
     
  14. Sponsored Ad
  15. Tronds

    Tronds Member

    Messages:
    122
    Joined:
    Sep 26, 2011
    Shooter:
    35mm
    The CAS Registry Number 92-43-3 also gives this information on http://www.chemicalbook.com/CASEN_2654-58-2.htm
    ?Name?

    4,4-Dimethyl-1-phenyl-3-pyrazolidone
    ?CAS?

    2654-58-2
    ?Synonyms?

    4,4-DIMETHYL-1-PHENYL-3-PYRAZOLIDINONE
    4,4'-DIMETHYL-1-PHENYL-3-PYRAZOLIDONE
    4,4-DIMETHYL-1-PHENYL-3-PYRAZOLIDONE
    DIMEZONE
    DIMEZORE
    LABOTEST-BB LT00440816
    TIMTEC-BB SBB003657
    4,4-dimethyl-1-phenyl-3-pyrazolidinon
    4,4-dimethylphenidone
    nsc215239
    4,4-Dimethyl-1-phenyl-3-pyrozolidinone
    4,4-Dimethyl-1-phenyl-3-pyrazolidione
    3-Pyrazolidinone, 4,4-dimethyl-1-phenyl-
    4,4-Dimethyl-1-phenyl-3-pyrazolidone (Dimezone)
    4,4-Dimethyl-1-phenyl-3-pyrazolidon
    4,4-DIMETHYL-1-PHENYL-3-PYRAZOLIDONE DIMESON
    Phenidone D
    DIMEZONE (4,4-DIMETHYL-1-PHENYL-3-PYRAZOLIDINONE)
    dimethyl-phenylpyrazolidine DPP
    4,4-Dimethyl-1-phenylpyrazolidin-3-one

    Please notice that Phenidone D is also known as Dimezone, the version with out the S-ending.
     
  16. analog what is that?

    analog what is that? Member

    Messages:
    172
    Joined:
    Nov 26, 2011
    Shooter:
    Multi Format
    There 3 types of Phenidone (or Dimensione) make a note of the variation in molecular weight, this has a large impact on the formula....
    Couple this with possible and expected variations in activity between them, we need to be very careful here....

    So now the question is, does the experts chiming in on this thread know of differences between these and has recommendations on what CAS number we should get?
     
  17. Photo Engineer

    Photo Engineer Subscriber

    Messages:
    25,586
    Joined:
    Apr 19, 2005
    Location:
    Rochester, NY
    Shooter:
    Multi Format
    I've stated before that stability in alkali goes up in the series Phenidone, Dimezone, and Dimezone S. The last word is that Dimezone S was the preferred agent and all new Kodak formulas would have used it. All Kodak instant films used it. Dimezone S is about the same in activity as the others. It appears to be less active, but that is partly due to the molecular weight compared to Phenidone.

    I think that some scanned examples of films produced by this developer compared to Xtol would be useful.

    PE
     
  18. Ryuji

    Ryuji Member

    Messages:
    1,416
    Joined:
    Jan 15, 2005
    Location:
    Boston, MA
    Shooter:
    Multi Format
    As far as I know, Kodak never changed the pH of XTOL. pH of 8.20 and 8.37 would require serious adjustment in development time.

    But you are using single junction gel-filled electrode, so I am not sure how trustworthy your measurements are.
     
  19. Ryuji

    Ryuji Member

    Messages:
    1,416
    Joined:
    Jan 15, 2005
    Location:
    Boston, MA
    Shooter:
    Multi Format
    The variants have differences but they are mostly related to solubility (Dimezone is least soluble, Phenidone B and Dimezone S are a bit more soluble, Phenidone A is most soluble) and stability (Phenidone A is least stable in alkaline solution, Phenidone B a bit better; Dimezone and Dimezone S are about the same and better than Phenidone A/B) and there is not much to worry about in terms of adjusting the quantities. If you are preparing developers from powder and for immediate use, Phenidone A or Dimezone S is best. Otherwise, Dimezone S is the only winner.
     
  20. Ryuji

    Ryuji Member

    Messages:
    1,416
    Joined:
    Jan 15, 2005
    Location:
    Boston, MA
    Shooter:
    Multi Format
    OP said pH was 8.20 with 2.8g AA. Before that, you were saying below 8.00 in the other thread. Now you are saying 8.33. Are you not worried about these huge discrepancies? Something is wrong in your system.
     
  21. albada

    albada Subscriber

    Messages:
    741
    Joined:
    Apr 10, 2008
    Location:
    Escondido, C
    Shooter:
    35mm RF
    Very good! I was waiting for somebody to notice that difference. I recently got a pH meter, and was struggling with reconciling its measurements. Also, the other thread has a different amount of AA.

    Anyway, I haven't heard anyone say that they already knew about this formula, so it appears to be new. I'll do more tinkering and testing, but it's lower priority, so results won't come soon.

    Mark Overton
     
  22. albada

    albada Subscriber

    Messages:
    741
    Joined:
    Apr 10, 2008
    Location:
    Escondido, C
    Shooter:
    35mm RF
    Here are scans of test strips, identically exposed, and developed with XTOL and PC-Sulfite.
    The XTOL scan:
    3-00-XtolNormalLoRes.jpg And a crop: 3-00-XtolNormalCrop.jpg

    And the PC-Sulfite scan:
    4-08-PCSulfite2p8LoRes.jpg And a crop: 4-08-PCSulfite2p8Crop.jpg

    These images are darkish because I set the white-point as high as possible in the scanner, to clip as little data to white as possible (i.e., maximize the dynamic range). The black-point was set to the left side of the histogram (which was always the same). Gamma was 1.5.
    This is part of my camera-collection, lit by the overhead tungsten candelabra. It's hard lighting, which creates plenty of specular reflections to see how the dense part of negatives are doing. Unfortunately, my Coolscan IV ED scanner doesn't have enough dynamic range to cover such specular reflections well (and still show shadow-detail in the neg's), so many reflections clip to white.

    In the crops above, PC-Sulfite appears to have slightly less grain than XTOL. That's not true. In 22X loupes, they seem to have the same grain. The scanner's focus has a little variation, and the film isn't held perfectly flat, so grain is defocussed by unpredictable amounts. To get sharp images of grain, I want to photograph negatives in a microscope.

    Mark Overton
     
  23. dynachrome

    dynachrome Member

    Messages:
    998
    Joined:
    Sep 16, 2006
    Shooter:
    35mm
    I don't know what the advantage of this developer is. You can change the formula and make PC-TEA. This completely eliminates the sulfite and produces a developer with much better keeping qualities. Triethanolamine (TEA) can be heated safely using a water bath. The resulting concentrate, usually used at 1:50, makes a less toxic and versatile working solution.
     
  24. Tronds

    Tronds Member

    Messages:
    122
    Joined:
    Sep 26, 2011
    Shooter:
    35mm
    Great for those who can get TEA.
    Her in europe, TEA is clos to impossible to get, so we have to resort to other methods of doing this.
     
  25. Ryuji

    Ryuji Member

    Messages:
    1,416
    Joined:
    Jan 15, 2005
    Location:
    Boston, MA
    Shooter:
    Multi Format
    I don't know why you didn't see me saying it. It's not new. It's one of many things that are obvious to any chemist (including myself) but scrapped due to obvious shortcomings.
     
    Last edited by a moderator: Dec 31, 2011
  26. Ryuji

    Ryuji Member

    Messages:
    1,416
    Joined:
    Jan 15, 2005
    Location:
    Boston, MA
    Shooter:
    Multi Format
    Between these images, the XTOL negative clearly has more contrast and accutance than your PC-Sulfite. You can't judge a developer by comparing things like this.