• Welcome to Photrio!
    Registration is fast and free. Join today to unlock search, see fewer ads, and access all forum features.
    Click here to sign up

How much phenidone or metol with Ascorbate?

Recent Classifieds

Forum statistics

Threads
201,725
Messages
2,829,148
Members
100,916
Latest member
mikenickmann99
Recent bookmarks
0

Murray Kelly

Member
Allowing Ads
Joined
Jan 31, 2007
Messages
661
Location
Brisbane, Australia
Format
Sub 35mm
Is there a rule of thumb which will tell me how much less developing agent I would use if one sustituted AA or ascorbate for some of the sulfite in a developer formula?

This assumes the pH is kept the same and superadditivity occurs.

I am curious to know as I would like to trial a POTA-like developer with phenidone (normally 1.5g/L) which as usual, relies on the sulfite to remove phenidone breakdown products and set the working pH. Something along the lines of D-23 but for microfilms.

Since the pH is close to borax pH, and the ratio of ascorbate to phenidone is 40:1 (or more) for 'regeneration' of spent phenidone (and metol), would that regeneration allow the use of say, half, or a third of the phenidone. i.e. 750mg or 500mg per litre? Borax woud set the pH at 9.1. I am trying to save sulphite use here altogether as you can see.

Any helpful hints or pointers to how much the phenidone (or metol) could be cut back as it works and reworks on the silver? This could save me an awful lot of phenidone.

Murray.
 

Ryuji

Member
Allowing Ads
Joined
Jan 15, 2005
Messages
1,415
Location
Boston, MA
Format
Multi Format
If you are trying to make a special purpose low contrast developer, you are better off without ascorbate. The reason why POTA works the way it does is because Phenidone is the sole developing agent and there is no superadditive agent.
 
OP
OP
Murray Kelly

Murray Kelly

Member
Allowing Ads
Joined
Jan 31, 2007
Messages
661
Location
Brisbane, Australia
Format
Sub 35mm
Thanks Ryuji. My understanding was that the ascorbate/AA didn't actually 'add' at pHs associated with borax or lower? All it did was to regenerate the phenidone or metol and not contribute any developing effect itself.

Is this not true? They are superadditive at pH9 or lower?

Murray

If you are trying to make a special purpose low contrast developer, you are better off without ascorbate. The reason why POTA works the way it does is because Phenidone is the sole developing agent and there is no superadditive agent.
 

gainer

Subscriber
Allowing Ads
Joined
Sep 20, 2002
Messages
3,699
You could try an experiment, but you will find that Ryuji is correct. If you want the characteristics of POTA, use only the Phenidone with sulfite. Phenidone and ascorbate are a different colored horse than Phenidone and sulfite, even at the pH of borax.

The same data that showed that Metol and ascorbate seemed to be equivalent to Metol and sulfite also showed that Metol and hydroquinone together without sulfite were no different from Metol alone. Superadditivity is not so straightforward as is sometimes assumed. It is not the ascorbate that activates the Phenidone, but the other way round, according to some experts. We cannot generalize the results of experiments with Metol to predict the results of experiments with Phenidone. Remember that D-23 is not anything like POTA when it comes to contrast.

Now, if you want a Phenidone developer that is similar to D-23 but without sulfite, that can be arranged.
 
OP
OP
Murray Kelly

Murray Kelly

Member
Allowing Ads
Joined
Jan 31, 2007
Messages
661
Location
Brisbane, Australia
Format
Sub 35mm
That's bad news. Just when I thought I had a handle on this stuff.
However I have tried your D-23 substitute and it works. Thanks.
Obviously theory and practice diverge - I thought I was on a winner here.
All I wanted to do was make the phenidone work longer.

Murray


Now, if you want a Phenidone developer that is similar to D-23 but without sulfite, that can be arranged.
 

gainer

Subscriber
Allowing Ads
Joined
Sep 20, 2002
Messages
3,699
The real trouble is that theories diverge from each other. I'm not as well studied as I sometimes pretend, but I have seen mention of superadditivities between certain developing agents that do not seem to show that the experimenters even considered omitting the sulfite, without which there is no superadditivity. Does anyone ever state that, eg., Metol and hydroquinone are superadditive in the presence of sulfite ion? Most often it seems that ascorbate is considered as a substitute for hydroquinone. In fact, it can be a substitute for both hydroquinone and sulfite in the same developer. In the Pyrocat developers, when they are put up (as we say in the country) in glycol, a very small portion of ascorbic acid, which is soluble in glycol, does the job of sulfite, which is not very soluble. Any superadditivity that may occur is not obvious.
 

gainer

Subscriber
Allowing Ads
Joined
Sep 20, 2002
Messages
3,699
I got on my pedestal and forgot the main point. Actually that has more to do the 81 years standing there.

PC-TEA is a pretty good developer that will last a long time in stock.
 
OP
OP
Murray Kelly

Murray Kelly

Member
Allowing Ads
Joined
Jan 31, 2007
Messages
661
Location
Brisbane, Australia
Format
Sub 35mm
It's mainly the Imagelink I'm working with as my Copex Rapid isn't sold to the likes of us, in single bulk rolls anymore. I ended up with hundreds of feet of Imagelink and is hasn't been so pictorial even at an EI 0f 30. (as compared to Copex R at 80).

The copex would deliver in Gainer's d-23 substitute (ph:0.25g/AA:9g/Borax:25g in a liter) but Imagelink doesn't. I wondered about a sulfite free POTA.

There's other soups to try and I will have to plough thru them. Sigh. (what a mixed metaphore!).

Thanks all
Murray
 

dancqu

Member
Allowing Ads
Joined
Sep 7, 2002
Messages
3,649
Location
Willamette V
Format
Medium Format
It is not the ascorbate that activates the Phenidone,
but the other way round, according to some experts.

I think that likely the case. Most PC formulas specify
phenidone levels on the order of 0.00x %. In my view
such a low level would not even qualify such a developer
as being of the compensating type.

Take Beutler's for example; a classic developer of
the compensating type. The level of metol is 0.1 %.
It would have to be diluted 1:24 to equal the
phenidone levels of at least a few PC
developers. Dan
 

Ryuji

Member
Allowing Ads
Joined
Jan 15, 2005
Messages
1,415
Location
Boston, MA
Format
Multi Format
Regenerating Phenidone means removing the oxidized Phenidone from the system. Oxidized form of Phenidone strongly inhibits further development by Phenidone, and this is why Phenidone used alone makes such a low contrast, low density image, but the contrast is rapidly increased by adding a more potent reducing agent that can rapidly reduce the Phenidone radical. This is exactly how superadditivity works.

Thanks Ryuji. My understanding was that the ascorbate/AA didn't actually 'add' at pHs associated with borax or lower? All it did was to regenerate the phenidone or metol and not contribute any developing effect itself.

Is this not true? They are superadditive at pH9 or lower?

Murray
 

Ryuji

Member
Allowing Ads
Joined
Jan 15, 2005
Messages
1,415
Location
Boston, MA
Format
Multi Format
Percentage and superadditivity are different matters.

Percentage and compensation are also different matters.


I think that likely the case. Most PC formulas specify
phenidone levels on the order of 0.00x %. In my view
such a low level would not even qualify such a developer
as being of the compensating type.

Take Beutler's for example; a classic developer of
the compensating type. The level of metol is 0.1 %.
It would have to be diluted 1:24 to equal the
phenidone levels of at least a few PC
developers. Dan
 

Ryuji

Member
Allowing Ads
Joined
Jan 15, 2005
Messages
1,415
Location
Boston, MA
Format
Multi Format
I recommend you to read GIP Levenson's (Kodak Harrow lab) series of beautiful work on superadditivity. Also recommended is work by Umberger (E. I. du Pont de Nemours) on surfactant model, and another series of beautiful work by Pontius (Kodak Rochester lab).

Effect of sulfite on both single developers and superadditive developers is well studied and well documented.

James had such a simple and appealing charge barrier theory, and while it is probably very true, in reality, the work of those three named above explains the development mechanism better, and the latter also offers much more insight into the developer.

The real trouble is that theories diverge from each other. I'm not as well studied as I sometimes pretend, but I have seen mention of superadditivities between certain developing agents that do not seem to show that the experimenters even considered omitting the sulfite, without which there is no superadditivity. Does anyone ever state that, eg., Metol and hydroquinone are superadditive in the presence of sulfite ion? Most often it seems that ascorbate is considered as a substitute for hydroquinone. In fact, it can be a substitute for both hydroquinone and sulfite in the same developer. In the Pyrocat developers, when they are put up (as we say in the country) in glycol, a very small portion of ascorbic acid, which is soluble in glycol, does the job of sulfite, which is not very soluble. Any superadditivity that may occur is not obvious.
 

gainer

Subscriber
Allowing Ads
Joined
Sep 20, 2002
Messages
3,699
I recommend you to read GIP Levenson's (Kodak Harrow lab) series of beautiful work on superadditivity. Also recommended is work by Umberger (E. I. du Pont de Nemours) on surfactant model, and another series of beautiful work by Pontius (Kodak Rochester lab).

Effect of sulfite on both single developers and superadditive developers is well studied and well documented.

James had such a simple and appealing charge barrier theory, and while it is probably very true, in reality, the work of those three named above explains the development mechanism better, and the latter also offers much more insight into the developer.

Ryuji, I would love to be able to go to a real library and browse for those and any others on the subject. The nearest such place is at least 100 miles of painful travel, and then I would not be assured of finding them. Can you suggest a preferred place to buy them through the net? I will, of course, search. Titles would help. What I have now are "The Theory of the Photographic Process", third edition, "The Principles of Optics" by Hardy and Perrin, "Photographic Researches of Hurter & Driffield" compiled by Ferguson, and the 58th edition of the CRC Handbook of Chemistry and Physics.

Meanwhile, the section of the chapter "Kinetics of Development" titled "Superadditivity" in "The Theory...." does not once mention sulfite. The graph showing the effect of relative proportions of Phenidone and hydroquinone does not give a clue as to the need for sulfite. The earlier graph in the same chapter showing the effect of sulfite, ascorbic acid or hydroquinone on development by Metol shows that there was no increase in rate of development by Metol as hydroquinone was added. Even if the PQ mixture was synergistic without sulfite while the MQ mixture was not, the two sets of experiments show that we cannot conclude that sulfite is not needed for PQ synergism because the other ingredients of the PQ developer were not mentioned.

Now, the MQ and the MA developers tested without sulfite were vastly different one from the other. We cannot tell from the graph whether the ascorbate was regenerating the Metol, or deactivating the oxidation products of the Metol. The author supposes that the sulfite deactivates while the ascorbate regenerates. Apparently, the hydroquinone does neither without sulfite, which means that the MQ mixture is not synergistic. I don't see the error in my logic. I see the lack of data other than what I get from my own experiments, and so would really like to do more reading. I'm sure the original reports had more detail.
 
OP
OP
Murray Kelly

Murray Kelly

Member
Allowing Ads
Joined
Jan 31, 2007
Messages
661
Location
Brisbane, Australia
Format
Sub 35mm
Isn't it odd how one uses a very strong concentrated developer or a very! dilute one for a long time to achieve low contrast?

Murray
 

Ryuji

Member
Allowing Ads
Joined
Jan 15, 2005
Messages
1,415
Location
Boston, MA
Format
Multi Format
The graph showing the effect of relative proportions of Phenidone and hydroquinone does not give a clue as to the need for sulfite. The earlier graph in the same chapter showing the effect of sulfite, ascorbic acid or hydroquinone on development by Metol shows that there was no increase in rate of development by Metol as hydroquinone was added. Even if the PQ mixture was synergistic without sulfite while the MQ mixture was not, the two sets of experiments show that we cannot conclude that sulfite is not needed for PQ synergism because the other ingredients of the PQ developer were not mentioned.
You must realize that the rate of development is only one aspect of developer, and distinguish this from a range of factors that must be considered in formulating practical developers. For the latter purpose, there are other requirements, such as photographic speed, compatibility with a wide range of emulsion types, tonality, granularity and keeping properties.

Now being specific to the rate of development, your reading as summarized above is correct. Hydroquinone can regenerate oxidized Phenidone more effectively than oxidized Metol. The presence of sulfite may not be very obvious in PQ rate of development, but it has a useful effect that may not be obvious depending on the quantities of hydroquinone. That is, sulfonated hydroquinone is effective in regenerating oxidized Phenidone but not oxidized Metol.

In practical b&w developers, it is customary to include sulfite or other forms of sulfur dioxide salts, because of the factors listed above. You can't deny the reasons behind this by just arguing the development rate.

Now, the MQ and the MA developers tested without sulfite were vastly different one from the other. We cannot tell from the graph whether the ascorbate was regenerating the Metol, or deactivating the oxidation products of the Metol. The author supposes that the sulfite deactivates while the ascorbate regenerates. Apparently, the hydroquinone does neither without sulfite, which means that the MQ mixture is not synergistic. I don't see the error in my logic. I see the lack of data other than what I get from my own experiments, and so would really like to do more reading. I'm sure the original reports had more detail.

Original report is one thing, but newer research relied more heavily on more direct and relevant aspect of electrochemistry. Electrochemistry was widely recognized to be a very useful tool in photography in 1960s, and in Kodak Rochester lab alone, a huge deal was made with this one branch of chemistry, using a range of techniques like cyclic voltammetry. People like Paul Gilman, J. E. Jones, et al. collaborated with their electrochemists to study a wide range of sensitizing dyes, which is also an electrochemical phenomenon. Carroll and West were also interested in this subject, but Brooker (Brooker and West are dye experts) retired around that time. Pontius, Thompson, Cole, Willis and others (they are electrochemists) worked on developers. Reading James 3rd edition is not a good idea for this particular subject, which saw significant progress after the publication of the book. James 4th edition is a better read (I don't recall why I sent you the 3rd... sorry!) If you appreciate the results of electrochemical research in developers and sensitizing dyes, you will realize how powerful the approach was. Electrochemical studies of photographically useful compounds were also very actively carried out in East Germany and Japan in 1960s.

Hydroquinone does regenerate oxidized Phenidone or Metol without sulfite, but sulfite makes this process a lot more efficient by removing oxidized hydroquinone by sulfonation reaction. Ascorbate does not require sulfite to remove its oxidized form from the system because it hydrolyzes by itself rapidly, but sulfite remains a useful addition in practical developers for the reasons I listed above.
 
Last edited by a moderator:

dynachrome

Member
Allowing Ads
Joined
Sep 16, 2006
Messages
1,840
Format
35mm
I don't remember whether I ever tried dilute PC-TEA with Technical Pan or Imagellink HQ/FS films. I have tried diluting Microphen 1:5 according to the information shown on unblinkingeye.com. Microphen keeps fairly well and may be easier to mix up than just the phenodine and sodium sulfite in POTA. The flexibility of 35mm equipment makes the use of document films for continuous tone work worth putting up with when it can be effective. In situations where this flexibility is not as important I would rather use ACROS in 6X7 format developed in Fuji Microfine. It takes extraordinary effort, technique and equipment to come close to this 6X7combination with 35mm equipment and film in an 11X14 or 16X20 print. For times when I just want to make trouble for myself I will shoot 105mm Imagelink HQ or FS cut down and spooled to 120 size. The EI is very low but the print quality, for the right subject, can be very high.
 

gainer

Subscriber
Allowing Ads
Joined
Sep 20, 2002
Messages
3,699
Ryuji, you provided me with photocopies of selected chapters, which I greatly appreciate, and suggested I get the Third Edition, which I bought second hand a number of years later. Apparently, it's previous owner had been one branch or another of my former employer, NACA. It had "Aeronautical Research Laboratories" stamped inside the covers, but no other identification. Had I known it was available, I would have borrowed before I retired in 1982. I did find Hardy & Perrin to be very useful in some optical work in Human Factors at NASA as well as my own photography. There was also an English translation of a Russian translation from English of works on photographic research that was interesting. The 1957 edition of the CRC Handbook had a section on photography that my 1977 edition does not have, with lots of "homely" formulas including recipes for glues, hectograph copiers, developers, etc.

It's interesting to search Google or Yahoo for names of well known authors like Levenson, Pontius, Umberger, etc. Athletes are much more common. Hydroquinone is more often listed for its use for bleaching skin than anything else.

Sandy King found a small amount of ascorbic acid to be a good substitute for sulfite in his glycol-soluble Pyrocat series. Hydroquinone is also glycol-soluble, but doesn't to work any better than more catechol. It can be used in place of catechol where the color of the stain is not important.
 

Alan Johnson

Subscriber
Allowing Ads
Joined
Nov 16, 2004
Messages
3,374
Isn't it odd how one uses a very strong concentrated developer or a very! dilute one for a long time to achieve low contrast?

Murray

H&W Control relies on phenidone 0.52 g/L working strength to give pictorial contrast with microfilm at full emulsion speed.Ryuji said the oxidized form of phenidone strongly inhibits further development and this is why phenidone alone makes such low contrast.
PC-TEA 1:100 has phenidone 0.025g/L and relies on overexposure and underdevelopment to get pictorial contrast.Probably a different mechanism.A developer that does not contain phenidone or dimezone will probably always give lower film speed.
 

gainer

Subscriber
Allowing Ads
Joined
Sep 20, 2002
Messages
3,699
I don't use overexposure with PC-TEA. When I'm not sure, I bracket, but that has more to do with uncertainty of scene brightness range when I have to use an average reading. PC-TEA has more than just Phenidone, but not much more in number of ingredients. It may be that microfilms have more of a tendency to depression of the interception point of the family of characteristic curves, and I might find that would cause me to expose more, but I have found little depression with films like FP4+ or HP5+. Phenidone has a reputation of minimizing that depression in sulfite solution. I guess I will have to try some microfilm.
 

Alan Johnson

Subscriber
Allowing Ads
Joined
Nov 16, 2004
Messages
3,374
Yes,I meant Microfilm in PC-TEA 1:100 has to be overexposed.
Not sure Copex Rapid is available in the US at present,but Bluefire Police film from Frugalphotographer.com is I believe a slightly slower version.Try EI's less than 16 with PC-TEA 1:100 as a start.
 

strangepics

Member
Allowing Ads
Joined
Dec 4, 2007
Messages
27
Format
35mm
Ryuji, Gadget Gainer: I love PC-TEA with 400 speed film, but it sucks for pushing Neopan 1600 (or anything else for that matter). Are there any plans to develop an ascorbate version of something like Microphen? Is it possible? Would be nice not to dump borates and bromides, etc. down the drain. Jay de Fehr gave us GSD-10, which is nice, but glycin is expensive (and very toxic?).
 
Photrio.com contains affiliate links to products. We may receive a commission for purchases made through these links.
To read our full affiliate disclosure statement please click Here.

PHOTRIO PARTNERS EQUALLY FUNDING OUR COMMUNITY:



Ilford ADOX Freestyle Photographic Stearman Press Weldon Color Lab Blue Moon Camera & Machine
Top Bottom