Modern Rodinal Substitutes Part II

Ian Grant · Aug 31, 2009

The big problem with both the Ilford & Kodak charts is they don't take into account dilution of ID-11/D76 or Perceptol/Microdol-X where the developers begin to behave quite differently at 1+3.

Ian

Keith Tapscott. · Aug 31, 2009

Ian Grant said:
The big problem with both the Ilford & Kodak charts is they don't take into account dilution of ID-11/D76 or Perceptol/Microdol-X where the developers begin to behave quite differently at 1+3.

Ian

Ilford do cite ID-11 diluted 1+3 as yielding the highest sharpness while Perceptol and Microdol-X also provide good performance at the same dilution.
I have tried all of those developers and I can`t see much, if any difference in grain between D-76/ID-11 1+3 and the extra fine-grain developers 1+3, although it might show with huge magnifications.
I find that D-76/ID-11 tends to compress the tonal range when diluted 1+3 while Perceptol and Microdol-X provides more sparkle at 1+3 with good sharpness. I use 1+1 with D-76, although I have not tried it 1+2 yet.
BTW, have you read the United States Patent Office number 3,161,513 (Patented Dec, 15, 1964)? Photographic developer compositions containing an antistain agent?

Good luck with your quest for a Rodinal substitute.

Ian Grant · Aug 31, 2009

Yes, I've got that Patent amongst a heap of others. Example 4 & 6 are a very slight re-working of the Wellington & Ward Borax MQ developer and a side step in the evolution of D76

Ian

Photo Engineer · Aug 31, 2009

Ray Rogers said:
What films do these data apply to, most strictly, in your knowledge/opinion?

(How were these charts actually constructed?
The developers are mentioned, but on what films?
Was there any "weighting" of the results that you know of? (80% modern 20%traditonal... or some such? )

BTW
What developers/dev. agents do you know to be better?

Ray;

I know nothing about the data behind the chart nor its method of construction. I can infer how it was done, but that is just inference.

I can say that Dimezone-S is far better than Phenidone as an example of better all round developing agents.

PE

Photo Engineer · Aug 31, 2009

Ian Grant said:
Yes, I've got that Patent amongst a heap of others. Example 4 & 6 are a very slight re-working of the Wellington & Ward Borax MQ developer and a side step in the evolution of D76

Ian

This is the seminal "Anti Dichroic Fog" patent among other claims hidden in it. It was one of Henn's major works and is cited by A&T in the FDC. This is not the answer to the real problem, nor does it correctly give the "secret" ingredient of Microdol X, which is also used elsewhere from what I understand.

PE

Photo Engineer · Aug 31, 2009

Ian Grant said:
Would you buy it as R09 from Calbe and sell it as Gainerol

There's an interesting cemical called "Oxygen Scavenger" which is sold by a bulk photographic chemical supplier.

I've never seen it in any published formulae but it's sold in liquid form in sizes up to 1000 litre IBC's - Ammonium Bisulphite

Ian

You would not want to put Ammonium Bisulfite into a developer! It is great in fixers though.

PE

Ian Grant · Aug 31, 2009

Photo Engineer said:
Ray;

I can say that Dimezone-S is far better than Phenidone as an example of better all round developing agents.

PE

But then there's the original Phenidone and then Phenidone Z and various other derivatives.

Many companies have used commercial "Phenidone" - Ilford, May & Baker (Champion), Agfa, Orwo (Calbe), Paterson, Forte, Foton, Foma, Fotospeed and a whole host of smaller companies. Between them they have all produced a wide and varied range of excellent developers using Phenidone in combination with one or more additional developing agent.

Dimezone-S isn't an "all round" developing agent, nor is Phenidone, because unlike Metol, p-Aminophenol, Pyrocatechin, Hydroquinone etc they are not practical as sole developing agents except in very limited uses.

I don't know what form my original Ilford Phenidone was I'd guess Phenidone Z, I only finished it a couple of years ago, the date stamp was 1962, it has exceptionally good keeping properties

Ian

Photo Engineer · Aug 31, 2009

Ian;

I was comparing two developers with very similar structures under identical conditions in my thinking. Phenidone and Dimezone-S are basically cyclic hydrazine derivatives. In alkali, the Phenidone ring opens and becomes inactive much more rapidly than Dimezone-S and the activity is somewhat lower. For this reason, Kodak used Dimezone-S in the PR-10 pods due to the high alkali content and the need for quick development.

So, for a quick OTOMH answer, those are two to compare, and if you do, (and which I have done), the Dimezone-S comes out ahead.

PE

Kirk Keyes · Aug 31, 2009

Photo Engineer said:
You would not want to put Ammonium Bisulfite into a developer!

It might get a little stinky...

gainer · Aug 31, 2009

Would potassium metabisulfite be less likely to be oxidized to a sulfate than potassium sulfite? Some extra KOH would be needed, but the combination might be less expensive to the hobbyist who makes relatively small batches. Or, can one of you tell me a source of relatively small amounts of the liquid concentrate?
I have what I believe to be an excellent Metol analog of Rodinal, but have only been able to test the sodium sulfite version. Even so, it seems to be capable of greater SBR and better shadow detail than any of the many Rodinal expedients I have tried.
The attachments are from scans of a 10X print of a 35 mm EDU 400 Ultra neg. That puts the detail at about 30X, enough for a 30"x45" print from the full width of the negative. The viewing distance for such a print for proper perspective would be about 54" (no grain sniffing allowed).

Photo Engineer · Aug 31, 2009

Patrick;

My literature reports that there have been explosions associated with working with Metabisulfite due to its strong reducing power. I would prefer to work with sulfite myself.

IDK about your developer but the reports here vary saying that the Metol version is good or bad depending on the individual. I think more tests are indicated.

PE

Ian Grant · Aug 31, 2009

Patrick, there's something nagging away in my mind about Metabisulphite. Yes the early Rodinal type formulae used it & Hyroxide to form Sulphite, at one point that was the best way of producing the Sulpite in solution.

We've had this discussion before but there is also the subtle difference between Bisulpite & Metabisulpite, and last time I was in the UK I found a reference and short extract from a Kodak paper on the subject, which I posted here on APUG. Kodak Bisulpite is in fact a mixture of Bisulphite & mainly Metabisulphite, and Kodak were referring to the interchangeability of their Bisulphite with Metabisulphite. J.T Baker sell both forms in bulk.

At some point before WWII Agfa began using Sulphite, I think something else is happening as we also know that around then they were also adding anti-foggant.

The referance to Oxygen scavenger yesterdaym (Ammonium Bisulphite) was what triggered my thought, and knowing that Metabisulphite in a developer helps cut dichroic fog.

In the wine trade Metabisulpite solution is used as an anti-oxidant, and steriliser as it's more powerful than Bisulphite, but no-one seems to explain why satisfacorily, It has a lot to do with free SO2.

Ian

Ian Grant · Aug 31, 2009

Photo Engineer said:
Patrick;

My literature reports that there have been explosions associated with working with Metabisulfite due to its strong reducing power. I would prefer to work with sulfite myself.

PE

In our developer applications Metabisulphite is perfectly safe. Over the years I've used many metric tonnes, I'd get through 25kg every couple of days and we were adding it to Aqua Regia (Nitric & Hydrochloric acid) to generate SO2.

Home winemakers regularly use Metabisulphite in their kitchens, either as a powder or as Camden tablets.

Metabisulphite is also used in ID-13, D153 and equivalents, the Caustic Hydroquinone graphic arts developers

Ian

Ian Grant · Sep 1, 2009

Photo Engineer said:
Ian;

I was comparing two developers with very similar structures under identical conditions in my thinking. Phenidone and Dimezone-S are basically cyclic hydrazine derivatives. In alkali, the Phenidone ring opens and becomes inactive much more rapidly than Dimezone-S and the activity is somewhat lower. For this reason, Kodak used Dimezone-S in the PR-10 pods due to the high alkali content and the need for quick development.

So, for a quick OTOMH answer, those are two to compare, and if you do, (and which I have done), the Dimezone-S comes out ahead.

PE

Yes Phenidone does hydrolyse and G.I.P.Levenson and L.F.A.Mason state that because of this Kodak & Ilford used Dimezone & Phenidone -Z which is why both Kodak & similar Ilford developers using them have a good shelf life.

Ian

Kirk Keyes · Sep 1, 2009

Ian - do you know if what Ilford sells in dry powder (125 g bottles I think it was) back around 1980 as "Phenidone" is actually Phenidone or Phenidone-Z?

gainer · Sep 1, 2009

There is an advantage of the liquid concentrate when you know exactly how much sulfite you need. When you are experimenting, You must prepare the solution you think you want in order to test it. If you decide you need to double the sulfite, adding the liquid concentrate will change the total volume more than would adding the solid sulfite, or even the KOH + bisulfite.

In the meantime, I got some of the 45% w/w solution and mixed a batch with 222 grams of the sulfite solution, 22.7 grams KOH and 34 grams of Metol in water to make a liter. I'm too sleepy now, at 2:00 AM, to do any more.

gainer · Sep 1, 2009

Ian Grant said:
Patrick, there's something nagging away in my mind about Metabisulphite. Yes the early Rodinal type formulae used it & Hyroxide to form Sulphite, at one point that was the best way of producing the Sulpite in solution.

We've had this discussion before but there is also the subtle difference between Bisulpite & Metabisulpite, and last time I was in the UK I found a reference and short extract from a Kodak paper on the subject, which I posted here on APUG. Kodak Bisulpite is in fact a mixture of Bisulphite & mainly Metabisulphite, and Kodak were referring to the interchangeability of their Bisulphite with Metabisulphite. J.T Baker sell both forms in bulk.

At some point before WWII Agfa began using Sulphite, I think something else is happening as we also know that around then they were also adding anti-foggant.

The referance to Oxygen scavenger yesterdaym (Ammonium Bisulphite) was what triggered my thought, and knowing that Metabisulphite in a developer helps cut dichroic fog.

In the wine trade Metabisulpite solution is used as an anti-oxidant, and steriliser as it's more powerful than Bisulphite, but no-one seems to explain why satisfacorily, It has a lot to do with free SO2.

Ian

My wine-making friends sell their's. They smoke the insides of the bottles with a sulfur candle. The powers that be make them put "Contains sulfur" on the label.

As Scripture says, after perversion by me, It's not what goes into the mouth (of the bottle) but what comes out that defiles a (photographer) person. If we put in bisulfite or the British bisulphite along with KOH our film will see K2SO3.

Ian Grant · Sep 1, 2009

Kirk, some where I have references to "Commercial Phenidone" as Phenidone-Z.. Plain Phenidone doesn't keep at all well in alkali solutions, and is partly soluble in water, where as Phenidone-Z has poor solubility unless the solution is alkaline and keeps well.

A problem is Ilford use "Phenidone" as a generic "Trade name", but Mason of Ilford discusses the problems of Phenidone then goes on to state (Photographic Processing Chemistry 966/1975) "In order to reduce this trouble, two 4-substituted derivatives were introduced commercially a few years ago "Phenidone-Z" Ilford "Dimezone" Kodak. (His editor was Levenson from Kodak)

In practice Ilford only began using "Phenidone" commercially around 1951/2 because of the problems, and Ilford's PQ developers etc keep well in concentrate form so were definitely not using plain Phenidone.

I have Ilford's 1960 trade price list in front of me and Phenidone is sold in 10g -500g quantities, but doesn't say what form, that may well ahve been a trade secret. As I said earlier the Phenidone I had adted 1962 kept exceptionally well over 40 years, and there was no discernible difference in activity when I bought fress stock 2 or 3 years ago.

It's quite possible Ron (PE) used "Plain Phenidone" at Kodak in his tests against Dimezone

Ian

Ian Grant · Sep 1, 2009

gainer said:
If we put in bisulfite or the British bisulphite along with KOH our film will see K2SO3.

That's the theory & practice but Metabisulphite is not Bisulphite and something more happens when it's dissolved, there's far more free SO2

True Bisulphite (powder) can only be bought as a lab reagent and it's unstable.

Ian

Ian Grant · Sep 1, 2009

Kirk Keyes said:
Ian - do you know if what Ilford sells in dry powder (125 g bottles I think it was) back around 1980 as "Phenidone" is actually Phenidone or Phenidone-Z?

That's a different question to the one I answered, you've re-written the post

It'll be Phenidone-Z, (unless they changed to another derivative), but my recent Phenidone behaves the same as my 1962 Phenidone in Film & Print devs.

Ilford published Phenidone Formulae in the Feb 12th 1954 issue of the British Journal of Photography.

Ian

Photo Engineer · Sep 1, 2009

Dimezone-S at Kodak was called HMMP or Hydroxy Methyl Methyl Phenidone. It has the best balance between keeping and being a powerful developing agent.

The Bisulfite anion HSO3- decomposes rapidly to SO3-- and then scavenges oxygen to form SO4-- or sulfate anion.

The metabisulfite anion is much more powerful a reducing agent, and one reference I have seen states that it can catch fire during the grinding process to break up lumps. It undergoes exactly the same reactions as above but the initial breakdown from metabisulfite to sulfite or bisulfite (pH dependant) is very quick and strong. This is Na2S2O5 or the S2O5-- anion. The Metabisulfite gives one mole of SO2 and one mole of SO3 upon decomposition in water, both of which end up making HSO3- or the equivalent. It is acidic in water.

A second reference gives no comment about Sodium Metabisulfite catching fire. However my references do ascribe this to the Potassium salt

So, I would tend to say take precautions with the Potassium salt.

PE

Ian Grant · Sep 1, 2009

Photo Engineer said:
Dimezone-S at Kodak was called HMMP or Hydroxy Methyl Methyl Phenidone. It has the best balance between keeping and being a powerful developing agent.

The Bisulfite anion HSO3- decomposes rapidly to SO3-- and then scavenges oxygen to form SO4-- or sulfate anion.

The metabisulfite anion is much more powerful a reducing agent, and one reference I have seen states that it can catch fire during the grinding process to break up lumps. It undergoes exactly the same reactions as above but the initial breakdown from metabisulfite to sulfite or bisulfite (pH dependant) is very quick and strong. This is Na2S2O5 or the S2O5-- anion. The Metabisulfite gives one mole of SO2 and one mole of SO3 upon decomposition in water, both of which end up making HSO3- or the equivalent. It is acidic in water.

A second reference gives no comment about Sodium Metabisulfite catching fire. However my references do ascribe this to the Potassium salt

So, I would tend to say take precautions with the Potassium salt.

PE

Could have done with that Metabisulphite explanation when there was the specific thread, Gainer & I kept back & forth on the subject

On a safety note, Potassium Metabisulphite is always sold in bulk as a liquid, and that's how Agfa would have used it to make early Rodinal.

The formulae at the start of the thread use Sulphite, except the early versions Andresen designed, which is widely published.

Ian

Photo Engineer · Sep 1, 2009

It seems to me that there is just a tiny need to know some chemistry in order to design new developers and fixes.

It also seems that this knowledge will explain many early practices and will indeed relate to safety in the modern day photo lab.

PE

Ian Grant · Sep 1, 2009

The chemistry was sound that's what I've said before about metabisulphite but others look at the words Kodak Bisuphite and assume simple "Bisulphite" when in fact Kodak's MSDS shows it's mainly Metabisuphite.

Ian

gainer · Sep 1, 2009

Meanwhile, I AM doing more tests. The trouble is that life tests may require a long time. That would be good. I put a few ounces of the latest all K metolal in my brisker at 104 F to age for a week or so. If it still works, I'll do another test every week until it does not work. The attachments show the first test. The film is EDU 400 Ultra. I also have HP5+ and FP4+ that I will test.

Modern Rodinal Substitutes Part II

Ian Grant

Keith Tapscott.

Ian Grant

Photo Engineer

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Ian Grant

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Kirk Keyes

gainer

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