Experience with ID-24

[RauschenOderKorn]

I wanted to ask everybody if there is some practical experience with ID-24 with different papers / dilutions / development times. As this paper developer can be tweaked to achieve warm-tone - sepia - brown and even red tones, I wanted to give it a try to see how it works.

Any experience / recommendations?

 

[Gerald C Koch]

I really would not get my expectations worked up. Developers like ID-24 were created for the papers of their day. When the EPA and its EU equivalent nixed the use of heavy metals such as lead and cadmium the new generation of papers lacked the flexibility and most of the character of the classic ones. Attempts to resurrect the older emulsions without the heavy metals failed miserably. My experience with warm tone developers and modern papers is limited but not a very successful one. So give ID-24 a try however a voice tells me you are not going to see red tones and the like. You will most likely get some warmth though.

 

[pentaxuser]

I'd like to see examples of different dilutions giving sepia, brown and red tones. Do you have any examples or is this something you have read about? If it can do anything close to sepia, brown or red tones then this is truly an amazing developer.

You will no doubt conclude I am sceptical and you will be right

pentaxuser

 

[RauschenOderKorn]

I have only read about it. I want to give it a try, but do not want to waste time & materials, that is why I posted here.
During the weekend, I have given it some research, and found some interesting things:

About a year ago, a similar thread has been opened and it seems MGIV and MG Warmtone give disappointing results with this developer.
(there was a url link here which no longer exists)

Futhermore, the ID-24 Formula with Glycin in the Darkroom Cookbook by Steve Anchell is not the original ID-24 from Ilford. Reviewing the Ilford Formulae (Third Edition), ID-24 is a speciality developer for Chlorine base emulsions with Hydrochlorochinon (=Arduol=Chloroquinol=...) as developing agent and a different combination of development time / dilution than given in the darkroom cookbook. This original ID-24 formula is also published by Tim Rudman in his Toning Book, with the remark that he never tried it and that he doubts that good toning results might be achieved after using this developer.

I have been trying to research Hydrochlorochinon as a developing agent, and have found little information. It seems, this developing agent was used for certain applications in the beginning but eventually fell totally out of favour. Eder in one of his books give some details and an old East German publication has some info. Both say that the outstanding property of Hydrochlorochinon is that it produces warm-brown tones. Furthermore, it seems to get restrained by Bromide at the same rate as Glycin. Nevertheless, the outstanding property of Glycin is described as compensating and not to produce special tones, so I wonder if it is an adequate substitute. Given that information, I doubt very much that the Glycin-based ID-24 will produce red tones. Probably, I will give it a try developing the print normally, and then rehal with a copper-sulphate-NaCl bleach and then redevelop in the original ID-24 and fix in plain hypo.

Hydrochlorochinon is not available at my traditional suppliers of photochemistry in Germany, but can be order it at Sigma Aldrich directly (65€ / 100g). Interestingly, they also list Hydrobromochinon, so I was wondering if that will work as a reasonable developer, too?

 

[Ian Grant]

I'd like to see examples of different dilutions giving sepia, brown and red tones. Do you have any examples or is this something you have read about? If it can do anything close to sepia, brown or red tones then this is truly an amazing developer.

You will no doubt conclude I am sceptical and you will be right

pentaxuser

The last paper I used that could yieldvery warm sepia to reddish brown tones was the older Agfa Record Rapid before the Cadmium was removed, in Agfa Neutol WA or Ilford ID-78. Actually that's not strictly true I did get reddish tones once with the very last batch of Forte Polywarmtone but this was exceptionally fresh paper at the time and hadn't aged properly.

Modern warm-tone developers like Neutol WA and Ilfrord ID-78 are much better than ID-24. ID-78 was once commercially available as a powder developer, Ilford Warmtone developer is effectively the liquid version. I'd add that Neutol WA and ID-78/Ilford Warmtone are very close and to all intents interchangeable,

RauschenOderKorn - One problem with US books of formulae is most were taken from the Photo Lab Index which were riddled with errors, Mostly typos but also many coversion errors going drom anhydrous to mono-hydrated and crystalline. The 3rd Edition of the Darkroom Cookbook was thoroughly crosschecked with manufacturers literature and a large number corrected and developes like ID-24 dropped because Chloroquinol has effectively been out of use for 40+ years, ID-78 replaced it.

Ian

 

[RauschenOderKorn]

The 3rd Edition of the Darkroom Cookbook was thoroughly crosschecked with manufacturers literature and a large number corrected and developes like ID-24 dropped because Chloroquinol has effectively been out of use for 40+ years, ID-78 replaced it.

Actually I have used the third edition of the Darkroom Cookbook (I also have an earlier edition, and the errata, ... I know what you are talking about), but it still includes ID-24. In the instructions of ID-24, it says: "Normal Exposure should be determined by first using Ilford ID-78".

So in your experience, the ID-78 Hydrochinon/Phenidone will give better results than the ID-24 Hydrochinon/Glycin or Hydrochinon/Chloroquinol and trying the latter will basically be the waste of time & material & money I am trying to avoid?
Looking at the literature I have at hand, I was under the impression that Chloroquinol was never a widespread developing agent. Do you know why?

 

[Ian Grant]

Glycin and Chloroquinol were always difficult to get in Europe except in large commercial quantities, Ilford used to use Glycin in Ilfosol and both Jonhsons and May & Baker used Chloroquinol. I think Johnsons made Chloroquinol and they ceased manufacturing raw chemicals in the 1960's, they supplied Ilford with some raw chemicals, I have a bottle of Ilford Amidol which states it was made by Johnsons of Hendon.

By the time I began photography seriously in the late 1960's Chloroquinol was no longer readlily available and PQ warm tone developers were commercially availble. In the mid 1980s I tried quite a few of the warm toned developers designed to give large colour shifts but papers had changed even by then and the extremes were harder to achieve and the colours not always particularly pleasing.

After WWII photo papers eveolved to suit the newer films and modern ways of working pioneered by people like Hans Windisch before WWII in Die Neu Foto Schule / The New Photo School. Put simply before the war most plates /films were given generous exposure and processed to higher contrasts and densities than we do today and the papers suited those negatives which don't print as well on modern papers. Windisch (and others in Europe) went for a different approach to get the highest possible results from miniature films (35mm & 120), in the US peole like Ansel Adams were approaching LF in their own way. In both cases more accurate exposure and keeping development times just sufficient to achieve the right tonal range and contrast.

I've written before about seeing an exhibition of early Kertesz work at the Barbican, London some years ago, all small contemprary prints on warm tone papers, wonderful colours and great sublety. Later I saw a larger exhibition of his work, all modern prints quite a few of the same negatives and in comparison they were quite different, while very good prints they lacked the feel of the older contemporatrt prints.

Glycin or Chloroquinol aren't magic bullets for warm tones, with the Cadmium gone from papers it's only possible to achievea more limited hift in warmth by development alone, it's still quite a reasonable shift but it's not the "sepia - brown and even red tones" you asked about. You need toners to get to those these days and they often work best with neutral tone papers.

Ian

 

[Gerald C Koch]

Echoing a bit what Ian said. Chrorohydroquinone is a very nice developing agent. It easily produced warm tone images. It is also capable of being used alone as a film developer. In this respect it is similar to metol.. CHQ was used in Ethol UFG, Edwal FG-7, and Champlin 17 (the only Champlin developer which chemically made any sense). Those that check the MSDS for FG-7 will not see it listed however. When CHQ became difficult to obtain Edwal just synthesized it from p-benzoquinone, and hydrochloric acid.

 

[Photo Engineer]

That "synthesis" is problematic at best. They use Quinone + HCl which does give Cl-HQ, but then it goes on to oxidize with even the smallest amount of O2 present to give Di-Cl-HQ. It is reported to be 4x more active than HQ alone. (See attached)

With Sulfite present, it would probably give the Cl-HQ-Sulfonate.

The best actual synthesis is in anhydrous benzene with gaseous HCl at about 80C and 4 atm pressure. Very ungood.

This is why I doubt that Edwal got what they expected in their developer which was Q + HCl + Sodium Sulfite + NaOH in an undisclosed sequence.

PE

 

[Gerald C Koch]

That "synthesis" is problematic at best. They use Quinone + HCl which does give Cl-HQ, but then it goes on to oxidize with even the smallest amount of O2 present to give Di-Cl-HQ. It is reported to be 4x more active than HQ alone. (See attached)

With Sulfite present, it would probably give the Cl-HQ-Sulfonate.

The best actual synthesis is in anhydrous benzene with gaseous HCl at about 80C and 4 atm pressure. Very ungood.

This is why I doubt that Edwal got what they expected in their developer which was Q + HCl + Sodium Sulfite + NaOH in an undisclosed sequence.

PE

Thanks, I wondered about the actual reaction because it never seemed to work out right on paper. However, at the time I didn't care enough to follow it further. I did synthesize another developing agent mentioned in Glafkedes pyridyl hydroquinone by refluxing quinone with pyridine.

Jerry

 

[RauschenOderKorn]

Well, I have been able to find out some things about Adurol / Chlorohydroquinon from the original Ilford ID-24.

First of all, in the very beginning Adurol referred to both Bromohydroquinon and Chlorohydroquinon, but later (quite early) only Chlorohydroquinon was used.

I have found that data on Chlorohydroquinon is only available in old resources, like e.g. the 1941 17th Edition of "Rezepte Tabellen" by Josef Maria Eder. He states that Chlorohydroquinon is basically more active than Hydroquinon, does not require a strong accelerator - K2CO3 is his recommended, it is not affected by temperature changes very much, and bromide will slow it just at the right rate. This of course all only valid in order to develop old 1920s and 1930 style home made emulsion on glass plates .

Hard facts from Eder: Chlorohydroquinon dissolves very well in water (aprox 92,3-100 g in 100ml @ 15 degrees centigrade), it dissolves nicely in a 10% Na2SO3 solution (aprox. 65 g / 100ml ) and also dissolves well in a mixed solution of Na2SO3 and Na2CO3. According to Eder it is actually the developing agent which is easiest to dissolve in water. There are several recipies (Arduol alone and Arduol/Metol). In general, Eder has less data on Adurol than on other developers, I do not know why.

In Junge/Hübner "Fotografische Chemie" 1989 (5. Edition - VEB Fotokinoverlag Leipzig, an East German Publication), they state about Chlorohydroquinon that it has the same properties as Bromohydroquinon and is "similar to Hydrochinon (see there). For the brown development of papers." No more data is given, and as far as I can reconstruct from Orwo recipes and instructions I have, Chlorohydroquinon was not available in the GDR either, at least not through the official ORWO channels.

The best reference to developing papers seems to be actually Ilford which recommend the original ID-23 for black-brown tones and ID-24 with Chlorohydroquinon for brown to red tones for the Ilford Chlorona paper, a historic Chlorine-Bromide Emulsion paper. After that, I have found nothing.

Chlorohydroquinon and Bromohydroquinon are both available at Sigma Aldrich, Chlorohydroquinon rather unpure 85%, technical grade (aprox. 65 €/100g) and Bromohydorquinon extremely expensive (aprox 65 € per ONE gramm).

I am thinking about giving Chlorohydroquinon a try. I know that I will not get any red tones, and that there are not any magic bullets.

The following is the Ilford ID-23 recipe, which I think might work:

0,5 g Metol
6,2 g Chlorohydroquinon
6,2 g Hydroquinon
100 g Sodium sulphite
100 g Sodium carbonate
0,8 g Potassium bromide
Water to make 2 liters
Dilute 1:3 for warm-black tones - Dilute 1:5 for sepia and overexpose aprox. 50%. Development Time approx. 2 min @ 18 degrees centigrade

Would it make sense to modify this recipe to adapt it to modern papers, e.g. increasing bromide a little?
Which paper would you recommend, I have the following available: ORWO BN, Argenta Brom BS, Adox MCP & MCC, Agfa MCP and Ilford MGIV?

Recommended reference developer:

ID-78

????

Fix: Plain Hypo or will a Ilford Rapid do???

Any other ideas?

 

[RauschenOderKorn]

One problem with US books of formulae is most were taken from the Photo Lab Index which were riddled with errors, ...

Might this be the reason why in the Darkroom Cookbook ID-24 Chlorohydrochinon was switched for Glycin? I doubt that these two development agents are interchangeable that easy.

 

[Gerald C Koch]

Might this be the reason why in the Darkroom Cookbook ID-24 Chlorohydrochinon was switched for Glycin? I doubt that these two development agents are interchangeable that easy.

In general developing agents are not interchangeable. You have to compare the redox potentials of each to get a better understanding. Then too you must make adjustments in a formula when you do substitute. When the developing agent atomal was no longer available it effectively killed off Agfa's Atomal developer. Nothing else worked quite the same.

 

[RauschenOderKorn]

Then too you must make adjustments in a formula when you do substitute.

And that is exactly what did not happen in the Darkroom Cookbook ...

 

[Photo Engineer]

I would suspect that solubility data. It indicates nearly infinite solubility and a decrease in base.

The data I have suggests it is very soluble in hot water but not so much so in cold water which disputes the above, so I find most data on Cl-HQ to be apocryphal. It certainly is expensive and is no magic bullet.

BTW, at 4X the activity of HQ, in a developer with HQ at equal concentration and considering the difference in MW, I wonder if you would see any Cl-HQ reactivity at all, and at that level of Sulfite, any aerial oxidation would lead to substitution of something onto the resulting quinone ring. See my above scheme.

PE

 

[Ian Grant]

The following is the Ilford ID-23 recipe, which I think might work:

0,5 g Metol
6,2 g Chlorohydroquinon
6,2 g Hydroquinon
100 g Sodium sulphite Crystalline 50g Anhydrous
100 g Sodium carbonate Crystalline 37.5g Anhydrous
0,8 g Potassium bromide
Water to make 2 liters
Dilute 1:3 for warm-black tones - Dilute 1:5 for sepia and overexpose aprox. 50%. Development Time approx. 2 min @ 18 degrees centigrade

Would it make sense to modify this recipe to adapt it to modern papers, e.g. increasing bromide a little?
Which paper would you recommend, I have the following available: ORWO BN, Argenta Brom BS, Adox MCP & MCC, Agfa MCP and Ilford MGIV?

Recommended reference developer:

????

Fix: Plain Hypo or will a Ilford Rapid do???

Any other ideas?

As warmtone papers get colder with age I'd useAdox MCP/MCC or Ilford Warmtone, there's no point is using a bromide paper as they barely show a shift in warm tone developers. For a reference us Neutol WA or Ilford Warmtone developer., or make up ID-78. Fixer will make no difference but don't over fix because warmtone papers/prints can be affected if left in fixer too long.

The major problem is the Chloroquinol available isn't Photographic grade. The reality is that switching from Metol to Phenidone in early (mid 1950s) commercial Ilford MQ/PQ developers caused some issues/complaints because of shifts in image/tone/colour. This lead to their re-formulation with the addition of Benzotriazole to hold back the colour shift and the introduction of a new commercial Ilford warm tone developer in powder form, ID-78.

You can find some saying PQ developers give colder tones than their MQ equivalents but it's the other way around unless Benzotriazole has been added. A classic example was Agfa Neutol WA available in powder form which was a MQ developer and the liquid Neutol WA a PQ version which gave even warmer tones. I used both in the late 1980s.

Ian

 

[RauschenOderKorn]

Thanks, guys.

I think it is best to accept the advice, and give ID-78 or any of the other warmtone developers mentioned by Ian a try. in the end, CHQ is not available in photo quality, the available formulas do leave some question marks and the right papers are not available either. I guess I will just leave this for a rainy Sunday afternoon with nothing else to do.