Using only hydroquinone as a developer?

I have finally gotten around to trying the 'Create your own formula' (developer formula tests) in The darkroom cookbook, 3rd edition, pages 27 - 28. Here one makes up various combinations of a set of chemicals, to see what they each do in a print developer, in this case D72.

I have just done the 'Hydroquinone and sodium sulphite only' part, but the first print appeared blank after about 10 minutes development at 21C. I did it a second time, with fresh solution, thinking that the graduates etc may be contaminated. So I washed them well, but I got the same result with a second print. As a comparison, 'Metol and sodium sulphite only' gave a very weak print after 8 minutes, just previously.

I then went on to add to the HQ and SS solution, (one chemical at a time then making a print) sodium carbonate, followed by potassium bromide, both of which gave positive prints very quickly and in the expected time limit.

I'm still confused why the HQ and SS didn't produce any print detail at all. Is this correct?

I'd be especially keen to hear from anyone who has also done this test. To recap, I have TDC 3rd edition, with the test being on pages 27 - 28.

Terry S

tezzasmall said:

I'm still confused why the HQ and SS didn't produce any print detail at all. Is this correct?

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Hydroquinone by itself is effective as a developer at relatively high (10??) pH. Sodium sulfite is only mildly alkaline.

bernard_L said:

Hydroquinone by itself is effective as a developer at relatively high (10??) pH. Sodium sulfite is only mildly alkaline.

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There it is!

As posted here on Photrio back in 2005: https://www.photrio.com/forum/threads/ph-effect-on-film-development.10550/post-142310
Note how there's basically no activity whatsoever for HQ below pH9.4 or so. Sodium sulfite will settle around pH9 or so if memory serves.

tezzasmall said:

I then went on to add to the HQ and SS solution, (one chemical at a time then making a print) sodium carbonate, followed by potassium bromide, both of which gave positive prints very quickly and in the expected time limit.

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You've made essentially a lith developer (although your mix was probably too high in sulfite to give proper infectious development). Yes, this works fine, as you've found.

That's great guys! Thanks for the quick replies.

It's a shame that expected results weren't printed with this information after the article or later in the book, and then referenced to.

Many thanks.

Terry S

koraks said:

There it is!

As posted here on Photrio back in 2005: https://www.photrio.com/forum/threads/ph-effect-on-film-development.10550/post-142310
Note how there's basically no activity whatsoever for HQ below pH9.4 or so. Sodium sulfite will settle around pH9 or so if memory serves.

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'Developing' by C I Jacobson 1948 gives the pH of 10% sodium sulfite as 9.7, the pH with carbonate would be over 11.

Alan Johnson said:

'Developing' by C I Jacobson 1948 gives the pH of 10% sodium sulfite as 9.7, the pH with carbonate would be over 11.

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Doesn't this plus the first chart indicate that the OP should have gotten a much better print after 8 minutes than he got?

pentaxuser

pentaxuser said:

Doesn't this plus the first chart indicate that the OP should have gotten a much better print after 8 minutes than he got?

pentaxuser

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The Darkroom Cookbook 3rd edition p28 that is referred to above does not specify the amount of sodium sulfite to be added and nor does the OP. 10% is the only concentration for which there is any pH data in the book I mentioned. Quite likely a lower concentration would have been used by the OP which would have given a lower pH at which HQ was hardly activated, in line with prediction from the chart.
It was meant to be a teaching example in TDC 3.

Alan Johnson said:

The Darkroom Cookbook 3rd edition p28 that is referred to above does not specify the amount of sodium sulfite to be added and nor does the OP. 10% is the only concentration for which there is any pH data in the book I mentioned. Quite likely a lower concentration would have been used by the OP which would have given a lower pH at which HQ was hardly activated, in line with prediction from the chart.
It was meant to be a teaching example in TDC 3.

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Fine but my question was about the OP's use of metol with sodium sulphite in his second attempt where it appears that metol is quite active The comment accompanying the graphs was that sodium sulfite will settle at around 9 when the metol graph seems to show it is quite active. However even at 8 mins the paper was showing little image

Hence my puzzlement at metol's seemingly poor performance

pentaxuser

pentaxuser said:

The comment accompanying the graphs was that sodium sulfite will settle at around 9 when the metol graph seems to show it is quite active.

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Concentration and development time aren't stated on that graph. Nor is it stated here in the thread for the experiment OP did.

I expect the experiment goes like "try this ingredient alone...now add sulfite, see nothing much happening still...now add another developer to create a superadditive pair and BOOM" So the TDC experiment likely uses concentrations and times that deliberately produce a fairly weak image with only one developing agent, so that the difference with a superadditive pair is nicely visible. Just my guess though.

Well, sodium sulfite in my experience has pH just under 8 at 72F mixed at 100g per liter with distilled water from Walgreens. So, maybe there are false assumptions at play.

What's the target pH of D23? This should give an insight into the practical pH a sulfite-activator-only developer would have. There's the effect of the metol, too, of course, but IDK if that's particularly big. I can't find a reference right now, but I recall D23 being comparable to XTOL in terms of pH - so a little north of 8.0 or so.

Saganich said:

Well, sodium sulfite in my experience has pH just under 8 at 72F mixed at 100g per liter with distilled water from Walgreens. So, maybe there are false assumptions at play.

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Thanks. You may well be right and it is an explanation of why Sodium Sulphite added to Metol may not or does not result bring up the activity level up enough to make other than marginal hence the 8 mins with just a faint image

You are right,as are the others who said the same, namely the OP does not mention the amount of sodium sulphite used but it appears that even vast amounts of it may not work for a paper developer although 100g per litre with 7.5g of metol is fine for films

koraks is right about how the text in the Darkroom Cookbook should have read to make sense as an instructive experiment and maybe it does say something like koraks has worded it but if it does then I would not have expected the OP to be surprised when hydroquinone with sodium sulphite did nothing and metol with the same ingredient did very little

pentaxuser

Alan Johnson said:

The Darkroom Cookbook 3rd edition p28 that is referred to above does not specify the amount of sodium sulfite to be added and nor does the OP. 10% is the only concentration for which there is any pH data in the book I mentioned. Quite likely a lower concentration would have been used by the OP which would have given a lower pH at which HQ was hardly activated, in line with prediction from the chart.
It was meant to be a teaching example in TDC 3.

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Alan: There are only some ingredient amounts mentioned in the text for the test that I did, but it states near the beginning of the text, 'Start with a general-purpose paper developer, such as Kodak D-72, and dilute as you would for a normal print.' It then makes small references to this formula, which is printed on page 86, as Formula #252.

The D-72 formula given that I followed is:

Water, 750ml
Metol, 3g
Sodium sulfite, 45g
Hydroquinone, 12g
Sodium carbonate, monohydrate, 80g
Potassium bromide, 2g
Water to make 1.0 litre

Dilute 1:1 to 1:4

I dilute at 1:2

Development times 1 1/2 to 3 minutes.

I develop for 1 1/2 minutes for RC papers and 3 minutes for FB papers.

koraks said:

I expect the experiment goes like "try this ingredient alone...now add sulfite, see nothing much happening still...now add another developer to create a superadditive pair and BOOM" So the TDC experiment likely uses concentrations and times that deliberately produce a fairly weak image with only one developing agent, so that the difference with a superadditive pair is nicely visible. Just my guess though.

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Koraks: Yes, your assumption is correct.

pentaxuser said:

Thanks. You may well be right and it is an explanation of why Sodium Sulphite added to Metol may not or does not result bring up the activity level up enough to make other than marginal hence the 8 mins with just a faint image

You are right,as are the others who said the same, namely the OP does not mention the amount of sodium sulphite used but it appears that even vast amounts of it may not work for a paper developer although 100g per litre with 7.5g of metol is fine for films

koraks is right about how the text in the Darkroom Cookbook should have read to make sense as an instructive experiment and maybe it does say something like koraks has worded it but if it does then I would not have expected the OP to be surprised when hydroquinone with sodium sulphite did nothing and metol with the same ingredient did very little

pentaxuser

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Pentaxuser: One is directed to add the full amount in the formula of both sodium sulphite (45g) and the metol (3g) into the SS and metol only formula.

There is also no text stating what each chemical added should / would do, hence why I had to ask why there was no image when using just HQ and SS. As stated, initially I thought that I had contaminated the liquid some how or put the wrong amount of ingredients together. And I'll be totally honest that I'm not that chemically aware, as yet, to know what each of the additions should do. I am quickly becoming more aware though, as I do each test, and then refer back to the book, to re-read the test text at least. I also re-read the text given for each chemical used, which is printed later in the books pages. So, although I would have preferred some text, maybe later in the book, explaining what would happen throughout the test after the addition of various chemicals, I have found the answers by re-reading other sections of the book and from more knowledgeable contributors on here, who have answered my questions quickly, for which I thank you all.

Terry S

koraks said:

What's the target pH of D23? This should give an insight into the practical pH a sulfite-activator-only developer would have. There's the effect of the metol, too, of course, but IDK if that's particularly big. I can't find a reference right now, but I recall D23 being comparable to XTOL in terms of pH - so a little north of 8.0 or so.

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I have measured the initial pH of 1 liter of D23 at room temperature in distilled water for my previous 3 batches as 7.81 (7/5/23), 7.82 (7/2/24), and 7.75 (12/30/24). These were measured after the addition of 100ml of used D23 to top off the bottle, the third I measured before and after; 7.69 before and after adding 100 ml of old D23, 7.75. The old D23 was 8.89

It rises over time reaching 8.89 after about 700ml of D23R. The sweet spot is just north of 8, as Koraks mentioned, but over 8.5 the tonality starts to feel off and by 9 that's pretty obvious.

There were Hydroquinone only print developers, however they were designed to give very reddish warm tines with old style warm tone Chlorobromide papers (which had cadmium in the emulsions)..

Agfa 120 and Agfa 123 were two, they are essentially the same except Agfa 120 has 2g/l Potassium Bromide and Agfa 123 25g/l Bromide. They needed longer exposures and long development times. The older Record Rapid could produce nice very reddish brown tones, but after the Cadmium was removed the paper was far more limited in terms of colour shifts with development.

Note: Agfa (Orwo) 120 is not the same as Agfa Ansco (GAF) 120.

Ian