Would I be missing anything if I use D-23 instead of D-76?

[Alan Johnson]

I don't have that paper available, but taking the quote at face value, isn't he comparing metol in MQ developers with phenidone in PQ developers?

Increased contrast with hydroquinone is also found with metol as illustrated in p173-177 here:

Developing The Negative Technique : Kurt I. Jacobson, Ralph Eric Jacobson : Free Download, Borrow, and Streaming : Internet Archive

Eighteenth edition, revised, updated and reprinted. Epson V750, Vuescan, ScanTailor, Adobe Acrobat

archive.org

 

[pentaxuser]

OK and thanks for the answers koraks and Yeshizu. I am a little clearer, I think, on why we can say that each film requires only 0.12g of Metol for development in theory as it were but there is no way that can be spread across all of a film properly in less than a very long time or seemingly even an eternity which isn't practical

Effectively you need a lot more Metol than is theoretically required for it to cover the whole film sufficiently in a reasonable time for practical development to take place

So from this might a reasonable conclusion be that the nature of Metol's action requires much of it to be wasted i.e. you have used with 4 films the full 1L of developer and its 7.5g of Metol and yet there is something like 7g of Metol that was not used at all?

There remains for me at least the practical question of what may still be the scope for scaling down in terms of the amounts of Metol and Sulfite. Maybe the answer is none and this was determined during testing by Kodak which was why Kodak stated that it was 7.5g of Metol and 100g of Sulfite? This was the right quantities of both chemicals to meet the requirements of D23? As Yeshizu says economising on the two quantities might be possible but you would end up with a different developer with different qualities

So in terms of "practical" economy it may be that the limits are 8 x35mm films or 4 x120 films with stock D23
using a Jobo rotary processor but only 4 and 2 respectively using inversion agitation

At 1+1 using a rotary processor the D23 stock involved drops to 70ml for a 35mm film and 120ml for a 120 . While 1+1 changes the qualities of subsequent negatives anyway, it raises the question of whether only 70ml stock is sufficient to get the same negatives as would have been obtained with inversion agitation with 125ml of stock?

Is the answer to that a Yes on the basis that the additional agitation from a rotary processor makes up for the lower stock quantity or No because the halving of stock to 70ml makes the D23 behave differently such that you would get usable negatives but they would not be the same as those from a 1+1 dilution using inversion agitation where the stock is 125ml?

Comments on my speculative thoughts are welcome

I have enjoyed this as a learning exercise

Thanks

pentaxuser

 

[Yezishu]

Based on previous formulas, I believe there are several approaches:

1. As you mentioned, agitation and proper loading can help reduce the required liquid volume.
2. Replenishment restores the working solution to its normal concentration after use.
3. Accepting some performance differences for lower usage—for example, switching to a developer optimized for low-concentration, high-alkalinity conditions, renaming it as Rodinal.
4. Adding a less ideal but inexpensive reducing agent to regenerate oxidized Metol, maintaining its concentration (part of superadditivity). For instance, use 2g Metol with more hydroquinone as in D-76.
This effect is more pronounced in phenidone-ascorbic acid developers, where phenidone can be used at mg/L levels, but continuously regenerated by about 2g/L of ascorbic acid. Compared to using phenidone alone at 1–2g/L, ascorbic acid is inexpensive, widely available, and non-toxic. If use 10 mg of phenidone per roll, 5 grams of phenidone can develop 500 rolls.

 

[Yezishu]

I've been pondering the question posed in the title of this thread (Would I be missing anything if I use D-23 instead of D-76?). It almost boils down to 'What did hydroquinone ever do for us?'

My experience of metol-only development is chiefly with Thornton's 2-bath formula. For the vast majority of scenes, I get negatives that print straight or with minimal manipulation on grade 2 or 2 1/2 (Ilford Multigrade Classic). If they don't, it's usually because I have cocked-up the exposure. So why would I need more contrast? If I was routinely having to use grade 3 or higher, I might understand, but that's not the case.

Price! Based on my current chemical sources, if I set the price of 100g phenidone at 100, the price of metol is only slightly lower (approximately 95), hydroquinone is about half the price (around 45), ascorbic acid (chemical grade) is roughly one-seventh (about 15).

On the Photoformulary, phenidone 10g is $14.95, metol 100g is $16.95, hydroquinone 100g is $8.95, and ascorbic acid 100g is $12.95.

While prices vary by location and package and grade, it is clear that, when producing and packaging in large quantities, using 2g of metol plus 5g of hydroquinone is significantly more cost-effective than using 7.5g of metol alone. Manufacturers like Kodak would seek to reduce raw material costs wherever possible, if they can provided product quality remains unaffected.

 

[snusmumriken]

Price! Based on my current chemical sources, if I set the price of 100g phenidone at 100, the price of metol is only slightly lower (approximately 95), hydroquinone is about half the price (around 45), ascorbic acid (chemical grade) is roughly one-seventh (about 15).

On the Photoformulary, phenidone 10g is $14.95, metol 100g is $16.95, hydroquinone 100g is $8.95, and ascorbic acid 100g is $12.95.

While prices vary by location and package and grade, it is clear that, when producing and packaging in large quantities, using 2g of metol plus 5g of hydroquinone is significantly more cost-effective than using 7.5g of metol alone. Manufacturers like Kodak would seek to reduce raw material costs wherever possible, if they can provided product quality remains unaffected.

My cynical alter-ego would like to believe this, but the Ilford Manual of 1958 (revised 1966) specifically said, "The success of these mixtures depends upon the fact that their photographic properties are superior to those of the components taken separately" [my emphasis]. Is the explanation that in 1966 emulsions needed that extra contrast, whereas with today's emulsions we don't really need hydroquinone but it makes good manufacturing economics?

Increased contrast with hydroquinone is also found with metol as illustrated in p173-177 here:

Developing The Negative Technique : Kurt I. Jacobson, Ralph Eric Jacobson : Free Download, Borrow, and Streaming : Internet Archive

Eighteenth edition, revised, updated and reprinted. Epson V750, Vuescan, ScanTailor, Adobe Acrobat

archive.org

Sure, yes, I have that book and I understand about super-additivity. But my question was, why do we need that extra contrast if in most circumstances metol alone produces a negative that prints on Grade 2 or 2 1/2?

 

[Alan Johnson]

Sure, yes, I have that book and I understand about super-additivity. But my question was, why do we need that extra contrast if in most circumstances metol alone produces a negative that prints on Grade 2 or 2 1/2?

Some (not all) report that D-76 (or ID-11 etc) can be used to provide more highlight contrast than D-23, and more sparkle:

Dull results with D23 stock

I have developed two rolls of D-23 stock and they are fairly dull. One is with Fomapan 200 and other HP5+. Is it normal to get fairly dull results. Do you normally have to over expose half a stop or so? I did develop two rolls with 1+3 and the results is much nicer. What is your experience?

www.photrio.com

 

[Yezishu]

My cynical alter-ego would like to believe this, but the Ilford Manual of 1958 (revised 1966) specifically said, "The success of these mixtures depends upon the fact that their photographic properties are superior to those of the components taken separately" [my emphasis]. Is the explanation that in 1966 emulsions needed that extra contrast, whereas with today's emulsions we don't really need hydroquinone but it makes good manufacturing economics?


Sure, yes, I have that book and I understand about super-additivity. But my question was, why do we need that extra contrast if in most circumstances metol alone produces a negative that prints on Grade 2 or 2 1/2?

Uh, I want to say that price is one obvious factor from my perspective, but not everything else is equal. Ian mentioned some considerations at the time:

Could plain D-23 still be good choice?

I am long term D-76 and later XTOL user, but as I have moved towards to tray and tank development (with 4x5) which requires larger volumes of developer, I am thinking to mixing developer myself. It should cut costs. Why D-23? Because it was formulated for replacing D-76 which wasn't robust...

www.photrio.com

These factors may depend on the situation—for example, when I'm mixing for one-time personal use, I don't care about storage stability, or whether the developing time increases by 50%. The difference in cost per batch is also negligible to me(how many rolls can I shot each year?). But these factors might be important in commercial settings. Another example is the use of very tiny additives in commercial developers. These aren't as popular in personal mixing, because accuracy issues can lead to significant differences (for instance, if a formula calls for 3mg of something in 1L solution—if I have to mix 500 ml new solution each time, I may rather use a formula that doesn't require such precise measurements).

 

[Donald Qualls]

if a formula calls for 3mg of something in 1L solution—if I have to mix 500 ml new solution each time, I may rather use a formula that doesn't require such precise measurements

If I had reason to use a developer that called for this (like the "homeopathic" amount of potassium iodide in one formula or another) I'd start by making a stock solution of known strength in a photographically inert solvent that lets the solution store well -- distilled water for things like potassium iodide and other simple salts, 91% isopropyl or propylene glycol or similar for active chemicals like phenidone. If I have a 1% solution w/v, then 1 mg is 0.1 ml -- easy enough to measure with a suitable syringe. Honestly, though, as home-mixed developers go, any advantages over D-23 are very small.

 

[Vaughn]

Dektol is a pretty nice developer for film, also. Especially for bumping up the contrast a bit. I also use Ilford's Universal PQ developer for this reason.

I use to use Microdol-X for Panatomic-X and later for 4x5 film...used at 1:3 with the thinking that dilulting the developer would reduce the concentration of the silver solvent and get a little bit more sharpness at the expense of a little bit more grain.

Girders, Golden Gate Bridge
Developed in straight Dektol
4x10 carbon print

 

[Donald Qualls]

Dektol is a pretty nice developer for film, also.

Especially if fine grain isn't a primary driver.

 

[Nicholas Lindan]

I used to use Microdol-X [1:3] for Panatomic-X ...

Same here.

I hold that fine grain developers are for fine grain films.

As stated before, I think TMax-100 in Microdol is the finest grain combination outside of Tech Pan.

Contrary to popular belief, using Microdol at 1:3 doesn't result in coarser grain with TMax-100. The grain does, hoewever, get a mushy appearance compared to FS - but to see it you have to enlarge 35mm to 16x24" and examine the print with a 10x loupe. At FS Microdol's grain has a nice salt-and-pepper texture, a bit like Plus-X in D-76 1:1.

Using Microdol 1:3 does preserve TMX's film speed, unlike FS where I find Microdol/TMX looses a stop and a half.

Microdol with TMax used to produce dichroic fog but I haven't seen that recently. Which is good as my supply of Microdol-X has run out and I am back to using plain-ole DIY Microdol.

Unfortunately the creamy large-format-like look of Tech Pan doesn't appear with the TMX/Microdol combination even though the grain is comparable. With Tech Pan the LF look begins to fall apart at anything larger than an 8x10 print.

 

[Vaughn]

Especially if fine grain isn't a primary driver.

True -- I only contact print w/ alt processes. However, a friend scanned the 4x10 negative of the above girders and made a 7 foot long inkjet print of it for a show. I just took a look at the print (it's been a few years!) and the grain is definitely not course, but the exact structure is difficult to tell in the print. Things are a little too disorganized around here right now for my to easily grab the negative.

 

[Donald Qualls]

I only contact print w/ alt processes.

Even if you enlarged, from 4x10 by the time someone can see the grain they're too close to the print to see the image. In general, grain doesn't matter much once you're bigger than 6x9 cm.

 

[Vaughn]

That is true. Ah, but sometimes bringing them in 'too' close can be part of the image. And I want to make it worth their while.

Perhaps it is an effect of me being so near-sighted and being able to focus down to around 5 inches away. I like images that work at varying viewing distances...that draw the viewer close and then sends them back again.

 

[F4U]

I always hated that Kodak dropped Microdol X. Back in the day I could use ANY of the Kodak 35mm or 120 films and get perfect sharpness, grainless prints. And it had a curious way of acting almost as if to be a pyro developer. The negatives seemed to have a translucence and curious sepia sort of appearance. Whether you over exposed or underexposed, you could always get a nice print, it seemed. But maybe age comes with it's rose-colored glasses and recollections of younger, energetic years. Now I just get a couple pounds of ebay sodium sulfite every few years and a little jar of Elon/Metol and mix my own D23. It's not Microdol X because it's too grainy to qualify as Mirodol X. Actually it's more like D76. But it's cheap, dependable, and doesn't ever seem to go bad. Now i''m old and see no need to change. Anything better is so finely nuanced of an improvement as to not be worth the effort.

 

[Donald Qualls]

But it's cheap, dependable, and doesn't ever seem to go bad.

And if you replenish, you have to add one more ingredient (or two if you make your own metaborate in solution) but it gets even cheaper, plus some folks prefer the "look" of negatives from the well seasoned developer.

 

[Ian Grant]

Crawley ,BJP Dec 16 1960 p684 explained this.
"The presence of metol also assists discrimination in the highlights, which in some PQ developers are liable, the author finds, to 'run away'."
In other words, hydroquinone gives a more contrasty negative.

That's Crawley trying to justify why he sometimes used 3 developing agents in his film developers. Ilford Autophen was a PQ variant of ID-11/D76 and remarkably stable, it was sold to photo finishing labs.

In the early 1980s the use of 3 developing agents was discussed over a business lunch while I was having meeting with Ilford in Mobberley. A senior Ilford research chemist was present and mentioned when he started working for Ilford they were manufacturing Paterson's Crawly chemistry. He mentioned that Crawley's developers would have been far better using only 2 developing agents. He was rather scathing.

The exception is where Kodak and Ilford used Pyrogallol as an Oxygen scavenging agent in two MQ deep tank developers, and their replenishers, in the 1930s.

Ian

 

[john_s]

.........................

The exception is where Kodak and Ilford used Pyrogallol as an Oxygen scavenging agent in two MQ deep tank developers, and their replenishers, in the 1930s.

Ian

Also, HC-110 contains pyrocatechol, in addition to hydroquinone a version of phenidone. The amount varies widely between editions of the MSDS, and I've lost track of the various versions.

 

[Pixophrenic]

I've ordered a 1L kit of D-76 and I am looking forward to developing film with the gold standard developer. That will help establish a baseline of what a developed film is supposed to look like.

But... Long term, I'd rather use developers that I can mix myself or are concentrates that never go bad. That would better suit the sporadic & random nature of my photography hobby. I have Rodinal, PC-TEA, and the ingredients & tools (e.g. milligram scale) to mix D-23 in small batches. I know that Rodinal (and I think also PC-TEA?) will give a different look to D-76 because D-76 is a solvent / fine-grain developer. But D-23 is also a fine-grain developer. D-23 is apparently a lower contrast than D-76, but my understanding is that contrast is something I can learn to control with over/under exposure and push/pull processing.

Is there any reason it might not be a good idea to use D-23 as my single fine-grain developer?

My answer to this question is "no" but there is an important detail. You did not specify which would be your sources of metol and sulfite if you decide to make D23 from scratch. If you already have a digital microscale, for the same amount of money you could get a cheap pH meter. Buying a commercial D76 or ID11 has the advantage of quality control for ingredients, while your scratch mixing needs that too, if only in the form of controlling the pH of the developer. Sodium sulfite is particularly suspect chemical, and you may encounter one that is substantially contaminated by residual sodium carbonate. You D23 would then have a substantially higher pH than intended (pH ~8). It will not only develop faster, it would have a tendency to over-development with larger grain, and it will also have a shorter storage time, all other conditions being equal.
Similarly, making D76 from scratch has the same caveat. Its pH should be 8.6 to 8.8, otherwise the same set of problems will be encountered.
Here I am deliberately not getting into what is fundamentally bad about both developers.

 

[pentaxuser]

My answer to this question is "no" but there is an important detail. You did not specify which would be your sources of metol and sulfite if you decide to make D23 from scratch. If you already have a digital microscale, for the same amount of money you could get a cheap pH meter. Buying a commercial D76 or ID11 has the advantage of quality control for ingredients, while your scratch mixing needs that too, if only in the form of controlling the pH of the developer. Sodium sulfite is particularly suspect chemical, and you may encounter one that is substantially contaminated by residual sodium carbonate. You D23 would then have a substantially higher pH than intended (pH ~8). It will not only develop faster, it would have a tendency to over-development with larger grain, and it will also have a shorter storage time, all other conditions being equal.
Similarly, making D76 from scratch has the same caveat. Its pH should be 8.6 to 8.8, otherwise the same set of problems will be encountered.
Here I am deliberately not getting into what is fundamentally bad about both developers.

So depending on the purity of the sulfite which may be suspect for the reasons you give but will be unknown to the user the dev time for D23 varies as does its speed

If my conclusion from your above quote is correct, what might be the range of speed and dev times encountered

Can I also ask whether you found this to be case in your use of D23 and what might be the frequency of the problems, assuming such problems arise

Are these problems with purity true of all home-made developers and if not which home made developers are free of these defects?

Thanks

pentaxuser

 

[dcy]

Considering that so many people have been quite happy with D-23 for so many decades, I am skeptical that variance of purity is an issue worth worrying about.

To make sure I am not misunderstood: I make no claim as to whether the purity of metol or sulfite varies. I am saying that the success of D-23 across time and location tells me that the argument probably academic. For example, it is possible that the effect of any purity variance is smaller than people can detect on the final negative. Or perhaps the effect is smaller than the variance due to differences in agitation methods, water temperature, or exactly when you start the timer.

I can tell you that my very first batch of D-23 had no trouble producing correctly developed negatives.

 

[dcy]

Are these problems with purity true of all home-made developers and if not which home made developers are free of these defects?

I would argue that any popular homemade developer must, almost tautologically, have little enough variance to have many happy users.

 

[pentaxuser]

I would argue that any popular homemade developer must, almost tautologically, have little enough variance to have many happy users.

You may very well be right but Pixophrenic's reply may have suggested otherwise. It is almost certainly true that enough contamination will cause problems but I wasn't sure if Pixophrenic was talking about matters in the abstract or had suffered the problems he mentions himself hence my questions

Whenever I see something being said that looks worth further exploration I try to follow it up seeking more information

No doubt Pixophrenic will clarify matters for me in his reply

pentaxuser

 

[chuckroast]

My answer to this question is "no" but there is an important detail. You did not specify which would be your sources of metol and sulfite if you decide to make D23 from scratch. If you already have a digital microscale, for the same amount of money you could get a cheap pH meter. Buying a commercial D76 or ID11 has the advantage of quality control for ingredients, while your scratch mixing needs that too, if only in the form of controlling the pH of the developer. Sodium sulfite is particularly suspect chemical, and you may encounter one that is substantially contaminated by residual sodium carbonate. You D23 would then have a substantially higher pH than intended (pH ~8). It will not only develop faster, it would have a tendency to over-development with larger grain, and it will also have a shorter storage time, all other conditions being equal.
Similarly, making D76 from scratch has the same caveat. Its pH should be 8.6 to 8.8, otherwise the same set of problems will be encountered.
Here I am deliberately not getting into what is fundamentally bad about both developers.

If you have bad lab technique, compromised chemicals, a lousy scale, etc. you can always find a mechanism to screw things up.

We have far better thermometers, scales, and a chemical supply chain than ever existed for the layman when D-23, D-76, D-72, DK-50, et al were first brought to life. Assuming reasonable care and storage of the components, there should be no issue of huge variability in rolling-your-own.

I routinely mix my own D-23 and Pyrocat-HD[C] reliably and with consistency. D-23 having only two components is dead simple to make. I use distilled water to mix my solutions to be stored in brown glass bottles in a cupboard. The only problem I have ever experienced was unexplained Pyrocat-HD failure one time, which seems to be something others have run into. For this reason, I switched to -HDC.

After mixing a batch of fresh developer stock, I do sacrifice some film to confirm proper developer action, just in case.

 

[Pixophrenic]

So depending on the purity of the sulfite which may be suspect for the reasons you give but will be unknown to the user the dev time for D23 varies as does its speed

If my conclusion from your above quote is correct, what might be the range of speed and dev times encountered

Can I also ask whether you found this to be case in your use of D23 and what might be the frequency of the problems, assuming such problems arise

Are these problems with purity true of all home-made developers and if not which home made developers are free of these defects?

Thanks

pentaxuser

The fact that sulfite quality may be variable is known since the beginning of the 20th century. The first mention known to me comes from a book of Baron von Huebl “Development of plates with uncertain exposure” of 1919.

And yes, I saw the problem as soon as I made D76 from scratch and compared it to the commercial one. To give you an example, when I make D76 from scratch, using sulfite from any of the two commercial sources available where I live, I do not need to use borax, because the pH would already be 8.5 and the development time taken from a published table will be correct. With D23 I actually had to add sodium metabisulfite to reach the rated pH of 8-8.2, because otherwise I did not get the expected softness and smaller grain. Actually, now for one shot use I prepare Windisch formula, which is roughly D23 diluted with 2 parts of water, pH 7.9-8.0 and develop for 10 minutes at 80 F. If I do not observe the pH, I am certain to get a systematic overdevelopment, which is not fatal, of course, but depending on the film and the subject matter, the results may be less than ideal, mostly “discrimination of highlights” will be affected.

Finally, IMO all strictly metol-sulfite developers (that is without additional alkali) are strongly sulfite quality-dependent, because metol has a relatively steep pH dependence of speed between 8 and 9. With commercial D76 one will get a paradox that with only 20% more metol the development time drops, while common logic suggests that with more developing agent you should get a faster developer. I observed this problem with all developers that contain metol as the main agent in high sulfite, for example Edwal 12, which if not adjusted to pH 7.5 as its author recommends, is a completely different developer. Quite often I was puzzled having found a metol developer without pH listed, because it would be a different beast depending on what pH were set. One such example is the Paul Farber developer, which I voluntarily adjusted to pH 8.8 (to inhibit pyrogallol as a developing agent), but I have no way of knowing if this was the original intention. I hope this rather lengthy explanation helps.