Lith developer formulation question

Tyndall Bruce

A
Tyndall Bruce

  • 0
  • 0
  • 22
TEXTURES

A
TEXTURES

  • 4
  • 0
  • 47
Small Craft Club

A
Small Craft Club

  • 2
  • 0
  • 46
RED FILTER

A
RED FILTER

  • 1
  • 0
  • 37
The Small Craft Club

A
The Small Craft Club

  • 3
  • 0
  • 43

Recent Classifieds

Forum statistics

Threads
198,902
Messages
2,782,769
Members
99,742
Latest member
stephenswood
Recent bookmarks
2
Joined
Apr 14, 2016
Messages
814
Location
Bavaria, Germany
Format
Medium Format
If the 2 g/l free sulfite level is generally accepted

Literature quotes these 2 g/l (e.g Haist and others), but it all seems to track back to the same primary source (which I have not been able to locate - if anybody has it available, I would be very interested).

In my opinion it is important to note, that these 2 g/l relate to the development of LITH FILM in mostly undiluted developers to achieve a high Dmax (for Lith. film this would be around >4). I doubt this can be applied 1:1 to paper lith development, but who knows ...

In my personal experience you can add a lot more sulfite than 2 g/l, but it affects the image & colours you get, and the lith effect is a little slower with more sulfite present. So the snatch point becomes more of a snatch period, but actually I like that.
 

Gerald C Koch

Member
Joined
Jul 12, 2010
Messages
8,131
Location
Southern USA
Format
Multi Format
In order to have infectious development the sulfite content of the developer must be kept to a very low level. Traditionally this is accomplished by the reaction between formaldehyde and the sulfite ion to form the formaldehyde sulfoxylate ion. The sulfoxylate provides a source of sulfite ions as needed while the actual level remains very lower. In place of formaldehyde acetone can also be used. Trying to formulate a high contrast infectious developer without using either of these two chemicals is a bit like trying to make an omelet without eggs.

In place of formaldehyde in the form of formalin, a solution of formaldehyde gas in water, paraformaldehyde can also be used. Paraformaldehyde is a linear polymer of formaldehyde and is a white powder. It is used in many high contrast developers to replace the problematic formaldehyde.
 
Last edited:

Rudeofus

Member
Joined
Aug 13, 2009
Messages
5,081
Location
EU
Format
Medium Format
I have read on many occasions, that Formaldehyde is a fogging agent. Why doesn't it fog film or paper in a lith developer?
 

Gerald C Koch

Member
Joined
Jul 12, 2010
Messages
8,131
Location
Southern USA
Format
Multi Format
I have read on many occasions, that Formaldehyde is a fogging agent. Why doesn't it fog film or paper in a lith developer?

I have never heard this but considering that formaldehyde is a very reactive chemical would not be surprised. However the presence of the sulfoxylate adduct in these developers not only keeps the level of sulfite very low but also the amount of free formaldehyde very low.
 

Rudeofus

Member
Joined
Aug 13, 2009
Messages
5,081
Location
EU
Format
Medium Format
I have never heard this but considering that formaldehyde is a very reactive chemical would not be surprised. However the presence of the sulfoxylate adduct in these developers not only keeps the level of sulfite very low but also the amount of free formaldehyde very low.
This patent states, that fogging induced by Fomaldehyde was well known many decades ago. It would have been very attractive as hardener in developers back then, and given how willingly med school students exposed themselves to Formaldehyde back then, its toxicity would not have been much of a concern.

Formation of sulfoxylal adduct apparently didn't save the situation in developers, and sulfite was amply present in all developers back then. Someone else stated here in this thread, that about 3% of sulfite and Formaldehyde stays in solution unbound.
 
Joined
Apr 14, 2016
Messages
814
Location
Bavaria, Germany
Format
Medium Format
In place of formaldehyde acetone can also be used. Trying to formulate a high contrast infectious developer without using either of these two chemicals is a bit like trying to make an omelet without eggs.

Given Formaldehyde's unpleasant smell I assume that both venues have been researched in the past, with nothing much to show.

I don´t know. There are at least three commercial products available which do not rely on formaldehyde/acetone:

-> Moersch Easylith (https://www.fotoimpex.de/shop/images/products/media/10445_2_MSDS_DE.pdf)
-> Moersch SE5 Lith (https://www.fotoimpex.de/shop/images/products/media/11390_2_MSDS_DE.pdf)
-> LP Superlith [also known as Rollei / Compard Superlith] (http://www.maco-photo.de/files/images/SIDA_LP-Superlith_en.pdf)

I was not able to find any MSDS of Rollei Lith, but according to the markings on the product itself, there should not be any formaldehyde/acetone either (I also do not know if this is a separate product or just rebranded LP/Compard/Rollei Superlith in a different container).

About the possible sulfite level: I have tested my own brew with up to 11 g/l and Tim Rudman has published a formula (originally by Kate Mokac) in "The World of Lith Printing" containing containing 12 g/l.

I would not focus too much on the 2 g/l which were researched under particular and probably non-aplicable circumstances and at least twenty years before anybody thought about lith development of papers in trays.

And have you never asked yourself why 2 g/l independent of the HQ level? If you go to Grant Haist´s book - chapter 11 - the referenced developer contains only 2,5 g/l of HQ. For this HQ level, 2 g/l of sulfite seem very plausible to affect the developer´s properties. But you can easily build a lith developer containing 10 g/l HQ - or even more. Why should the critical sulfite level not rise?
 

Rudeofus

Member
Joined
Aug 13, 2009
Messages
5,081
Location
EU
Format
Medium Format
The MSDS indeed mention no Acetone or Formaldehyde, but they don't mention any substituent either. Makes me wonder whether these are indeed just HQ, alkali and in the case of SE5 an extra bottle with sulfite/bisulfite. No idea what working solution shelf life of such a concoction would be. I have done one experiment myself with HQ+NaOH in a tray, and you could literally watch this liquid go dark.

About sulfite levels: I have a "Kodak D-52 Selectol" formula here with (among other stuff) 6 g/l HQ and 23 g/l Sodium Sulfite. Since this is anything but a lith developer, I would conclude that 23 g/l effectively prevents infectious development. Whether the upper sulfite limit lies at 2 g/l or at 22.9 g/l, we'll probably won't find that in literature, and there won't exist a static upper sulfite level limit anyways. This is likely not only dependent on HQ levels, but on HQ activity levels. As HQ is oxidized by developable silver halide, it is either fully scavenged by sulfite or it isn't. The "isn't" case is typical for lith development, and which one takes place, depends on pH, HQ levels, diffusion speed, presence of other silver solvents and emulsion type.
 
Joined
Apr 14, 2016
Messages
814
Location
Bavaria, Germany
Format
Medium Format
The MSDS indeed mention no Acetone or Formaldehyde, but they don't mention any substituent either.

The MSDS only needs to mentions hazmats. As sulfite (at least in Germany) in not a hazmat but actually a food additive (E221) and also sodiumbromide is not considered a hazmateither, both are not mentioned in the MSDS. Nevertheless, sulfite is part of the Moersch Lith B solutions as the MSDS states that burning the part B will release sulphur dioxide.

The MSDS mentions a solid content of 59% out of which 30%-40% is carbonate. This leaves a 19%-29% of solids which are not hazmat, which certainly limits the available choices. There is sulfite, there should be a little bromide, maybe there is some ascorbic acid, but we can only guess.
 

Bob Carnie

Subscriber
Joined
Apr 18, 2004
Messages
7,735
Location
toronto
Format
Med. Format RF
I have used Nova Lith A B - Fotospeed LD20 A B - and Moresch A B lith developers with great success and would be happy with all of them.

Aristo Lith was not working in my darkroom.

Do any of these scratch mixes compare to the top three I listed??
 

Rudeofus

Member
Joined
Aug 13, 2009
Messages
5,081
Location
EU
Format
Medium Format
The MSDS only needs to mentions hazmats. As sulfite (at least in Germany) in not a hazmat but actually a food additive (E221) and also sodiumbromide is not considered a hazmateither, both are not mentioned in the MSDS. Nevertheless, sulfite is part of the Moersch Lith B solutions as the MSDS states that burning the part B will release sulphur dioxide.
I would hazard a guess that many sulfur containing compounds would release SO2 when burned, And the MSDS for part C does mention sulfite, so they have no reason to keep it secret in part B MSDS.

The MSDS mentions a solid content of 59% out of which 30%-40% is carbonate. This leaves a 19%-29% of solids which are not hazmat, which certainly limits the available choices. There is sulfite, there should be a little bromide, maybe there is some ascorbic acid, but we can only guess.
I don't think that Ascorbate would survive very long in such an alkaline liquid. Since Moersch went through the whole effort of decoupling alkali from sulfite containing concentrate, I would be very surprised if they suddenly had close to 20% sulfite in their concentrate B. Not that I could point out an alternative explanation ...
 
Joined
Apr 14, 2016
Messages
814
Location
Bavaria, Germany
Format
Medium Format
I would hazard a guess that many sulfur containing compounds would release SO2 when burned

I totally agree, yet per MSDS there are no other substanes in the B part containing sulphur (I think we also need to distinguish between the SE5 Lith and the Easylith - the Easylith B should have sulfite).

I don't think that Ascorbate would survive very long in such an alkaline liquid.

It was just a wild guess. But the ascorbate should survive as Wolfgang Moersch offers an ascorbate/phenidone based developer (Moersch SE3 Cold).

Since Moersch went through the whole effort of decoupling alkali from sulfite containing concentrate, I would be very surprised if they suddenly had close to 20% sulfite in their concentrate B.

Decoupling: I have tried to keep lith developer working solution (some would say a concentrate: Easylith 1A+1B+8H2O) overnight in a glass bottle with Tetenal Protectan. Several times, I poured a clear liquid - no brown colour - in the bottle which had only been used for a few prints (dev. time of the last print around 3 min) and it came out clear and no trace of brown, so there should not have been significant aerial oxidisation. Nevertheless, after 24-48 hours of storage, the developer had become inactive and useless. So I guess the decoupling between A and B is necessary to avoid some kind reaction bewween the ingredients. Decoupling the sulfite in the SE5 Lith kit permits the advanced and experienced user to exactly tweak the developer to the paper and desired image (e.g. sulfite in parts controls the graininess). Nevertheless, the Easylith B should contain some sulfite, as there is no "C"-part for the Easylith.
 

Gerald C Koch

Member
Joined
Jul 12, 2010
Messages
8,131
Location
Southern USA
Format
Multi Format
To fling another shoe into the works you must use hydroquinone as the developing agent. AFAIK this is the only developing agent that undergoes infectious development. So you cannot use ascorbic acid in any form.

The famous portraitist G Paul Bishop used acetone in his developer to create a source of hydroxide ions. So yes acetone will also work.
 
Last edited:

Gerald C Koch

Member
Joined
Jul 12, 2010
Messages
8,131
Location
Southern USA
Format
Multi Format
I've been trying to develop a decent lith developer with mixed success. I've figured out the right balance between hydroquinone, sod. sulfite, and KBr for me. I'm using saturated Pot. carbonate as the alkali. I'm basically not happy with the developer life both on the shelf and in the tray. With help, I figured out I want the Part A to have a pH of 4.....what is the best acid to achieve that? Regarding the tray life, is there anything other than sodium sulfite that would serve as an anti-oxidant? Thought about ascorbic acid, but it seems that adding a developing agent would be a bad idea.
Anyway any insight from the chemists out there would be greatly appreciated.

Before you run off and waste a lot of time, effort and chemicals read up on all you can get on the theory of lith printing.
 

Gerald C Koch

Member
Joined
Jul 12, 2010
Messages
8,131
Location
Southern USA
Format
Multi Format
Thanks. Sulphite levels need to be low, no doubt. But I would assume that "low" in this context in relative to the HQ level and depending to a certain extent on bromide level and exposure times, too.

I was just curious where the max. 2g/litre are originating. Grant Haist is an excellent source (unfortunately I have not been able to buy a copy), but Tim Rudman quotes a lith developer recipe (The World of Lith Printing, page 150 second paragraph) "My single-solution lith developer recipe" by Kate Mokac containing 60g sodiumsulfite / liter to be diluted 1:5, i.e. 12 grams / liter of working solution.



Actually I have already tried it, and I can get excellent results with way higher levels than 2 grams / litre of working solution.

Yes the concentration level of sulfite in a working developer should be from one to two geams per liter.
 

Rudeofus

Member
Joined
Aug 13, 2009
Messages
5,081
Location
EU
Format
Medium Format
Yes the concentration level of sulfite in a working developer should be from one to two geams per liter.
Is this something you can confirm from personal experimentation, or just from some literature reference?
 

Rudeofus

Member
Joined
Aug 13, 2009
Messages
5,081
Location
EU
Format
Medium Format
The famous portraitist G Paul Bishop used acetone in his developer to create a source of hydroxide ions. So yes acetone will also work.
It is well known, that Acetone will work, but it binds to sulfite much more weakly than Formaldehyde. As a result, Acetone Sulfite adduct will have more free sulfite in solution than Formaldehyde Sulfite adduct, and if the amount of free sulfite has an upper ceiling for proper lith action, less Acetone Sulfite adduct can be added. Shelf life will be less as a result.
 
OP
OP
Mark Fisher

Mark Fisher

Member
Joined
Dec 13, 2003
Messages
1,691
Location
Chicago
Format
Medium Format
Before you run off and waste a lot of time, effort and chemicals read up on all you can get on the theory of lith printing.
Thanks. I have a fair understanding (at least as much at Tim Rudman's book could teach me)....at least the infecteous development equations. My effort will be based from existing formulas, MSDS sheets/ingredients list of commercial developers, and any patents I can dig up. I don't want to plow ground that people have already plowed, but I do have minimal chemistry knowledge. I hope to limit the sodium sulfite/metabisulfite to a minimum through other chemicals that may reduce aerial oxidation by some other means. We'll see. It may be a dead end, but I'm a fairly dedicated lith printer and I've spent my entire career developing products. Hopefully, I can make up for my lack of deep photochemistry knowledge. BTW - I have a stupid amount of photochemicals already as I like to mix my own where it makes sense.
 

Gerald C Koch

Member
Joined
Jul 12, 2010
Messages
8,131
Location
Southern USA
Format
Multi Format
Is this something you can confirm from personal experimentation, or just from some literature reference?

The limits that I quote are from various texts explaining infectious development.
 
Last edited:
Joined
Apr 14, 2016
Messages
814
Location
Bavaria, Germany
Format
Medium Format
To fling another shoe into the works you must use hydroquinone as the developing agent. AFAIK this is the only developing agent that undergoes infectious development.

On a practical level you are right, HQ is the only substance researched and easily available.

On an academic level, this would be very interesting to look into. I have literature indicating that various configurations of Chloro-/Bromo-/Sulfo-HQ derivates eagerly form semiquinones. So other substances could be suitable, too.
 

Gerald C Koch

Member
Joined
Jul 12, 2010
Messages
8,131
Location
Southern USA
Format
Multi Format
Remember that ascorbic acid and its derivatives are also developers and that its incorporation in a lith developer would likely screw it up.
 
Joined
Mar 18, 2005
Messages
451
Location
Toronto
Format
Medium Format
Regarding the use of ascorbic acid in lith developers, Patrick Gainer made a few mentions of it:

https://www.photo.net/discuss/threads/vitamin-enriched-d-23.19471/

http://unblinkingeye.com/Articles/VitC/vitc.html (about 3/4 of the way down in the paper developer portion of the article)
I tried applying this information in 2015, and did get infectious development. Dmax was dissapointing, and contrast was not as high as I could get with commercial developers like LD20. So it worked, but not well - I think there is a way to strike the right balance though. If it could extend tray life and not interfere with infectious development, it would be worth pursuing.

The formula for Pako Lith Developer (Published in Haist's Modern Photographic Processing, and other places) calls for ascorbic acid.

Also in Modern Photographic Processing, Haist write that "Ascorbic acid has been detected in commercial lith developers for some years and has recently been patented as the antioxidant". He gives a simple formula of:

3g sodium sulfite
3g ascorbic acid
12g hydroquinone
2.6g potassium bromide
and sufficient sodium carbonate monohydrate to give a pH of 10.05
in 1000ml water​
 
Joined
Apr 14, 2016
Messages
814
Location
Bavaria, Germany
Format
Medium Format
The information from Patrick Gainer is quite interesting. So ascorbic acid is not super-additive with HQ (I have another source in literature confirming that, but unfortunately it is quite old) and if you do not push the pH too far, it will not show significant developer activity. This should be useful.

I will give the formula quoted by Marco a try soon and maybe test some variations. But I first have to make the prints for the BPX26 :smile:.
 

grainyvision

Subscriber
Joined
Feb 19, 2018
Messages
695
Location
Denver, Colorado
Format
Multi Format
I referenced this thread a lot in devising my own lith printing formula. It seems to work well with reasonable tray life, but unfortunately short shelf life. The sulfite in my acidic part A works a bit too well and turns into mildly pressurized sulfur dioxide. The developer works great with no change in color over several months, but the sulfite ratio is wrong and inconsistent over time. ie, initially you need to add no sulfite. Later you need to add 0.2-0.8g depending on how old the part A is.

The developer is named ModernLithEZ. Instructions below (numbers in [] brackets are for doubling, for my own reference)

Part A:
Start with 80ml[160] of hot distilled water (distilled water is absolutely necessary here!)
1ml[2] triethanolamine 99% grade
0.1g[0.2] salicylic acid
5g[10] sodium sulfite
1g[2] boric acid
10g[20] ascorbic acid
11g[22] hydroquinone (not all will dissolve)
Top to 200ml[400] with hot propylene glycol
This may require some heating to dissolve all of the hydroquinone

Part B:
Start with 140ml[280] of cold or room temperature distilled water
10ml[20] triethanolamine 99%
8g[16] sodium hydroxide — DANGER
1.2g[2.4] potassium bromide
100g[200] potassium carbonate, anhydrous — DANGER
Top to 200ml[400] with cold distilled water. The solution should clear up significantly.

Part C — A simple 1% solution of polyethylene glycol 3350
200ml of water
2g of PEG-3350 (sourced in the US as “MiraLax”)

Part D (optional) — A simple 5% potassium bromide solution
100ml water
5g potassium bromide

Usage: Start with 30ml of part A added to 900ml of water, followed by 30ml of part B and 1ml of part C. Top to 1L with water. Ratios can be adjusted wildly to tune results and to optimize for different papers. Use as a lith developer, with over exposure of 2 stops or more to vary contrast, and pulling the print when it looks right.​

This formula is an especially difficult challenge as my goal is not just to make a reasonable homebrew lith developer without formaldehyde yet having good tray and shelf life, but to also allow this developer to work on modern materials. The key factors I've learned is that the ratio amount of bromide to other components must be fairly low. Modern materials, especially RC papers, seem to suffer from the "lith bromide bleaching" effect. This is an effect where bromide+hydroquinone in low sulfite solution can actually render latent image centers undevelopable, meaning even with re-exposure it will not develop. I've observed this effect many times in figuring out these formulations. The effect is time and bromide sensitive... so, if the developer is too slow the effect can happen as well. It's a very difficult one to figure out... Regardless, as-is, this formula works for decent tray life when fresh. It doesn't work perfectly with as many papers as I'd like (Ilford MGFB and Adox FB papers give weird "pepper balls") but it works with a decent subset of them.

Months later, I'm now looking at a refresh of this formula to simplify it and try to figure out a method of flattening this sulfite "evaporation" problem. The part A obviously is a bit too acidic but would benefit from a bit more sulfite. I'd like to exclude hydroxide and TEA from part B, considering if I should move the bromide from part B to part A, etc.

Specific notes in this formulation that should be inspiring regardless:

* propylene glycol isn't "necessary" here, most manufacturers use diethyl glycol as it's cheaper. Neither seem to be photo active. The key benefit is propylene glycol will have less oxygen solubility than water, and hydroquinone is more soluble in it than water
* Boric acid was used on the recommendation in this thread, to prevent fog. I'm not 100% sure it's actually beneficial here.
* The part C is the real key innovation here. I believe it can be added in small amounts to nearly any homebrew developer to cure the "homebrew lith" look that causes LD20 and similar developers to give strikingly different results from any homebrew lith developer.
* The TEA is used here in part A because it is a chelating agent, same for salycilic acid. It should preserve the ascorbic acid (though it seems sulfur dioxide will destructively preserve ascorbic acid too)
* The TEA is used in part B in a higher amount to boost alkalinity slightly forming a weak buffer. It also potentially gives warmer results by being a silver solvent, and it is a preservative. It does react with hydroquinone oxidation products in some non-determined way. A TEA+hydroquinone+water mixture without sulfite will be transformed upon standing several hours into a normal contrast print developer upon adding carbonate. I've seen absolutely no research of this reaction and haven't studied it much though
* I'd prefer to avoid hydroxide for both safety and stability reasons in the part B. It was used because I was nearing the solubility limits on carbonate for neutralizing the ascorbic acid, and either way this much carbonate becomes a bit expensive
* The ascorbic acid is confirmed to act as a good preservative for hydroquinone. It becomes active in a way resembling weaker hydroquinone above pH 12
* For modern materials specifically, low sulfite and low bromide amount seems to be the key, but also slightly higher alkalinity. Very much sulfite at all gives obvious differences to dmax on RC papers

That being said, anyone on this thread have any ideas for this formula?

Studying the EasyLith MSDS, it is surprisingly sparse. Key things I think:

* Sulfite is in both part A and B (notice "burning emits sulfur dioxide" warning, typical of sulfite containing solutions)
* Boric acid I believe is a poison and thus must be listed on an MSDS, but it is not listed in either part A nor B. Borax is also not listed. Apparently this effect was not important for EasyLith
* A non-toxic preservative, like ascorbic acid is likely in part A. There is no indication of how the pH of 5.5 is reached, nor how the ascorbic acid is kept stable if that is the case. Maybe there is some non-toxic but more stable cousin to ascorbic acid used here?
* The carbonate in part B is only up to 40%. This rules out using a significant amount of ascorbic acid, unless they balanced it out with ascorbate and/or partially neutralized the acid. Otherwise 40% solution added in equal ratios would likely not bring pH up enough
 

Rudeofus

Member
Joined
Aug 13, 2009
Messages
5,081
Location
EU
Format
Medium Format
This is really great, and I will try to get this Polyethylene Glycol 3350 compound.

About this part B: it contains lots of Potassium Carbonate, and I wondered, whether you need that much to obtain strong buffering, or just to raise pH. If you just want to raise pH, then you might want to consider Trisodium Phosphate, which reaches higher pH than carbonates, but is more mundane than hydroxides.

PS: Many developers use Sodium Ascorbate or Sodium Isoascorbate and thereby avoid explicit addition of hydroxides or other strong alkalis.
 
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