New HC-110 Formula

[alanrockwood]

If we abstact of the nuances of formulation, it seems to me that there is nothing supernatural in the HC-110. In my humble opinion, this is a completely ordinary phenidone-hydroquinone developer, concentrated on an anhydrous basis. Its fundamental difference from many other concentrates based on organic base and solvents - is the use of the sulfur complex (IV) of diethanolamine (DEA-SO2) ... Which acts as a source of sulfite ions (apparently not only this function, possibly more - silver solvent and part of pH regulator).
Naturally, this is the main problem in the preparation of such a concentrate at home, since it is not easy to obtain DEA-SO2. But it is quite possible. Bubbling DEA with sulfur dioxide, obtained from sulfite treated with concentrated acid (H2SO4), could probably give an acceptable result.
Naturally, it will be necessary to find out the equivalent ratios of replacing ordinary sodium sulfite with such a DEA complex, but this is apparently a matter of experimentation. As well as the regulation pH of solutions.
Unfortunately, in my country it is quite difficult to obtain DEA for personal experiments (and TEA is not suitable, since it has a much lower ability to form a complex with sulfur dioxide - almost three times) and I can't check these my assumptions.

Thanks for the informative post. Do you have any references on the solubility of SO2 in DEA and TEA? I am interested in reading more.

Also, I wonder if the solubility of SO2 in TEA might actually be high enough.

 

[Alan Johnson]

I recall that an approximation to the original version of HC110 was published in the film developing cookbook, as mentioned here:
http://www.covingtoninnovations.com/hc110/
The solvent action came from the DEA-sulfur dioxide complex, but making that is an industrial process as DEA is very hazardous.

 

[bnxvs]

Thanks for the informative post. Do you have any references on the solubility of SO2 in DEA and TEA? I am interested in reading more.
Also, I wonder if the solubility of SO2 in TEA might actually be high enough.

Unfortunately, I have not seen such information in English. All I could find on this topic was an article in Russian (http://heraldchem.onu.edu.ua/article/download/79510/79461). It contains very indirect data, but it’s at least some “fulcrum” in a further search.
Maybe I’m wrong, but I believe that the data indicated in the MSDS just show the approximate ratio of DEA and sulfur dioxide (that is, the content of sulfur dioxide in the complex).

I recall that an approximation to the original version of HC110 was published in the film developing cookbook, as mentioned here:
http://www.covingtoninnovations.com/hc110/
The solvent action came from the DEA-sulfur dioxide complex, but making that is an industrial process as DEA is very hazardous.

The process, in principle, is not so dangerous if carried out at home lab using good ventilation and personal protective equipment. The DEA itself is no more dangerous than the often used TEA. And sulfur dioxide is certainly poisonous, but in high concentrations. If you don't sniff a flask with reagents and do not carry out reactions in a locked toilet room, I think nothing bad will happen. )))
Naturally, I highly recommend DO NOT doing this without basic chemical protection skills.

p.s. I also do not understand very well, why the catechol was introduced into the composition. This is the dihydroxybenzene isomer (as well as hydroquinone), but more active. Moreover, its quantity is very small. In my opinion, this can be explained (presumably) by the following reasons:
1) there is a certain super-additive relationship in the composition of these three developing agents
2) catechol is introduced to compensate for the oxidation of phenidone in order to maintain an equilibrium ratio of phenidone and hydroquinone
I would be grateful for your opinion on this matter.

 

[mohmad khatab]

Unfortunately, I have not seen such information in English. All I could find on this topic was an article in Russian (http://heraldchem.onu.edu.ua/article/download/79510/79461). It contains very indirect data, but it’s at least some “fulcrum” in a further search.


The process, in principle, is not so dangerous if carried out at home lab using good ventilation and personal protective equipment. The DEA itself is no more dangerous than the often used TEA. And sulfur dioxide is certainly poisonous, but in high concentrations. If you don't sniff a flask with reagents and do not carry out reactions in a locked toilet room, I think nothing bad will happen. )))
Naturally, I highly recommend DO NOT doing this without basic chemical protection skills.

The only solution is to turn to God to make Sister Olga agree to help me again by translating that document.
- There is nothing wrong ,
I will talk to Mr. Olga, who is a Russian woman, her father was one of the Russian chemists and they had the oldest photographic laboratory in the heart of Moscow, and her great father was preparing all formulas from scratch, where he considered that buying any pre-made developer is considered as A scientific insult to him and to the Soviet people (at that time).
After this great man died, Olga got married and traveled to work with her husband and currently resides in the United Arab Emirates.

It helped me translate some Russian documents.
I will ask her again, you may agree to help me.

 

[bnxvs]

In addition to the general cognitive value of this article, only one paragraph is of interest (p. 16, last paragraph), which refers to the stability constants of complexes with sulfur dioxide in ethanol solutions of ethanolamines. And there is a link to interesting material on this issue (article in a Ukrainian magazine), but, unfortunately, I have not been able to find it in the public domain so far. Perhaps for this I'll have to make a separate order in the technical libraries of Ukraine, since the article is in Ukrainian (I understand this language a little).

"According to UV spectroscopy, complexes of the composition SO2 · Н3-nN (CH2CH2OH) n are realized in ethanol solutions of ethanolamines. The stability constants of these compounds are numerically equal to (2.10 ± 0.30) * 10 ^ -3, (2.34 ± 0.60) * 10 ^ -3 and (0.78 ± 0.13) * 10 ^ -3 for mono-, di- and triethanolamine, respectively. The calculated values of the stability constants are consistent with the pKa of ethanolamines in ethanol"

 

[Alan Johnson]

https://books.google.co.uk/books?id=qUZnDwAAQBAJ&pg=PR37&lpg=PR37&dq=iminodiethanol+sulfur+dioxide&source=bl&ots=Pz1wiugi8q&sig=ACfU3U2Ul_lNCtYX9S-uWO8EkHx1eU7-uA&hl=en&sa=X&ved=2ahUKEwjU84-DjNLoAhWgR0EAHTwCDSoQ6AEwC3oECA0QKQ#v=onepage&q=iminodiethanol sulfur dioxide&f=false
Approx formula of original HC-110. IDK at what temperature iminodiethanol (DEA) is reacted with SO2, re safety.

 

[MattKing]

Maybe I’m wrong, but I believe that the data indicated in the MSDS just show the approximate ratio of DEA and sulfur dioxide (that is, the content of sulfur dioxide in the complex).

I believe that is the old version of HC-110.
Here is the link to the new US MSDS:
http://sds.kodakalaris.com/temp/SDS US English - KODAK HC-110 Developer.pdf?t=637217224470487176

 

[bnxvs]

I believe that is the old version of HC-110.
Here is the link to the new US MSDS:
http://sds.kodakalaris.com/temp/SDS US English - KODAK HC-110 Developer.pdf?t=637217224470487176

Thanks. I'll update my archive. But I don't see a fundamental difference. Base is the same - three developing agents, the organic forms of sulfite and bromide, plus additives.
But the old, original form that Alan Johnson mentioned was different. There is no catechol in it.

IDK at what temperature iminodiethanol (DEA) is reacted with SO2, re safety.

In those sources that I managed to find, there are no recommendations on the temperature regime. As I understand it, the adsorption of SO2 and hydrogen sulfide occurs in amines at a natural ambient temperature. This technology is quite widely used in the processing of hydrocarbons, etc. When quarantine ends, I will try to consult with chemical engineers on this issue.

 

[bnxvs]

This is what one chemist answered me about the technology for producing the DEA-SO2 complex:

Such a solution can be obtained by passing a small excess of SO2 through a suspended solution of DEA in water, or another solvent***. The excess SO2 is then removed by heating. If the solvent is carefully evaporated (in vacuum) to the end, then you can get a free complex, however, being 1: 1, it does not have a crystalline form, but is a yellow oily liquid.

*** - I think - e.g. ethanol, toluene, benzene

 

[BradS]

.....But I don't see a fundamental difference. Base is the same - three developing agents, the organic forms of sulfite and bromide, plus additives...

And Kodak has repeatedly said there is no practical difference between this new concoction and its predecessor.

 

[mohmad khatab]

This is the formula based on the link sent by the master. With the previous post

In addition to the general cognitive value of this article, only one paragraph is of interest (p. 16, last paragraph), which refers to the stability constants of complexes with sulfur dioxide in ethanol solutions of ethanolamines. And there is a link to interesting material on this issue (article in a Ukrainian magazine), but, unfortunately, I have not been able to find it in the public domain so far. Perhaps for this I'll have to make a separate order in the technical libraries of Ukraine, since the article is in Ukrainian (I understand this language a little).

The research study is in the library of the University of Odessa, Ukraine ,, (Faculty of Physical Chemistry),
We have some friends who live in Odessa. Maybe someone can help us, go to that library on its own and copy those scientific papers.
The translation of the entire file is a very exhausting issue. Mr. Olga almost seemed to apologize for the translation of this study, but she said if I specify one page, which is more important, it can be accomplished.
Yes, she is a woman who works as an employee and she has family and children.

 

[Pixophrenic]

I don't see anything there that would produce the "syrup" consistency of HC-110. I've been a user of this Kodak elixir for many years, and believe me, i wish the formula were public, because Kodak can change it without warning, and someday they may even quit making it entirely.

Fortunately, I can still make D-23, D-72, and D-76 from ingredients (and the replenishers for D-23 and D-76), and if I want long-lasting syrup, I can go dig up the formula for PC-TEA -- Phenidone, Vitamin C, and triethanolamine, just those three ingredients. Most of the time, though, for film I'll just use Parodinal (made from acetaminophen, aka paracetamol) -- if I can find lye again locally.

AFAIK, the syrupy appearance of HC-110 is due to the presence of polyvinylpyrrolidone, which can be sometimes found as a jellylike precipitate at the bottom of old HC-110 packages. Apparently, it has no effect on development speed. The true originality of HC-110 formula was to get rid of water entirely, but for practical reasons 30% potassium sulfite also makes a concentrated developer with a very long shelf life. My HC-110 also clearly contains some catechol, most likely as an additional preservation agent. I think what the original user is trying to say that it is possible to compose an active phenidone-hydroquinone developer which will come very close, imagewise, to HC-110.

 

[Raghu Kuvempunagar]

AFAIK, the syrupy appearance of HC-110 is due to the presence of polyvinylpyrrolidone, which can be sometimes found as a jellylike precipitate at the bottom of old HC-110 packages.

Is the developer discussed in this patent HC-110?
https://patentimages.storage.googleapis.com/45/c6/25/25d6b6bd1d9126/US3552969.pdf

A liquid developer concentrate is prepared by mixing about 20 C the following components:
2,2'-iminodiethanol-sulfur dioxide addition product -------------------------------------- 31.0
2,2'-iminodiethanol --------------------------- 9.0
2,2'-iminodiethanol hydrobromide -------------- 1.5
1-phenyl-3-pyrazolidone ----------------------- 0.5
Hydroquinone ------------------------------- 6.0
2-aminoethanol ------------------------------ 5.0
Ethylene glycol ------------------------------ 10.0
0.25 gram of polyvinylpyrrolidone (PVP Grade K-15, a commercial product of General Aniline and Film Corporation, New York, N.Y.) having a molecular weight of about 10,000 is dissolved in each liter of the resulting mixture. One part by volume of the mixture is diluted with 31 parts by volume of water at about 20° C.

 

[Donald Qualls]

Hmm. General Aniline and Film Corporation -- GAF, right? Didn't they fold a while back?

Ethylene glycol is pretty syrupy, but I guess 10% by weight might not be enough to fully account for the viscosity. I wouldn't think a quarter gram per liter of anything could do so, however.

 

[cmacd123]

Hmm. General Aniline and Film Corporation -- GAF, right? Didn't they fold a while back?
.

NO, they make shingles for houses these days.

 

[Raghu Kuvempunagar]

Hmm. General Aniline and Film Corporation -- GAF, right? Didn't they fold a while back?

The patent is from early 70's.

I wouldn't think a quarter gram per liter of anything could do so, however.

Polyvinylpyrrolidone was used primarily for dealing with dichroic fog according to the patent. Viscosity of HC-110 is probably due to dieathanolamine & addition products used in the formula.

 

[Wayne]

decades

 

[MattKing]

Does anyone know how long the shelf life of unopened HC-110 is? Thank you.

decades

True - for the old stuff.
As for the brand new, recently revised, manufacture has been moved back to the USA version - the answer is unclear, but probably not nearly as long.

 

[Wayne]

True - for the old stuff.
As for the brand new, recently revised, manufacture has been moved back to the USA version - the answer is unclear, but probably not nearly as long.

Right. I'm referring to the old stuff cuz that's the only stuff old enough to have sat around unopened. ;-) I'm a newcomer to this thread and haven't read it all, but is there any reason in the formula change to expect much shorter life?

 

[MattKing]

is there any reason in the formula change to expect much shorter life?

Yes - see bill troop's post (yes, that bill troop) from August 14, 2019 - it shows as post #26 in the thread for me.
EDIT: Photo Engineer (Ron Mowrey) posted something similar about eleven posts later.

 

[Wayne]

Yes - see bill troop's post (yes, that bill troop) from August 14, 2019 - it shows as post #26 in the thread for me.
EDIT: Photo Engineer (Ron Mowrey) posted something similar about eleven posts later.

Welp...that sucks.

 

[Donald Qualls]

It could be worse -- at least Neo-HC-110 works like the old, same dilutions and, as far as I've heard, same characteristics. It's just that now, there's no reason to prefer HC-110 over Ilfotec HC or Legacy L110 or whatever over work-alike is out there (and considerable reason not to spend twice as much for the Kodak name).

 

[BradS]

Right now at Freestyle...
Kodak HC-110 : $35 / liter
Ilford Ilfotec HC : $65 / liter
LegacyPro L110 : $31.68 / liter

I'm happy to pay $3.32 extra (which is roughly 10% more, NOT twice as much) for the Kodak brand.

 

[BradS]

Why is Ilford nearly double the cost of kodak?

I'm a simple man of humble origin. I confess, I do not know.
Adam Smith would tell us that it has something to do with supply and demand.

 

[MattKing]

I'm a simple man of humble origin. I confess, I do not know.
Adam Smith would tell us that it has something to do with supply and demand.

And also might just reflect that the Kodak product is once again manufactured in the USA while the Ilford product is manufactured in Germany (I think).
And equally important, there may be a better distribution network happening now in the USA for the Kodak product once again manufactured in the USA - so much of the pricing complication comes from distribution, which isn't handled directly in North America by either Kodak Alaris or Harman Technology.

 

[37th Exposure]

Any reason Ilfotec HC won’t last? I don’t expect it to last forever but the latest Anchell/Troop Film Developing Cookbook says it is still close to the Kodak formula. I am sick of Kodak always changing the darn formula or something at the drop of a hat and bought Ilfotec this time despite the price. The bottle says original unopened bottles will keep indefinitely. I am willing to pay extra because Kodak is getting too flaky. At least Ilford has some sense of consistency.