New HC-110 Formula

[thebasementzone]

You will need a Bunsen flask, a large amount of toluene (or other volatile solvent). You will also need good ventilation as volatile solvent vapors are explosive and toxic.
It is possible to obtain a complex of sulfur dioxide in DEA by bubbling SO2 through a solution of DEA in toluene. After saturation of the solution with sulfur dioxide, it will be sufficient to remove the toluene with slight heating at low pressure.

p.s. And if you are interested in the "new" formula, then everything is simpler. In fact, the main difference between the old formula and the new one is the replacement of the sulfur dioxide complex in DEA with a saturated water solution of potassium sulfite (± 65%).
I would recommend you do a "new formula". It is simpler, safer, and doesn't require complex equipment.

The new formula would be what I would like to attempt. I need to figure out some space and equipment for processing. Is there anyone on here who has attempted creating the new formula?

 

[alanrockwood]

You will need a Bunsen flask, a large amount of toluene (or other volatile solvent). You will also need good ventilation as volatile solvent vapors are explosive and toxic.
It is possible to obtain a complex of sulfur dioxide in DEA by bubbling SO2 through a solution of DEA in toluene. After saturation of the solution with sulfur dioxide, it will be sufficient to remove the toluene with slight heating at low pressure.

p.s. And if you are interested in the "new" formula, then everything is simpler. In fact, the main difference between the old formula and the new one is the replacement of the sulfur dioxide complex in DEA with a saturated water solution of potassium sulfite (± 65%).
I would recommend you do a "new formula". It is simpler, safer, and doesn't require complex equipment.

Just a safety warning here, speaking as a professional chemist, a bunsen burner should never be used to heat volatile organic solvents like toluene. Use and electric heating mantle instead. A bunsen burner is too much of a fire hazard. (By the way, I said "professional chemist" which is true, although it has been many years since I used either a bunsen burner or a heating mantle. My specialty has been in another area that seldom uses those items, but the advice I gave is from my training in school.)

 

[Ernst-Jan]

speaking as a professional chemist, a bunsen burner should never be used to heat volatile organic solvents like toluene.

Well I am not a professional chemist, but just someone with common sense and I also think it is not the smartest idea to use fire to heat something like toluene. I think it is nasty stuff anyway (well I know it is componet of thinner, maybe other things make it nasty)

 

[bnxvs]

I don't know English very well, but how could I be understood in this sense - to heat DEA with toluene ??? If so, my apologies. The SO2 source will need to be heated !!! I hope you read a little chemistry textbooks before doing anything. It makes no sense to fully describe the production technology here, there is a mass of materials on the Internet on this issue.
p.s. I have successfully manufactured both the "old" and "new" versions of the DIY HC-110, but I am afraid that I will not be able to correctly describe the process in English, so that it is safe for you )))

UPD >> Wow, It's my mistake. I rely too much on auto-translator. And it replaced the term "Drexel bottle" with "Bunsen flask")))))) I don't understand how this happened. Perhaps this is how autocomplete worked, but I did not pay attention. Sorry guys! I hope no one has yet had time to set fire to their house ?!

 

[alanrockwood]

I don't know English very well, but how could I be understood in this sense - to heat DEA with toluene ??? If so, my apologies. The SO2 source will need to be heated !!! I hope you read a little chemistry textbooks before doing anything. It makes no sense to fully describe the production technology here, there is a mass of materials on the Internet on this issue.
p.s. I have successfully manufactured both the "old" and "new" versions of the DIY HC-110, but I am afraid that I will not be able to correctly describe the process in English, so that it is safe for you )))

UPD >> Wow, It's my mistake. I rely too much on auto-translator. And it replaced the term "Drexel bottle" with "Bunsen flask")))))) I don't understand how this happened. Perhaps this is how autocomplete worked, but I did not pay attention. Sorry guys! I hope no one has yet had time to set fire to their house ?!

Don't worry. No harm done.

 

[pentaxuser]

Don't worry. No harm done.

No and thank goodness I was covered completely by Direct Line Home insurance which I bought from that nice man Harvey something.He was always popping up on U.K. TV

pentaxuser

 

[thebasementzone]

I don't know English very well, but how could I be understood in this sense - to heat DEA with toluene ??? If so, my apologies. The SO2 source will need to be heated !!! I hope you read a little chemistry textbooks before doing anything. It makes no sense to fully describe the production technology here, there is a mass of materials on the Internet on this issue.
p.s. I have successfully manufactured both the "old" and "new" versions of the DIY HC-110, but I am afraid that I will not be able to correctly describe the process in English, so that it is safe for you )))

UPD >> Wow, It's my mistake. I rely too much on auto-translator. And it replaced the term "Drexel bottle" with "Bunsen flask")))))) I don't understand how this happened. Perhaps this is how autocomplete worked, but I did not pay attention. Sorry guys! I hope no one has yet had time to set fire to their house ?!

No need to apologize! I appreciate the information you have been able to provide even with translation barriers.

If you would be able to provide the process for the new formula in your language. I would pay to have it professionally translated.

 

[bnxvs]

OK. In short, regarding the "new" formula, the process of making a DIY concentrate looks like this:
1. Prepare 65% potassium sulfite solution in distilled water. If you do not have a dry reagent, it can be obtained in a solution from metabisulfite and potassium hydroxide (be sure to control pH)
K2S2O5 + 2KOH → 2K2SO3 + H2O
2. Dissolve the required amount of hydroquinone in a small amount of propylene glycol (or ethylene glycol, but it is toxic)
3. Carefully, gradually pour the solution of potassium sulfite into the hydroquinone solution (on magnetic stirer)
4. Then add phenidone (dymezon, methyl-phenidone), borax, a little DEA (or a little more TEA), potassium bromide and mix thoroughly and for a long time until completely dissolved.
5. At the end, you can add a little polyvinylpyrrolidone (as was the case in the Kodak patent), but it seems to me doubtful that modern photographic emulsions are highly prone to dichroic fog. I skip this step usually.
At the end, the pH of the prepared concentrate should be adjusted to 10.0 (9.9 more precisely) with potassium hydroxide. Do not use alkaline buffering agents for this (eg TEA).
I have kept such a homemade concentrate in a half-empty bottle for more than 6 months and it has not lost its properties (did not darken, did not precipitate). I store it at room temperature, as I suspect that the problems with crystals in the "new" HC-110 are related to storage in refrigerators. And since the concentrate solution is on the verge of supersaturation, negative temperatures can cause crystallization of hydroquinone and sulfite. However, these are just my guesses, nothing more.
p.s. I hope you understand this my opus)))

 

[thebasementzone]

OK. In short, regarding the "new" formula, the process of making a DIY concentrate looks like this:
1. Prepare 65% potassium sulfite solution in distilled water. If you do not have a dry reagent, it can be obtained in a solution from metabisulfite and potassium hydroxide (be sure to control pH)
K2S2O5 + 2KOH → 2K2SO3 + H2O
2. Dissolve the required amount of hydroquinone in a small amount of propylene glycol (or ethylene glycol, but it is toxic)
3. Carefully, gradually pour the solution of potassium sulfite into the hydroquinone solution (on magnetic stirer)
4. Then add phenidone (dymezon, methyl-phenidone), borax, a little DEA (or a little more TEA), potassium bromide and mix thoroughly and for a long time until completely dissolved.
5. At the end, you can add a little polyvinylpyrrolidone (as was the case in the Kodak patent), but it seems to me doubtful that modern photographic emulsions are highly prone to dichroic fog. I skip this step usually.
At the end, the pH of the prepared concentrate should be adjusted to 10.0 (9.9 more precisely) with potassium hydroxide. Do not use alkaline buffering agents for this (eg TEA).
I have kept such a homemade concentrate in a half-empty bottle for more than 6 months and it has not lost its properties (did not darken, did not precipitate). I store it at room temperature, as I suspect that the problems with crystals in the "new" HC-110 are related to storage in refrigerators. And since the concentrate solution is on the verge of supersaturation, negative temperatures can cause crystallization of hydroquinone and sulfite. However, these are just my guesses, nothing more.
p.s. I hope you understand this my opus)))

Thank you! This may take me a little time to get this formula made as I need some equipment to acquire. I will keep you posted on the progress!

 

[thebasementzone]

OK. In short, regarding the "new" formula, the process of making a DIY concentrate looks like this:
1. Prepare 65% potassium sulfite solution in distilled water. If you do not have a dry reagent, it can be obtained in a solution from metabisulfite and potassium hydroxide (be sure to control pH)
K2S2O5 + 2KOH → 2K2SO3 + H2O
2. Dissolve the required amount of hydroquinone in a small amount of propylene glycol (or ethylene glycol, but it is toxic)
3. Carefully, gradually pour the solution of potassium sulfite into the hydroquinone solution (on magnetic stirer)
4. Then add phenidone (dymezon, methyl-phenidone), borax, a little DEA (or a little more TEA), potassium bromide and mix thoroughly and for a long time until completely dissolved.
5. At the end, you can add a little polyvinylpyrrolidone (as was the case in the Kodak patent), but it seems to me doubtful that modern photographic emulsions are highly prone to dichroic fog. I skip this step usually.
At the end, the pH of the prepared concentrate should be adjusted to 10.0 (9.9 more precisely) with potassium hydroxide. Do not use alkaline buffering agents for this (eg TEA).
I have kept such a homemade concentrate in a half-empty bottle for more than 6 months and it has not lost its properties (did not darken, did not precipitate). I store it at room temperature, as I suspect that the problems with crystals in the "new" HC-110 are related to storage in refrigerators. And since the concentrate solution is on the verge of supersaturation, negative temperatures can cause crystallization of hydroquinone and sulfite. However, these are just my guesses, nothing more.
p.s. I hope you understand this my opus)))

Do you have a preferred mixing formula ratio that that you have found yields a satisfactory volume of concentrate?

 

[bnxvs]

I used a ratio of phenidone to hydroquinone from 1:26 to 1:33. pH of the concentrate, according to MSDS, should be about 10.0. DEA is needed very little, about 5-10 ml (can be replaced with technical TEA). Potassium bromide - at your discretion (whichever is best for your favorite film) from 0.5 to 2 g per 250 ml of concentrate.
All other substances are listed in the MSDS.

 

[thebasementzone]

Thank you!

 

[alanrockwood]

This thread is now approaching two years old. Has anyone bought the new HC110 long enough ago to at least get some idea of its shelf life?

And by the way, I don't recall if this question has been asked yet: Is the new HC110 the same thing as Legacy Pro L110?

 

[markjwyatt]

This thread is now approaching two years old. Has anyone bought the new HC110 long enough ago to at least get some idea of its shelf life?

And by the way, I don't recall if this question has been asked yet: Is the new HC110 the same thing as Legacy Pro L110?

My HC110 expired in 8-2020, and still works well. I last used it about 2 weeks ago. I think I bought it in late 2019.

HC110 is a proprietary formula, so it is unlikely Legacy Pro L110 is the same.

 

[Alan Johnson]

OK. In short, regarding the "new" formula, the process of making a DIY concentrate looks like this:
1. Prepare 65% potassium sulfite solution in distilled water. If you do not have a dry reagent, it can be obtained in a solution from metabisulfite and potassium hydroxide (be sure to control pH)
K2S2O5 + 2KOH → 2K2SO3 + H2O
2. Dissolve the required amount of hydroquinone in a small amount of propylene glycol (or ethylene glycol, but it is toxic)
3. Carefully, gradually pour the solution of potassium sulfite into the hydroquinone solution (on magnetic stirer)
4. Then add phenidone (dymezon, methyl-phenidone), borax, a little DEA (or a little more TEA), potassium bromide and mix thoroughly and for a long time until completely dissolved.
5. At the end, you can add a little polyvinylpyrrolidone (as was the case in the Kodak patent), but it seems to me doubtful that modern photographic emulsions are highly prone to dichroic fog. I skip this step usually.
At the end, the pH of the prepared concentrate should be adjusted to 10.0 (9.9 more precisely) with potassium hydroxide. Do not use alkaline buffering agents for this (eg TEA).
I have kept such a homemade concentrate in a half-empty bottle for more than 6 months and it has not lost its properties (did not darken, did not precipitate). I store it at room temperature, as I suspect that the problems with crystals in the "new" HC-110 are related to storage in refrigerators. And since the concentrate solution is on the verge of supersaturation, negative temperatures can cause crystallization of hydroquinone and sulfite. However, these are just my guesses, nothing more.
p.s. I hope you understand this my opus)))

Yes, but as I noted before, this solution will contain rather less sulfite than DDX
https://www.photrio.com/forum/threads/new-hc-110-developer-not-the-same.176138/page-4#post-2310558

 

[bnxvs]

Yes, but as I noted before, this solution will contain rather less sulfite than DDX
https://www.photrio.com/forum/threads/new-hc-110-developer-not-the-same.176138/page-4#post-2310558

Yes, but even this small amount is more than necessary to perform the function of a preservative. In such "homeopathic" formulations, I don't think sulfite has any other significant task.

 

[Grim Tuesday]

So, what is the ruling on longevity? I have some of this stuff in a sealed, amber glass bottle with no very little airspace from August 2019. What are my odds that it will still be good?

 

[MattKing]

Has it dis-coloured?
If not, I would expect that it will be fine. Even if it has darkened slightly, it may very well be fine.
I have seen no reports of unexpectedly short life from the new version - just concerns about it not being likely to be extraordinarily long lasting (think many years).
Less than two years was far less than the expected life of the old HC-110.

 

[grat]

So, what is the ruling on longevity? I have some of this stuff in a sealed, amber glass bottle with no very little airspace from August 2019. What are my odds that it will still be good?

50/50. Either it will, or it won't. Due to a near infinite number of variables, and my crystal ball being in the shop for repairs, the best way to answer this question is for you to mix up some developer, and develop a test image.

Then you'll have absolutely valid information, and you can share it with us, so we get a better idea of how the new HC-110 formula behaves.

 

[alanrockwood]

Is there anyone here with access to a mass spectrometer, preferably a mass spectrometer with an electrospray ion source? If so it shouldn't be too hard to figure out what the composition of the old HC-110 is, and the new one as well. Ideally it would be a Q-ToF mass spectrometer, so one could get the accurate mass measurement of the components, and also the MS/MS spectrum. Even better would be an FT-ICR mass spectrometer.

 

[grat]

No one's actually interested in factual information regarding the new HC110. They'd much rather have something to complain about instead.

 

[bnxvs]

The sages of old said: word is silver, silence is gold.

 

[NB23]

No one's actually interested in factual information regarding the new HC110. They'd much rather have something to complain about instead.

people complain about the lack of factual information regarding hc-110-New

 

[Lachlan Young]

HC-110's formulae has effectively been disclosed in various patents - a bit of common sense about what the adducts supply should make substitution of components relatively obvious...

Or if anyone really wanted to evolve it a bit, HC-110 seems to have been aimed at replacing DK-60a/ DK-50 and multiple dilutions thereof in a non-aqueous concentrate - nothing to stop anyone making a PQ substitution on those (or Ascorbate) and replacing the borates with newer buffering.

 

[alanrockwood]

How about just using it and not pretending mass spectrometry is going to yield information useful to anyone here.

That's certainly one approach, and I won't say it is an invalid one... on an individual-by-individual basis. However, many of us are interested in knowing what the composition is, and for those of us who are interested in the question your approach of ignoring the composition is not the preferred one.

By the way, one question that has come up is whether there is water in the new formulation. I wonder if cobalt chloride-based test strips would answer that question. However, the test strips might not work if the water fraction is too low. Any other thoughts on analyzing for water? Maybe some kind of fractional distillation might work, although the possibility of an azeotrope might complicate that approach. Alternatively, come kind of chromatographic separation of water from the non-aqueous components might be possible. NMR might be worth looking into. Karl Fischer titration might work, but it relies on oxidation of SO2 by I2, so the sulfite or sulfite equivalent in the developer concentrate might complicate the analysis. Also, redox-active components in a solution can interfere with Karl Fischer titration, and since a developer solution contains reducing agents that might complicate the analysis.

Another possibility might be to use a semi-permeable membrane that is permeable to water but not other components. The membrane could separate two chambers, one containing the HC-110 concentrated and one containing an anhydrous alcohol. After waiting for a period of time (an unknown period of time at this point) the water content of the alcohol could be measured using the Karl Fischer method. The idea behind this would be to allow water to enter the alcohol but not the other components.