Diethylene glycol purpose in developers (E6 FD)

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Anon Ymous

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Hi...

Lately I've been reading about E6 homebrew formulae and I found references to the 4,366,234 US patent (Wheatcroft et al). It's a patent about the synthesis of hydroquinone monosulfonate salts, a key ingredient in the E6 first developer. I can understand the purpose of the rest of the ingredients used, but don't understand what diethylene glycol is used for. Does anyone know why it is used and if it can be omitted?
 

Gerald C Koch

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Diethylene glycol is used as a solvent to keep organic compounds like developing agents in solution. See the patent for HC-110. Glycols are also used to lower the freezing point of developers intended for cold climate use.
 

timmct

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When I worked at Sprint Systems of Photography there were two different Glycols used in some of the formulae; ethylene glycol and diethylene glycol. I still have notes on that but will only be able to share that information with those that wish to be in contact outside of this forum.

Definitely a "universal" solvent (there are others in the Sprint formulae) but I have doubts that the anti-freeze characteristics are intended within the context of photochemistry. Even when shipping across the country (USA) in the winter, glycol contents were not intended to keep the product from freezing.
 

Gerald C Koch

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When I worked at Sprint Systems of Photography there were two different Glycols used in some of the formulae; ethylene glycol and diethylene glycol. I still have notes on that but will only be able to share that information with those that wish to be in contact outside of this forum.

Definitely a "universal" solvent (there are others in the Sprint formulae) but I have doubts that the anti-freeze characteristics are intended within the context of photochemistry. Even when shipping across the country (USA) in the winter, glycol contents were not intended to keep the product from freezing.

I was speaking about use in artic regions. I have some formulas that are good down to 0F. Before digital cameras you either developed on site or waited for the next ship to relieve the expedition.
 

dE fENDER

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Oh wow, that's a lot of stuff there, but I don't speak Russian, so I'll need to translate it somehow. That said, is it hydroquinone monosulfonic acid synthesis at page 28? 200g hydroquinone in 600ml water and add to that 120ml sulfuric acid 98%?

It is. In 600 ml hot water at 60-70 C dissolve 200g hydroquinone, then with stirring, slowly add 120 ml sulfuric acid 98%. The glass with the mix put to hot plate and boil the mix for 1.5 hours. When contents had been evapurated by 1.5 part, glass should be removed from hot plate, cooled and then put to freezer chamber of the fridge for 5-6 hours. The precipitate is brown crystal. You should filtered them, then recrystallize. After recrystallization hydroquinone monosulfonic acid should be dryed, but below 60 C.
 
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Anon Ymous

Anon Ymous

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It is. In 600 ml hot water at 60-70 C dissolve 200g hydroquinone, then with stirring, slowly add sulfuric acid 98%. The glass with the mix put to hot plate and boil the mix for 1.5 hours. When contents had been evapurated by 1.5 part, glass should be removed from hot plate, cooled and then put to freezer chamber of the fridge for 5-6 hours. The precipitate is brown crystal. You should filtered them, then recrystallize. After recrystallization hydroquinone monosulfonic acid should be dryed, but below 60 C.

Thank you! And then I assume you need to neutralise it with KOH, NaOH, or perhaps a Na/K carbonate salt. Anyway, that was mostly curiosity, I don't have the means (lab apparatus) to perform this synthesis.
 

dE fENDER

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If your purpose to get a hydroquinone monosulfonic salt, then yes. But in the book the quantity specified for the acid, not for the salt (which is producing during dissolving reagents).
This synthesis can be made at home without lab equpment, using only kitchen heat-resistant glassware or enamelware.
 
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Anon Ymous

Anon Ymous

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Oh, yes I realised after posting that the formula given uses the acid, which is neutralised by KOH, according to the order of addition.
 

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The hydroquinone monosulfonate ion is a weak developing agent. Kodak sold it for some years under the name BD-1 (balanced developing agent #1) as the potassium salt. It is formed normally during the use of hydroquinone containing developers such as D-76 and probably accounts for some of the activity changes in the developer in a replenished system. Kodak used it to simulate a MQ or PQ replenished system eliminating the need to season the developer. Hydroquinone monosulfonate is also used in low contrast developers for microfilm when it is used for general purpose photography. IIRC it is used in at least one Spur developer.
 

Rudeofus

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Oh, yes I realised after posting that the formula given uses the acid, which is neutralised by KOH, according to the order of addition.
I have seen neither a source for, nor a cost effective synthesis for, nor an E-6 formula using Hydroquinone Monosulfonate free acid. The patent you linked to in your first thread post creates the sodium salt of HQMS, and nearly all the E-6 formulas I have seen so far use the potassium salt.
 

dE fENDER

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I have seen neither a source for, nor a cost effective synthesis for, nor an E-6 formula using Hydroquinone Monosulfonate free acid. The patent you linked to in your first thread post creates the sodium salt of HQMS, and nearly all the E-6 formulas I have seen so far use the potassium salt.
The message is about discussion of the book from my link at #2, p.5 and p.28.
 

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The synthesis was published here on APUG many years ago. Use Potassium Sulfite, Hydroquinone and Hydrogen Peroxide. The more concentrated the Peroxide the more concentrated the HQMSK will be at the end. As you go up in concentration, the reaction becomes very vigorous and generates a lot of heat so beware.

As for Ethylene Glycol, it is a very nasty poison, but Propylene Glycol is often used. Diethylene Glycol is also quite poisonous. All of these are used as antifreezes and as solvents for organics in developer concentrates. If an alkali is desired, then Triethanol Amine can be used.

PE
 
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Anon Ymous

Anon Ymous

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The synthesis was published here on APUG many years ago. Use Potassium Sulfite, Hydroquinone and Hydrogen Peroxide. The more concentrated the Peroxide the more concentrated the HQMSK will be at the end. As you go up in concentration, the reaction becomes very vigorous and generates a lot of heat so beware.

On the subject of HQMS synthesis I found parts of two interesting relevant papers. Sadly, only an "abstract" is available, the rest is behind a paywall. The first is a 1951 paper by James E. LuValle and the second a 1985 paper by James P. Youngblood, both employed by Kodak when these papers were published. So, the mechanism of synthesis is roughly this:

Under the right pH conditions, hydroquinone reacts with oxygen (peroxide) and forms p-benzoquinone. This seems to produce some more hydrogen peroxide as a byproduct.

P-benzoquinone reacts with a sulfite salt and gives the equivalent hydroquinone monosulfonate salt, plus some metal hydroxide. If sodium sulfite was used, then HQMS-Na salt and NaOH will be produced.

Sulfite present during these reactions can also be further oxidised to sulfate.

So, it seems that the key reaction is the one converting HQ to p-benzoquinone, but I'm not entirely sure that simply mixing HQ, peroxide and sulfite will convert 100% of HQ to HQMS. Apart from that, we still don't know the quantities of sulfite and hydroxide present at the end, which probably makes it even more problematic (I assume sulfate can be just disregarded). Perhaps a better way would be to synthesize pure p-benzoquinone first and react it with the right amount of sulfite, but this is quite a nasty chemical substance.

P-benzoquinone can be produced by reacting HQ with peroxide, but usually an iodide catalyst should be present, if good yields are desired. The catalyst could be I2, or an iodide salt like KI, but given that iodide is a powerful restrainer, any impurities at the final product can cause problems.
 
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Anon Ymous

Anon Ymous

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By the way, the HQ + peroxide + sulfite mixture doesn't seem to heat vigorously because of the HQ + peroxide reaction. I just tried mixing 20ml of 2,8% peroxide with a small (at most 1g) quantity of sodium sulfite. The reaction took place at ~15,5°C and within at most 2' it had reached 38°C, where it stabilised.
 

Rudeofus

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If the synthesis is done correctly, the heat will come from the HQ+Peroxide reaction.

That Peroxide+Sulfite reaction may also take place, but when you synthesize HQMS, you will try to keep that reaction to a bare minimum. Otherwise you just end up with a mix of HQ and Sodium Sulfate - not exactly what you want for E6 FD :wink:
 

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The sequence, as shown many times before here and given in Haist, is the oxidation of HQ to Q and then the reaction of Q with SO2= to give HQMS-(Na or K depending). The oxidant is peroxide.

PE
 
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