How To Buy Potassium Hydroquinone Monosulfate

My friend indicated that extracting a "reasonably" pure solid from it would be difficult, since I don't have a laboratory like he has access to. Hmm.... maybe it's time to buy him a nice Christmas present this year?

Sciencelab lists the potassium salt. I have purchased form them in the past.

The Link http://www.sciencelab.com/page/S/PVAR/10415/SLH1723

Evan Clarke

Ok, by comparison, HQSulfonate free acid is rather insoluable by comparison, and so it might be possible to purify by acidification and then washing with DW or Acetone or something like that. I may play with this a bit and see what is up.

I'll keep you posted.

PE

I tried the following:

25 grams of Sodium Sulfite (anh) or 0.2 moles

Dissolve in 366 ml of distilled water

Add 11 grams of HQ or 0.1 moles

Temperature 68F or 20C.

Add slowly with stirring 133 ml of 3% H2O2 or about 0.15 moles.

Temperature rose slowly during addition to 100F or 38C. (this could boil over if you are not careful and ruin you and the mixture) The pH was about 7.0 at this time.

The solution was clear and colorless this whole time but slowly began to turn straw colored as it cooled. A sample was taken and acidified strongly to try to form a precipitate of the sulfonic acid derivative, but there was no effect except for the evolution of some sulfur dioxide gas.

It is now sitting in my sink with me wondering what I should try next. It appears to me that purification may be rather difficult due to the solubility and the excess of Sodium Sulfite. I'll let it stand overnight and try some other things and keep you posted.

This seems too simple. Like all simple things, there may be a gotcha in here somewhere.

PE

Well, it looks promising enough. I too agree that it's suspiciously simple. Is it possible to use the solution as is?

Not unless you want a 50% excess of sodium sulfite.

There is too much missing from that formula such as addition rate, temperatures, addition method and purification method.

Today the clear solution sits with no change. An acidified beaker of some with extra peroxided added has turned dark orange. The odor of sulfite is gone, so I've oxidized the excess sulfite to sulfate.

Now, I might be able to purify it by adding calcium or magnesium sulfate, but then I have to reconvert to the HQMS sodium salt. This becomes tedious and expensive. The price on that reference earlier begins to look more and more attractive!

PE

I know this is my chemistry ignorance speaking but will reducing the sodium sulphite to 16g ameliorate some of the problem. How much HQMS was produced? About 21 grams?

I guess begging Photographer's Formulary to stock potassium hydroquinone monosulphonate might be easier.

Patent on making Sodium Hydroquinone Monosulfate

Here is a link to a patent from 1982 on making and using Sodium Hydroquinone Monosulfate. The patent describes what PE did, but does not try to dry it, instead they use it in a developer solution right away.

http://www.freepatentsonline.com/4366234.html

On another note, I have noticed some formulations of first / B&W developers use a borax/boric acid buffer system, and others use carbonate/bicarbonate. Is there much difference between these two, especially if the final product is pH balanced with NaOH?

Photo Engineer said:

I tried the following:

25 grams of Sodium Sulfite (anh) or 0.2 moles

Dissolve in 366 ml of distilled water

Add 11 grams of HQ or 0.1 moles

Temperature 68F or 20C.

Add slowly with stirring 133 ml of 3% H2O2 or about 0.15 moles.

Temperature rose slowly during addition to 100F or 38C. (this could boil over if you are not careful and ruin you and the mixture) The pH was about 7.0 at this time.

The solution was clear and colorless this whole time but slowly began to turn straw colored as it cooled. A sample was taken and acidified strongly to try to form a precipitate of the sulfonic acid derivative, but there was no effect except for the evolution of some sulfur dioxide gas.

It is now sitting in my sink with me wondering what I should try next. It appears to me that purification may be rather difficult due to the solubility and the excess of Sodium Sulfite. I'll let it stand overnight and try some other things and keep you posted.

This seems too simple. Like all simple things, there may be a gotcha in here somewhere.

PE

Click to expand...

How about doing it in ethanol? Sodium Sulfite is insoluble in it, but Hydroquinone is soluble in Ethanol (I -think- it's about 20g/L at 24.5 celsius, may be remembering it wrong), left over sulfite shouldn't be dissolved then and you could dry it?

IDK about ethanol. Never done it. Kind of an expensive way to make it IMHO. Drink the ethanol instead!

I tried bigger batches and different formulations and this baby can get very hot very quickly, so please be careful.

PE

US 4,366,234 in E-6 process

I have been using the Wheatcroft et al. ( U.S.patent 4,366,234 ) approach of in-situ formation of sodium hydroquinone sulfonate over the last year. This methodology works very well to provide an E-6 first developer with limited run-to-run variability and extended longevity. However, a cursory evaluation of the patent disclosure indicates a potential problem with stoichiometry in the hydroquinone oxidation reaction. The relevant passage is as follows:

“A first solution was made by dissolving in 150 mls. water, 12.5 g. of sodium sulphite and 5.5 g. of hydroquinone; the pH of the resulting solution was raised to about pH9 and 5 mls. of 40 volumes hydrogen peroxide was then added and the formation of sodium hydroquinone monosulphonate occurred rapidly.
A second solution was prepared by dissolving in 150 mls. of water the following ingredients:”

5.5 grams HQ (MW=110)=0.05 moles
5 ml. 12%H2O2 (1.03 g/ml.)= 5.15 grams (MW=34)=0.15 moles

Thus, a 3X molar quantity of peroxide over HQ is being used in the presence of excess sodium sulfite.

As the product has a MW of 212, 10.6 grams of the sodium HQ sulfonate results in the patent procedure. The patent formulation is for 500 ml of developer, which translates to 21.2 grams per liter. This of course is comparable to the liter quantity of the potassium salt found in Fuji patents, and many other locations on the web.

This VOLUME...... contains this PERCENTAGE
of hydrogen peroxide
10 volume or V10 3%
20 volume or V20 6%
30 volume or V30 9%
40 volume or V40 12%

The specific gravity of 12% H2O2 is found to be 1.03 in an online MSDS
The specific gravity of 3% H2O2 is found to be 1.01 in an online MSDS

It is known that the product sulfonate can again be oxidized hydrogen peroxide to produce a di-sulfonate salt of much lower activity in a developer. I thus limited my work to a stoichiometric oxidation of HQ with just 1 mole of 3%(drugstore) peroxide. I was also working with a high-sulfite stock solution from another project which had 12g. HQ, 1 g. phenidone B, 2 g. NaBr, and 50 grams of sulfite per liter.

250 ml of this stock solution contains 3g. HQ ( .027 mole)

.027 mole H2O2 via the 3% solution(assumed specific gravity=1)=30.5 ml. I backed off ever so slightly to 30 ml.
(98mole%), which was added slowly with vigorous stirring. It was also assumed that the excess sulfite present would maintain the slight alkalinity required for the reaction. There is indeed an exotherm here, but it is not at all dangerous. This solution (280 ml.), after stirring for 1 hour, was then treated with restrainer stock solutions, KSCN, and Na2CO3 to make the final developer (285 ml….enough for 1X35mm. In a Nikor).

Standard E-6 time/temp protocol, along with NaBH4 reversal and a color developer close to Stephan’s ((there was a url link here which no longer exists)) gave excellent contrast, with extended gray scale densities, when compared to a PQ substitute developer.

In the end, I needed less KI than normally indicated, and a lower color developer pH than used by Stephan in order to fine-tune color balance.

Brookse,
In your calculation:

5 ml. 12%H2O2 (1.03 g/ml.)= 5.15 grams (MW=34)=0.15 moles

Don't you have to take into account that only 12% of the 5.15 g is H2O2, not the entire amount to calculate how many moles are there? I am assuming the 12% is by weight of H2O2 to H2O.

Yes, you are correct..I had some trouble transcribing my notes! The patent is three fold DEFICIENT in peroxide. 5ml. of a 12% solution=0.61 g H2O2=.018 moles..(X3= .054).

Is there really a deficient?

The way I read it, 5 ml of H2O2 40% are needed.
This will give you a demand of about 16ml H2O2 12% for a total of 500ml developer solution.
What interests me more is till which degree of completion this reaction will lead and how much time will be needed therefor.

Assuming reaction goes to 100% (for one Liter developer solution)
0.2 mol sodium sulfite
0.1 mol Hydroquinone
0.15 mol H2O2

Will give
0.1 mol Hydroquinonemonosulfonate sodium salt
0.05 mol Sodium sulfate
0.05 mol Sodium sulfite residuals
And an (for my brain) unclear amount of NAOH

What will be in deficient (in the final solution) is sodium sulfite, which I add normally in the dimension of 0.18 mol (22.7g) per liter…
Anybody have an idea of this?

Regards, Stefan

Stefan, again I caution all that even with 3% H2O2, this reaction generates quite a bit of heat and can actually boil over if you are not careful!

PE

Dear PE !!

I’m aware of that, experiments this way should be done with some care, I totally agree!
But do you have an idea of the expectable completion of the process? It’s hard to believe that in the absence of catalysts all the HQ is transformed to HQMS. I would expect some HQ residuals as well as some unwanted benzoquinones…

Anyway, going to try it

Regards Stefan

You have been warned. Solutions of hydrogen peroxide above 3% can be dangerous. The slightest speck of dust introduced to the original container can cause the peroxide to explosively decompose. Its solutions should always be kept refrigerated.

Organic synthesis is complicated, reactions are usually not stoichiometric. You seldom get a pure product.

There are too many people on APUG playing with chemistry. The most dangerous people are those who think they know what they are doing. The problem with taking precautions is that they only work if you completely understand what you are doing. It is always the unexpected that gets you.

Oh my god!

In fact I’ve done that “synthesis” yesterday night with usual precaution.
Simply haven’t used the solution already, my time is limited. On the other hand I want to make a second batch with prolonged reaction times.

It get’s warm, as indented by an exothermic reaction, but not over 45-47°C, if enough cold water is used as a basis (400ml).
This is the most essential part, beside goggles, gloves and clean / well prepared homebrewing.

Especially the (known) lack of predictable stoichiometric results was the reason for my question… Maybe somebody already has some experiences with this HQMS Homebrew and the use of it, beside Mr. Whetcroft and brooks…

Regards, Stefan

p.s. Don’t get me wrong, I honor your warnings clearly, but did you ever bleached your hairs ( preferably to a bluish white) ? Well, I can tell you, THAT is an reaction I would not recommend to anyone…

In organic synthesis the yield of a particular product often depends on the temperature of the reaction mixture. Low temperature may favor one product while higher temperature another. So some one else's result may not be useful unless you know the temperature.

In this particular case my warning was directed primarily at the hydrogen peroxide itself and not the synthesis of the sulfonate.

walter23 said:

JD Photo chem?

Click to expand...

JD Photochem went out of business over a year ago....

If the HQ - Peroxide - Sulfite solution is clear or tan, you have a good reaction. If it turns dark brown or green, you have a bad reaction.

Now, that is based on HQ to HQMS and Sulfite to Sulfate. However, the molar ration may vary quite a bit between these two. This is the "unknown" factor that Jerry spoke of in his posts. The only way to fix it is to purify the HQMS, removing the Sulfite and Sulfate. Then you know what you have.

But, this purification is difficult and time consuming.

PE

Dear PE!!

The prepared solution (1) was clear and developed within one hour a very light/bright yellow tint.
This part looked fine so far. What makes me wonder about is, that solution 2 (with the phenidone in, amber/yellow color)
discolorates if mixed together with solution 1 to form the final developer.

Anyway, we just started a barbeque, will check that later…

Regards, Stefan

Ok here my results.

By homebrewing HQMS out of HQ it looks like essentially less HQMS is formed than is used normally in standard E6 first developer.
This means of course in addition that there are residuals of more active pure HQ. Same Times, routines and ingredients as in my actual homebrew gave me Slides overdeveloped about one Aperture, with weak D max and an overall yellow/green shift.

Not too promising… But this have to be said too, tonality looks good, color crossover is not visible or overlaid by color shift at the moment .

I’ll try the next days a second formulation where Solution 1 has significant more time for reacting (24 hours instead of one), but I suspect pure HQMS is definite the better option and this processing variant is not worth the hassle…

Regards, Stefan

Another batch / some words to disclose my “Wheatcroft HQ / HQMS attempt”.

Yesterday a new solution 1 was created and stored for 6 hours. The solution was then brought to 500 ml and divided into 5 samples, stored in glass bottles in a water basin.
Sample Zero was kept unchanged, onto sample 1 where added 1ml H202 (30%), onto sample 2 where added 2ml H2O2, onto sample 3 3ml, onto sample 4 where added 4ml H202 to induce further oxidation.
Sample 2 , 3 and 4 showed a visible coloration towards orange/pink after a few minutes, 10 minutes later sample 1 began to change color too.
Sample 4 and 3 seems to decolorize / change color more to yellow after a few minutes more.

These 5 samples will now spend the night in the sink so give enough reaction time.
By the way, the color of sample 1 and 2 looks promising, bright orange/slightly pink, like freshly dissolved HQMS…
My hope is to transform the HQ residuals as far as possible to HQMS without creating larger amounts of benzoequinone (which does have a yellow color and will be probably present in sample 3 and 4).
----------------------

Hmmm…
10 hours later sample zero is still crystal clear, sample 1 (with the smallest addition of H202) show quite intense pink (darker than last night) coloration.
Sample 2, 3 and 4 show weaker coloration (sample 4 the weakest) and tend more to yellow.

Sample 1 looks so-so partway useable, but (over) oxidized, whereas sample 3 and 4 looking suspicious to benzoequinone.
Presuming that sulfite is still present some hyrdoquinonedisulfonate could be formed. (this is hypothetical, can’t analyze that)

In a perfect world a next approach would follow, to come as close as possible, via a very slow titration to the point where coloration begins…
But my time is limited and I do stop this now!

As Gerald Koch and PE mentioned earlier, this HQMS homebrew method will probably NOT produce a constant concentration of ingredients this easy way. Therefore it looks not very usable for getting constant E6 processing parameters, as necessary. This was a bit time consuming, maybe predictable but interesting (like the auto didactical attempt).

If HQMS is not available at all, it will be less difficult and more predictable to brew an (semi) adequate HQ/P or HQ/M/P first developer in the “Watkins” or “ZoneV” tradition.
Brew the “ZoneV” variant preferably without Benzotriazole which can give a slight magenta/green crossover. The latter FD behaves quite well, especially if a Carbonate / bicarbonate buffer is included and the pH is set properly to 9.65 at 25°C, but is (knowingly) not stable (which was the reason for this struggle…).

Hope not having bored you,
Regards, Stefan