Another Rodinal Formula

Gerald C Koch · Feb 15, 2016

Rodinal Substitute

Distilled water ………………………………………………………………… 150 ml
Paraminophenol …………………………………………………………………… 55.0 g
Potassium sulfite, 45% w/w……………………………………… 750.0 ml
EDTA Na4 …………………………………………………………………………………… 20.0 g
Potassium hydroxide ……………………………………………………… 45.0 g
Distilled water to make …………………………………………… 1.0 l

First prepare the sulfite solution notice that it is a weight to weight ratio. Then mix the formula in the order given in the recipe. Do not substitute sodium salts for the potassium ones. In addition use the paminophenol free base and not the hydrochloride salt.

Laurent Wirmer, Fotolabor-Seite

JW PHOTO · Feb 16, 2016

I have never had good luck making my own Rodinal, but might try this one just for the heck of it since I do use Rodinal and just ordered another bottle. It would be interesting to compare this recipe to the new bottle I will be getting.

Gerald C Koch · Feb 16, 2016

JW PHOTO said:
I have never had good luck making my own Rodinal, but might try this one just for the heck of it since I do use Rodinal and just ordered another bottle. It would be interesting to compare this recipe to the new bottle I will be getting.

I am interested in what caused your difficulty with other formulas. Rodinal type developers are made a little differently than other developers but the difference is not that much. Perhaps I could help. Over the years I've made quite a bit either as Rodinal or Kalogen.

baachitraka · Feb 16, 2016

Unfortunately those raw chemicals are rather very expensive here in Germnay.

50g Paraminophenol = €21.18
150ml Potassium Sulfite = € 9.04
50g EDTA Na4 = € 7.02
100g Potassium Hydroxide = € 7.02

I feel little sad.

Rudeofus · Feb 16, 2016

I am surprised that they use EDTA as calcium sequestering agent in a developer with target pH > 12.

@baachitraka: 1l of Rodinal concentrate should last you a loooooong time ...

baachitraka · Feb 16, 2016

Yeah, 1l is cheaper here.

Gerald C Koch · Feb 16, 2016

Paraminophenol should be very cheap as it is produced in metric ton quantities as a starting material for scores of other chemicals.

Rudeofus · Feb 16, 2016

@baachitraka : Potassium Sulfite in this list (and also the sources I know of) is way overpriced, and you end up much cheaper if you substitute it with Potassium Metabisulfite and Potassium Hydroxide from the same source.

PS: I think you get 250ml Potassium Sulfite 45% solution for € 9.04, not only 150 ml

PPS: Even then it is overpriced

baachitraka · Feb 16, 2016

Fotosuvatlar is my local source but I don't know whether they are overpriced.

pdeeh · Feb 16, 2016

If I tried to source these materials within the UK, the only place I can find to buy Potassium sulfite charges £14 (+delivery on top of course) for 250g
50g of p-aminophenol (HCl not free base) from Silverprint is about £30 (+delivery on top of course), and add another £15 or so for the EDTA and Hydroxide.

(Or I could buy two packs of paracetamol (£0.50) and use the Potassium metabisulfite, Sodium sulfite and Potassium hydroxide I've already got in my box of tricks and get something even cheaper than RO9 )

baachitraka · Feb 16, 2016

For the time-being Dk76b* is the only formula I mix at home, but will be happy to have one more formula that lasts longer.

* I got some sodium metaborate.

baachitraka · Feb 16, 2016

1l of Adonal cost around €22...

Rudeofus · Feb 16, 2016

baachitraka said:
Fotosuvatlar is my local source but I don't know whether they are overpriced.

I did not refer to Suvatlar in general, but the price for Potassium Sulfite looks odd if you compare it to Potassium Metabisulfite and Potassium Hydroxide price. I found that same strange pricing with my local sources, that's why I recommended substitution.

But let's face it: at €22 for 1 l of Rodinal it will become difficult to justify home brewing it, unless you use it by the metric ton. There is a Dead Link Removed here which shows Rodinal recipes as they evolved over time, and the 1941 version appears to be by far the simplest and cheapest one for home brewing purposes, and IMHO the only one where home brewing could end up cheaper than the commercial product.

JW PHOTO · Feb 16, 2016

Gerald C Koch said:
I am interested in what caused your difficulty with other formulas. Rodinal type developers are made a little differently than other developers but the difference is not that much. Perhaps I could help. Over the years I've made quite a bit either as Rodinal or Kalogen.

Gerald,
I tried the Tylenol route and thought I followed the instruction right, but I never really got any crystal growth. I aged it for the right amount of time, but when I tried it on some Chinese GP3 film I could barely make out any image at all. Almost clear negatives. I gave up and went back to the store-bought stuff. I just ran out of my store-bought Rodinal, but when I was digging around in my chemical stash I found a bottle of original Rodinal from 1989. It had about 1/2 inch in the bottom so I thought I'd test it. I just overhauled a Mamiya 1000 DTL camera and had to test it with some Ultrafine Extreme 100 film. I processed the film in the old Rodinal 1+50 for 10 min. @ 68F. The negatives look absolutely perfect. Hard to believe a film developer can still be alive after nearly 27 years in a near empty bottle. My new bottle will arrive from Freestyle on Friday and I'll be good for a long time to come. John W

Gerald C Koch · Feb 19, 2016

JW PHOTO said:
Gerald,
I tried the Tylenol route and thought I followed the instruction right, but I never really got any crystal growth. I aged it for the right amount of time, but when I tried it on some Chinese GP3 film I could barely make out any image at all. Almost clear negatives. I gave up and went back to the store-bought stuff. I just ran out of my store-bought Rodinal, but when I was digging around in my chemical stash I found a bottle of original Rodinal from 1989. It had about 1/2 inch in the bottom so I thought I'd test it. I just overhauled a Mamiya 1000 DTL camera and had to test it with some Ultrafine Extreme 100 film. I processed the film in the old Rodinal 1+50 for 10 min. @ 68F. The negatives look absolutely perfect. Hard to believe a film developer can still be alive after nearly 27 years in a near empty bottle. My new bottle will arrive from Freestyle on Friday and I'll be good for a long time to come. John W

Actually you shouldn't get any crystal growth. When you add hydroxide solution to the Tylenol pills the active ingredient will react and dissolve leaving you with a slurry of tablet binder. Filter this off to get the developer concentrate. Not quite the same as Rodinal as the solution also contains sodium acetate. But that is inactive as a developer. The resulting concentrate will be a bit softer working than true Rodinal.

Several other substituted aminophenols also form phenolates such as Metol. There are formulas for Metol-Caustic developers. IIRC Ethol once sold one such developer as Ethol Blue.

Alan Johnson · Feb 19, 2016

Donald Qualls Parodinal contains an excess os sodium sulfite which forms crystals:
http://www.digitaltruth.com/data/formula.php?FormulaID=144
Potassium Sulfite is much more soluble and stays clear:
(there was a url link here which no longer exists)

Gerald C Koch · Feb 19, 2016

The problem with all these Tylenol based developers is that they cannot be made accurately. Traditionally Rodinal is made by "titrating" the paaraminophenol by adding 50% potassium hydroxide solution to a slurry of paraminophenol and potassium bisulfite. As hydroxide is added the solid begins to dissolve. To prevent any excess of hydroxide you stop adding hydroxide just before all the pap dissolves. With all the insoluble tablet binder present you cannot do this. So all there various preparations have an excess of hydroxide which effects their stability and activity.

The way I would do it would be to reflux a mixture of the crushed tablets and dilute hydrochloric acid. The acetyl group on the pap will be removed. The pap will dissolve as the hydrochloric acid salt. The insoluble binders will remain. The solution would be cooled and the binders filtered off. Then a calculated amount of sodium carbonate with a small amount of sulfite would be added. The free base would then precipitate and be filtered off. From it you can follow the usual Rodinal preparation procedure.

The reflux apparatus can be as simple as an Erlenmeyer flask with a one hole stopper and a 2.5 foot length of glass tubing. The tubing acts as a primitive condenser. The solution is gently boiled with the vapor reaching 2/3 the way up the tubing. The flask should be large enough so it is never filled more than halfway. The tube should not extend into the solution and be well above it. To avoid "bumping" add a small, 1/4 inch smooth pebble or glass sphere to the liquid. The reaction is fairly fast and 30 min of gentle boiling should do the job. Since some HCl gas and acetic acid fumes will escape this should be done outdoors. You could also substitute sulfuric acid to avoid any HCl release.

You should be able to easily produce all of pap you need using this method. The flask, stopper and tubing should cost about $10. You will also need a hotplate.

Alan Johnson · Feb 24, 2016

It's on Wikipedia that Rodinal was patented in 1891 by Dr Momme Andresen, but in 1894 another formula appeared on p289 of the American Annual of Photography:
RODINAL.
Metabisulfite of potassium................30 gm.
Para-amidophenol hydrochlorate........10gm
Potassium hydrate............To neutralization
Water............................................100gm
This developer permits to be diluted in the proportion of 1:40

Trask · Feb 8, 2019

Alan Johnson said:
It's on Wikipedia that Rodinal was patented in 1891 by Dr Momme Andresen, but in 1894 another formula appeared on p289 of the American Annual of Photography:
RODINAL.
Metabisulfite of potassium................30 gm.
Para-amidophenol hydrochlorate........10gm
Potassium hydrate............To neutralization
Water............................................100gm
This developer permits to be diluted in the proportion of 1:40

How do you think the 1894 reader would understand “to neutralization?” My limited understanding of Rodinal chemistry leads me to believe that “neutralization” may mean that Potassium Hydrate is added until a precipitate forms — is that the case for this formula?

Alan Johnson · Feb 9, 2019

https://babel.hathitrust.org/cgi/pt?id=mdp.39015067127459;view=1up;seq=359
I would guess that you are right but never studied the history of how these old terms changed.

Another Rodinal Formula

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