Rodinal - original recipe?

[Nikola Dulgiarov]

RobK, thanks for sharing more info!!!

 

[Edwardv]

I have in collection the Rodinal recipe given to the allies at the end of WW2 when they over-ran the Agfa Wolfen factory. The quantity I seem to think is 1100 litres or thereabouts. I did put it up here years ago on another thread but the moderators had it down inside 10 minutes! As it's clearly public domain now I could have another go...

Would like to see the formula if you still have it? Thank you.

 

[Nikola Dulgiarov]

I think we all would like to see it

 

[gainer]

Simplifying Rodinal Preparation
I have found that the results of using p-aminophenol base instead of the hydrochloride and sodium sulfite instead of the metabisulfite or bisulfite are the same for all practical purposes.
The amount of hydroxide required is very much reduced. The formula then becomes:
Water...................................400 ml
sodium sulfite, anh..............85 grams
sodium hydroxide................13.8 grams or 19.3 grams of potassium hydroxide.
p-aminophenol.....................40 grams
Dissolve the sulfite and the hydroxide, then add the p-aminophenol.
Water to make 500 ml.

With these proportions, about 2.5 grams of p-aminophenol should be precipitated The idea is this: aerial oxidation of aminophenol in the presence of sulfite produces the monosulfonate and sodium hydroxide. The sodium hydroxide acts on precipitated p-aminophenol to form sodium aminophenolate, which is soluble. Thus a new molecule of sodium aminophenolate is formed for every molecule that is oxidized by air. I think this reaction keeps the stock solution activity nearly constant until all the precipitated crystals have been dissolved. The color of the stock solution changes over time due to oxidation, but the activity does not. At the least, the oxygen
dissolved in the water that was used to make the solution should be scavenged without loss of soluble developing agent.

It seems to work. Whether or not my reasoning is correct, the instructions on the side of my old Rodinal bottle work as well with this homemade version as with the original contents. If you are worried about the difference between sodium and potassium salts, you can substitute 1.25 times the weight of potassium sulfite and 1.4 times the weight of potassium hydroxide for the sodium salts. If you are concerned about having enough p-aminophenol precipitate, add more.
The formula usually used produces some sodium or potassium chloride, which this formula does not. The chloride is a very weak restrainer, but if it concerns you, add a bit of non-iodized table salt. You can usually get potassium chloride at a pharmacy if you want to try that.


Now if you wish you may put the p-aminophenol in a separate solution. P-aminophenol is soluble in propylene glycol. In that solution there is less probability of aerial oxidation than in the water solution with sulfite to protect it. Thus, solution "A" would be 40 grams of p-aminophenol dissolved in enough propylene glycol to make 500 ml. Solution "B" would be the other ingredients listed above dissolved in enough water to make 500 ml. The working solution would be equal parts of "A" and "B" dissolved in water. The dilution 1:1:48 would be equivalent to 1 part Rodinal in 49 parts water.

 

[Ian Grant]

Would like to see the formula if you still have it? Thank you.

It's been published many times already here on APUG but the nti-foggant isn't listed just a code number P.1347, however it appears to be a Benzene sulphonate, and Agfa worked on these in the 1930's, patenting their use in developers.

The research was initially into wetting agents but the Benzene sulphonates were found to have other properties. They are used by Fuji as anti-oxidants and are also found in Instant print materials.

"The British RAF report into the "Agfa Film Factory - Wolfen" reported by G.C. Brock, London : H.M.S.O. gives a formula for Rodinal as:

Dissolve 34 kg of para-aminophenol in 340 litres of water. Add 558 kg of a 30% solution of potassium sulphite at 55C followed by 50 kg of a 34% potassium hydroxide solution, then 5.52 kg of potassium bromide in a little water. Add 42 g P.1347 (an Agfa-specific anti-foggant). Filter and allow to stand for 14 days."

Ian

 

[RobK]

I used next :

"

Wasser 75 ml
p-Aminophenol 5.5 g
Kaliumsulfit sicc. 4 g
Kaliumhydroxid 4 g
Kaliumbromid 1 g
Na4EDTA 2 g
Wasser auf 100 ml

" (Combined Intelligence Objectives Sub-Committee 1945)
The amount of Potassium Sulfite must be wrong imo -- In the 1910 formula from Dr Andresen (with metabisulfites) it is much higher : 30% or so. (as sulfites then).
It's somewhat confusing : the Americans were convinced they caught some rocket-fuel specialists at the Calbe plant, it took 14 days ... etc ...

But I used the 4% KOH -- I know, more recent MSDS's show less : 2.3 - 2.6 % (Calbe - ex Leverkusen) ; the paRodinal formula (from the web) something like 6% NaOH !! (after the conversion of the paracetamol).

I use the same developing times as for R09, seems to be fine.
A sample at 1+60 (just a test on PanF)
http://users.telenet.be/bobkeppens/2010/J8Kb.jpg

and a combination with Potassium Ascorbate and Borax :
http://users.telenet.be/bobkeppens/experimenten/RODINAL_C03.jpg

The first one without a restrainer, the 2nd contains KBr.

(I sometimes use iodized salt as a restrainer (0.1%) , it seems the mix of iodates, ferrocyanides and fluorides is really strong stuff -- not sure it's restraining or bleaching ;-)

regards

RobK

 

[Ian Grant]

" (Combined Intelligence Objectives Sub-Committee 1945)
The amount of Potassium Sulfite must be wrong imo -- In the 1910 formula from Dr Andresen (with metabisulfites) it is much higher : 30% or so. (as sulfites then).
It's somewhat confusing : the Americans were convinced they caught some rocket-fuel specialists at the Calbe plant, it took 14 days ... etc ...
RobK

In the two long threads about "Original" Rodinal there's an explanation of how Metabisulphite & Hydroxide where used to form the Sulphite in Rodinal.

The RAF report formula was a WWII version it's quite probable that chemicals were in short supply so the cut in Sulphite may have been a consequence.

Dr M Andresen (or Agfa) never published the formula for Rodinal which has always used the free base of Paraminophenol (Paramidophenol) while the formula publishe in Andresen's Agfa Photo-Handbuch uses Paramidophenol hydrochloride (salzsaures).

Ian

 

[Trask]

RobK:

Any chance of putting that formula into English for those of us challenged by the German language? And I'd like to know what amounts of Potassium Bromide and Borax you added, as I really like the look of that landscape -- looks kind of like a steel etching. Thanks.

 

[Ian Grant]

Wasser - Water75 ml
p-Aminophenol 5.5 g
Kaliumsulfit sicc. - Potassium Sulphite 4 g
Kaliumhydroxid - Potassium Hydroxide 4 g
Kaliumbromid - Potassium Bromide 1 g
Na4EDTA - EDTA-Na4 2 g
Wasser auf - Water to 100 ml

In many ways this is as far from Rodinal as Kodak's High Definition developer was from D23, it'll give higher definition than Rodinal which like D76, D23 etc uses a high sulphite content to produce finer grain

Ian

 

[gainer]

Wasser - Water75 ml
p-Aminophenol 5.5 g
Kaliumsulfit sicc. - Potassium Sulphite 4 g
Kaliumhydroxid - Potassium Hydroxide 4 g
Kaliumbromid - Potassium Bromide 1 g
Na4EDTA - EDTA-Na4 2 g
Wasser auf - Water to 100 ml

In many ways this is as far from Rodinal as Kodak's High Definition developer was from D23, it'll give higher definition than Rodinal which like D76, D23 etc uses a high sulphite content to produce finer grain

Ian

That amount of KOH is enough to make 7.9 grams of p-aminophenol into the aminophenolate. Are you sure you didn't mean to specify the metabisulphite?

 

[gainer]

Or is it the EDTA that requires the extra?

 

[Ian Grant]

That amount of KOH is enough to make 7.9 grams of p-aminophenol into the aminophenolate. Are you sure you didn't mean to specify the metabisulphite?

I didn't post the formula only added the English translation, I should have added that "sicc" is anhydrous.

In this case I think the excess Hydroxide is more akin to the high pH used in high definition acutance developers used very dilute at high alkalinity.

Ian

 

[Clay2]

Have a look at Ed Buffalo's site here:

http://unblinkingeye.com/Articles/Rodinal/rodinal.html

Best regards,

/Clay

 

[Murray Kelly]

I believe I may have been the first in this thread to put Rob's formula for 250ml in post #20. He has a lot of experience with the brew and whatever one may say about the minutiae of inter-reactions resulting in sulphones and sulphonates etc etc, have a look at his pictures and tell me I'm wrong in believing whatever he is throwing into the pot the final result is good to look at. The proof of the pudding, as it goes, is in the eating.
I agree the OP was about original formulae for Rodinal and it still isn.t settled (ever?) but he did start with a very old source and that must count for something! :=)
Can it be that the original Rodinal is the modern Holy Grail?
Just some random thoughts
Murray
PS - not in Brisbane but the UK near Windermere.

 

[RobK]

"Potassium Bromide and Borax you added"

4.4g/L Potassium Ascorbate (not Br) and 1 g/L Borax (Sodium tetraborate decahydrate) for Rodinal 1+50. (concentrate containing 10g/L KBr ). use 75% of the normal 1+50 developing time.

"uses a high sulphite content to produce finer grain"
Yes, but Rodinal 1+25 is lower than 2%, probably too low to be acting as a silver-solvent.
Strangely adding sulfites into a Rodinal working solution doesn't do much. (I really tried 10% extra sulfites working sol).
But it worked well (even at 5%) with an Ascorbate - Caffeic Acid developer.
(well, maybe/probably caffeic acid is already converted into a quinone)

regards

RobK

 

[RobK]

Maybe best to show some samples with this (probably) 1945 replica.
However I use around 10% Potassium Sulfites (not the 4%) - but I start with Potassium Metabisulfite, when the pH is high enough they (from bisulfites) will be almost all converted into sulfites.

My normal dilution 1+60
http://users.telenet.be/bobkeppens/Retrodinal/I8103_klein.jpg
(larger)
http://users.telenet.be/bobkeppens/Retrodinal/I8103.jpg
(all on 50iso cine-copy film -- the film has no anti-halation layer)

24x24mm size negatives (Solinar 35mm lens)
http://users.telenet.be/bobkeppens/Retrodinal/streetrod01.jpg
(larger)
http://users.telenet.be/bobkeppens/Retrodinal/streetrod01-groot.jpg
as said .. no anti-halation layer (see next)
http://users.telenet.be/bobkeppens/Retrodinal/streetrod02.jpg

1+80 (good tonality imho)
http://users.telenet.be/bobkeppens/Retrodinal/1+80test.jpg

at 1+200 I do not like it anymore
http://users.telenet.be/bobkeppens/Retrodinal/1+200.jpg

same with adding 10% extra sulfites in the working solution, imo more contrast/less compensating.

IIRC 1+40 and made with a Voigtländer Lanthar (only a triplet) -- a 50% crop
http://users.telenet.be/bobkeppens/Retrodinal/50%crop.jpg

It develops not exactly the same as the Leverkusen Rodinal (used it for more than 20 years), but it's close.

regards

RobK

 

[Nikola Dulgiarov]

RobK - Thanks!

 

[Greg Heath]

RODINAL RECIPES

I ran across this online....

http://www.thorleyphotographics.com/?p=282

 

[Gerald C Koch]

I ran across this online....

http://www.thorleyphotographics.com/?p=282

The formulas given at the website show only a general resemblance to Rodinal. True Rodinal was made using potassium hydroxide not sodium hydroxide. Developers made with potassium salts tend to be more active than those made with other alkalies.

Potassium bisulfite (bisulfite of potash) and potassium hydroxide (potash lye) were probably used in the original formula. These two chemicals were readily available in Germany as percentage solutions because the anhydrous chemicals are unstable and expensive. The Wolfen recipe is the only one that I would consider to be authentic as it was the recipe actually used by Agfa in its Wolfen factory. We therefor definitely know its provenance. You can tell this from the chemical amounts used. This recipe makes something like 750 to 800 liters of developer. It is not a simple task for a non-chemist to attempt to downsize the formula to make smaller amounts.

Agfa Rodinal (Wolfen Recipe)

This is the formula which was collected from the Agfa Wolfen plant in 1945.

Distilled water ………………………………………………………………… 340 l
Paraminophenol …………………………………………………………………… 34 kg
Potassium bisulfite, 30% w/w at 55°C ……………… 558 kg
Potassium hydroxide, 34% w/w………………………………… 50 kg
Potassium bromide* ………………………………………………………… 5.52 kg
Agfa P.1347 antifoggant …………………………………………… 42 g

* The potassium bromide should first be dissolved in a small amount of water.

Dissolve 34 kg of para-aminophenol in 340 litres of water. Add 558 kg of a 30% solution of potassium bisulphite
at 55C followed by 50 kg of a 34% potassium hydroxide solution, then 5.52 kg of potassium bromide in a little
water. Add 42 g P.1347 (an Agfa-specific anti-foggant). Filter and allow to stand for 14 days.

 

[Greg Heath]

Thanks !

How different is this from what we can purchase today from Adox....Adox Adonal ?

 

[Gerald C Koch]

Adox is certainly no going to reveal the recipe of what they sell. In a way this whole thread is of little consequence. There are as many formulas for "authentic" Rodinal as fleas on a hound. Unless someone has made a serious mistake they will all produce very similar results. Believe me I have been down this road before.

 

[Patrick Robert James]

I don't see the point in trying to get the original formula. They all are in practice about the same.

I have been using Gainer's EZ Rodinal formula for a few years now. It is Sodium based instead of Potassium but delivers the same result. I also add some Benzotriazole to it as well just for giggles which is something Ian suggested. I have been using Rodinal for a couple of decades and can't tell the difference between the EZ Rodinal and any commercially prepared version, for whatever that is worth.

 

[Greg Heath]

Adox is certainly no going to reveal the recipe of what they sell. In a way this whole thread is of little consequence. There are as many formulas for "authentic" Rodinal as fleas on a hound. Unless someone has made a serious mistake they will all produce very similar results. Believe me I have been down this road before.

I just find it interesting, if anyone had anything different. I have made the PaRodinal, and it works great, but just doesn't have the shelf life of my Adox 500ml bottle that's 2 years old and going strong. It's easier just to stock up and pay $15 and be done, but it's still fun to mix my own from time to time...

Greg

 

[Gerald C Koch]

I just find it interesting, if anyone had anything different. I have made the PaRodinal, and it works great, but just doesn't have the shelf life of my Adox 500ml bottle that's 2 years old and going strong. It's easier just to stock up and pay $15 and be done, but it's still fun to mix my own from time to time...

Greg

For something a little different. During WWI Rodinal was not available in the US or Canada. This lead an American photographer to design his own version using Metol and hydroqinone made the same way as Rodinal.

(there was a url link here which no longer exists)

 

[Xmas]

For something a little different. During WWI Rodinal was not available in the US or Canada. This lead an American photographer to design his own version using Metol and hydroqinone made the same way as Rodinal.

(there was a url link here which no longer exists)

The concentrated paraaminophenol formula was available any one can mix up a clone. When the patent expired everyone did. I used Azol as a kid.