Rodinal Substitutes?

[gainer]

You were right, Jurgen. I doctored the remains of the 500 ml I had made by adding 10 grams of sodium bisulfite to bring the pH down roughly where it would be without the extra 9 grams/liter of sodium hydroxide. The HP5+ negative at 1+25 is much better. I'll try a new batch from scratch when my supplies come in. Thanks.

 

[Peter Schrager]

go Patrick!!

Mr. Gainer-please keep us updated on this. I'd rather just make it for myself. To hell with Agfa et al for the way they treat us. Once you've come up with a proper formula I can make enough for MY lifetime supply.....
Best, Peter

 

[Gerald Koch]

I wonder how many complaints Photographer's Formulary get every year to the effect "I mixed everything in the kit but the Rodinal turned out completely black." It needs to be stressed that the developer will oxidize VERY rapidly if there is ANY excess hydroxide. By leaving a small amount of precipitate you insure that there is no excess. Think of the end point in a titration where the indicator is the precipitate.

 

[gainer]

I wonder how many complaints Photographer's Formulary get every year to the effect "I mixed everything in the kit but the Rodinal turned out completely black." It needs to be stressed that the developer will oxidize VERY rapidly if there is ANY excess hydroxide. By leaving a small amount of precipitate you insure that there is no excess. Think of the end point in a titration where the indicator is the precipitate.

Well, mine that I mixed from p-aminophenol and that had the extra 9 grams/liter, did not oxidize rapidly. OTH, the stuff I mixed from the old p-aminophenol.HCl was black as coal from the start. I seem to remember that the kit I got from the Formulary also produced very dark Rodinal from the start.

The problem that I had with trying to leave a litle precipitate was that the reaction upon adding hydroxide solution was slow. The visual feedback was delayed enough that I added too much hydroxide. I can't quite imagine that a manufacturer mixing a large vat of Rodinal would rely on that visual feedback, especially nowadays when the purity of many of the chemicals is good enough not to depend on titration. If it is essential to leave the reaction incomplete, I think it might be better to calculate the amount of hydroxide required and subtract a little, say 1%, for good luck.

I think I realize now that the number of molecules of hydroxide should equal the number of molecules of p-aminophenol when I use the sulfite instead of the metabisulfite. If that produces a pH that is high enough, then all the gossip about Rodinal having a lot of potasium hydroxide is just that. Why is it considered such a hazardous material for shipping? It may be because the label shows what went in, not the effective compounds that result.

 

[Jürgen]

You were right, Jurgen. I doctored the remains of the 500 ml I had made by adding 10 grams of sodium bisulfite to bring the pH down roughly where it would be without the extra 9 grams/liter of sodium hydroxide. The HP5+ negative at 1+25 is much better. I'll try a new batch from scratch when my supplies come in. Thanks.

I don't want to be critical but I did a few calculations on the rodinal formula in the darkroom cookbook. After converting the HCl salt to base and assuming all 400ml of KOH is used it appears to be about 0.5 molar in para aminophenol, about 55 grams. This would require about 20 grams of NaOH. Not sure about the sulfite.

Also the pH of your formula at 1:25 would be about 12, at 1:50 about 11.6.

Jurgen

 

[Gerald Koch]

The problem that I had with trying to leave a litle precipitate was that the reaction upon adding hydroxide solution was slow. The visual feedback was delayed enough that I added too much hydroxide.

The formula which I use says to first add x milliliters of the hydroxide solution. Then it says to add the hydroxide slowly until there is a sudden darkening of the solution. At this point the hydroxide should be added very slowly until most of the remaining precipitate dissolves but a small amount is left. Using this method the bulk of the hydroxide can be added all at once.

Sodium or potassium hydroxide and potassium metabisulfite are all of variable purity and may vary by several percent from batch to batch. This necessitates "titrating" the bisulfite/pap mixture with the hydroxide solution. I have made many batchs of "Rodinal" and have never had much difficulty. Should one overrun the endpoint it is easy to add a small amount of metabisulfite to bring back some precipitate.

 

[gainer]

I don't want to be critical but I did a few calculations on the rodinal formula in the darkroom cookbook. After converting the HCl salt to base and assuming all 400ml of KOH is used it appears to be about 0.5 molar in para aminophenol, about 55 grams. This would require about 20 grams of NaOH. Not sure about the sulfite.

Also the pH of your formula at 1:25 would be about 12, at 1:50 about 11.6.

Jurgen

Criticism is good. I had to do enough of it and endure enough of it while working at NASA to know the value of it.

I don't think the amount of sulfite is critical, as long as it is not in the bisulfite form. Then, of course, it would have a considerable effect on the amount of hydroxide required.

I ordered a big bunch of p-aminophenol to play with. I'm thinking another wat to go about this variation in purity would be to use the calculated amount of hydroxide and see if there remains any precipitate. If so, leave it alone. If no, add a little p-aminophenol.

I'm quite happy with the results I got after I reduced the pH with bisulfite in accord with your previous helpful criticism. Of course, this adds a little to the net sulfite content, but this is very small in the working solutions even if it were double. I could experiment with that as well.

I found that p-aminophenol is on the list of hazardous materials, which is probably the reason some do not want to ship it. They should be able to ship it by UPS ground, but that leaves out overseas I guess.

 

[gainer]

No new results, but some new thinking on my part. I have seen several recipes for Rodinal, as have we all, and have concluded that the ones that start with 100 g p-aminophenol.HCL are fro1.5 or 2 liters of stock, as they start with one liter before adding the hydroxide solution. The one recipe I saw with 50 g started with 500 ml, added hydroxide to almost dissolve the solids, then brought the solution up to 1 liter. 50 grams of the hydrochloride contains about 37.5 grams of the p-aminophenol, which is about 0.344 gmw. If I start with the base p-aminophenol, I should only need 0.344 gmw of a hydroxide, which is about 13.7 grams of sodium hydroxide. The sulfite is a little trickier to calculate, but 150 grams of potassium metabisulfite in water = 0.675 gmw which can be replaced by 1.349 gmw of potassium bisulfite, which after all is done amounts to 1.349 gmw of any soluble sulfite. That would be 170 grams of sodium sulfite in the liter of concentrate. I conclude that a solution of 37.5 grams of p-aminophenol, 170 grams of sodium sulfite and 13.7 grams of sodium hydroxide should make a liter of a sodium Rodinal Expedient. We will see.

 

[Gerald Koch]

Not only are there many recipes for Rodinal like developers there are several which use Metol and hydroquinone. Both these developing agents form phenolates with hydroxides just like paraminophenol. The following recipe which appeared in the Dignan Newletter is based on one from 1917 when Rodinal was hard to obtain because of WWI. The original formula was sold commercially in 1917 and was published by the author Paul L. Anderson in his book The Technique of Pictorial Photography", J. B. Lippincott, 1939.

Kalogen

Distilled water (50°C) .................. 750 ml
Metol ....................................... 13.5 g
Sodium sulfite (anhy) ................... 180 g
Hydroquinone ............................ 53.0 g
Sodium hydroxide ........................ 35.0 g
Potassium bromide ....................... 5.0 g
Benzotriazole, 1% ....................... 80.0 ml
Distilled water to make ................. 1.0 l

Dissolve the ingredients in order. When the hydroquinone is added a heavy white precipitate will form which will dissolve when the hydroxide is added.

For films dilute 1+49, average development time is 5 minutes at 20C. For papers dilute 1+11 to 1+14. Results are very similar to Dektol.

This developer has a very long shelf life of at least 2 years in fully filled bottles.

Like Rodinal this is not a fine grain film developer but the grain is crisp and pleasing.

 

[df cardwell]

Patrick, and all

Going through a box of books today... an early 1920's ( although undated ) softcover book entitled, "AGFA Photo-Handbook" by Dr. M. Andresen.

Like this so far ?

Besides having all kinds of interesting things to do WITH Rodinal, there are two formulae in the chapter entitled AGFA Developer Chemicals for "AGFA Paramidophenol (hydrochloride)".

Page 262

"AGFA Paramidophenol (hydrochloride) in combination with caustic alkalies produces a rapid developer, whilst with potass. carbonate, or soda carbonate it forms a very slow and clean-working developer".

FORMULA 20: Two-solution
A. Paramidophenol hydrochloride 20 grms. 175 grs.
Water 1000 c.c.s. 20 ozs

B. Soda sulphite, cryst. 120 gms. 525 grs
Potass. Carb 120 gms. 525 grs
Water 2000 c.c.s. 20 ozs.

NOTE: this is not a typo by me, but I wonder about Agfa's typesetter !

For use, mix 1 part of Solution A with 2 parts of Solution B. The above developer is slow and clean working.

And,

Formula 21: Concentrated single solution.

Dissolve:
Potass metabisulphite 30 gms 1 oz
in
Water 100 c.c.s 3 1/2 ozs
and then add:
Paramidophenol hydrochloride 10 gms. 160 grs.

To the solution thus prepared add slowly, stirring all the time, concentrated caustic lye until the precipitate which forms at first is just redissolved. Keep this solution in well closed bottles and mix with 10 to 30parts of water.

The above is a very rapid developer.



Again, there is no date, and I ascribe it as '20s based on the outfits worn by the people in the illustrations. More accurate dating could be done by examing the details of flashpowder packaging, and so on.

That's it ! Have fun.


Isn't this more fun than digital ???

 

[bogeyes]

spectrum 1

Found this, never used it though.

 

[Lee Shively]

Not being of the chemical-concocting type, I kind of lost track of this thread with all the formulas involved. Somebody might have mentioned it and I missed it, but Photographer's Formulary website says they will be introducing an already mixed, liquid form of their Rodinal substitute shortly. The mix-it-yourself kits have been discontinued.

 

[Gerald Koch]

Not being of the chemical-concocting type, I kind of lost track of this thread with all the formulas involved. Somebody might have mentioned it and I missed it, but Photographer's Formulary website says they will be introducing an already mixed, liquid form of their Rodinal substitute shortly. The mix-it-yourself kits have been discontinued.

I wonder what they will charge. I have always found that their kits are overpriced for what you get.

 

[Fotohuis]

We have enough original Agfa Photo Rodinal in our supply chain. We can offer 10% discount on the second bottle.
All European APUG members will have no problem till at least next year.

best regards,

Robert

 

[gainer]

I have found that the following recipe gives the results of Rodinal with no fuss in the making.

Start with 700 ml water at room temperature.
Add 170 grams of anhydrous sodium sulfite, 14 grams sodium hydroxide, and stir till dissolved. Warming it a little won't hurt. Add 40 grams p-aminophenol (not the hydrochloride). It will not all dissolve. Add water to make 1 liter. When you transfer from the mixing vesel to storage, do not filter out the sediment. Use it like AGFA Rodinal.

 

[jim appleyard]

I have found that the following recipe gives the results of Rodinal with no fuss in the making.

Start with 700 ml water at room temperature.
Add 170 grams of anhydrous sodium sulfite, 14 grams sodium hydroxide, and stir till dissolved. Warming it a little won't hurt. Add 40 grams p-aminophenol (not the hydrochloride). It will not all dissolve. Add water to make 1 liter. When you transfer from the mixing vesel to storage, do not filter out the sediment. Use it like AGFA Rodinal.

Pat, How can that much sulfite give results like Rodinal? That's quite a bit of sulfite, even more than D-25, which by some accounts gives soft negs. Am I missing something?

 

[Ole]

Am I missing something?

Dilution. Diluting that stuff 1:100 gives 1.7g sulfite per liter of working solution, which is not a lot at all.

 

[jim appleyard]

Right, dilution! It looks like I was missing something after all! Thanks Ole, I'll have to try that recipe.

 

[Donald Qualls]

Here's another Rodinal Substitute you guys can try: acetaminophen, aka paracetamol. It converts to para-aminophenol in a strongly alkaline hydroxide solution; a little sulfite preserves it. A recent thread on f295 includes images scanned from film developed in this stuff: http://f295.tompersinger.com/cgi-bin/Blah/Blah.pl?b=lab,m=1132019056

The formula used was:

50 ml water
3 g acetaminophen (6 tablets, 500 mg size, crushed)
4 g sodium hydroxide (Red Devil Lye)
10 g sodium sulfite anhydrous

According to original article, dilute 1+39, use like Rodinal 1+25 (which makes it equivalent to R-09). Based on Daryl's results, I'd suggest trying same concentration as Rodinal.

This is quite close to Gainer's simple Rodinal substitute -- a little more sulfite, but otherwise very similar. The acetyl group cleaved off the acetaminophen is only about 5% of the molecular weight, and of course one could adjust the proportions if needed to control the developing characteristics, but I'm certainly planning to try this. BTW, the amount above is enough to develop 8 rolls of 35 mm at 1:25, or 32 rolls at 1:100...

 

[Lee L]

The Kalogen is already in the formulas/recipies area, but the other contributions in this thread should be put there as well for reference without a lot of searching.

Lee

 

[Photo Engineer]

Just some information here.

The Lye that I get here is often rather crummy stuff. If it is not pure white flakes, don't use it.

Acetaminophen and other drug intended or vitamin intended chemicals often contain fillers such as starch which will cause cloudy colloidal suspensions of the filler. These fillers can lodge in gelatin leading to a grainy appearing effect in the final film. So, be careful and filter out that stuff.

Finally, the real Rodinol formula is unique and does not need any benzotriazole or bromide as antifoggant. Its particular chemistry related characteristics have not really been caught or captured by anyone here. I wonder if anyone out there (that I have not told) will be able to discover what I'm referring to?

There is room for a whole family of Rodinol type developers with a range of subtle characteristics based on my observations in the lab. One thing I must point out is that properly mixed Rodinol or its work alikes should not ever have a purple color. The final stock solution should resemble tea.

Good luck to you all.

PE

 

[Gerald Koch]

The Lye that I get here is often rather crummy stuff. If it is not pure white flakes, don't use it.

Finally, the real Rodinol formula is unique and does not need any benzotriazole or bromide as antifoggant. Its particular chemistry related characteristics have not really been caught or captured by anyone here. I wonder if anyone out there (that I have not told) will be able to discover what I'm referring to?

One thing I must point out is that properly mixed Rodinol or its work alikes should not ever have a purple color. The final stock solution should resemble tea.

Red Devil brand lye is very good. It is a free flowing granular product, perfectly white, and the consistency of fine sugar. It also keeps better, not taking up moisture readily, as it comes in a screw cap bottle.

Some years ago Agfa changed the Rodinal formula and it now contains potassium bromide which is listed in the current MSDS. It now also contains EDTA.

Some years ago I used to make a Rodinal type developer. Since the p-aminophenol hydrochloride that I was using was rather brown I would remove the color with decolorizing charcoal. The formula had you the prepare the free base by precipitating it from a sodium carbonate solution. The free base was a cream color. The developer made from this purified base was a pale lilac color.

 

[Photo Engineer]

Thank you Ron and Gerald for sharing your expertise, it is most welcome.

You are welcome.

I have found that it is possible to make a developer that does not require any antifoggant, gives good film speed and fine grain, but is not as active as Rodinal. To match (or excede) the activity of Rodinal, I've had to increase the pH, and add a drop or two of BZT.

You should be able to make it without the AF. Agfa did for years. The addition of EDTA was to take into account the varying salt content of water supplies. EK has done the same to all formulas over the years.

I'm seeing a range of colors from very brown-purple, to the pale lilac color, with the light tea in between. I've assumed that the dark brown stuff is more oxidized than the lighter stuff, and that the lilac stuff hasn't fully hydrolysed.

Ron, what does the purple color indicate?

Oxidized developer most likely or polymerized products resulting from oxidized developer. The actual Rodinol should be a clear tea color with a crystal or two floating in suspension.

There are many Rodinol formulas out there, but the original still worked well. Never forget that!

PE

 

[Gerald Koch]

One of my photo chemistry books (can't remember which) states that p-aminophenol produces the least amount of fog of any of the commonly used developing agents. Since this book was written some time ago the list of commonly used developing agents was longer than it is today.

The MSDS for p-aminophenol says that it should be white or light brown when pure but the color may turn to violet when exposed to air.

 

[Kirk Keyes]

One thing I must point out is that properly mixed Rodinol or its work alikes should not ever have a purple color.

I ain't no stinkin' organic chemist, but I'll take a wild guess here -

The purple color that comes from the tylenol (acetominophen) is from a rearraingement of the methyl group on the end of the chain part of the acetominophen molecule with the C=O that is between said methyl group and the amine group that connects to the phenol ring. Once that is rearranged, then the new molcule can react with another similarly rearrainged acetominophen molecule, end to end. This would make a molecule twice as long and it would have enough aromaticity/ring structure resonance that it would support the absorption of light.

I don't have a name for this molecule, but it would be nearly identical to a commonly used dye, indigo. The only difference between the acetominophen based dye and indigo would be -OH group from the phenol portion of the acetominophen hanging off both ends which would tweek the color of the molecule a little bit from the color of true indigo.

Ron - does this happen because too high of a pH is used in the hydrolysis of the acetomino part from the phen part?

Kirk - www.keyesphoto.com

PS - the original question addressed here should be an "extra credit" question on an organic test!