Modern Rodinal Substitutes Part II

[Kirk Keyes]

For some odd reason, you made me think of the person who, upon being exposed to a treatise by Thomas Acquinas on "The Divine Simplicity" said "If that's His simplicity, I can't imagine what His complexity would be like."

I agree with the comment on Acquinas, but how hard is a titration? After learning to use the balance, titration is usually the first thing they teach you in chemistry class.

You could probably use USP ascorbic acid to titrate against if you really wanted to give it a try...

 

[gainer]

I agree with the comment on Acquinas, but how hard is a titration? After learning to use the balance, titration is usually the first thing they teach you in chemistry class.

You could probably use USP ascorbic acid to titrate against if you really wanted to give it a try...

It wasn't the difficulty of the process that stimulated my wit, it was the fact that it seemed that you expected every APUGer to have the chemicals and to be able and willing to go through that for a Rodinal fix which might or might not be better than store-bought. Seemed more complex than it is, and I'd have to wait a week for delivery of the test gear.

I'll have to see what indicators my hot tub test kit has. I have USP ascorbic acid.

 

[Kirk Keyes]

I don't expect every Apugger to have all these chemicals. But I figured a tinkerer like you would be interested.

Personally, I've not seen much need for Rodinal, despite my interest in the discussion. I've actually bought only one bottle, in about 1983, and I think I tossed it about 2000.

 

[Kirk Keyes]

You can use your pH meter too if you like. Just titrate to pH 7. I was trying to keep it simple by mentioning an indicator. But nowadays, most tinkerers will have a pH meter.

 

[gainer]

Ian;

I think HC-110 is rather good as a developer and has good shelf life. I think that some of the higher dilutions of HC-110 have not been fully exploited and may prove to approach Rodinal. I also believe that a Metol based Rodinal, if stable, would be superior to Rodinal.

PE

Some years ago, I used HC-110 a lot, even for developing paper. For film, I usually added a modicum of ascorbate. For paper, I added some carbonate and some sulfite, IIRC. It was always reliable and quick to prepair, which was a virtue at the time. I was working for NASA, principal oboist for both Peninsule and Norfolk Symphonies, and photographing guest artists at dress rehearsals, providing them with prints the next day. Did I mention having six kids?

I have a portion of a bottle a couple of years old, looks and works like new.

 

[gainer]

You can use your pH meter too if you like. Just titrate to pH 7. I was trying to keep it simple by mentioning an indicator. But nowadays, most tinkerers will have a pH meter.

I took your suggestion. I made some KOH using the K2CO3 and CA(OH)2. A 0.1 normal solution of ascorbic acid added slowly to a sample diluted 10:1 gave a pretty sharply defined transition form basic to acidic on my pH meter. I estimated closely enough for government work that the KOH I made was about 1.25 N.

 

[Kirk Keyes]

Actually, you don't even need to make the ascorbic (or KHP) to a particular normality. You can simply weigh a known amount into a beaker and add enough water to get the solution high enough for your pH electrode (or add your indicator), and then start titrating. It's kind of funny, as KHP does not even typically disolve into solution before the start of the titration. It will dissolve a bit, and then as the titration goes, the dissolved portion reacts with the KOH (or whatever basic solution you are titrating) and some more KHP will dissolve. As you are getting near the endpoint of the titration, all the KHP will go into solution.

So the important thing when doing this is to know how much KHP (or ascorbic) you wieghed out so you can do the calculation to determine the normality of the base. So typically, when standardizing bases, one puts the standard acid in the beaker, and then titrate with the base. But it works the other way too.

 

[BobNewYork]

Some years ago, I used HC-110 a lot, even for developing paper. For film, I usually added a modicum of ascorbate. For paper, I added some carbonate and some sulfite, IIRC. It was always reliable and quick to prepair, which was a virtue at the time. I was working for NASA, principal oboist for both Peninsule and Norfolk Symphonies, and photographing guest artists at dress rehearsals, providing them with prints the next day. Did I mention having six kids?

I have a portion of a bottle a couple of years old, looks and works like new.

And what on earth did you do with all your spare time??

Bob H

 

[gainer]

And what on earth did you do with all your spare time??

Bob H

That's when my wife and I worked on making the kids. It was a lot of fun, too.

 

[gainer]

Actually, you don't even need to make the ascorbic (or KHP) to a particular normality. You can simply weigh a known amount into a beaker and add enough water to get the solution high enough for your pH electrode (or add your indicator), and then start titrating.

That in fact was what I did. I figured it would take a mole of KOH to neutralize each mole of ascorbic acid I put in. The swing from <7 to >7 in pH was abrupt enough to satisfy this need, even if my pH meter had been somewhat out of adjustment. I didn't find out tll later that the solubility of KOH is less than 2 MW/liter. DUH!

 

[gainer]

I didn't use a full MW of ascorbic acid. Just the mole fraction, w/176.

 

[Photo Engineer]

I would like to point out that the Normality may be more important than Molarity when it comes to Ascorbic Acid.

PE

 

[gainer]

One thing we know. If you have p-aminophenol and a strong alkali like KOH or K2CO3, you can develop film. Of course, without sulfite it will be grainy and lack film speed. Or will it? I tried this combination with 500 ml water, 1.5 grams p-aminophenol base, and enough of Sandy King's 75% K2CO3 part 2 to dissolve the p-ap. 8 minutes, 68 F, EDU 400 Ultra. The result is attached.

You will not see anything in this very rough test that you would not see in a Rodinal test using the same scene. What happened to the grain and all the other problems you might have expected from such an unadorned developer solution? Surely, you wouldn't expect to be able to make a long lived concentrated stock solution with just these two ingredients, but there are other ways to preserve solutions of p-aminophenol. One is to dissolve it in glycerine or in propylene glycol, and keep a bottle of Sandy's B solution handy.

I know for fact that at least 36 grams of p-aminophenol are soluble in a liter of either glycerine or propylene glycol. I have used either KOH or the carbonate with both of them, addig sulfite or not to the working solution. If I keep the sulfite to the proportions you would get by putting the suggested 384 grams in the stock, you would have only 7.7 grams in a liter of working solution. Seems hardly worth the trouble if you don't need it as a preservative for the stock.

You can get a handy little 4 fl. oz. bottle of very pure glycerine at most pharmacies to play with. 9 or 10 grams of p-aminophenol will go into that with a little persuasion in the form of heating and stirring.

How much Pyrocat "B"? Some must go into forming the potassium aminophenolate, and some more into raising the pH to a decent working speed. My rough test used 5 ml when I diluted 10 ml of the p-aminophenol solution with 50 parts of water.

 

[gainer]

The direct scan of the negative showed meither the true resolution of the detail nor the grain. I made a 10X enlargement in the darkroom and scanned the attached detail view from it.

I measured base+fog of the negative at 0.24, the darkest point of the scene at .28, and the scene highlight at 1.3. This range is a little large for grade 2 so I made the print on Arista VC with 30 Y filtration.

 

[gainer]

With regard to film speed: I set my camera for 400, the box speed, and to bracket plus & minus 1/2 stop. What I have shown here is from the box speed.

 

[Alan Johnson]

Metol is said to be sensitive to hydrolysis in alkaline media:
http://books.google.co.uk/books?q=metol+hydrolysis+karlheinz+keller&btnG=Search+Books

Now I read this book,the google quote gives the wrong impression.It is in fact phenidone which the book says is sensitive to hydrolysis in alkaline media.
There is nothing about metol hydrolysis.

 

[Photo Engineer]

Alan;

Something goes on with Metol in alkali. It turns dark right off even with lots of sulfite present, and it begins giving off a strong odor. This is the typical metol "breath of death". Since Metol is a stronger reductant (according to my references) than pAP, I do think something is going on.

We also have the reports here of Metol based Rodinal work alikes losing strength rapidly.

PE

 

[gainer]

I can't do much with Metol until I get some more. That batch that I put aside to age a while still needs to be tested again. Is it really necessary to have a single solution developer to produce the appearance of Rodinal? I think that we should broaden the search for means of preserving it beyond sulfite as I think I have with p-aminophenol in my previous posts. If I can make a 2-part developer having only p-aminophenol in the first part and only alkali in the second that has excellent speed, grain and resolution, even if it only lasts for an hour or so, It disproves some of my old beliefs about the role of sulfite, among others.

 

[Alan Johnson]

If 198g/L (1 molecular weight) sodium ascorbate is added to Metolal concentrate (M+A),the film speed is increased.For TMX EI: D-76=64,PC-TEA=80,M+A~160.The grain is reduced but could probably be restored to Rodinal like levels by making the concentrate more alkaline.Dev time M+A 1:50=2x that for Xtol 1+1.
www.ccohs.ca/oshanswers/chemicals/chem_profiles/sodium_hydroxide/

 

[gainer]

If 198g/L (1 molecular weight) sodium ascorbate is added to Metolal concentrate (M+A),the film speed is increased.For TMX EI: D-76=64,PC-TEA=80,M+A~160.The grain is reduced but could probably be restored to Rodinal like levels by making the concentrate more alkaline.Dev time M+A=2x that for Xtol 1+1.
www.ccohs.ca/oshanswers/chemicals/chem_profiles/sodium_hydroxide/

Now do it without sulfite, but with ascorbate.

 

[Alan Johnson]

Oh.Reviewing my notes,I did not put any sulfite in, so it was done without sulfite.
Metolal derivative,call it MA-1:
Water 150ml
Metol 8g-if the solution is heated, be sure to cool to room temp before adding the next ingredient, the hydroxide.
Sodium Hydroxide 15.6g
Ascorbic acid 35.2g
Water to 200ml
For use dilute 1:50, develop for about 2x the Xtol 1+1 time.
There are notes on sodium hydroxide safe use earlier in this thread.It attacks people and parts thereof.
www.ccohs.ca/oshanswers/chemicals/chem_profiles/sodium_hydroxide/

 

[gainer]

When we speak of grain, do we mean the size of the film grain or the appearance of granularity in the print from that negative? A resolution test chart is a help. It doesn't have to be an expensive one. A fairly coarse grid will show what we want to know. With lines and spaces of equal width in the original, photocopies may have wider lines than spaces in the negative due to infectuous development, or vice vesa due to certain edge effects. The whole business is complicated by scale effects from large to small formats. A perfectly sharp transition from black to white or light gray in the object will be seen by a subject to have a halo. An objective halo induced by development will be subjectively different in the same size prints from large and small format negatives. I think you all know these things, but I just want to make sure.

 

[Ian Grant]

Patrick raises a good point because Rodinal produces excellent fine grain with some films, so choice of film is equally as important.

Ian

 

[gainer]

Oh.Reviewing my notes,I did not put any sulfite in, so it was done without sulfite.
Metolal derivative,call it MA-1:
Water 150ml
Metol 8g-if the solution is heated, be sure to cool to room temp before adding the next ingredient, the hydroxide.
Sodium Hydroxide 15.6g
Ascorbic acid 35.2g
Water to 200ml
For use dilute 1:50, develop for about 2x the Xtol 1+1 time.
There are notes on sodium hydroxide safe use earlier in this thread.It attacks people and parts thereof.
www.ccohs.ca/oshanswers/chemicals/chem_profiles/sodium_hydroxide/

See www.unblinkingeye.com. Look for Vitamin C developers. There you will see some that are pretty close to what you have described above. Some of these developers are so easilly and quickly mixed that there is not much advantage to a concentrated stock, especially if you have a well-calibrated set of teaspoons.. Also, ascorbic acid and p-aminophenol base are soluble enough in glycol or glycerine to make a simple 2 part stock convenient, as I tested (crudely) in another post. If there is a definite need for sulfite, it can be added to the second part with the activator.

 

[Alan Johnson]

Vit C formulas may contain undissociated metol carbonate if there is such a thing,IDK.
Ascorbate probably does not form undissociated compound with metol which would be present as its aminophenolate.