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Photo Forum / Film Photography / Darkroom / December 2005

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Rodinal and Patrick Gainer

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lew - 21 Dec 2005 23:19 GMT
Gents & Patrick:
   I think I've assembled the ingredients, but I'd like to form a
rudimentary understanding of the differences between Patrick's formula
(below) and the one I dug out of Anchell which follows. I must admit that I
got the hydrochloride from the Photographer's Formulary before I read the
fine print.
   Can anyone weigh in on this?

Gainer Rodinal:
   700 ml water. Add 150 grams sodium sulfite and 14 grams of sodium
hydroxide. Red Devil lye will do. When the solids are dissolved, bring the
volume up to 1 liter with water, put the solution in a 1 liter storage
container and add 40 grams of p-aminophenol (not the hydrochloride), shake
well and serve. Use it as Rodinal.
   There will be some precipitate. This is the "few remaining crystals" of
the standard recipe and is the protection against aerial oxidation. Of
course, you don't believe me, but try it anyway.
ie
700 ml water
150g sodium sulfite
 14g  sodium hydroxide
 40g p-aminophenol

Here's the Anchell version
750ml water
100g    p-aminophenol hydrochloride
300g    potassium metabisulfite
200g    sodium hydroxide (actual amount determined while mixing)

-Lew
Michael Gudzinowicz - 22 Dec 2005 00:47 GMT
> Gents & Patrick:
>     I think I've assembled the ingredients, but I'd like to form a
[quoted text clipped - 3 lines]
> fine print.
>     Can anyone weigh in on this?

The primary difference is the choice of p-aminophenol base vs.
p-aminophenol*HCl. Usually the aminophenols and similar developing
agents are prepared as the acid salt... for instance, p-aminophenol
hdyrochloride, Metol, etc. The acid salts are very stable in powder form
compared to the free bases, and the acid salts are soluble in water.

The Anchell formula I have is quite different from that which you
posted. It is:

----------
Rodinal-type Developer

This formula is very similar to Agfa Rodinal. Rodinal is the oldest
proprietary formula in use today, the original formula dating back to
the 1880s. It is considered by some to be the finest all around film
developer, even for modern T-grain films.

Solution A
Water (125°F/52°C)             750.0 ml
P-Aminophenol hydrochloride         100.0 grams
Potassium metabisulfite         300.0 grams
Cold water to make             1 .0 liter

Solution B
Sodium hydroxide             50.0 grams
Cold water                 100.0 ml

CAUTION: When the 50% solution of sodium hydroxide is being made up,
heat is generated. The solution must be cooled before adding to the
developer.

Allow Solution A to cool. A precipitate of p-Aminophenol hydrochloride
will form. Slowly add, drop by drop, Solution B to Solution A until the
precipitate almost disappears. Do not dissolve all of the visible
precipitate! Leave a few crystals undissolved (as few as two or three).
---------

Actually, the precipitate that is formed is the free base, which is
ionized by base and goes back into solution.

This is another preparation for Rodinal which I pulled from an old
forgotten reference:

-----------
Rodinal Preparation:

Boil 250 ml water, cool to 125F, and add a few crystals of potassium
metabisulfite, followed by 20 g of para-aminophenol hydrochloride. After
the para-aminophenol-HCl dissolves, add 60 g potassium metabisulfite,
and stir until dissolved. Then add a solution of 40% (w/v) sodium
hydroxide which thickens the solution as the para-aminophenol base
precipitates, and then goes back into solution as the phenolate anion as
more sodium hydroxide is added. Stop the addition of sodium hydroxide
while there is still a small amount of precipitate left, and add water
to make 400 ml. Set aside to cool, and place in a glass bottle. A small
amount may come out of solution, but the addition of sodium hydroxide
will dissolve it. If there is no precipitate, excess sodium hydroxide
may be present, and a saturated potassium bisulfite solution may be used
to neutralize it. (The amount of 40% sodium hydroxide required is approx
70 ml.)

A small amount of precipitate is desired, since this occurs at the
lowest pH at which the para-aminophenol is in solution. The addition of
more base results in a higher pH at which the solution oxidizes more
rapidly.
----------------

Again, a small amount of precipitate is left in the solution, In a way,
the solubility of the base in the alkaline solution is being used as a
pH indicator to insure that an excessive amount of hydroxide isn't
present, that would give a very high pH and short shelf life. When I
used commercial preparations of Rodinal I transfered them to a glass
bottle and titrated them with bisulfite until the a few crystals
precipitate formed. I started the practice after Agfa changed the their
preparation (more basic - no crystals).
lew - 22 Dec 2005 01:49 GMT
Mine's from the Cookbook, p.162. Apart from the mixing instructions, they're
identical.

>> Gents & Patrick:
>>     I think I've assembled the ingredients, but I'd like to form a
[quoted text clipped - 77 lines]
> I started the practice after Agfa changed the their preparation (more
> basic - no crystals).
PATRICK GAINER - 22 Dec 2005 18:26 GMT
>Mine's from the Cookbook, p.162. Apart from the mixing instructions, they're
>identical.
[quoted text clipped - 87 lines]
>
>  

My "theory" on the reason for leaving some undissolved crystals is that
they extend the shelf life by a sort of regeneration. Aerial oxidation
of a molecule of p-aminophenol in the presence of sulfite produces a
monosulfonate and a molecule of the hydroxide, potassium or sodium
depending on which you used. If there is a molecule of  p-aminophenol
lying around in the bottom of the container, it will be converted to the
sodium (or potassium) aminophenolate which is the active agent in
Rodinal. and will replace the oxidized molecule. Actually, the main
reason for the undissolved crystals may be to get rid of all the oxygen
that was dissolved in the water when you mixed the solutions. At any
rate, the excess p-aminophenol  is precipitated and will not affect the
activity of the developer, so there is no need to be finicky about how
many crystals one leaves undissolved.

A similar developer can be made using Metol instead of p-aminophenol.
You will have to add enough hydroxide to change the hydrosulfate
(sulfuric acid) to sodium or potassium sulfate and some more to form the
sodium or potassium salt of the 4(methyl-amino)phenol. I leave quite a
bit undissolved, and it seems to be lasting qhite well. It gives a
little more shadow speed than Rodinal for the same contrast.

63 grams of Metol have about the same number of molecules as 40 grams of
the p-aminophenol, so you will need enough NaOH to neutralize 23 grams
of sulfuric acid in addition to the amount used for 40 grams of the
p-aminophenol base.
PATRICK GAINER - 23 Dec 2005 03:44 GMT
>>Mine's from the Cookbook, p.162. Apart from the mixing instructions, they're
>>identical.
[quoted text clipped - 113 lines]
> grams of sulfuric acid in addition to the amount used for 40 grams of
> the p-aminophenol base.

I goofed a little. There are not quite 23 grams of sulfuric acid in 63
grams of Metol. I forgot to account for the methyl part. For 63 grams of
Metol, I use 28 grams of NaOH and 150 grams Na2SO3 in a liter of water.
Some precipitate remains. It should be about 3 grams, but it looks like
more because the precipitatee is fluffy.
 
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