Modern Rodinal Substitutes Part II

Ian Grant · Oct 5, 2009

Photo Engineer said:
Ian;

It is well known that Benzene sulfonates help PPDs dissolve! In fact, a close analog, pTosyl (para Toluene Sulfonic Acid) is used for all CD3 developers and CD6 developers today.

PE

OK, earlier post #(there was a url link here which no longer exists) you had almost no knowledge of Benzene sulphonates

Now it's well known That's irrelevant, these are marginal chemical combinations in most uses. . . . . . . . .

What's important is that something else happens between PPD and Benzenesulphonates, it isn't just about helping PPD to dissolve, it's preventing oxidation as well.

The same inter-reaction is taking place with p-Aminophenol preventing or rather holding back oxidation.

There's an equilibrium complex involved, my extremely rusty Organic chmistry is returning, my Biochemistry was my strong point

Ian

Photo Engineer · Oct 5, 2009

Ian;

I know nothing about benzene sulfonate itself as an antioxidant.

As for the properties of benzene sulfonates or p-tosylates as antioxidants or as helpers in dissolving, it is known from fundamental chemistry that organic aryl amines (metol, pAP, and PPDs) all oxidize rapidly as free bases and dissolve slowly as free bases. If they are predissolved in an equmolar solution of ANY acid, then they dissolve much more rapidly in water and they are much more resistant to aerial oxidation

The key to this is pH though and not antioxidant properties of the benzene sulfonate or p-tosylate. Sulfuric acid was used and before that Hydrochloric Acid was used. Nowdays the develoer is dissolved in the sulfonate solution and this has been saturated with SO2 gas. The SO2 gas is the true antioxidant as is the pH an assist in achieving this effect.

This is true of all Kodak, Fuji and other color developer kits for C-41 and E6 alike.

We were in the process of converting when I was working on the CD-6 problem and I had to convert all of my molarity tables due to the difference in molecular weight of the two salts, the H2SO4 salt and the p-Tosyl salt. I used to get the developers in powder or crystal form and had to dissolve them in water with Sulfite. Remember the "pinch of sulfite" rule in making Metol containing developers?

And, these p-Tosyl salts are major chemical contributioins.

BTW, benzene sulfonic acid is (C6H5)-SO3H and p-Toluene Sulfonic Acid is CH3-(C6H4)-SO3H, differing by CH2 only and it is expressed as a CH3- replacing one H-. They are virtually identical. But, benzene and napthalene sulfonates as sodium salts, especially with ballast groups are better known as detergents.

PE

pavelt2tk0 · Oct 6, 2009

Photo Engineer said:
Grant;

AFAIK, Benzenesulfinian is Benzene sulfinic not sulfonic which would be -sulfonian or somehing like tht. Polish speakers please verify my very rusty translating efforts of organic chemistry.

An afterthought: We might ask pavel if he can verify that his Russian translation is benzene sulfonic..... That might also be questioned in view of my notes on Sulfinic acids.

PE

Gentlemen,

Really - I made with mistake with transliteration: the chemical stated in the book and the one I used is Sodium Benzenesufinate. And I assume the polish literation is the same.
I tried to look for different sources about sulfonate and sulfinate, and it seems that both of them can be used as ani-oxidants. There is not much info unfortunately.

Ray Rogers · Oct 6, 2009

pavelt2tk0 said:
Gentlemen,

Really - I made with mistake with transliteration: the chemical stated in the book and the one I used is Sodium Benzenesufinate. And I assume the polish literation is the same.
I tried to look for different sources about sulfonate and sulfinate, and it seems that both of them can be used as ani-oxidants. There is not much info unfortunately.

Thanks for the confirmation, Pavel.

Ian Grant · Oct 6, 2009

There's huge issues of translations here, what we, Pavel etc are reading today is based on whether translation was made correctly in the late 1940's early 50's.

I'm not 100% on one anti-oxidant yet, and will keep looking for more contemporary (1930's information hopefully from Agfa sources.

Ian

Photo Engineer · Oct 6, 2009

Go here to see the spelling of benzene sulfinic acid in czech.

Dead Link Removed

There is more doubt growing in my mind about this. Sulfinic acids and Sulfonic acids are distinct in Polish, Czech and all other languages I have researched.

One is -SO2H and the other is SO3H, and they differ in activity much as sulfite and sulfate do, thus explaining the antioxidant properties claimed for the Sulfinates in literature.

PE

Ray Rogers · Oct 6, 2009

Photo Engineer said:
Go here to see the spelling of benzene sulfinic acid in czech.

Dead Link Removed

There is more doubt growing in my mind about this. Sulfinic acids and Sulfonic acids are distinct in Polish, Czech and all other languages I have researched.

One is -SO2H and the other is SO3H, and they differ in activity much as sulfite and sulfate do, thus explaining the antioxidant properties claimed for the Sulfinates in literature.

PE

Just to put things side by side,

Benzensulfinan sodny =
Benzenesulfinic acid, sodium salt, dihydrate
CAS: 25932-11-0

and

Benzensulfonan sodný =
Benzenesulfonic acid sodium salt
CAS: 515-42-4

Notes:
1.
On the Czech words for sodium given here, an accent mark is found on only one of the two, but this is possibly an error IDK.

(Sometimes non-speakers leave off such marks when they don't know how to make them.)

2.
Ian mentioned Polish... are Czech and Polish the same here?

3.
There are still a few outstanding points;

a. Kirks q. about Benzyl Alcohol
b. My q. about AO activity in general
c. Ian's q. about sulphonate functioning as an AO and
it's infrequent mention as an AO and its more common mention in
association with photothermography.

Photo Engineer · Oct 6, 2009

Well, I missed Kirk's comment about Benzyl Alcohol. Help me.

As for the names, in Czech translations they seem to use Natrium derivitives for Sodium but Polish seems to use Sodowi or sodny. So, you make up your own mind. The constant seems to be Sulfinic and Sulfonic.

PE

Ray Rogers · Oct 6, 2009

Kirk Keyes said:
Didn't benzyl alcohol serve this porpose as well - as a cosolvent?

This one.

In response to post #300:

Originally Posted by Photo Engineer
It is well known that Benzene sulfonates help PPDs dissolve! In fact, a close analog, pTosyl (para Toluene Sulfonic Acid) is used for all CD3 developers and CD6 developers today.

Photo Engineer · Oct 6, 2009

Benzyl Alcohol was only used in color developers. It assisted in transition of the oxidized color developer into the coupler solvent and it increased dye yield by this. It has not relationship to the present discussion in any way.

PE

Kirk Keyes · Oct 6, 2009

Photo Engineer said:
Benzyl Alcohol ... It has not relationship to the present discussion in any way.

Oh well...

I think there is a hazard to having the last post on a page. People always seem to skip right past them onto the next page...

gainer · Oct 7, 2009

Photo Engineer said:
Ian;

I know nothing about benzene sulfonate itself as an antioxidant.

As for the properties of benzene sulfonates or p-tosylates as antioxidants or as helpers in dissolving, it is known from fundamental chemistry that organic aryl amines (metol, pAP, and PPDs) all oxidize rapidly as free bases and dissolve slowly as free bases. If they are predissolved in an equmolar solution of ANY acid, then they dissolve much more rapidly in water and they are much more resistant to aerial oxidation

PE

So help me, I am not trying to make fun of you but of myself. I was trying to remember where I used the term "PPD" before. Suddenly it came. It is from a previous life and there it means "Post Prandial Depression", which is what makes one want to fall asleep after a meal. It is an important part of Human Factors Research.

gainer · Oct 7, 2009

Kirk Keyes said:
Oh well...

I think there is a hazard to having the last post on a page. People always seem to skip right past them onto the next page...

Don't feel neglected. I have had it happen that the last post on a page when I started a reply was not the last post when I finished my post, so my post skipped one.

Photo Engineer · Oct 7, 2009

gainer said:
So help me, I am not trying to make fun of you but of myself. I was trying to remember where I used the term "PPD" before. Suddenly it came. It is from a previous life and there it means "Post Prandial Depression", which is what makes one want to fall asleep after a meal. It is an important part of Human Factors Research.

I'll use pPD then in the future to denote the para or lower case "P". I'm glad you were wide awake.

PE

Kirk Keyes · Oct 7, 2009

gainer said:
It is from a previous life and there it means "Post Prandial Depression", which is what makes one want to fall asleep after a meal.

What do they call it when after looking at screen after screen of mass spectral data, you start to fall asleep? That's what was just happening to me. (But then is a bit after lunch too...)

gainer · Oct 7, 2009

Kirk Keyes said:
What do they call it when after looking at screen after screen of mass spectral data, you start to fall asleep? That's what was just happening to me. (But then is a bit after lunch too...)

You see? That is why it is so important in the study of Hunan Factors. Even piloting an aircraft can be a boring task. Another factor is the homing instinct. It has been known to make a pilot so anxious to get home that he does not go around on a landing attempt when he really should have.

premo · Sep 30, 2010

This has been fascinating, even if hard for me to follow. However, being a dumb farmer, I can talk about the use of surfactants in relationship to pesticides. They are used to slow down the evaporation of the water content of the spray, increasing it's effectiveness. The best surfactant I ever used was 1 quart of #2-D diesel fuel and 2 capfuls of Dawn dishwashing detergent per 300 gals of tank mix.

Modern Rodinal Substitutes Part II

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