Resource icon

Modern Rodinal Substitutes Part II

On the edge of town.

A
On the edge of town.

  • 5
  • 3
  • 71
Peaceful

D
Peaceful

  • 2
  • 11
  • 199
Cycling with wife #2

D
Cycling with wife #2

  • 1
  • 3
  • 85
Time's up!

D
Time's up!

  • 1
  • 1
  • 79

Recent Classifieds

Forum statistics

Threads
198,256
Messages
2,771,767
Members
99,581
Latest member
ibi
Recent bookmarks
0

Photo Engineer

Subscriber
Joined
Apr 19, 2005
Messages
29,018
Location
Rochester, NY
Format
Multi Format
Ian, Patrick;

According to my texts, the Sodium Bisulfite available commercially is mostly Sodium Metabisulfite. The same texts do not claim that for the Potassium salt. So, apparently, the Sodium salts are in equillibrium in the solid and liquid state.

PE
 

Kirk Keyes

Member
Joined
Jun 17, 2004
Messages
3,234
Location
Portland, OR
Format
4x5 Format
Originally Posted by Photo Engineer said:
You would not want to put Ammonium Bisulfite into a developer!

It might get a little stinky...

And I've been reminded about another reason not to use it.

The ammonium ion is an excellent silver halide solvent and it will fog the film as a result.
 

Kirk Keyes

Member
Joined
Jun 17, 2004
Messages
3,234
Location
Portland, OR
Format
4x5 Format
Meanwhile, I AM doing more tests.

Pat - can you do some step wedges or something in addition to your flowers? We might learn a bit more in your tests than how your flowers are aging.
 

Kirk Keyes

Member
Joined
Jun 17, 2004
Messages
3,234
Location
Portland, OR
Format
4x5 Format
It'll be Phenidone-Z, (unless they changed to another derivative

So all these years I've been using a molecular formula for Phenidone that was short one methyl group! Oh no!!!!
 

Photo Engineer

Subscriber
Joined
Apr 19, 2005
Messages
29,018
Location
Rochester, NY
Format
Multi Format
Pat - can you do some step wedges or something in addition to your flowers? We might learn a bit more in your tests than how your flowers are aging.

It would be good to have some reference wedges or photos as well to compare contrast and speed.

PE
 
OP
OP
Ian Grant

Ian Grant

Subscriber
Joined
Aug 2, 2004
Messages
23,251
Location
West Midland
Format
Multi Format
Ian, Patrick;

According to my texts, the Sodium Bisulfite available commercially is mostly Sodium Metabisulfite. The same texts do not claim that for the Potassium salt. So, apparently, the Sodium salts are in equillibrium in the solid and liquid state.

PE

In a few previous post I listed the variation of that equilibrium in Commercial Sodium Bisulphite (Kodak and JT Baker - very similar), and the purer Sodium Metabisulphite plus a reference to a Kodak paper on substitution ratio of one for the other.

Potassium Metabisulphite is sold in Home Brew shops and Boots The Chemist (UK) used to stock it. in 250gm Bottles.


Now back to Rodinal :D


What I was trying to suggest or rather asking is the effects of "the one SO2 and one mole of SO3 upon decomposition in water, both of which end up making HSO3- or the equivalent. It is acidic in water."

I'm referring to the "Orginal formula" Andresen suggests, and many book from Agfa in the early 1900's right through to the recent Darkroom Cookbook.

Yes it's definitely acid until the formulae is balanced with Hydroxide, my point is something different is happening when Metabisulpite's used because of the SO2 & SO3 which won't happen if we used the equivalent amount of Sulphite.

In most developers using small amounts of Metabisulphite it's probably irrelevant but in this old developer with such a high level it has to make a difference.

Ian
 

Kirk Keyes

Member
Joined
Jun 17, 2004
Messages
3,234
Location
Portland, OR
Format
4x5 Format
Yeah - speed and contrast would be really nice.

Inquiring minds want to know!
 

Photo Engineer

Subscriber
Joined
Apr 19, 2005
Messages
29,018
Location
Rochester, NY
Format
Multi Format
Ian;

My point was that the SO3-- reacts to form H2SO3 and SO2 reacts to form H2SO3 (Sulfurous Acid) in acidic solution. If pure SO3 itself is present, then you get H2SO4. The main difference is the final pH and the presence of Sulfuric Acid from any nonionic Sulfur Trioxide which would be minimal in any case.

I think it is mainly the amount of Sulfite present as a preservative and silver halide solvent that is notable here. That is my own opinion though.

PE
 

Kirk Keyes

Member
Joined
Jun 17, 2004
Messages
3,234
Location
Portland, OR
Format
4x5 Format
H2SO3 is dissolved SO2. If the pH is too low, the SO2 is driven out of solution and it's stinky. (I'm on a stinky roll these days.) If the pH is higher, then the SO2 stays in solution as the sulfite ion, SO3--. The SO3-- ion is a good oxygen scavenger, which is one of its main uses in developers, and it is converted to sulfate, SO4--.

In other words, metabisulfite quickly becomes sulfite in solution. If the pH is high enough, there's no free SO2 gas dissolved in the solution. If the solution is acidic enough, you get back the SO2 gas from the dissolved sulfite and you can still have some sulfite ion in solution, but there's not some sort of "metabisulfite" ion present at any time in the solution.
 

gainer

Subscriber
Joined
Sep 20, 2002
Messages
3,699
I used to do the step wedges a lot. Many things have happened in the meantime. Things as well as memories have been lost. Ron, did you learn all that you know in school, or is much of it the result of experience and practice? Please don't refer to my lack of education in chemistry. I have had an attack of meningo-encephalitis since then that nearly took me to the pearly gates, and left me having to relearn many things. At least I know enough to ask questions, and am still capable of learning. That I can count among my blessings.

I'll see what I can do with step wedges. I'll have to relearn that as well.
 

Kirk Keyes

Member
Joined
Jun 17, 2004
Messages
3,234
Location
Portland, OR
Format
4x5 Format
my point is something different is happening when Metabisulpite's used because of the SO2 & SO3 which won't happen if we used the equivalent amount of Sulphite.


What's different is that metabisulfte gets you a little more sulfite ion per gram of stuff than bisulfite does and even more than sulfite does - discounting pH effects between the three.
 
Last edited by a moderator:
OP
OP
Ian Grant

Ian Grant

Subscriber
Joined
Aug 2, 2004
Messages
23,251
Location
West Midland
Format
Multi Format
H2SO3 is dissolved SO2. If the pH is too low, the SO2 is driven out of solution and it's stinky. (I'm on a stinky roll these days.) If the pH is higher, then the SO2 stays in solution as the sulfite ion, SO3--. The SO3-- ion is a good oxygen scavenger, which is one of its main uses in developers, and it is converted to sulfate, SO4--.

In other words, metabisulfite quickly becomes sulfite in solution. If the pH is high enough, there's no free SO2 gas dissolved in the solution. If the solution is acidic enough, you get back the SO2 gas from the dissolved sulfite and you can still have some sulfite ion in solution, but there's not some sort of "metabisulfite" ion present at any time in the solution.

So we have a free SO3-- oxygen scavenger in the very early Rodinal type developer :D Perfect because this helps prevent Dichroic fog and maybe why Anti-foggants needed to be added when they switched to using Potassium Sulphite.

Rodinal is working at "Beutler" like levels of concentration, so the SO3-- is likely to be more critical.

Next point is obviously as the SO3-- is converted in localised areas to sulphate it will harden the emulsion . . . . . . .

So we have a bit of logic for the three distinct phases of Rodinal that we know of:

1 Primitive what we've just discussed "The Classic Formulae"

2 Middle age - ? & when they switched from Metabisulphite to Sulphite, now we see Antifoggant and Bromide needed possibly for the edge effects - Still made by Calbe

3 Agfa/A&O current Rodinal, less p-Aminophenol, higher pH - 14 more bromide etc

That's my theory anyway :smile:

Ian
 

Kirk Keyes

Member
Joined
Jun 17, 2004
Messages
3,234
Location
Portland, OR
Format
4x5 Format
Next point is obviously as the SO3-- is converted in localised areas to sulphate it will harden the emulsion . . . . . . .

That seems to be a bit of a stretch... And then why not say that for any developer that has sulfite in it?
 

Photo Engineer

Subscriber
Joined
Apr 19, 2005
Messages
29,018
Location
Rochester, NY
Format
Multi Format
What's different is that metabisulfte gets you a little more sulfite ion per gram of stuff than bisulfite does and even more than sulfite does - discounting pH effects between the three.

This was my point as well but hidden in the chemistry.

PE
 

Photo Engineer

Subscriber
Joined
Apr 19, 2005
Messages
29,018
Location
Rochester, NY
Format
Multi Format
Ron, did you learn all that you know in school, or is much of it the result of experience and practice?

I'll see what I can do with step wedges. I'll have to relearn that as well.

Patrick, after nearly 8 years of college courses in chemistry and hours of lab work there to finish a thesis plus over 40 years of photographic work, (32 at Kodak and 3 in the USAF + working in a photofinisher lab to pay for college) I have to say that I learned every step of the way. I cannot keep it all in memory and have a huge chemistry library here at home at my disposal. It includes a lot of books on photography as well, but I have thrown out most all journal articles.

As for tests, comparison tests would be most useful if you cannot do step wedges. A picture taken and developed with 2 develpers such as Rodinal and Metolal would be nice.

PE
 

Kirk Keyes

Member
Joined
Jun 17, 2004
Messages
3,234
Location
Portland, OR
Format
4x5 Format
I'll see what I can do with step wedges. I'll have to relearn that as well.

Don't worry about that, Pat - There's lots of people that would be more than happy to help you with this and give back to you some of ideas that you've given to us.
 

Mike1234

Member
Joined
Jul 6, 2009
Messages
1,908
Location
South Texas,
Format
4x5 Format
Man, I am so glad you guys are here to do all the difficult theorizing and critical testing. My feeble mind is crap these days. It seems that there are better alternatives to what I used a zillion years ago and I was VERY happy with good old Rodinal and selenium toning. I was convinced that I was going to avoid B&W and doing my own processing but, dad-blast-it, these options are very intriguing!!
 

gainer

Subscriber
Joined
Sep 20, 2002
Messages
3,699
Encephalitis can do strange things to a brain. It made my brain like a library without an index. The "books" were there, but I couldn't remember where I hid them. It could have been worse.
 

Mike1234

Member
Joined
Jul 6, 2009
Messages
1,908
Location
South Texas,
Format
4x5 Format
Hmm... maybe that's my problem... or just Alzheimer's plaque. Yeah, that's what I need. A good old fashioned brainwashing!!
 

Photo Engineer

Subscriber
Joined
Apr 19, 2005
Messages
29,018
Location
Rochester, NY
Format
Multi Format
Well, for those of you interested in mixing your own Rodinal, I would like to add some caveats on the NaOH or KOH solution used.

Making a 50% NaOH solution involves 50 g of NaOH diluted to 100 ml for a wt / vol solution or 500 g diluted to 1000 ml for a larger quantity. You must start with ICE COLD distilled water, about 25 - 30 ml or 250 - 300 ml depending on volume. The slow addition of NaOH solid is so exothermic, it can crack some glass containers and can actually melt some plastic containers. You should have a large container of cold water to chill your mixing vessel.

After you are done, there is much residual heat and you should cool the mix in a large mixing vessel. Make sure that no excess water gets into your diluted 50% solution.

Leave the cap loose as it cools or the reduced pressure due to air cooling or volume reduction may crack the storage container. Glass can shatter, plastic can melt or crack. Do not store the final solution in glass, as NaOH can etch glass and can dissolve some inexpensive glasses. A spill will ruin most floors even concrete.

Wear a lab coat with sleeves, old shoes, dirty clothes and protective glasses along with rubber gloves.

That is how I just did it, and what I experienced and I am an old hand in the lab. Be careful, don't disfigure yourself or blind yourself from a tiny splash and don't ruin your darkroom from a spill.

Have some automobile battery acid on-hand in case of a spill. I bought a gallon of 37% battery acid to have here just in case before I did this.

Be happy, be safe, mix Rodinal by any formula with care. Mixing the NaOH or KOH is the first dangerous step. Adding this to the pAP and Bisulfite is no snap either. Take care when you do it. It is an acid base neutralization.

PE
 

Kirk Keyes

Member
Joined
Jun 17, 2004
Messages
3,234
Location
Portland, OR
Format
4x5 Format
Have some automobile battery acid on-hand in case of a spill. I bought a gallon of 37% battery acid to have here just in case before I did this.

While I agree with very nearly 100% of what PE says, I have to say that I disagree with the suggestion that 37% sulfuric acid be used in the case of a 50% or other concetrated acid spill. 37% sulfuric is still very acidic and I'd suggest using something weaker, like vinegar or dilute (i.e. 10% or less) hydrochloric or sulfuric acid.

Using an acid this concentrated will invariable release even more heat and fumes and it will not make cleaning up easy. I've seen people in the lab I worked at use concentrated bases to neutralize concentrated acid and get burned much worse than the acid alone would have caused. It's the same principle at play here that should be avoided.

To clean up a concentrated hydroxide spill, I would suggest the following:

Solutions of sodium or potassium hydroxide greater than 10% have a contact rating of 4 - that means they are extreme hazards (i.e. they are corrosive). If you have contact during a spill, you should remove all contaminated clothing and then flush the contacted skin with large amounts of water.

For cleaning up the mess, you should use the folowing protactive equipment - goggles or a face shield, an apron or some old clothes, and proper gloves. Make sure the area is well ventilated.

You should contain and recover any spilled liquid when possible - wiping up with paper towels or spill pads will work well here. When the bulk of the spill has been contained, the residues from spills can be diluted with water and then neutralized with a diluted acid - dilute acetic, hydrochloric, or sulfuric will work here. Absorb neutralized caustic residue on clay, vermiculite or another inert substance and package in a suitable container for disposal.

See this MSDS for 50% sodium hydroxide for more info: http://www.jtbaker.com/msds/englishhtml/s4037.htm

I do completely agree with PE about being careful when preparing 50% hydroxide solutions. I would suggest only using Pyrex or other lab-type glassware as regular glass is just too likely to break if the solution gets too hot or too hot too fast.

Do use very cold water, but I'd also suggest having a water bath of very cold water to set the container that you are mixing the solution in into. Add a few hydroxide pellets to the container and stir it continuously with the container sitting in a cold water bath. When thats dissolved, add a few more pellets and continue mixing. As the water bath begins to warm up, dump it out and refill the bath with cold water. This is another reasons to use a Pyrex-type container as it needs to be able to potentially hold a hot solution while sitting in a cold bath of water. Regular glass containers and plastic may not be able to handle these conditions. When the solution is mixed transfer it to a HDPE plastic container for long term storage.

Another tip - do not simply dump all your hydroxide pellets into the container all at once. It will not only get very hot, but the pellets will simply sink to the bottom of the container and glue themselves together and make a big, hard brick of hydroxide that will be a very big pain the butt to get dissolved. (I have not done that personally, but I did see someone else to that... and I ended up cleaning that lump of hydroxide out of the container.)

If you are going to mix large amounts, I'd suggest simply buying some. You can buy sodium hydroxide that's already at 50% concentration. After making up a gallon of 50% hydroxide one time, I've decided that I have better uses of my time and I don't like to take the risk that's involved in making large amounts of hydroxide solutions.
 
Last edited by a moderator:
OP
OP
Ian Grant

Ian Grant

Subscriber
Joined
Aug 2, 2004
Messages
23,251
Location
West Midland
Format
Multi Format
Health & Safety Issues

Well I won't be mixing it. Is the ready made stuff safe to use?

Fotch, commercial Rodinal is no worse than most other developers, and there's far worse chemicals used in most households on a regular basis.


A couple of comments, I haven't advocated making up the old "Classic Rodinal" formula with it's higher level of Hydroxide, but we have discussed the formula.

The amount of Potassium Hydroxide needed in the two formula I advocated in the opening post in Part 1 of this discussion is significantly smaller, at the highest 27g/litre. Potassium Hydroxide is harder to handle accurately as it comes in pellet or stick form unlike Sodium Hydroxide, but it is easy to buy as a 40% solution which is possibly the best option.


Health & Safety


Now Ron & Kirk have actually raised some more serious and fundamental issues about safety and handling chemicals used by many photographers, which are equally relevant elsewhere, and we need to remember that Lith devs etc are in far more common use and many use Hydroxide solutions. Equally many Toners & Bleaches use acids like Hydrochloric and Sulphuric.

I'm fairly certain Kirk will have some kind of Safety guide where he works. In the UK chemical suppliers/manufacturers have to supply an MSDS/COSHH data sheet with each chemical the first time you buy it. (HSE - Control of substances hazardous to health (COSHH). Equally any company using any chemical must have the relevant data sheet.

Using this data a Lab in the UK is required to draw up a COSHH Report on all the chemicals and processes it uses, which covers all aspects of safety, handling, what to do in the case of an accident etc, but with relevance to the volumes and way a chemical is going to be used. Copies of this usually hang on a wall in each relevant room in a lab so available for immediate use. (Ours were near to where the most dangerous chemical were used or stored).

It sounds heavy, companies try and sell you software to do it, but in fact it's easy as nearly everything is in the MSDS sheets, and often handling & safety codes are in major chemical suppliers catalogues.

What's missing is a free, easily printable, safety guide for photochemistry, no-one's going to buy a specific book, and while almost all manufactures from Ilford, Kodak etc through to the Photographers Formulary provide MSDS sheets it's not usuably in a practical form.

Unfortunately I don't have access to a framework to drop the data into, it's archived in the UK, but perhaps if some has something between us we can put together informaton particularly for the most hazardous chemicals used in making up your own photo chemicals and emulsions.

Ron's right about safety, and I know Kirk is aparticularly safety conscious from numerous posts he's made in the past.

Ian
 
Photrio.com contains affiliate links to products. We may receive a commission for purchases made through these links.
To read our full affiliate disclosure statement please click Here.

PHOTRIO PARTNERS EQUALLY FUNDING OUR COMMUNITY:



Ilford ADOX Freestyle Photographic Stearman Press Weldon Color Lab Blue Moon Camera & Machine
Top Bottom