PYRO-TRIETHANOLAMINE DEV FROM PF ?

[Guillaume Zuili]

Hi,
Some of you use this dev ?
How far can you go with replenishment ?
Any tips ?
G.

 

[juan]

I used it about 25-years ago. It works - I found it did not provide full film speed, but I didn't know as much then as I do now, so the problem could have been me. I used a gallon with replenishment for well more than a year.
juan

 

[Removed Account2]

Any leads on data and early development?=

 

[Mike Wilde]

An interseting idea. I use TEA in home mixed colour developers like for RA-4 that are quite alkaline. PMK is great, yes a bit of speed loss, but getting the B bath to dissulve all of the alkali is something I have never conquered. TEA is in a imilar pH range, but is a liquid.

 

[Guillaume Zuili]

I am getting deep tank to process a lot of film in a minimum of time. And this Pyro formula trickles me.
If I can replenish and keep going it's great. I'm not worried for the loss of speed.

 

[nworth]

I used this developer some years ago. It is excellent. True, it does not provide the film speed that D-76 does, but the penalty is quite small. One of the principal characteristics of Pyro-TEA developer is its long life. If kept from air, the concentrate will last for years. (Air reduces its life a lot.) It has very high capacity in working solution. I didn't try replenishment, but making up the volume with concentrate would probably work until the air got to the solution. Note that this is a non-staining pyro developer.

Pyro-triethanolamine film developer
Oxalic acid 1.5 g
Potassium metabisulfite 3.9 g
Pyrogallol 46 g
Metol 16 g
Sodium sulfite 116 g
Triethanloamine 12 ml
WTM 4 l
Dilute 1:1 for use. Develop Tri-X 5-1/2 minutes

 

[juan]

Yes, that's what I did - made up the volume with concentrate. As I recall, this was a formula used in the newspaper business where lots of film needed to be processed rather quickly. IIRC, Paul Farber wrote an article in the early 80s about the developer and convinced PF to make up kits.

I suspect the large amount of sodium sulfite prevents staining. I don't remember if it tans (hardens) the emulsion or not. I'd give it a try again if I weren't happy with what I'm doing now. Maybe I will anyway.
juan

 

[Removed Account2]

I have a question here: what is the point of the TEA, given the small volume, compared to the large volume of water?
4 Litres of water will surely contain enough dissolved oxygen to oxidize anything in the liquid?

Also 12ml fluid should be way below what is necessary to dissolve all those chemicals??

(I'm new to this developer, never gave this a thought before)

EP

 

[Mike Wilde]

One of the keys to DIY developer mixing stock solutions that keep well is to take your distilled or reverse osmisis filtered water, and boil it in a good sized nearly full stainless steel pot with a lid that fits well before you use it to mix the chemistry. I boil gently for at least 10 minutes, and then turn off the heat and let it cool (usually overnight) without removing the lid. I decant into 4L glass jugs, and keep it on hand as the need to mix arises.

The boiling drives off a reasonable amount of the dissolved gasses.

 

[Removed Account2]

OK boiling will drive off gases that start dissipating in the minute the heat is turned off.

Like for instance one idea to keep oxygen off is using a common siphon (remember them?) fill it with CO2 gas DRY, and use thw valve to fill the bottle(s) with heavier than air CO2 gas, thereby keeping oxygen out of the bottle.

BUT! CO2 absorbs fairly quickly into solution and will alter pH in solutions that are close to neutral..... so its give and take.

My question is : what was just 12 ml of TEA supposed to do in a massive solution with 4 liter of water (4000 ml) that sucks up all oxigen it comes in contact with?

 

[nworth]

Thank you for noticing the error in the formula I posted. The amount of TEA in the formula should be 120 ml, not 12. The Photographers' Formulary formula is slightly different. As posted on their website, it is:

Metol 17.8 g
Oxalic Acid 1.7 g
Potassium Metabisulfite 4.3 g
Sodium Sulfite 140.0 g
Pyrogallic Acid (Pyro) 51.2 g
Triethanolamine 133 ml
Water to 4 liters

 

[Removed Account2]

OK one more question : (I guess it is too late for you to go back and edit the formula, false formulas on the net is annoying, it was dangerous, when I was discussing reloading ammunition and someone posted wrong type of powder...)

But these two formulas, the3 last and the revised first : will all the ingredients dissolve on the TEA, and will this be like a sticky goo, referred to elsewhere? This should store *forever* in a closed bottle, most likely?

 

[Removed Account2]

Revised formula


Pyro-triethanolamine film developer
Oxalic acid 1.5 g
Potassium metabisulfite 3.9 g
Pyrogallol 46 g
Metol 16 g
Sodium sulfite 116 g
Triethanloamine 120 ml

Water to make 4000 ml

Dilute 1:1 for use.
Develop Tri-X 5-1/2 minutes

 

[Alan Johnson]

Triethanolamine is an alkali accelerator:
http://photo.net/black-and-white-photo-film-processing-forum/00QbGz
It will not,in absence of water, dissolve the ionic sulfur groups in metol,metabisulfite or sulfite.
Oxalic acid has been tried to coat powders to improve their stability,IDK if that is its purpose here.

 

[Mike Wilde]

TEA is a fair bit more liquid when warmed. I set it in a bowl of hot water to pour in the winter here; it 'freezes' solid below 20C I think I recall.

 

[CBG]

Two questions...
1. Since the two formulas presented here are in different order, what is the correct sequence for what gets added when?
2. NWorth's version looks essentially a tiny bit more concentrated than Erik's. The ratios are not constant, but the general drift is that they should act much the same. Are they from a common "ancestor" formula?

 

[Relayer]

I think that all formulas in this thread maybe incorrect. I found next formula for this developer here

Metol 17.8 grams
Oxalic Acid 1.7 grams
Potassium Metabisulfite 4.3 grams
Sodium Sulfite 140.0 grams
Pyro 51.2 grams
Triethanolamine 133 ml
Water to make 2 gallons

2 gallons = 7.57l, so we can calculate amount for 1l

Metol 2.4 grams
Oxalic Acid 0.23 grams
Potassium Metabisulfite 0.6 grams
Sodium Sulfite 19 grams
Pyro 6.8 grams
Triethanolamine 18 ml
Water to make 1l

still don't understand why we need Oxalic Acid in formula. pH buffer?

 

[Gerald C Koch]

I suspect the large amount of sodium sulfite prevents staining. I don't remember if it tans (hardens) the emulsion or not. I'd give it a try again if I weren't happy with what I'm doing now. Maybe I will anyway.
juan

You are correct this is NOT a staining developer.

The TEA raises the pH of the solution to allow the developinjg agents to work. It also acts as a mild silver halide solvent to provide finer grain. Agfa made Studional (Rodinal Special) which was also based on TEA. This was a good developer which never really caught on in the US.

 

[grainyvision]

Bumping an ancient thread here. But has anyone figured out why oxalic acid is present in the developer? I imagine if it was for pH buffering purposes, then the easier to find citric acid would've worked. iirc they are around the same potency

 

[Mark Booth]

CORRECT FORMULA:
Submitted by Mark Booth
Seattle, Washington USA
8-14-2021

Previous to this posting there have been some variances in the formula and revisions on this thread, so here is (the original formula) so for added clarification here is the exact formula as it originally appeared.

I have the original article before me. I was fortunate enough to find a near mint copy of the Photographic July 1984 article by Paul Farber, Where’s The Water? pg. 84, so I bought the copy—this magazine also has an amazing life-tribute to Ansel Adams and a photographic essay on the Mount St. Helens eruption. Brought back vivid memories for me!

“Where’s The Water “ article sorta humorously implies that the formula can be used again and again for almost eternity, “until the water itself” is almost gone…. and it still seems to process film. (Paraphrased) The big idea is that with proper storage and replenishment many have used the Pyro Triethanolamine developer for years.

I am posting the formula exactly as shown by Paul Farber. The original formula was first published by the late Will Connell in U.S. Camera Magazine. I will show it in grains (not grams) or oz or gallons exactly as Paul Farber shared. You can do the math conversion or go to google for the easy conversions. Keep in mind, this formula makes a 2x concentration that should be diluted 1:1 with water to make a working solution. My method is to have a 1-gallon( brown glass jug) of working solution and 2-separate 32oz (brown glass bottles) of the 2x concentrate for use as replenisher. Once the volume drops-down an ounce or two, I simply add a little concentrate to bring up the volume. This is what Paul Farber mentions in the article.

Original Formula:

Oxalic acid…………………..26 grains
Potassium metabisulfite……66 grains
Pyrogallic acid (Pyro)………1-1/2 oz, 134 grains (Farber shows both measurement options)
Metol…………………………274 grains
Sodium sulfite………………4-1/2 oz
Triethanolamine…………….4-1/2 oz (liquid)
Water to make 1-gallon (US) concentrate for working solution dilute 1:1
Distilled or purified water recommended in article which is standard practice by most.

In my own experience over the many years this developer formula is outstanding for a broad range of gradation and I find it bullet proof and not finicky whatsoever. Actually, it’s fun to make and use and to marvel at how well and long it works—to me it seems to only get better with some age and a dozen or so rolls of film through the classic soup. My 1-gal jug of P.T. is well over 2-years old—I just use care with storage and replenish as needed. Pyro and metol are considered super additive and whether used in a staining or non-staining solution many feel the combination produces finely held tonal separation.

P.T. is not a compensating film developer. I find that it handles most normal scenes fine and I’ve never blown out highlights—of course, I live in the often cloudy and rainy Pacific Northwest, but if D-76 works for you with highlights and contrast then P.T. should present no problems in my opinion.

If one likes BERGGER BER49, or the look of other classics— AGFA ATOMAL, TETENAL EMOFIN or KODAK MICRODOL-X film developers then I would say Pyro Triethanolamine will not disappoint whatsoever. I find these classic fine grain and non-compensating developers to be very similar characteristically to P.T.

My processing times are only guidelines, depending on your exposure methods and film ratings, or enlarger light sources and paper emulsions your results may vary. Just to share a couple processing times that work for me…. Kodak TMY 400 10-mins and Bergger Pancro 400 15-mins @70F/20C. If you like a low contrast negative perhaps cut your time by 20% and you should be safe. If one UV contact prints for alternative processes you will need a significantly higher gamma but for typical enlargement practices these times should serve as a good starting point.

In one of the threads above someone asked about the purpose of Oxalic acid. I’m not a photographic chemist but oxalic acid has historically been used as a reducing agent alongside of other reducing agents like pyro. Today, it’s photographic use is seen in alternative processes. In general, oxalic acid has many modern uses to boost cleaning and remove certain deposits and stains. Perhaps one of our forum “chemist” can correct or enlighten on Oxalic acid and it’s photographic uses? Feel free to let us know more!

I recommend, testing a few rolls with your favorite film and see if you’re as impressed as I am with the results.

As many know, Photographer’s Formulary provides a pre-made kit or raw chemistry—I prefer to self formulate but the kit makes it easy!

I hope this information is helpful and provides some clarification!
- Mark