Glycol-Metaborate instead of TEA?

Paul Verizzo · Apr 7, 2009

Hi, I'm back. Took a long break and here I am again.

I've decided to go with a lot of flow and look into ascorbic acid developers. Seems to have the results I've been looking for down other, less productive roads. I've not tried Xtol because of the 5 liter thing, times dilution, just unappealing.

Closer to my interest is the PC-Glycol and PC TEA work started by Patrick Gainer. Especially the former so that I could twiddle with accelerators. I'd not bought either glycol or TEA because I wasn't sure I wanted to spend the money (especially for shipping liquid).

So I recently checked out my Prestone Extended Life Anti-Freeze. Whaddya know, the chemicals I recall being in there decades ago are gone: "Silicate, phosphate, borate, and nitrite free." Whoopee! It is ethylen glycol, diethylene glycol, sodium 2-ethyl hexanoate, and neodecanoate. I presume the latter two are the corrosion inhibitors and they don't sound very photographically active.

As is known, the phenidone and ascorbic acid readily dissolved in the hot glycol. A further experiment with a new batch of the glycol showed that sodium sulfite does not dissolve. Oh well, I was trying to emulate Xtol in that matter. I guess it will have to be added separately.

Then I wondered about the sodium metaborate/Kodalk/Balanced Alkali. It went into solution like sugar in water. I put 1/4 tsp in 100ml of glycol, which is about 1.2 grams. I then diluted it 1:9 and got a pH of 9.1. I doubled the water and the pH is 8.6. Doubling again to 400ml, down to 8.2. Very effective buffering. Obviously one can alter the amount of metaborate to meet a target pH in dilution.

So is there a reason to prefer TEA over metaborate? Does TEA offer any buffering action? Metaborate sure doesn't smell bad as many posters frequently remind us.

What say you?

Photo Engineer · Apr 7, 2009

Yeah, there is a reason. Don't pour your borate solutions out anywhere near citrus trees. Kodak originally eliminated borates from EP3 and C-41 among other color processes due to complaints from the citrus industy of California and Fla due to borate toxicity!

PE

gainer · Apr 7, 2009

If it works, use it. However. I think the pH of TEA is a bit higher. Why not mix the PC in glycol and whatever alkali you want in a separate solution? I think this approach would give the greatest versatility for experimentation.

Paul Verizzo · Apr 7, 2009

Photo Engineer said:
Yeah, there is a reason. Don't pour your borate solutions out anywhere near citrus trees. Kodak originally eliminated borates from EP3 and C-41 among other color processes due to complaints from the citrus industy of California and Fla due to borate toxicity!

PE

With all due respect, PE, you are a stuck record on this. Have you ever heard of anyone dumping used developer around their grapefruit?

Tons more boron in the air or from Twenty Mule Team in the laundry than any few grams in a liter of developer.

Paul Verizzo · Apr 7, 2009

gainer said:
If it works, use it. However. I think the pH of TEA is a bit higher. Why not mix the PC in glycol and whatever alkali you want in a separate solution? I think this approach would give the greatest versatility for experimentation.

I think the metaborate will give you pretty much what you want. I only tested that little bit, I'm sure it can be many times over. As you probably know, metaborate has a nice long line of linearity between quantity and pH.

jim appleyard · Apr 7, 2009

Paul Verizzo said:
... Have you ever heard of anyone dumping used developer around their grapefruit?

QUOTE]

It wouldn't surprise me. Hey, truth is stranger than fiction. Just go to darwinawards.com for some pretty dumb stuff.

Photo Engineer · Apr 7, 2009

Paul Verizzo said:
With all due respect, PE, you are a stuck record on this. Have you ever heard of anyone dumping used developer around their grapefruit?

Tons more boron in the air or from Twenty Mule Team in the laundry than any few grams in a liter of developer.

Paul;

No, I don't expect you or anyone to dump their effluent around their grapefruit, but the effluent from photo labs in Fla and Cal were enough to have the photo industry become aware of the problem. I don't want to see that problem perpetuated if it is not necessary.

I had heard that Fla and Cal were going to ban 20 mule team borax way back then as well just like phosphates, but I believe nothing came of it, even though at that time, as you say, more borax came from laundry than photofinishing.

So, who can explain why there was a reaction. I just want you to be aware of it, and as you seem to indicate, you are aware of it in spite of your question and intend to go ahead anyhow. So, what can I say.

Go ahead, use it. I really have no further say in the matter.

PE

Anscojohn · Apr 7, 2009

Wadeaminit!!. Are you guys telling me I can mix some developers in modern-day Prestone?

Jordan · Apr 7, 2009

Sodium 2-ethylhexanoate and sodium decanoate are surfactants. You may get foaming in your developer working solution, depending on their concentration. As for TEA, it does form a good buffer at around pH 7.8 (IIRC).

One interesting use of borates is in insect control -- if you mix a little borax with lots of sugar and make a syrupy solution, "nesting" bugs like bees will eat it and take it back to their hives / nests. Bye-bye bugs.

brianmquinn · Apr 7, 2009

You said,
"sodium metaborate/Kodalk/Balanced Alkali.
I put 1/4 tsp in 100ml of glycol, which is about 1.2 grams.
I then diluted it 1:9 and got a pH of 9.1
I doubled the water and the pH is 8.6
Doubling again to 400ml, down to 8.2
Very effective buffering.
Obviously one can alter the amount of metaborate to meet a target pH in dilution."

A 10 fold dilution of an acid (Like HCl) OR base (LIKE NaOH) with NO buffering will show a ONE pH unit change. I don't know why you would get such a large change in pH with just doubling (twice) the amount of water. Are you using pH test strips that may be interacting in a strange way with the other chemicals in your mix?

Paul Verizzo · Apr 7, 2009

brianmquinn said:
You said,
"sodium metaborate/Kodalk/Balanced Alkali.
I put 1/4 tsp in 100ml of glycol, which is about 1.2 grams.
I then diluted it 1:9 and got a pH of 9.1
I doubled the water and the pH is 8.6
Doubling again to 400ml, down to 8.2
Very effective buffering.
Obviously one can alter the amount of metaborate to meet a target pH in dilution."

A 10 fold dilution of an acid (Like HCl) OR base (LIKE NaOH) with NO buffering will show a ONE pH unit change. I don't know why you would get such a large change in pH with just doubling (twice) the amount of water. Are you using pH test strips that may be interacting in a strange way with the other chemicals in your mix?

I can only tell you what I measured. Yes, pHydrion strips, but no, no other chemicals in this simple mix. The colors, for once, were spot on the comparisons printed on the label.

albada · Sep 28, 2012

In the thread on (there was a url link here which no longer exists), I stated that I had discovered that sodium metaborate dissolves in propylene glycol. It turns out that I was not the first to discover this (or publicly disclose it, anyway). That honour might belong to Paul Verizzo:

Paul Verizzo said:
Then I wondered about the sodium metaborate/Kodalk/Balanced Alkali. It went into solution like sugar in water.

There you have it. He discovered it 3.5 years before I did. And it's an important discovery because sodium metaborate is a useful enough alkali in developers that Kodak practically named it after itself ("Kodalk").

BTW, does anyone know where Paul went? This site says his last posting was 1.5 years ago.

Mark Overton

Paul Verizzo · Sep 29, 2012

albada said:
BTW, does anyone know where Paul went? This site says his last posting was 1.5 years ago.

Mark Overton

Boo!

I've not been active in photography/photochemistry in that time frame. Seems like more time, frankly. Assorted reasons, most due to my life and changing interests, having little to do with photography. But one does:

I'm not a master printer, not by a long shot. But I can crank out decent prints on a good inkjet, have me a wide carriage Canon. Sooooo........ I came around to using Kodak HD 400 (discontinuted) and Ektar 100 as universal films. Although I've putzed plenty with developing my own C-41, for reliability I'd get it developed for $3-5, scan it, then I could manipulate and print via computer and Epsons in either color or B&W.

The long exposure curves and extremely fine grain give results hard to attain (especially together) in B&W films.

Funny, in the last 24 hours I was looking at my enlarger and knowing that I will be cleaning out the house within a year, wondering if it was time to be rid of it. And what about my (refrigerated) papers, my (refrigerated and lead bagged) films, and my chemicals. Sad.

Now here's a time marches on sadness: I live in Sarasota, Florida, a burg of some 50,000 full time residents. There was a camera store downtown that grew into a regional chain when we moved here in 1959. In fact, the house we bought was from the owner of those stores. Anyway, long closed down, now a restaurant, what else? Further anyway, the last "real" camera/photo store has announced their dissolution, a Wolf Camera. Good staff, always fun to poke around and see what's on sale, my preferred C-41 developer.

A few days ago I met this young woman, recently out of college, not sure how the topic came up, but she said, "I had a film camera once when I was a little girl."

Sigh.

nworth · Sep 29, 2012

There was a long thread a little while ago about Suzuki's use of TEA and salicylic acid as chelating agents in ascorbate developers to prevent the sudden death syndrome. Small amounts of TEA were used for that; it was not used as a solvent. In any case, such small additions might be valuable in a PC-Glycol developer.

albada · Sep 30, 2012

nworth said:
There was a long thread a little while ago about Suzuki's use of TEA and salicylic acid as chelating agents in ascorbate developers to prevent the sudden death syndrome. Small amounts of TEA were used for that; it was not used as a solvent. In any case, such small additions might be valuable in a PC-Glycol developer.

It was suggested that Suzuki explored TEA and salicylic acid because alternatives were hard to get. Kodak uses DTPA in XTOL, and I've found a couple of places to get it:

http://www.sigmaaldrich.com/catalog/product/aldrich/d1133?lang=en&region=US
http://www.sciencelab.com/page/S/PVAR/SLD3751

It isn't cheap, but quantities are large enough that you'll only need to buy it once. Also watch out for the difference between pure DTPA and the DTPA-Na5 (pentasodium salt) that Kodak uses. For a concentrate such as glycol-metaborate, the pure stuff should be soluble in organic solvents and the salt might not be (posted by the chemist, Gerald Koch, in another thread).

Mark Overton

Glycol-Metaborate instead of TEA?

Privacy & Transparency

Privacy & Transparency