How long does glycin keep?

Photographers Formulary and the Anchell books stress the need for

fresh glycin. Does anybody have real world experience with the

keeping qualities of glycin kept in a cool dark dry storage area?

Also, FX-2 stock solutions are said to keep for a year in full sealed

bottles. How 'bout partially filled bottles? Back when glycin was

sold by Kodak under the Kodurol name, I find it hard to believe they

turned their stock over every few weeks, as modern literature

suggests is necessary. Or maybe that's why it fell from favor?

I have a feeling that it ages very quickly, even more so when diluted and exposed to air. As you say, this is probably why it is no longer popular.

Fresh Glycin is ivory-white and turns beige/brown after three-four months. It's best to mix the developers as soon as possible, and even better strong stock solutions with a higher contents of Sodium Sulfite so the developers will keep longer. I have bottles with Ansco 130 I mixed a year ago, and they are still fine. Glycin film developers containing Potassium Carbonate can be mixed to a very strong solution and be filled in small glass bottles. I use Tetenal Protectan antioxidation gas in the bottles.

Keeping property is one concern, but another that bothers me more is the limited sources of glycin. What if I have to move somewhere else where I can't jusify paying for shipping from PF? What if PF stops selling it?

 

I keep some dry chemicals in vacuum sealed tupperware. The most visible effect I see is reduced moisture, but oxidation should also be retarded though I am not sure how much difference it makes.

 

Vacuum sealing works very well if used with a developer solution in a partially filled bottle.

Until recently, I used Photographers' Formulary version of Ansco

130. I recall being cautioned by people at PF not to order too

much at once because of problems with the Glycin keeping.

While I liked the prints produced with 130 very much , I've

stopped using it because I noticed that I was EXTREMELY tired

after a printing session--much more than what would be normal

from standing up while working for 8-10 hours. I concluded that,

even though my darkroom is fairly well ventilated, I might have

been poisoning myself with the glycin. I've switch to a

phenadone-based paper developer (Ilford Universal) and have

much more energy after long printing sessions. BTW, my prints

haven't suffered much at all.

Robert: It's highly unlikely that 'fumes' from the developer would have affected you at all. Almost all that evaporates from aqueous developer solutions is water vapour, carrying <i>extremely</i> small quantities of the dissolved chemicals with it. Beside which, Glycin isn't the most toxic of developing agents by a long way.<br>If you're dabbling your bare hands in the developer, then that's a different matter. You're likely to get far more chemicals into your body through skin absorbtion, than you are from breathing fumes.<p>I'd recommend you use one rubber surgical glove (or better yet, non-allergenic Nitrile) on your 'wet' hand, and keep a non-gloved dry hand for handling paper etc. That way you don't come into contact with the developer, and you don't risk scratching your prints with cumbersome tongs either.<br>Nitrile surgical gloves cost about $10 US for a box of 100. That's 10c a printing session. Quite a bargain for protecting your hands from dermatitis, and your prints from being scratched, I'd say.

Pete,

 

I know it seems unlikely and I certainly didn't do a controlled

experiment comparing the effects of Ansco 130 and Ilford

Universal on my body, but the fatigue certainly seemed real and

doesn't occur with non-Glycin developers. FWIW, I always use

tongs--more to prevent contamination and stained prints than as

protection.

The reason I asked this is because I use chemistry slowly and in small volumes. Ok, I'm not a prolific shooter :-) Anyway, my 3/4 full FX-2 mixed 4 months ago gave low density on a test roll. The dry glycin I have is about 6 months old, so I made a new batch. No problems at all, and the measured density is right back where it should be. I know all the reasons not to do it, but I always measure the density of the exposed leader portion of my film, and it's proven to be an excellent monitor for the developing process. Normal for me is 2.00 and the expired developer was giving about 1.6. I believe glycin is quite toxic, though I wouldn't expect any fume problem. 130 is a slow developer and I found it tiring to use just because of that! What I'm more worried about is that glycin is a very light fluffy substance, and is easily made airborn. I take great caution to avoid this, and that's why I haven't tried filling the bottle of raw glycin with inert gas to improve life. Should be ok for mixed solution though. Finally, I'm not going to stop using it out of fear that it won't be available someday, any more than I'm going to stop using film for the same reason ;-)

Brenner in Germany does also sell Glycin. I don't know who makes it, but it's not Photographers Formulary.

FWIW, in a conversation that I had not too long ago with someone at Photographers Formulary we discussed glycin and its potential danger. The person I spoke with told me that they break the lumps of newly made glycin up by hand (this is the last step before packaging I think). She considered it to be quite safe in the dry form. Could it be that the dangers of glycin are overstated?

 

I have Glycin thats about 9 months old. Its been stored in a cool dry area in a plastic bag with the air squeezed out. Its still good as far as I can tell. I think your FX2 going bad may have to do with that formula or its handling rather than the glycin.

Hi Henry, I'm pretty sure my problem was just too much air in the bottle. I'm making smaller batches now- 1/2 liter. My 6 month old glycin was also stored in a cool dry place, and seems fine. It's just a light beige color. About my comments on the 130 print developer- I made a new bach with fresh everything, and it acts more quickly, though the image comes up in a linear fashion, rather than suddenly like Dektol. I have to admit though, for RC paper, it's almost impossible to tell which print was developed in 130 vs. Dektol. I'm going to try some warmtone paper and see how it does with that.

The person I spoke with told me..

 

--------

 

Whoa, hold 'er there. Thats the same person who is selling it to you! ;-) Did she also tell you how nasty it is to make? Its toxicity isnt over or underrated IMO. Its safe if you are careful and potentially dangerous if you arent.

 

Ryuji, if you move you'll still have to order from PF, unless you move overseas. The guy from Artcraft (is his name Art Craft? anyway..) was hoping to start making it but I dont think he ever did. Its a real PIA, from what I've heard. And its nasty to make, much nastier than it is to use.

 

I think glycin fell out of favor because cheaper alternatives were developed, although one could easily argue they displaced it rather than replaced it

I have some powder thats been sitting here for about a year, but I have no plans to use it soon. I guess I'll find out how it keeps when I get around to using more of it. I also have some stock print developer that I mixed a year ago, that I'm going to try before dumping it. Now that just might still be good.

 

Oh BTW, Fotochem in Canada USED to carry glycin, but I dont think they do anymore. they got it from-you guessed it.

Hi Wayne, Just curious, do you know the raw materials or process for producing glycin? I have to believe that Photographers Formulary isn't huge, and that the stuff can be made on a small scale. Also, try mixing up some FX-2 with the glycin you have. I've been extremely happy with the acutance and general "look" of the stuff, and was surprised at how fine the grain is. It's a bit like Rodinal, but with much less obtrusive grain, even after fooling around with sodium ascorbate additions. OTOH, it's easy to get into these belief things without a real controlled side by side test :-)

Nope I know nothing about the process, just disjointed bits and pieces I've picked up from talking to people. PF is understandably not giving out recipes, but I'm sure a diligent person could dig one out of the literature or find a (old retired Kodak) chemist somewhere. But it is a nasty, unpleasant chemical to make and I think that deters most would-be's. (or maybe PF made that up to discourage it? I doubt it tho)

 

I only shoot 8x10 in B&W so Rodinal's grain isnt a problem for me. ;-)

Unfounded hysteria really raises my blood pressure.

 

An MSDS for glycine/glycin can be found at:

 

http://avogadro.chem.iastate.edu/MSDS/glycine.htm

 

Glycin/Glycine (same stuff) is a small mollecule amino acid. The stuff is running around in your body, and is needed in the functioning of the GABA neuronal system. If your body is without glycin you die. Luckily the greatest producers of glycin are living organisms, such as ourselves. After that come half a dozen chemical houses (or maybe one chemical house and half a dozen guys with labels).

 

Glycine is available in health food stores as a nutritional supplement. It is used as a flavor enhancer. And it is used in some antacids.

 

Scary stuff, right?

 

For the low down numbers, the stuff is half as toxic as salt:

 

NaCl Oral, rat: LD50 = 3000 mg/kg

Glycin Oral, rat: LD50 = 7930 mg/kg

 

As far as making the stuff:

 

From http://www.seilnacht.tuttlingen.com/Chemie/ch_glyci.htm

 

The first glycine synthesis was accomplished by Braconnot in the year 1819. He manufactured it by cooking glue with diluted sulfuric acid. The outdated name of glycine "Glycocoll" originates from this synthesis, the name meaning "sweet glue". Glycine arises whenever protein materials are split. Today glycine is made from chlorine acetic acid and ammonia.

 

Anybody see the film "Fierce Creatures?"

Unfortunatelly, I must say Nicholas is incorrect in assuming that glycine and glycin as used in photographic processing are same substance.

 

Glycine (an amino acid and neurotransmitter) is as he described. For more details on this substance, systhesis, receptors, and pharmacology, see biochemistry and pharmacology literature.

 

Photographic glycin is a short name for p-hydroxyphenylaminoacetic acid or p-hydroxyphenylglycine. For more details, see photographic chemistry lieteratyre, obviously. If you do search for this short name, "glycin", on general chemistry literature or more simply on the web, you'll get a lot of stuff talking about the substance mentioned in the previous paragraph. Be careful. Attached scribble may be of some use.

 

Glycin is less active (in almost every sense) than metol or p-aminophenol in lower end of usable pH range, but if the pH is high, glycin can be just as active. In addition, glycin is known to be an effective physical developer whereas metol and p-aminophenol are not a physical developer at all.

I sit corrected and humbled.

 

However, look at:

 

http://www.chemicalland21.com/arokorhi/lifescience/foco/GLYCINE.htm

 

Glycin is the German spelling for the amino acid "glycine" and as such "glycine" and "glycin" are sometimes used interchanceably. And I have found reference to "Glycine (photographic)".

 

Appologies to all.

Yeah it's really confusing. But if you look at my scribble, photographic glycin contains aminoacetic acid glycine as a part of it. The hydrogen is taken away and it attaches to hydroxyphenyl at para position to make photographic glycin.

 

It's a nice summary web page, but all I find there is about aminoacetic acid glycine, not photographic p-hydroxyphenylaminoacetic acid.

If you are referening to the web page at

 

http://www.chemicalland21.com/arokorhi/lifescience/foco/GLYCINE.htm

 

it has gylcine's other names listed as _both_ "Aminoacetic Acid" (glycine) and "p-Hydroxyphenylaminoacetic Acid" (photographic glycin).

 

I wonder what they call photographic glycin in Germany?

Yeah they do say p-hydroxyphenolaminoacetic acid, but that's incorrect. If you look at the structure of glycine there is no "phenyl" part and it should be obvious. I think someone who didn't know was involved in the editing process or something. Either way, what they are talking about on that page is aminoacetic acid and not p-hydroxyphenolaminoacetic acid. Again, if one looks around, the info on plain aminoacetic acid is far outnumbered so be very careful.

What an interesting thread. I have visited PF and perhaps I can shed some light.

 

PF is a very small company, probably five or six employees, not all of whom are full time. They have been manufacturing and selling chemicals to photographers, by direct mail, for nearly 30 years. They are fully conscious of risks and observe proper handling procedures. They do not lie to people about chemical safety to con them into buying chemicals. If they tell you glycin deteriorates over some period of time, they are passing along their experience. Feel free to do your own tests and come to your own conclusions. My own experience is that it lasts, sealed, cool and dark, less than a year before the color gets to the point I don't trust it. I have not done tests, because I have no doubt the chemists who have, for 100 years, described it as short-lived, are correct. I try to use mine in six months.

 

The manufacture of glycin is not trivial but it is not particularly challenging for a trained organic chemist with modest laboratory facilities, which is actually quite a good description of PF now that I think of it.

 

As far as I can tell, glycin is no longer used in industrial photochemistry because:

there are cheaper, easier alternatives;

it is not useful for processing color film or paper;

and there is no business case for creating new (or reviving old) b/w chemicals, since b/w is such a small fraction of the marketplace.

 

It is not highly superadditive, in fact subadditive with some developers, and its forte is extremely soft development (very poor selectivity) which is also the forte of phenidone, which is much, much cheaper to make, store, and use.

 

Having said all that, it's a wonderful developer for many uses, and I'm glad PF keeps making it. I intend to keep buying it. If we all keep buying it, that's what will keep PF motivated to keep making it.

 

David Foy