Rotten egg fixer. Any of you chemists know why?

Dave Krueger · Aug 17, 2010

I did a search for this a while back and found others who have had this happen, but didn't really find what I was looking for. My fixer (working solution) has come down with a bad case of rotten egg smell. The brand is Ilford Hypam and the concentrate is four years old.

It seems to still work fine and the smell doesn't really occur until after light use of the working strength solution for a couple weeks. Since I didn't experience this when the concentrate was new, I assume it's a change in the concentrate.

I'm wondering if anyone knows what chemical reaction is spoiling the concentrate and whether there is anything I can do to delay the problem. If it's a reaction caused by air, perhaps storing new concentrate in smaller full glass bottles would help.

Since I don't really trust the fixer anymore, I just purchased a new bottle of concentrate.

This problem happened after a lull in my photography activities, so I expect to use up the new bottle much more quickly, but I'm still curious as to what mechanism is causing this. So... Does anyone know what's going on with this fixer? Any of you photography chemists care to take a stab at answering?

Photo Engineer · Aug 17, 2010

The rotten egg smell takes place when acidic fixers go bad. Do not trust the fixer. It is forming small particles of Sulfur in it suspended in the fixer solution and the smell is Hydrogen Sulfide gas.

Start over with fresh fixer.

PE

Sirius Glass · Aug 17, 2010

Photo Engineer said:
The rotten egg smell takes place when acidic fixers go bad. Do not trust the fixer. It is forming small particles of Sulfur in it suspended in the fixer solution and the smell is Hydrogen Sulfide gas.

Start over with fresh fixer.

PE

Not using it at that point is a contraceptive => Sulfur-denial

Steve

lxdude · Aug 17, 2010

Don't throw it away-send it to flatulent1. He uses it for cologne.

Sirius Glass · Aug 17, 2010

lxdude said:
Don't throw it away-send it to flatulent1. He uses it for cologne.

Now that is a GAS!

Photo Engineer · Aug 17, 2010

A case of ass i dosis?

PE

Tom Kershaw · Aug 17, 2010

I dispose of print fixer working solutions after a week if left out in trays. Film fixer I use one-shot in the Jobo or for a few rolls when hand processing.

Tom

Sirius Glass · Aug 17, 2010

Photo Engineer said:
A case of ass i dosis?

PE

Is "of ass i dosis" what they put in milk? I think is called sweet of ass i dosis.

Steve

tlitody · Aug 17, 2010

Dave Krueger said:
I did a search for this a while back and found others who have had this happen, but didn't really find what I was looking for. My fixer (working solution) has come down with a bad case of rotten egg smell. The brand is Ilford Hypam and the concentrate is four years old.

It seems to still work fine and the smell doesn't really occur until after light use of the working strength solution for a couple weeks. Since I didn't experience this when the concentrate was new, I assume it's a change in the concentrate.

I'm wondering if anyone knows what chemical reaction is spoiling the concentrate and whether there is anything I can do to delay the problem. If it's a reaction caused by air, perhaps storing new concentrate in smaller full glass bottles would help.

Since I don't really trust the fixer anymore, I just purchased a new bottle of concentrate.

This problem happened after a lull in my photography activities, so I expect to use up the new bottle much more quickly, but I'm still curious as to what mechanism is causing this. So... Does anyone know what's going on with this fixer? Any of you photography chemists care to take a stab at answering?

I've had problems with hypam in the past. It has sulphur in it and it precipitates out in the bottle. I suggest you shake up the bottle and pour out a little. If it is cloudy or has bits in it then I would bin the hypam bottle and buy some more.
This happened to me with a full but quite old bottle. There was a layer of sulphur in the bottom of the bottle.
If you can get hold of it, Agfa FX Universal is good fixer that is very slightly akaline and lasts for a very long time without going off. It is actually used for colour neg and prints hence it needs to be alkaline (acid fix destroys colour dyes). But it works well with B+W film and prints too. It's cheap too.
A minilab may get some for you if they are still making it.

Dave Krueger · Aug 17, 2010

Photo Engineer said:
The rotten egg smell takes place when acidic fixers go bad. Do not trust the fixer. It is forming small particles of Sulfur in it suspended in the fixer solution and the smell is Hydrogen Sulfide gas.

Start over with fresh fixer.

PE

Uh-oh. The Kodak application note for toners says that hydrogen sulfide "can fog unexposed paper and film, and will oxidize unprotected silver images in negatives and prints".

I'll pitch the old fixer. Is this something that happens to fixer no matter how you store it or is it caused by air in the bottle? Is there anything I can do to prevent it from happening again?

Photo Engineer · Aug 17, 2010

The amount of H2S generated is rather low so there is probably no fog problem, but I agree that better safe than sorry.

Fixer goes bad with time and goes bad faster at acidic pH. Alkaline or neutral pH fixers last longer.

PE

lxdude · Aug 18, 2010

Dave Krueger said:
Uh-oh. The Kodak application note for toners says that hydrogen sulfide "can fog unexposed paper and film, and will oxidize unprotected silver images in negatives and prints".

If you've ever made something using fresh boiled eggs using a silver or silverplated utensil you've seen the effect. The utensil goes black.

Dave Krueger · Aug 20, 2010

Thanks for the replies. The smell is not very strong, but certainly noticeable and different from what I'm used to. I don't know much about fixers. I kind of mindlessly use a rapid fixer and just follow the instructions on dilution rates and fixing times.

The rotten egg smell from the brown toner is stronger. Because of the fog warning, I use it in the garage or outside. While the odor from the fixer is weaker, I have in open trays for several hours, so I'm glad I asked about it. Despite the fact that it smells the same, it never occurred to me that it might be the same gas as that produced by the toner. I guess that's what you'd call a brain fart (which probably also smells like hydrogen sulfide).

Marco B · Aug 20, 2010

Dave Krueger said:
....
My fixer (working solution) has come down with a bad case of rotten egg smell. The brand is Ilford Hypam and the concentrate is four years old.
....
I'm wondering if anyone knows what chemical reaction is spoiling the concentrate and whether there is anything I can do to delay the problem.
....
This problem happened after a lull in my photography activities, so I expect to use up the new bottle much more quickly

Dave Krueger said:
Is there anything I can do to prevent it from happening again?

Well, not going on a 4 year sabbatical seems to me to be a reasonable answer to your problems

Thinking about it, 4 years actually more sounds like a complete detox from analog photography, than a sabbatical...

pentaxuser · Aug 20, 2010

If it solely age related then it sounds as if there is nothing you can do but if exposure to air has an effect then try decanting the fixer into wine boxes when you get it. That way no air ever gets to the fixer and the wine tap is an excellent way to dispense the fixer for a mixing into a working solution. Actually I find it easier this way and would continue to do this even if it has no effect on preserving the fixer.

pentaxuser

Dave Krueger · Aug 20, 2010

pentaxuser said:
If it solely age related then it sounds as if there is nothing you can do but if exposure to air has an effect then try decanting the fixer into wine boxes when you get it. That way no air ever gets to the fixer and the wine tap is an excellent way to dispense the fixer for a mixing into a working solution. Actually I find it easier this way and would continue to do this even if it has no effect on preserving the fixer.

pentaxuser

That's what I was wondering. Since I just got a new 5 liter bottle, I was thinking I might divide it up and keep some of it in full glass or PETE bottles. I may do that anyway, since it will take me a while to get through the 5 liters.

Dave Krueger · Aug 20, 2010

Marco B said:
Well, not going on a 4 year sabbatical seems to me to be a reasonable answer to your problems

Thinking about it, 4 years actually more sounds like a complete detox from analog photography, than a sabbatical...

Well, the fixer is 4 years old, but the sabbatical was only a couple years. Sometimes I am very active photographically, and sometimes I go through chemicals very slowly. Anyway, when I bought the new bottle I failed to notice it was even bigger than the old 2.5 liter bottle. Hence my interest in seeing what I can do to stave off that deterioration. I'm not anticipating any more sabbaticals, though.

I can't quit analog photography. Half my house is dedicated to it. What good is a darkroom if not for photography? I mean in the legal realm. I've already been told it would make a great drug lab.

pentaxuser · Aug 20, 2010

Dave Krueger said:
That's what I was wondering. Since I just got a new 5 liter bottle, I was thinking I might divide it up and keep some of it in full glass or PETE bottles. I may do that anyway, since it will take me a while to get through the 5 liters.

You may have worked this out for yourself but with any bottle, unless so small that you empty it totally for a mixing, you are left with air which has to be expelled with varying degrees of success especially when the bottle is nearly empty. An empty wine bag and box cost nothing( assuming you drink wine or know of friends who do), will last for several cycles, will never allow air to enter and the tap does ensure very accurate and easy dispensing of the fixer.

pentaxuser

Dave Krueger · Aug 20, 2010

pentaxuser said:
You may have worked this out for yourself but with any bottle, unless so small that you empty it totally for a mixing, you are left with air which has to be expelled with varying degrees of success especially when the bottle is nearly empty. An empty wine bag and box cost nothing( assuming you drink wine or know of friends who do), will last for several cycles, will never allow air to enter and the tap does ensure very accurate and easy dispensing of the fixer.

pentaxuser

AH-ha. I see what you're saying now. For film developers I usually divide up the initial stock solution into 1 liter bottles and then transfer remaining concentrates to smaller and smaller bottles as I use them. That keeps the air to a minimum. I also store the unopened concentrates in the fridge.

The wine box things sounds like an interesting approach for the reasons you mention. The only thing I question is the permeability of he plastic. I've read that HDPE isn't that great as an oxygen barrier, so now I store my chemicals in glass, PETE, or barrier containers.

Where do you get the wine boxes? Do you just use ones that have been emptied of wine (preferably by the consumption method)?

pentaxuser · Aug 20, 2010

Dave Krueger said:
Where do you get the wine boxes? Do you just use ones that have been emptied of wine (preferably by the consumption method)?

I have no idea where you are located but most wine boxes in the U.K. are the 3L variety. Once you drink the wine, you simply open the box carefully, remove the bag and carefully prise out the dispenser tap. A broad knife blade will lever the tap out of its holder. Fill the bag with water and empty several times. it can be completely emptied by flattening the bag. Swill out the dispenser as well. Fill the bag with 3L( or 2.5L if you want equal amounts) of fixer and then gently squeeze the bag until the liquid rises into the neck then replace the dispenser tap. Place bag back into box and pull the tap out of the box opening. Tape up the box and that's it. You'll need two boxes of course for 5L.

It may be possible to buy a 5L bag and box. In the U.K. at home brew centres such 5L boxes are sold. If you are elsewhere, I'd be surprised if such things aren't available. Most countries sell wine boxes or cater for home brewers

pentaxuser

Rotten egg fixer. Any of you chemists know why?

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