Has this fixer gone bad?

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Bruce Watson

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Yesterday I opened a completely full half gallon jug (one of the Kalt brown plastic jugs designed for darkroom use) of Kodak Rapid Fixer. This fixer was mixed maybe two months ago (no hardener), stored in the darkroom which is maybe saw as high as 26C during the last couple of months.

When I opened the bottle I could see something floating on top of the fixer. It looked like tiny splinters, much longer than wide. Maybe 30 or 40 or so of whatever they are.

First: What is this floating stuff?

Second: Why did it happen?

Third: Can I still use the fixer?

Fourth: If I can still use the fixer, how do I filter the crap out of it so it doesn't end up embedded in my film?

Fifth: How can I keep this from happening in the future?

Sixth: How long will mixed film strength Kodak Rapid Fixer without hardener keep in a completely full jug? Would it be better to use glass bottles? Say, something like wine bottles using the VacuVin vacuum caps? I've used the wine bottles/ VacuVin system with XTOL and gotten eight months before I ran out of XTOL, so I'm pretty sure it works fairly well. I haven't done this with fixer because I didn't think fixer was a fragile as developers. I'm rethinking that idea now...

Any help appreciated.
 

MarkS

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Look for yellow sludge in the bottom of the bottle. If you have any, the sulfur has precipitated out, and the fixer will not work. Dump the fixer, cahnge the bottle.
If there's no sludge, try fixing some scrap film in a try, with the lights on. If it clears in the normal time, you're good to go.
 

CBG

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Hypo Check is a prepackaged solution you can add to a fixer to determine if it has become exhausted.

You can also make your own. From www.digitaltruth.com/techdata/fixtest.php :

Fix Test (Hypo Check)

Water 100 ml
Potassium Iodide 5 g

This solution should work well for modern rapid fixers based on Ammonium Thiosulphate, but for fix formulae based on Sodium Thiosulphate you may need to double the amount of Potassium Iodide.

Either solution should work fine as a basic indicator of fix exhaustion.

To use: Keep the solution in an eyedropper bottle (mark accordingly for safety).

Decant a small amount of fixer (approx. 10-20 ml) into a clear graduated cylinder and trickle a couple drops of the Fix Test into the cylinder.

If a white precipitate forms then the fix should be replaced.

If the solution remains clear, then the fix is fine.
 
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Bruce Watson

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OK, I've answered my third question -- the fixer still works just fine. Cleared a chunk of TMY-2 very quickly.

That leaves the other five questions. Anyone?
 

rwyoung

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The flecks are probably crystals that precipitated out when it got hot. Just guessing. You could probably get them to go back into solution with a good stir.

Coffee filters should work fine for getting the bits out. However if you use a smooth walled funnel, it will eventually stick to the funnel and no more filtering. Get around that by lifting the edges of the filter paper or get a real filtering funnel. A third option would be to use cotton wool (cotton balls or makeup applicators) and put a few of those in the bottom of the funnel instead of the coffee filters.

Fixer isn't as "fragile" as the developer. But if you like the idea of glass bottles with no headspace for air, then by all means go ahead.
 
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Fixer dosnt oxidize, which is usually what gives developer its shelf life in a liquid form. I would 1) give fixer a good stiring to see if the stuff in the bottom will go back into solution (you may need to heat it a bit). 2) test it. throw a bit of "film end" (the stuff you cut off a roll of film when rolling it). If it clears in 1-2 two minutes you should be okay using it, fix a scrap of paper as well to be sure that there is no staining occurring.

If you are still hesitant to use it, then dispose of it and mix new.
 
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Bruce Watson

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Interesting that I've been able to ask a question that in general flummoxed APUG. Then again, it's flummoxed every one, even Kodak. Here's what they said:

1) Floating stuff is unknown. Not fixer break down product. Could be reaction between fixer and plastic of Kalt jug.

2) Since we don't know what it is, we don't know what caused it.

3) Yes. But filter it first.

4) Suggested coffee filters or better.

5) Suggested: A) toss out offending bottle. B) Switch to glass. C) make partial mixes from concentrate. That is, if you only need a liter, only mix up a liter from concentrate. Concentrate should still last a couple of years in the now not-full factory bottle because it's not exposed to the oxygen in the mix water, which is considerably worse for oxidation of fixer than the oxygen in the air above the concentrate in the factory bottle. So saith the man from Kodak.

6) See answer to question five.
 

rwyoung

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Not sure how you interpret the responses to the question as having flummoxed everyone. There are (were) details missing so everything put forth here was speculation.

Speculation as to the crystals/floaties was put forth but like Kodak said, no samples to analyze, no idea what they are. However it is quite common to have a super saturated solution precipitate out "stuff" if it cools down. You had stated a possible maximum temperature (26C) but no minimum. Could also be the temperature cycling that triggered the formation. Dissolved salts from your water supply (didn't see mention of distilled water in the original post but could have missed that tidbit) could have been the seed for the "stuff". No mention in your original post about the history of the jug. Was it brand new? What was in it before? Have you been in the habit of cleaning the jugs between uses? If this was the first use, did you clean out the jug before using it (new does not equal clean)? How about cleaning the lids and the threads at the mouth? Keep your funnel clean (assuming you used one). Do you use proper technique when pouring and don't touch the mouth of the jug to the target vessel (can contaminate the storage container). Etc, etc.

I echo'ed your use of the word "fragile" because I wasn't sure if you understood the word "oxidize". Since your original post didn't use it I didn't either. But later somebody else introduced you to the word and yes, fixer doesn't seem to oxidize quickly like developers can. I believe however the thiosulfate (soduim / amonium) can turn into a thiosulfite over time and I think that is an oxidation reaction but at room temperature (or at least human tolerable temperatures) it isn't rapid. Chemistry was a long time ago and I just don't remember enough details (wish I did). But all that should have done is render your fixer worthless and you said it still passed the clear-a-film-scrap test. Perhaps Ian or PE or Kirk or Gainer will look in on this thread and pass judgement.

It should store just fine in plastic of the appropriate type. HDPE bottles (#2 or #3 I think, I can never remember the code numbers used for the recycling stamps) should be fine. Kalt should know how to make a plastic photo chemical bottle. Glass would be optimal but it is heavy and fragile once you get to 1/2 and full gallon size jugs. Plastic is much easier to deal with.

Mix as you go from a concentrate is best. Other than using up my stocks of powdered fixer for some things, I've switched to TF4 and mix from the stock bottle. If you can tolerate a little bit of amonia odor, this is the bee's knees. Or use the TF3 formula posted various places and make your own. Also with the TF4/TF3 you don't use the acidic stop bath, just distilled water so one less thing to mix for each session.
 
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MarkS

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The sulfur in ammonium thiosulfate (rapid) fixers will precipitate out of solution after a long period of storage, whether in concentrate form or at working strength; in both color and b/w fixers. I don't believe it to be an oxidation issue (in the RA-4 color paper process it comes from under-utilization and developer carryover). This usually takes years to happen, but who knows in your case? The yellow sludge I referred to in my first post is the result. If that happens it's easier just to toss (recycle) the jug along with the dead fixer because that stuff is just a pain to remove.
 
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Bruce Watson

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Not sure how you interpret the responses to the question as having flummoxed everyone. There are (were) details missing so everything put forth here was speculation.
Umm... because no one answered the questions I asked? You were the only one that didn't talk about sludge at the bottom of the container -- which I didn't mention because that's not what I was asking about. There is no sludge, so talking about sludge makes me think that the question flummoxed the responder. Not to mention the answer about sludge frustrated the questioner!

Speculation as to the crystals/floaties was put forth but like Kodak said, no samples to analyze, no idea what they are. However it is quite common to have a super saturated solution precipitate out "stuff" if it cools down.
I can understand why you'd say that about the stuff in the Kodak bottle. What I'm talking about is a dilution of that -- working film strength rapid fixer without hardener. I don't see how that could possibly be super-saturated. And a super-saturated solution will precipitate out enough to drop to saturated or just below anyway won't it? I remember something I did in a chem. lab thousands of years ago where you tap on a beaker of super-saturated something or other and watch a flurry of precipitation happen.

You had stated a possible maximum temperature (26C) but no minimum. Could also be the temperature cycling that triggered the formation. Dissolved salts from your water supply (didn't see mention of distilled water in the original post but could have missed that tidbit) could have been the seed for the "stuff". No mention in your original post about the history of the jug. Was it brand new? What was in it before? Have you been in the habit of cleaning the jugs between uses?
Temperature would only vary a degree C or so. The fixer sits in a cabinet in a darkroom in a more-or-less temperature controlled house. I did mix with steam distilled water. Don't remember if I mentioned that or not. The jug was not new, but it's only been used for Kodak Rapid Fixer. I do clean the jug between uses, including a final rinse with steam distilled water.

If this was the first use, did you clean out the jug before using it (new does not equal clean)? How about cleaning the lids and the threads at the mouth? Keep your funnel clean (assuming you used one). Do you use proper technique when pouring and don't touch the mouth of the jug to the target vessel (can contaminate the storage container). Etc, etc.
All that, yes. I do all that good clean chemistry stuff. Like not pouring anything back in the jug -- if I pour out too much fixer the extra goes down the drain, not back into the jug.

I echo'ed your use of the word "fragile" because I wasn't sure if you understood the word "oxidize". Since your original post didn't use it I didn't either. But later somebody else introduced you to the word

Now that's just condescending. But if it makes you feel better...

and yes, fixer doesn't seem to oxidize quickly like developers can. I believe however the thiosulfate (soduim / amonium) can turn into a thiosulfite over time and I think that is an oxidation reaction but at room temperature (or at least human tolerable temperatures) it isn't rapid. Chemistry was a long time ago and I just don't remember enough details (wish I did). But all that should have done is render your fixer worthless and you said it still passed the clear-a-film-scrap test. Perhaps Ian or PE or Kirk or Gainer will look in on this thread and pass judgement.
I was hoping that too. But nothing says anyone has to participate. I know I'm a poor writer. If I could write I wouldn't need photography so much! Perhaps if I'd asked the questions differently the problem would have generated more interest and therefore more responses. Sigh. A failing I've had to live with for more decades than I want to think about.

It should store just fine in plastic of the appropriate type. HDPE bottles (#2 or #3 I think, I can never remember the code numbers used for the recycling stamps) should be fine. Kalt should know how to make a plastic photo chemical bottle. Glass would be optimal but it is heavy and fragile once you get to 1/2 and full gallon size jugs. Plastic is much easier to deal with.
Kalt should. But I always seem to have trouble with the plastic bottles, especially the accordion types. And the Vacu-Vin stoppers work so well with wine bottles that I'll probably make that my standard from now on. And glass is so much easier to clean! Those accordion bottles are nearly impossible to get clean inside.

Mix as you go from a concentrate is best. Other than using up my stocks of powdered fixer for some things, I've switched to TF4 and mix from the stock bottle. If you can tolerate a little bit of amonia odor, this is the bee's knees. Or use the TF3 formula posted various places and make your own. Also with the TF4/TF3 you don't use the acidic stop bath, just distilled water so one less thing to mix for each session.
Like I said, this is where I'm heading. Mix as much as I need for a week or two and leave the rest as concentrate in the Kodak bottle. Should solve most if not all of my problems with fixer.
 

rwyoung

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It wasn't to be condescending. It was to try and use the same terms as your post knowing nothing about what you might or might not understand.

Anyway, THROW AWAY THE ACCORDION BOTTLES! :smile: Those things are way more trouble than they are worth.

One other question comes to mind that was never asked. Are you the only person using this chemistry? Can you imagine the problems that can occur in a shared darkroom. What a nightmare that would be.

And speaking of saturated solutions and parlor tricks check this out: http://www.wikihow.com/Make-Hot-Ice
 

Ole

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Fixer dosnt oxidize, which is usually what gives developer its shelf life in a liquid form. ...


Fixer oxidises too, it just doesn't turn brown like developer does. There's also a lot more thiosulfate in a fixer than there's developer in a stock solution, so it has to oxidise a lot before it matters.

Sulfur chemistry is complicated stuff which very few people can come even close to understanding. I won't even attempt. But "floating crystals" are usually the result of evaporation or temperature differences on the surface, and could be anything from gypsum (calcium sulfate dihydrate) which more soluble in cold water than in hot water; lots of other more complex sulfates, several sulfites, or even elemental sulfur.
 

dancqu

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When I opened the bottle I could see something
floating on top of the fixer.
Would it be better to use glass bottles?
Any help appreciated.

BEST to use Glass bottles. I always recommend the
Standard for chemical storage, Boston Rounds. Both
clear glass, there are amber and colorless. Plastic
Boston Rounds are available as well as a variety
of caps and narrow and wide mouth. They are
not expensive. Search for Boston Rounds.

BTW, what is hanging to the sides and at bottom of
that opaque brown bottle you've been using? Dan
 
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