What are the odds (old powder developer still sealed)?

i was digging in my storage, bringing some chemicals into my darkroom (I'm about to mix up some regular developer, since the Df96 monobath I mixed on March 28 seems to be getting weak and I'm getting far enough down my B&W film backlog not to want to mix another quart). In the process, I ran across a 5L package of XTOL -- with an expiration date of 2002.

The powders are not clumped, and there's still a slight vacuum inside the two bags. I have every reason to expect, therefor, that the dry ingredients in the bags have remained dry for the twenty or so years since the bags were filled.

Anyone want to suggest the likelihood that this developer (to be mixed using RODI high-purity water) will work just like brand new XTOL?

I also apparently have several packets of Kodak MQ Universal developer, a Dektol-like product that was sold in "just enough" powder packets, in boxes of six pairs of A and B packets -- each pair just enough to develop one tank full of film (32 ounces of working solution), or fill a developing tray (8 ounces) for sheet film/glass plate processing or print development. The developer is supposed to be good for two 120 or 135-36 rolls, 160 square inches of film. I've got four or five of these packets, still sealed and with unclumped powder inside. They have no marked expiration, but this product was discontinued fifty-some years ago; this box is old enough to have a handwritten price of 30 cents on it. Same question with these -- still good? Alternatively, is there a collector who'd give me a stupid amount for them? The box isn't perfect, but it's better than most you see on eBay...

I went through the same thing with some Dektol recently. I have several foil packs that will make 8 oz. of solution that are probably 20 years old. I had my doubts to start with but was almost certain once I opened the pack. It had turned brown and crystallized. I mixed it up just to make sure, nothing. I also have a few cans of Dektol that are the same vintage, it works just fine.

I have years old packages of powdered chemicals and I have never had a problem. You have to mix them and use them to know.

I bought a case of GAF 17, some old dektol, fix, and DK 50 in cans, fix, all worked just fine. My understanding that in days of can they used nitrogen to prevent oxidation. Dont know if packets use nitrogen or not.

Hi Donald, I'm in a similar situation to you. Just checked my developer stash and I have 2 packs of D76 expired in 2015 and a 5L pack of XTOL that expired in 2014. Not as old as yours and the packaging looks good and the contents feel nice and loose with no apparent clumping.

I'm going to buy a 5L 'bag' of of water branded Pureau over here and mix up the XTOL and then transfer the developer back into the bag, (much like wine in a box situation). I want to try the replenished regime with the XTOL, 2L of working solution with the remaining 3L in the boxed bag. The tricky part will be to guage how many films to process in the new working solution before I start replenishing. Most posts around this state 5 - 6 rolls and then start replenishment. This, of course, would depend on the volume of working solution. Ah well, I'll just have to keep an eye on it as I go.

As a bonus I can always draw on the 3L bagged XTOL if I want to try it at 1:1. This will be my first use of XTOL. Getting a bit weary with HC-110 which I bought with the intention to use with outdated film stock to reduce base fog. My film was way to old to benefit from HC-110 - FP4 and TMY which had expired in the early '90s.

Donald Qualls said:

(to be mixed using RODI high-purity water)

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Why don't you use plain tap-water?

My tap water is untreated, untested well water -- at a minimum, it contains considerable calcium (my coffee machine scales up), and it's known that iron ions in the water can kill XTOL of that vintage by destroying the ascorbate. I use it for dilution and wash steps (occasionally have to rewash with the RODI to get a spot-free dry), but I generally mix chemistry with the high-purity water, since we have the machine anyway (for a salt water aquarium).

What are the odds with 2002 Xtol? I'd say they're against you!

AgX said:

Why don't you use plain tap-water?

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Hi AgX, I always use distilled water for all photo chemicals except stop bath. The distilled ensures no iron, chlorine or other chemicals. I also have grit from my 95 year old iron pipes.

I also use distilled water for film developers. Although my city water is pretty good quality it is very hard, second I follow the directions from Photographers Formulary for MCM 100 which recommends distilled water, and feel that distilled water is a better choice when using highly concentrated developes like Rodinal. I have mixed D76 with city water and no problems.

I've had mixed results with Dektol of similar vintage and even newer. It took 4 one gallon packs to find one that was good. Even then, it mixed up looking like diluted tea but no precipitates and worked great. The rest looked like 3 day old coffee with lumps of creamer floating around. I found that if it looks like you're about to make cinnamon sugar toast with the Dektol, it's probably bad.

I use distilled water to make up X-Tol, because I use it replenished, and it is susceptible to iron in the water.
When I used to replenish HC-110 I did the same.
Other chemicals I use our tap water, which is quite good.

cramej said:

I've had mixed results with Dektol of similar vintage and even newer. It took 4 one gallon packs to find one that was good. Even then, it mixed up looking like diluted tea but no precipitates and worked great. The rest looked like 3 day old coffee with lumps of creamer floating around. I found that if it looks like you're about to make cinnamon sugar toast with the Dektol, it's probably bad.

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Yep, if your metol is as dark as cinnamon in powder form, you may be in for a bad experience. That said, I have a film can of metol that's been stored with my other chemicals, that someone sent to me back around 2005 to compare to new powder I had then -- apparently his stock was twenty years old, as it was still good when I got it (and it's still just off white).

I'm not worried about the Dektol -- once I find my bottle of hydroquinone (or look up the substitution ratio to replace it with ascorbate) I can make my own D-72 or C-72 or a phenidone-based equivalent on demand.

I'm interested in trying this XTOL because I was just about to start using Mytol as my primary film developer -- sodium ascorbate is on the way right now -- and this is what Mytol is intended to replicate. Obviously, I'd do clip tests before even considering putting my actual film into it -- but at the moment, I first have to find a container I can mix 5 liters in (got storage bottles, but I need a graduated bucket).

Donald Qualls said:

I first have to find a container I can mix 5 liters in (got storage bottles, but I need a graduated bucket).

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Mix it up in a gallon water jug - essentially 4 litres - and then dilute the mixed results.

MattKing said:

Mix it up in a gallon water jug - essentially 4 litres - and then dilute the mixed results.

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I was thinking how to do that. At present, I have 2L graduates and 2L and 1L PET storage bottles. I guess I'll have to buy a gallon of water for the jug (which is more or less what I did for the bottles -- 2L of store brand diet soda for 69 cents, or 1 L of club soda for 79 -- I have to presume the price differential is due to the smaller units). Once I have it mixed, and know how much there is (3.8 L in a gallon jug) I can dilute portions to correct strength precisely enough.

Okay, would have been cheaper to get a jug of water for the jug, but I just ordered a 4L graduate pitcher from Amazon for half the price of one that actually holds 5L. I'll go with that.

Okay, my gallon graduate arrived from Amazon yesterday, I have several 1L storage bottles (and will grab a couple more tonight on my way home from work), and I have time this evening, so I'm going to mix up the 5L Xtol package this evening and divide it into 1L and 2L bottles for stock and reserve. That'll give it a couple days to settle before I'm ready to develop in it on Saturday or Sunday. I will surely watch powder and liquid color, and (since I don't think phenidone turns brown as it oxidizes the way metol does) do a leader test as well before processing any film -- and assuming the developer is still good, I've got a couple rolls to process in it.

Assuming this stuff works at all, I plan to start replenishment, and when the reserve runs out, I'll either experiment with using Mytol to replenish the Xtol, or buy another package of Xtol (presuming it'll be available again in a few months).

I am glad to hear that I am not the only one who has some old chemistry around. Back in the 70s I bought a small case of Tetenal C-22 kits back from Germany. It was rated for C-22 and C-41 and I'd used quite a bit of it before switching to something else. I still have 4-6 kits left although I may have robbed the bleach out of one to make some reducer. I assume that the developer is probably good. It is packaged in separate glass vials and it still looks good. I may have to give it a try.

Want some 127 size Kodacolor-X to develop in it? I've got a few rolls around...

Okay, here's one (weak) data point: The Part A powder had a small percentage (much less than 5%, probably more like 1%) with an orange coloration, and when mixed into about 4L of RODI water (heated in the microwave to roughly 110F) the solution, when fully stirred and cleared, was a little brown, about the color of black tea brewed two minutes, no agitation, with a single bag in a 12 oz. cup (i.e. pretty weak tea). When everything was dissolved, I poured in the Part B powder, and the solution immediately lost its color (presumably due to the borax or additional sulfite); once that, also, was fully cleared and the microbubbles settled, the 1.25x strength stock was just barely off clear, similar in color to what I recall from D-76 stock or freshly mixed D-23, and had the distinctive aroma of developer. For each storage bottle, I measured 1/4 the bottle's storage volume of fresh RODI water, filled the graduate with over strength stock to the nominal volume, and poured the (now standard strength) stock solution through a funnel into the bottle (I used a 2L soda bottle for the working stock, because my Yankee Agitank requires 64 ounces for 4x5, and 1L bottles from club soda to store the reserve stock). However it happened, I wound up with 400 ml of over strength stock left over (I'm fairly sure I over diluted the working stock by 100 ml or so of water, but I'm certain it wasn't by anything like 400 ml); I made that up to 500 ml and stored it as well. In this last increment of stock solution, I inserted a piece clipped from a roll of 35mm, and I could see definite density in under a minute, with what looked like Dmax in about two and a half minutes. I don't recall what film stock that was (could have been Cinestill BWXX, or very old Tri-X, or just possibly XP2 Super), just a clip I kept on my darkroom counter for just this purpose -- but I'm now confident that the stock solution is effective.

The reserve bottles (3x 1L and the half liter of excess in a 20 oz. bottle I had around) and the 2L working solution are in PET beverage bottles, about as impermeable as anything that's cheap, with as much air squeezed out as possible without spilling (a couple ml of air in each bottle, at most).

Given the leader test results, I plan to process two 120 rolls of Fomapan in this stock over the weekend, and then replenish, to get the seasoning process started.

First impression is that, 18 years past expiration, XTOL powder in intact bags seems to be fine. If you have powder dated from the 90s or early oughties, however, I'd recommend mixing with distilled. deionized, or reverse osmosis purified water, to ensure against iron contamination in the water killing the ascrobate (and in consequence the XTOL). XTOL dated after 2006 or 2007 shouldn't require this precaution (Kodak made a change around 2005 to sequester iron as well as calcium in tap water to fix the "sudden XTOL death" issue).

Edit: Now I see the arithmetic error in my dilution: I should have been adding 20% volume of make-up water, not 25%, so all my stock is about 95% strength. Should make essentially no difference over the life of five liters of stock solution in replenishment.

Donald Qualls said:

My gallon graduate arrived yesterday.

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I am impressed, I have not even come across a Gallon graduate (in the true sense). My biggest graduate is 1L.

It should not be a problem, according to Ilford, They say that as long as powder chemical's are sealed in their packets they will last indefinably, and with id11 or other iklford powders as long as the powders are not brown then go ahead and mix them up,in fact Ilford , at least withb the ID11, which I use and over here do not put a use by or expiry date on the packets

AgX said:

I am impressed, I have not even come across a Gallon graduate (in the true sense). My biggest graduate is 1L.

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Well, I might be overstating it by calling it a "graduate" -- it holds 4L, and it's graduated in 500ml increments. I have a 1L and four 2L that are actually graduated pretty finely, and just ordered a couple 100ml syringes (to use for measuring small quantities, like replenishment and Parodinal concentrate).

R.Gould said:

It should not be a problem, according to Ilford, They say that as long as powder chemical's are sealed in their packets they will last indefinably, and with id11 or other iklford powders as long as the powders are not brown then go ahead and mix them up,in fact Ilford , at least withb the ID11, which I use and over here do not put a use by or expiry date on the packets

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That matches the basis for my "experiment". It's long been my understanding that dry chemical (metol powder in a sealed tub, for instance) lasts virtually forever. My partner suggested last night that the expiration likely was "lawyer added" -- a CYA to ensure Kodak (the old, pre-Chapter 11 Kodak) was off the hook if someone sat on a package of the powders for ten years and then lost important images (because no matter how many times they harp on "responsibility ends with replacement of the defective materials" someone will find a lawyer who can build a case on "Kodak knew about sudden XTOL death, and should have fixed it long before X date when my client bought the package").

However, there is the caveat, "as long as powder chemicals are sealed in their packets." It can be difficult to be certain the packet is still sealed, short of opening it and looking at the powders inside.

Much of the impetus for having "best before" dates on packaging flows from the requirements for various types of ISO and other certifications.
And with respect to powders in bags, the "best before" analysis may be more related to the projected life of the packaging material than the contents.
Using example numbers only, if statistically speaking, in 99% of the randomly selected and surveyed examples a type of packaging in normal storage remains intact for two years, than the "best before" date is chosen to be to years out.
The actual numbers and percentages and testing criteria are almost certainly different.

I mix photochemicals in a plastic paint bucket that I marked with 1 liter, 2 liter, 3 liter, 4 liter and 1 gallon levels. I heat the water to the temperature listed on the product package. I store the chemicals in 1 liter bottles or in the case of developers in 1 liter bladder bags so I can squeeze out the air.

Sirius Glass said:

I mix photochemicals in a plastic paint bucket that I marked with 1 liter, 2 liter, 3 liter, 4 liter and 1 gallon levels. I heat the water to the temperature listed on the product package. I store the chemicals in 1 liter bottles or in the case of developers in 1 liter bladder bags so I can squeeze out the air.

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That's pretty equivalent to what I've done here, and your paint bucket is just about the equal of my "graduate". The PET beverage bottles are easy to squeeze to remove the air (there's a tiny bubble in each, at present, because I didn't want to spill). They're designed to hold about 120 psi (8 bar) plus a safety margin, because they're sold filled with carbonated beverages, and they're impermeable enough to keep the beverage pressurized/carbonated for literally years. Plus, the 1L ones I have are water clear, so if there's any discoloration of the solution inside, I can see it (they're stored in a cabinet, in a darkroom, so light exposure shouldn't be a problem).