How to know if mixed D-76 has expired?

How do I know if mixed D-76 is still working fine, just looking at it? What are the signs that it has expired?

 

I have some D-76 in 150 ml glass bottles, just to the top. I mixed it like 2 years ago. In theory, it is good only for 6 months, but I know that it could last more if it is kept in good conditions, without air exposure.

 

I opened a bottle and it looks good, the same as before, as far as I remember, which is a bit yellowish.

 

If it looks good, does it work well? Or not necessarily?

It may have sediment so stain it through paper towel and try it with some images that are not important

The exact amount of color to indicate bad developer is hard to know.

 

Not so long ago, I used some old mixed HC-110(B), only slightly yellow, but the negatives

came out weak. Probably printable, (or scannable), but don't look like I expected.

Though I might also have had the temperature slightly off.

 

You might try a roll that isn't so important to see how well it does.

 

Otherwise, balance the cost of developer against the cost of film, to

decide if it is worth trying or not.

The only way to tell if it's good is to try it!

 

Snip a short length of 35mm leader off and drop it into an eggcupful of the developer brought up to 20 C. Give it the correct time, stirring occasionally, and then rinse the film and have a look at it. If it's gone black, then the developer's probably good. All this can be done in room lighting, and takes, what? 15 minutes at most.

I've used D76 older than that and it worked. But I'm not precise enough to know whether the negatives were a little thinner or not, they didn't look bad. I keep mine in a brown gallon photo jug inside a dark cabinet. D76 is still pretty cheap though, so mixing new stuff isn't a bad idea. Might as well remove another variable from the equation right? I like rodeo_joe's test above. You might check your fixer too if that is old.

 

I think non-transparent bottles and storing in a cool dark place is probably key to my experience. Let us know how it goes.

Thank you all.

 

Mixing new D-76 surely would be the safest way to go. But for me it is not as cheap as for some of you. Here the one gallon packet costs like 18 dollars, and the dollar rose a lot this year, more than 100%, so basically it is not so cheap to shoot film.

 

Anyway, I am interested in quality, but it would be a pity to throw away developer already mixed if it is as good as before, so that it is why I am interested in the facts.

 

[uSER=2403817]@rodeo_joe|1[/uSER] : if this solid, one-tone white image without details turns black in the negative at a given time, is that enough to conclude the developer works normally? In this test we don’t have different tones, shadows, contrast, sharpness of photographed things… couldn’t they change also? Or an old developer, with the passing of time, only gets weaker in general, something that could be compensated increasing the time?

 

Of course, I could also develop unimportant images like others suggested, but even in this case it would be interesting to know what an old developer could do to the image, to judge better the results.

As above, slightly bad developer will be just a little slower, and give weak negatives.

That can often be corrected by increasing development time.

 

Some developers have a table of time increments as it is used for more rolls,

and similar increase can be used for slight oxidation. But you really need to test with

appropriately exposed film. You can expose a few frames on a roll, then in the darkroom

(or changing bag) open the camera and cut off just those frames, put the in a reel

and develop them. A nice outdoor scene on a sunny day, using the sunny 16 rule,

might be a good choice.

 

When it looks dark like coffee, it is probably best to throw away.

 

When it looks like tea, it will probably work but maybe with a longer development time.

 

For print developers, if you judge the exposure with the same developer, it should work.

It isn't quite as easy for film developers.

 

I am always surprised at the cost of D-76, but that is in quart bags.

Gallon bags are only a little more expensive, so much cheaper per roll.

 

But my favorite developers are Diafine and HC-110, the latter is especially

popular for older film. (Sometimes 10, 20, or 30 years old.)

 

HC-110 is a little expensive for the 1L bottle, but it will do over 100 rolls.

T-Max developer is a little cheaper for the 1L bottle, and does fewer rolls.

 

The concentrates have a fairly long life, and you can mix up amounts that you can

use in a reasonable time.

If you want to refine my recommended rough test a bit more, then fix the test piece of film after developing it. That way you'll be able to assess the density better.

 

A properly developed negative should have a maximum density (fully fogged) in the region of 2.5 or slightly higher - maybe 2.8. This sort of density makes it difficult to read a printed page of text through. If you can easily see through the film, then it's under-developed and the developer is probably stale.

 

The maximum density test is thoroughly reliable in my experience. Developer doesn't fail in such a way that it preferentially develops highlights over mid-tones or shadows.

I've periodically used old developers - some weather time well, like Rodinal, others lose their effectiveness in relatively short times. A long time ago I studied chemical reactions for a living, and my advice is: if you want QUALITY and reliable results, go with recently prepared developer batches. If you can live with potentially lower or unreliable results, go with whatever you have, but test it first so you have a better chance for a successful outcome.

Thank you all.

 

Mixing new D-76 surely would be the safest way to go. But for me it is not as cheap as for some of you. Here the one gallon packet costs like 18 dollars, and the dollar rose a lot this year, more than 100%, so basically it is not so cheap to shoot film.

 

Anyway, I am interested in quality, but it would be a pity to throw away developer already mixed if it is as good as before, so that it is why I am interested in the facts.

 

[uSER=2403817]@rodeo_joe|1[/uSER] : if this solid, one-tone white image without details turns black in the negative at a given time, is that enough to conclude the developer works normally? In this test we don’t have different tones, shadows, contrast, sharpness of photographed things… couldn’t they change also? Or an old developer, with the passing of time, only gets weaker in general, something that could be compensated increasing the time?

 

Of course, I could also develop unimportant images like others suggested, but even in this case it would be interesting to know what an old developer could do to the image, to judge better the results.

 

 

I purchased my D-76 in the packets that make 1 liter at a time. If I have to discard unused solution it is not much. I am not sure of the shelf life of powder in sealed pouches, but it is certainly measured in years. Yes, the smaller packs are more expensive, but there is less waste.

I've been stewing a bit over whether or not there would be a good way to actually measure developer capacity.

 

It should be possible by titrating with a standardized potassium permanganate or potassium dichromate solution to at least compare the reducing capacity(which directly relates to the capacity of the developer) of old vs "fresh" developer. Both of those reagents are strong oxidizing agents(developers are reducing agents) and both are strongly colored in solution-basically one would add the permanganate or dichromate solution from a buret to a flask containing a known amount of developer, and the solution would remain colorless. As soon as enough had been added to fully oxidize the developer, the color(purple for permanganate, orange for dichromate) would persist. Of course, permanganate is a bit nicer to the environment and a bit easier to dispose of.

 

In any case, it's probably an academic exercise, but still something I might play with one these days...since I'm an analytic chemist and that's what we do :) .

Well, I will do the test with the leader. If it turns out to be positive, maybe then I will develop four or five images I will shoot on another roll, just to be sure. And if I am satisfied with the results, I will proceed to develop a roll I shot last week.

 

Thanks for all the information. I will inform you how things turn out.

I purchased my D-76 in the packets that make 1 liter at a time. If I have to discard unused solution it is not much. I am not sure of the shelf life of powder in sealed pouches, but it is certainly measured in years. Yes, the smaller packs are more expensive, but there is less waste.

 

In my city I can’t get 1l packets of D-76, only the 3,8l ones. I don’t know if Amazon or another seller would send me one of these packets, and how expensive that would be, I will have to find out.

 

I know that there are some people who mix only a part of the packet, with allegedly good results. I read some anecdotes in forums about this subject two years ago. I also know about HC-110, which seems to be a good choice for not so frequent shooters, although I would prefer to stay with the D-76 until I know it better. Anyway, right now, I just want to make these tests and decide what to do with my current mix. Then I’ll see. Thanks for the suggestion.

 

 

My first 24 D-76 bottles, for 24 1:1 developments, or 12 1:0 ones:

 

 

I know that there are some people who mix only a part of the packet, with allegedly good results.

 

With the caveat that I've not tried it, I'd be worried that the powder isn't truly homogenous. Also, the solids SHOULD age better than the mixed liquid, but once you've opened the packet you can still run the risk of subjecting the metol and hydroquinone to oxidation-something that shouldn't happen in a sealed packet.

 

3.8L(1 gallon) packets are the standard size available in the US for most Kodak powdered developers. Dektol and XTOL are the two other biggies that come to mind, although hypo is also available in a packet designed for 1 gallon.

 

My gut general is to throw it out when in doubt, but then the last couple of packets I bought in the US were about $8.

 

With all of that said, if the above photo is your stored D76, IMO you've made a good decision by splitting it up into small bottles that you can keep completely full. Air is the enemy of developers, and both minimizing the amount in the bottle as well as the exposed surface area at the top is to your advantage.

I think I did a partial mix of a print developer. First I shook/stirred/etc. the powder to make it reasonably mixed.

 

Yes it might not be perfect, but close enough.

 

I then weighed out the appropriate amounts and put the rest in a folded over original bag, inside a zip-lock bag.

 

But I have also had old unopened Kodak bags that came out brown powder, and mixed to brown solution.

 

It is usually easier to remake prints than original film, though.

I know that there are some people who mix only a part of the packet, with allegedly good results.

 

- That definitely isn't a good idea. The developing agents are stored in one packet, with no guarantee of an homogenous mix between Metol and Hydroquinone, while the other pack contains a large quantity of Sodium Sulphite and a very small quantity of Borax - again with not much hope of an homogenous mix.

 

Taking proportions of the packs will almost certainly result in some sort of developer, but it very probably won't be D-76!

- That definitely isn't a good idea. The developing agents are stored in one packet, with no guarantee of an homogenous mix between Metol and Hydroquinone, while the other pack contains a large quantity of Sodium Sulphite and a very small quantity of Borax - again with not much hope of an homogenous mix.

 

Taking proportions of the packs will almost certainly result in some sort of developer, but it very probably won't be D-76!

 

The powdered developers I buy(D-76 and Dektol) come with everything in a single packet.

 

In any case, I agree that getting a homogenous mixture would be exceptionally difficult. In fact, if I'm not mistaken the data sheets specifically advise against mixing only part of the packet for this very reason.

The powdered developers I buy(D-76 and Dektol) come with everything in a single packet.

 

- That shows how long it is since I actually bought any packeted developers!

 

I prefer a home-brewed Phenidone-Ascorbate formulation that imitates D-76, or HC-110.

 

I suppose since the bulk of D-76 is the anti-oxidant sulphite, then bunging it all in one plastic bag makes very little difference to the shelf-life. However, I believe that the main difference between D-76 and ID-11 was the inclusion of a sequestering (water softening) agent that was best dissolved first. This obviously can't be guaranteed with a single pack.

 

The Calgon-like (hexametaphosphate) ingredient was never disclosed in the published formula, but was definitely mentioned in one MSDS for D-76 that I downloaded.

The powdered developers I buy(D-76 and Dektol) come with everything in a single packet.

 

In any case, I agree that getting a homogenous mixture would be exceptionally difficult. In fact, if I'm not mistaken the data sheets specifically advise against mixing only part of the packet for this very reason.

 

There is a discussion on using old mixed developer, another on how much developer one needs in the tank.

 

In all cases, how particular one is about getting perfect results should be considered.

 

In my case, it was for print developer, so prints, and not negatives, would be affected.

 

If you base exposure time on test strips using the same developer, some tolerance for variation

is corrected in the test strip process. (More often, I use a Projection Print Scale.)

 

In the case of RA-4, Kodak recommends that you don't mix smaller batches, and then gives

instruction on how to do it. (Mostly it depends on accurate liquid measure.).

 

Gallon bags of D76 cost only slightly more than quart bags, strong incentive to split a bag.

 

Much of my current film use is playing with older cameras. Exact results aren't so important,

but mosty for having fun.

I mix D-76 in the one gallon format. Then I distribute it among empty glass Pellegrino water bottles, and use as needed. My trick is to always keep the bottles topped up with virtually no air, and tightly capped. When there will be any air gap, I put in clean glass marbles into the bottle to pack out air. I store in a very dark ~65 degree closet.

 

That is at full strength. I develop at 1+1.

 

I have had good luck with premixed full strength stored that way up to 4 months so far. I probably wouldn't trust anything out at 6 months.

I mix D-76 in the one gallon format. Then I distribute it among empty glass Pellegrino water bottles, and use as needed. My trick is to always keep the bottles topped up with virtually no air, and tightly capped. When there will be any air gap, I put in clean glass marbles into the bottle to pack out air. I store in a very dark ~65 degree closet.

 

(snip)

 

I learned about marbles from my grandfather 50 years ago, though

mostly for plastic bottles.

 

Seems to me that the next important thing is the seal on the cap.

 

I always liked the seal on Nalgene (plastic) bottles that are popular in chemistry labs.

(In college days, I used to buy them from the physics store room.)

 

Some oxygen can get through plastic, though the lab quality ones should

be better than home quality. I was never so sure about the ones actually

sold for photography, especially ones with a paper seal.

 

If you want to do even better, though I usually don't do it, deaerate the water first.

Hi, I did the tests.

 

1) The leader got gradually darker and at the time recommended for normal processing at 20ºC, it was black. How much black? I don’t know, I took the film and observed it closely, it was dark. Then I immersed it again for 2 minutes, to see if it went on getting darker. I don’t know for sure if that happened, probably not, cause I couldn’t see any difference.

 

2) Then I developed a strip of film with the same mix I used for the leader. And I think it came out just fine. As a matter of fact, I overdeveloped +1, because I exposed -1, something I usually do, and the roll I am going to process now will be “pushed” too. I compared the negative with others I processed this way and I don’t see any difference in density. Anyway, what I think is important is that the leader turned black at the normal time of developing.

 

I also used my 2 years-old mix of fixer (Ilford Rapid Fixer), which I previously tested watching the clearing time. It was just like before. And I know that it is possible to fix a lot of rolls with a mix. So, in my case, the six months recommended by Ilford for a solution of this fixer were also too cautious.

 

Next weekend, I am going to develop the other roll. If something goes unexpectedly wrong, I let you know.

 

Thanks again.

I kept the stock D-76 in the bottles I showed you before, just to the top. The bottles were kept in a box. And the box in a closet, against the floor. Temperatures were far from ideal. Well, in winter I guess it was okay. But in summers, even in the box in the closet, I think it is hot, at least 25ºC or more. But I read somewhere that the most important factors were air and light. And the liquid wasn’t exposed to any of these.

 

I also read somewhere that D-76 turns brown sometimes. Mine looks the same as before, as far as I remember. I mean, I don’t know if it is a tiny bit more yellowish or transparent, but it seems to be the same.

Hi, I did the tests.

 

(snip)

 

I also used my 2 years-old mix of fixer (Ilford Rapid Fixer), which I previously tested watching the clearing time. It was just like before. And I know that it is possible to fix a lot of rolls with a mix. So, in my case, the six months recommended by Ilford for a solution of this fixer were also too cautious.

 

Next weekend, I am going to develop the other roll. If something goes unexpectedly wrong, I let you know.

 

Thanks again.

 

As above, I have had more problems with old Ilford Rapid Fixer.

 

Well, one is that I often use Diafine, which doesn't want an acid stop bath.

That might mean more pH increase for the fixer.

 

They specify a pH range, and if you keep it within that range, it should work well.

 

I think I try to keep my fixer for less than a year, even if it isn't up to its rated capacity.

 

pH paper is probably good enough, and years ago I had some of that, but not now.

It may have sediment so stain it through paper towel

 

@kmac What do you mean by “stain”? To filter the developer? I’m sorry, my English is far from perfect.

 

And yes, my current 2 years-old D-76 has some sediments.

 

It has also had some black sediments after the process, since it was mixed. But this is probably another topic about which I am going to write another thread one of these days (with photos or videos to show exactly what I mean), to see if someone helps me to solve the mystery of these bloody sediments, which sometimes stick to the film, and then become part of the stop bath or fixer.