Developer Starter for Xtol/EcoPro?

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Donald Qualls

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I'll soon start a fresh tank solution of EcoPro (replacing my old Xtol) for long term replenishment, and I'd like to bypass the seasoning process and go direct to a steady state. For Flexicolor, this would be accomplished by making the tank solution using replenisher, a little water, and Flexicolor Developer Starter in the correct proportions.

Given Xtol is a supported replenishment system (albeit self-replenishing, with the developer stock solution being the replenisher), there ought to be a starter; I think I've read that Kodak used to sell a starter for it.

Any sources, or (ideally) a formula for a workable developer starter for use with Xtol (and by extension, EcoPro)? Just stock solution plus some iodide, or other stuff in it too?
 

MattKing

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The X-Tol datasheet includes directions for using C41 or E6 Starter.
The most recent version of the datasheet is dated 2018, so the catalogue numbers may be a bit of a challenge.
 
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Donald Qualls

Donald Qualls

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Well, as it happens, I have Flexicolor LORR starter on hand. I'll have to go dig up the Xtol datasheet.

Oh. Crap. I think Kodak Developer Starting Solution (146 6382) is a B&W starter that's no longer available. Different from C-41 starter. The other starters listed are for E-6 first dev starter (two different first devs), not color developer starters for anything.
 
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Donald Qualls

Donald Qualls

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Yes, that' the CAT 146 6382 at 6.5 ml/L of tank solution. That's from that exact reference, but I don't think that's a C-41 starter.

Anyway, one of the E-6 First Dev starters was the "new number" in a document I found from 2000, and Kodak doesn't even sell a replenished E-6 any more.

Looks like seasoning with film is the only solution.
 

cmacd123

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can you find a formuala for E6 starter? Perhaps comparing the formula for e6 developer and e6 replenisher?
 

McDiesel

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@Donald Qualls I instantly seasoned my Xtol by developing a bunch of old film in it (burned a few rolls). You can use "Reusing Developer" table from the Xtol datasheet to determine how much you need. (map the reused developer to replenished developer activity which is also mentioned in a few places in the datasheet) The math is fairly simple.
 

Sirius Glass

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@Donald Qualls I instantly seasoned my Xtol by developing a bunch of old film in it (burned a few rolls). You can use "Reusing Developer" table from the Xtol datasheet to determine how much you need. (map the reused developer to replenished developer activity which is also mentioned in a few places in the datasheet) The math is fairly simple.

I usually have enough rolls of time to seasoned XTOL. Otherwise it will be soon enough.
 

John Wiegerink

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I seasoned my very first batch with fogged paper that I wasn't going to use for anything. Worked just fine as far as I could tell and lasted several years. I'll do the same for the next batch (Adox XT-3) that I mix.
 

Craig

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I never bothered to season it, I used the fresh developer and the times until I had built up enough used solution to begin replenishment.
 

mshchem

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I have a bottle of the Kodak starter for XTOL. Ingredients are sodium chloride and potassium bromide. Usage is 6 mL/L. I've been tempted to taste it to see if there's even a discernible taste. It's a crystal clear water solution. I suspect that this stuff was mostly for Versamat type processors when switching to XTOL.

I use XTOL 1 shot, at least for the last decade, I bought this after it had set on a shelf for 15 years. Now it sets in my darkroom, it's nice to have:smile:.

Starters are the real thing. I'm not making light of it.
 
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Donald Qualls

Donald Qualls

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Ingredients are sodium chloride and potassium bromide. Usage is 6 mL/L.

Is that just what shows on the MSDS? There can be lots of stuff in there that's too low concentration be required for listing there. Even in that case, without knowing the concentrations it's just guesswork -- which means I'm better off just reusing stock solution for six rolls per liter before I start to replenish.
 

mshchem

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Is that just what shows on the MSDS? There can be lots of stuff in there that's too low concentration be required for listing there. Even in that case, without knowing the concentrations it's just guesswork -- which means I'm better off just reusing stock solution for six rolls per liter before I start to replenish.

This is what is shown on the label. I agree that without a formula it would be tricky. When I printed Cibachrome I would dilute unused developer 50:50 with used developer. After the 1st couple prints the "saved solution" got to an equilibrium. I used to be able to do the math but if I remember correctly after 4 or 5 passes it reaches a static level.

I know that you would need to have free film and a densitometer to do this with XTOL. Not practical.

Fuji sells E6 1st developer starter in huge quantities, again not practical.

If I still had access to the analytical lab I worked in during the good days I would crack the formula.
 
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Donald Qualls

Donald Qualls

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When I printed Cibachrome I would dilute unused developer 50:50 with used developer.

That's close to the method I've seen for replenishing D-23 over the longer term. Per John Finch (YouTube PictorialPlanet), you'd use up half the volume of your working solution in replenisher, then save 25% of the tank solution and add that to fresh stock to get seasoned developer immediately.

Xtol (like, presumably, XT-3 and EcoPro) doesn't have that limit on how long you can replenish (likely due to the relatively high replenishment levels). Obviously, I have sodium chloride on hand (food grade!); I also have potassium bromide in the darkroom cupboard. There's just no "low tech" way to know how much of those build up in the stock solution after processing six rolls per liter...
 
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Donald Qualls

Donald Qualls

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You know, @mshchem, I think it would get me closer even just to know the total salinity of that starter -- either via refractometer or specific gravity. Wouldn't tell me what the proportions are (though knowing both might give a range, since I believe refractive index is by mole while specific gravity is by molecular weight), but it would give a starting point.
 

mshchem

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You know, @mshchem, I think it would get me closer even just to know the total salinity of that starter -- either via refractometer or specific gravity. Wouldn't tell me what the proportions are (though knowing both might give a range, since I believe refractive index is by mole while specific gravity is by molecular weight), but it would give a starting point.

Let me check and see if I can get sp gr.
 

mshchem

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You know, @mshchem, I think it would get me closer even just to know the total salinity of that starter -- either via refractometer or specific gravity. Wouldn't tell me what the proportions are (though knowing both might give a range, since I believe refractive index is by mole while specific gravity is by molecular weight), but it would give a starting point.

OK, just up from the darkroom, 1.19 g/cc @ 19°C. I used a proper Nalgene PMP graduated cylinder that is calibrated TC/TD, the plastic is non-wetting, i.e. no meniscus. I tared the cylinder on a German made Sartorius electronic balance that has 500g capacity that reads out to 0.1g. There was a little bit of white crystals around the starter bottle cap, I managed to scrape a few milligrams onto a Post-it note. Definitely resembles both NaCl and KBr, little cubes.

I tasted it, tasted like table salt, at least more so, than when I put a single grain of vintage Kodak potassium bromide (4 Oz brown glass bottle marked 40 cents in a black wax pen). The KBr tasted cool like potassium chloride.
It could be that the salt was added as a preservative???

If I was younger and still had access to a good old Perkin Elmer AA/Emission spectrometer, but I walked away from that machine over 30 years ago.

If I don't post after tonight it will be because I was all wrong about the taste 😁🤪🧐
 

Mr Bill

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I don't have any concrete data in this specific case, but I think it ought to be fairly easy for the right person to come up with an approximate method to "season" fresh Xtol developer.

Of course it would be nice to have the right equipment to reverse engineer an existing starter solution. But it ought to possible to find something workable on a semi-shoestring budget. Rather than try to duplicate an existing starter I'd suggest to consider what happens during seasoning with film. Essentially the developed film is releasing some byproducts into the developer. Most significant are probably bromide ion, and for the more modern films very small amounts of iodide ion. So if someone has a bit of KBr, a decent scale, and a way to evaluate development, it ought to be possible to do a bit of trial and error testing.
 
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Donald Qualls

Donald Qualls

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Thanks, @mshchem. That's a little less than sea water specific gravity. Now, if we had a second point, we might be able to solve for the two concentrations. I was thinking refractometer, because different salts at the same refractive index ought to have different specific gravity. In other words, any proportion of KBr to NaCl could produce 1.19 g/cc, but there's probably only one that will also produce a particular refractive index.

Know anyone with a salt water aquarium (ideally a reef tank) who uses a refractometer to check their salinity? My partner just uses a hydrometer, since the salt mixes are interchangeable for that application and it's much easier to use -- and that level of precision just isn't needed -- but some salt water aquarists are equipment fixated...

BTW, tasting like table salt is what I'd expect even with a mix biased heavy to KBr. Our "salty" taste buds are very well attuned to chloride ions; ammonium chloride ("salmiak" as used in some Dutch candies) tastes more like table salt even than potassium chloride -- KCl tastes more "metallic" (I use it, in mixture with NaCl or by itself, as a salt substitute for a while every time one of my doctors wants me to cut down on sodium). Comparatively, our detectors aren't evolved to detect bromides (or iodides, for that matter) at all, because they aren't common in our environment (less soluble, and less abundant in the Earth's crust, than chlorides).

@Mr Bill This is essentially what we're trying to do, without involving a $100,000 (or more) spectrometer to directly measure the concentrations of the four relevant ions. It might well be "close enough" to make up a mixture of NaCl and KBr, 50/50 by mole, in solution at 1.19 g/cc, and put 6 ml of that in a liter of developer, and if we don't get any better information I'll do that (I've got KBr as well as KI on hand, but KI doesn't have a known history as a restrainer, so likely isn't relevant in this situation). I've also just gotten a scale that reads 0.1 g up to 3 kg (made for brewing pour-over coffee, of all things), and still have my reloading scale that reads down to 0.1 grain (at 15.4 grains per gram, that's about 6.5 mg) though it's much more fiddly to use.

Given that a dozen or so rolls (per liter) will bring me close to equilibrium if I just don't replenish for the first six (per liter), getting anywhere close to "seasoned" condition would let me avoid messing with changing my times over/after the first dozen or so rolls. I may just put 250 ml of water in a graduate on the scale, and add equal masses of NaCl and KBr to bring up to 1.19 g/ml (that would be, what, 47 g or so of mixed salt), bottle that up and label it, and call it good. It'll be better than no starter, and likely close enough to be indistinguishable without much closer controls than I normally put on the rest of my process.

FWIW, that's approximately a 190 g/l solution, which means 6 ml is about 1.4 g of mixed salts to the liter of developer stock.
 

Mr Bill

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@Mr Bill This is essentially what we're trying to do, without involving a $100,000 (or more) spectrometer to directly measure the concentrations of the four relevant ions. It might well be "close enough" to make up a mixture of NaCl and KBr, 50/50 by mole, in solution at 1.19 g/cc, and put 6 ml of that in a liter of developer, and if we don't get any better information I'll do that (I've got KBr as well as KI on hand, but KI doesn't have a known history as a restrainer, so likely isn't relevant in this situation).

Hi, my experience is primarily in color processes, where C-41 color neg process uses CD-4 developing agent. This IS strongly restrained by byproducts of film development. These were primarily bromide ion and a very small amount of iodide. I know this as a result of chemical analysis of a lot of samples.

(Background: I was the QC manager for a number of years in a large processing lab. My department had a decently equipped on-site chem lab in support of this. Also including a Perkin Elmer (yay!) AA unit with a silver tube. We used it pretty exclusively for silver analysis, including work for the company's one-hour lab division. Up until about the same time frame as mschem. We used to run bromide and iodide analysis with potentiometric titration using silver bar electrode vs double-junction reference. A pH meter showing mv readings is used; an automatic titrator takes a lot of the pain out of it.)

Anyway, I'm trying to save you some effort. I have no idea why the chloride is in the starter. But once a replenished system is running for a while this becomes irrelevant - only the film (and aerial oxidation/evaporation) come into play. So... you'll have a fair amount of bromide ion released and possibly a tiny amount of iodide ion. (If you think you know a film that uses silver chloride I'd be interested in knowing what it is.)

As I said before my primary experience is with color - I have no idea how sensitive Xtol is to the byproducts. (I'm guessing that it's fairly slight, mainly because it can be self-replenished.)

Anyway... I would suggest just doing a couple of test runs with a bit of KBr added. Provided that you have a way to evaluate development. I expect this is probably the quickest way to get close to where you wanna be.

To be frugal you could probably use a small amount, say 50 ml or so, of developer, then hand-process a small piece of film in the dark. Disposable forceps are a good way to hold the film, or possibly a small alligator clip, etc

Best of luck with it.
 

mshchem

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Hi, my experience is primarily in color processes, where C-41 color neg process uses CD-4 developing agent. This IS strongly restrained by byproducts of film development. These were primarily bromide ion and a very small amount of iodide. I know this as a result of chemical analysis of a lot of samples.

(Background: I was the QC manager for a number of years in a large processing lab. My department had a decently equipped on-site chem lab in support of this. Also including a Perkin Elmer (yay!) AA unit with a silver tube. We used it pretty exclusively for silver analysis, including work for the company's one-hour lab division. Up until about the same time frame as mschem. We used to run bromide and iodide analysis with potentiometric titration using silver bar electrode vs double-junction reference. A pH meter showing mv readings is used; an automatic titrator takes a lot of the pain out of it.)

Anyway, I'm trying to save you some effort. I have no idea why the chloride is in the starter. But once a replenished system is running for a while this becomes irrelevant - only the film (and aerial oxidation/evaporation) come into play. So... you'll have a fair amount of bromide ion released and possibly a tiny amount of iodide ion. (If you think you know a film that uses silver chloride I'd be interested in knowing what it is.)

As I said before my primary experience is with color - I have no idea how sensitive Xtol is to the byproducts. (I'm guessing that it's fairly slight, mainly because it can be self-replenished.)

Anyway... I would suggest just doing a couple of test runs with a bit of KBr added. Provided that you have a way to evaluate development. I expect this is probably the quickest way to get close to where you wanna be.

To be frugal you could probably use a small amount, say 50 ml or so, of developer, then hand-process a small piece of film in the dark. Disposable forceps are a good way to hold the film, or possibly a small alligator clip, etc

Best of luck with it.

I have done probably 100,000 chloride determinations, Corning pH meter in positive mV scale, silver billet and double junction reference electrode, titration with AgNO3 to a 323mV endpoint. There were no bromides or iodide present. (Livestock supplements)
I have no equipment any longer.

Can one distinguish Br- from Cl- with a potentiometer? Silver billet/bar etc???
 

Sirius Glass

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I don't have any concrete data in this specific case, but I think it ought to be fairly easy for the right person to come up with an approximate method to "season" fresh Xtol developer.

Of course it would be nice to have the right equipment to reverse engineer an existing starter solution. But it ought to possible to find something workable on a semi-shoestring budget. Rather than try to duplicate an existing starter I'd suggest to consider what happens during seasoning with film. Essentially the developed film is releasing some byproducts into the developer. Most significant are probably bromide ion, and for the more modern films very small amounts of iodide ion. So if someone has a bit of KBr, a decent scale, and a way to evaluate development, it ought to be possible to do a bit of trial and error testing.

I do not worry about it. When the replenished XTOL expires, usually from non use, I mix a new batch and start replenishing from roll number 1 and after roll 5 I consider it replenished. I use the same development times from the first roll on.
 

mshchem

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I do not worry about it. When the replenished XTOL expires, usually from non use, I mix a new batch and start replenishing from roll number 1 and after roll 5 I consider it replenished. I use the same development times from the first roll on.

You of course make a compelling argument. This is a bit of a challenge, detective case :smile: . I'm going to mix up a batch of the Adox version this weekend. We'll see how that goes, I still have some Alaris/Tetenal product, well supplied 😀
 

MattKing

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I just use a straight line approximation of the variance in development times between the stock times and, six rolls later, the replenished times.
And then I season to taste. :smile:
 

Sirius Glass

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I just use a straight line approximation of the variance in development times between the stock times and, six rolls later, the replenished times.
And then I season to taste. :smile:

Do you add Cholula Hot Sauce?
 
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