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Rudeofus
01-16-2012, 05:26 AM
1. why are you talking about chelating agent in relation to sulfite? They are unrelated issue.
[ ... ]
They are not really concerned about iron. (MQ and PQ developers are not very sensitive to iron, manganese and copper impurities, where ascorbate developers are super sensitive.)
According to PE they are not unrelated because Na2SO3 carries iron as impurity, and you confirmed that further down in your post. If ascorbate is part of most of the formulations here and highly sensitive to iron then Mark should seriously think about adding Na-EDTA, Calgon, Dequest or whatever.

2. In ascorbate developers, dealing with trace amount of iron impurities from any possible source (including water source and sulfite stock) is crucial for reliability, not just keeping property. I would not use an ascorbate developer without this measure, even for one-shot use, period.
I referred to your quote about sudden death of Xtol and your dislike of Na-EDTA and got the impression that these are related. Since I already have Na-EDTA I would like to use it as chelating agent and think I can do this as long as I don't keep the mix for more than a day or so.

You should study how "sudden death of XTOL" happened. It can happen in just a matter of an hour or two, and it does not discolor the solution at all.
Do you mean an hour after mixing the soup or that the change from good to mostly inactive happens within this time frame? I have read up on the Xtol sudden death syndrome and the conclusion seems to be that ascorbic acid oxidizes and does this faster if iron or calcium ions are present.

Again, these issues seem very important for devs which are sold commercially and/or stored for prolonged time frames but this is not an issue for my experiments yet. "Sudden death of Xtol" is a popular topic but I don't remember it being reported for freshly mixed Xtol.

3. Color process is a different problem. You have a lot of iron compounds in bleach bath. In some reversal processing, they need be thoroughly removed or it will turn into stain (very problematic in print processing). But the problem is different in ascorbate developers.

Just for the record: stefan4u used Calgon in his working formulation of C41 color developer, which is used before the iron heavy bleach hits the film. It seems iron and/or calcium cause more trouble in color processing than just stains, so the problems may be closer related than you think. Anyway, I'm afraid I won't go out and modify Marks recipes before I get my hands on a semidecent pH meter (soon, I promise).


4. You should really get some decent industrial chemistry references. Borate buffer is not a part of elementary chemistry but it is very common in industrial chemistry, and it is definitely important in understanding b&w film developers (as well as making your own). You should have data on concentration dependency, temperature dependency, etc. at your fingertips. Carbonate, phosphate, triethanolamine, diethanolamine, etc., are also important and useful. Those references will also have a chart on the hydration of the compound with respect to temperature and pressure.

I would love to and would welcome decent references here. But first things first, as you may have read we have just established that I used only 3/4 or the metaborate that Mark recommended. It was my first run of home brew developer, luckily it yielded usable results so I am highly motivated to go on with these experiments. The darkroom cookbook will arrive tomorrow so my knowledge of photo chemistry will at least quadruple over the next few weeks :whistling:

analog what is that?
01-16-2012, 06:59 AM
One more question: I set up a stock solution of metaborate from borax and lye in water. Is this stock solution reasonably stable or does it decompose somehow? If I let all the water evaporate from this mix: can I expect sodium metaborate crystals? If yes, what amount of water can I expect in these crystals?

I'd like to highlight this and hopefully somebody with experience will answer.

Ryuji
01-16-2012, 07:51 AM
According to PE they are not unrelated because Na2SO3 carries iron as impurity, and you confirmed that further down in your post. If ascorbate is part of most of the formulations here and highly sensitive to iron then Mark should seriously think about adding Na-EDTA, Calgon, Dequest or whatever.


Iím not supposed to comment on whatever the gentleman from upstate New York says, and he is not supposed to comment on my work or my statements, or anything related to me.

That said, you need to understand ďchelating ironĒ does not always do the same thing in this context. It is a very delicate matter, simultaneously concerning electrochemical *and* coordination chemistry aspect of iron as redox catalyst. This issue is not very specific to ascorbate developers, and it arises in some places in industrial chemistry as well as biochemistry. But in the context of photographic processing chemistry, ascorbic developer is by far the toughest case to deal with.



I referred to your quote about sudden death of Xtol and your dislike of Na-EDTA and got the impression that these are related. Since I already have Na-EDTA I would like to use it as chelating agent and think I can do this as long as I don't keep the mix for more than a day or so.

My answer is the same. EDTA makes it worse.



Do you mean an hour after mixing the soup or that the change from good to mostly inactive happens within this time frame?

If you really study cases of sudden death of XTOL you know the answer yourself.



I have read up on the Xtol sudden death syndrome and the conclusion seems to be that ascorbic acid oxidizes and does this faster if iron or calcium ions are present.

Calcium has nothing to do with it. Iron, manganese, copper, these are the problems. And you see, XTOL has a copious amount of DTPA, which is significantly more powerful than, but of generally of the same type of chelating agent as, EDTA. If DTPA isnít good enough, EDTA is not good at all. Neither is NTA.



Again, these issues seem very important for devs which are sold commercially and/or stored for prolonged time frames but this is not an issue for my experiments yet.

Are you ok with a developer that *may* die in an hour after mixing? I am not.

Of course, many people eat raw cookie dough and donít get sick. Some get sick but they tell themselves that the dough was old, and never seriously consider the real known risk just because the chance isnít that large.




"Sudden death of Xtol" is a popular topic but I don't remember it being reported for freshly mixed Xtol.

What are you talking about??
*Sudden* death of XTOL is about freshly mixed XTOL.



Just for the record: stefan4u used Calgon in his working formulation of C41 color developer, which is used before the iron heavy bleach hits the film. It seems iron and/or calcium cause more trouble in color processing than just stains, so the problems may be closer related than you think. Anyway, I'm afraid I won't go out and modify Marks recipes before I get my hands on a semidecent pH meter (soon, I promise).

There is no logical and semantic connection between each of your clauses above.

You need to understand the context of my previous comment about iron removal in color reversal print processing. The difficulty of the matter is considerably more than whatever context you are talking about Calgon. Calgon is not the first line of agent to try when you have any sort of iron related issue. It is more for calcium and magnesium.

Watch out for those books written for darkroom enthusiasts. They contain many overstatements, misleading statements, impractical suggestions, and some errors that people not familiar with the topic are not likely to find.

albada
01-16-2012, 12:10 PM
Are you ok with a developer that *may* die in an hour after mixing?

Ryuji, please provide links to postings on apug or PN that report home-brew ascorbate developers (not XTOL) dying in an hour. I've used chems from PhotoFormula after a few hours or the next day, and they've been fine. So links to failures would be helpful.

I'd like to second Rudeofus' request for references to books on industrial chemistry. I have much to learn.

Mark Overton

albada
01-16-2012, 01:01 PM
Chemistry can be a bitch sometimes ;) I incorrectly assumed you meant the tetra hydrate NaBO2*4H2O so it looks like your recipe still yields results even if the metaborate content is off by quite a bit. Using the same weight of tetra hydrate instead of dihydrate adds only 3/4 of the metaborate to the mix.

Perhaps it's the same stuff. I noticed that the decahydrate that I used is also written as Na2*B2*O4*4H2O, which merely doubles everything, and might be what you have. Here's a data-sheet showing both formulas: http://www.borax.com/pdfs/dist/DataSheet.Borates.SodiumMetaborate4Mol2010.pdf

Even with only 3/4 of the metaborate, your pH is probably between 8.0 and 8.1, reducing activity a bit, so your 2-stop push might only be a 1-stop.

Have you looked at your negs closely under a loupe? How did the shadow-detail come out?

Mark Overton

Rudeofus
01-16-2012, 01:11 PM
My answer is the same. EDTA makes it worse.
Does it make it worse because the iron bound by it is still or even more chemically active (like it is supposed to be in Ammonium-Ferric-EDTA) ? Or are there other effects I have not thought/learned about?

Calcium has nothing to do with it. Iron, manganese, copper, these are the problems. And you see, XTOL has a copious amount of DTPA, which is significantly more powerful than, but of generally of the same type of chelating agent as, EDTA. If DTPA isnít good enough, EDTA is not good at all. Neither is NTA.
Would Dequest 2010 be better? I have a possible source for it here in Europe (Tronds knows about this).

Are you ok with a developer that *may* die in an hour after mixing? I am not.

Of course, many people eat raw cookie dough and donít get sick. Some get sick but they tell themselves that the dough was old, and never seriously consider the real known risk just because the chance isnít that large.

What are you talking about??
*Sudden* death of XTOL is about freshly mixed XTOL.

Ryuji, the instances I have read about were about XTol from which 5l were mixed some time before and which then went from active to inactive within an hour. I am sure the "Sudden Death of Xtol" has been discussed extensively over the many, many years Xtol has been sold commercially and I take your word that this happened to a few people right after opening the concentrate.

Photo Engineer
01-16-2012, 01:51 PM
I have never seen a first hand account of XTOL "sudden death". I have heard of it being DOA when freshly mixed from early batches. Kodak revised the packaging to prevent this problem.

Iron sequestered by EDTA is much less active than free Iron, but it can still act as an oxidant and we see this in color bleaches that use EDTA or EDTA like compounds. Dequest OTOH, inactivates Iron so effectively that I have seen it decolorize Ferric salt solutions and deactivate bleaches.

So, I have worked with Dequest as an Iron salt deactivating chemical and have reported it at EK.

PE

Alan Johnson
01-16-2012, 03:10 PM
My experience agrees with Ryuji. As an example, here's a formula that gives grain matching XTOL under my 22x loupe, yet has low concentrations of phenidone and other components. This formula is for a concentrate yielding either 5 liters or 1 liter of working solution:



Working volume ----------> 5L .......... 1L
Propylene glycol .............. 75 .......... 15 ml
Sodium metaborate ......... 11 .......... 2.2 g
Ascorbic acid ................... 22.5 ....... 4.5
Phenidone ....................... 0.25 ....... 0.05 g
Propylene glycol to .......... 100 ........ 20 ml (should need to add only 5/1 ml)

pH = 8.0. Use 20ml per liter (1+49 dilution) into water containing 45 g/L sodium sulfite.
Develop for twice XTOL's times.




Mark Overton
I made up the developer above, call it D316 after the post number.It could be made by heating to 70C in a water bath.The 45g/L sulfite I weighed out is about 4 heaped teaspoons.The measured pH was 8.1.
HP5+ was developed in D316 for 2x the Xtol 1+0 time.
HP5+ for comparison was developed Xtol 1+1.
The EI I would use for sun/shade conditions, average metering, was D316=EI 320, Xtol 1+1 = EI 400.
Attached scans are of 0.1 inch square sections of negative scanned on an Epson V700 at nominal 4800dpi, sharpened equally.

Conclusions:
Xtol 1+1 gives finer grain and slightly higher speed.
D316 wrt its concentrate composition and dilution is practical and economical, probably near optimal.
Concentrate is a good developer but cannot be made so as to give as fine grain as Xtol,though close.

Rudeofus
01-16-2012, 03:43 PM
I have never seen a first hand account of XTOL "sudden death". I have heard of it being DOA when freshly mixed from early batches. Kodak revised the packaging to prevent this problem.
A simple web search yields quite a few reports but so does a search for "front focus" for just about any auto focus lens which could be attached to a Canon EOS body. I am confident that Kodak would have recalled and reformulated Xtol if this was a problem likely to happen to many customers of their product. What this means for us, though, is that we have to be careful with ascorbate based developers. We don't have the complete recipe for Xtol (the patent may not include improvements which have been kept as trade secrets) so we have no real insight how Kodak dealt with the potential sudden decay of ascorbate.


Iron sequestered by EDTA is much less active than free Iron, but it can still act as an oxidant and we see this in color bleaches that use EDTA or EDTA like compounds. Dequest OTOH, inactivates Iron so effectively that I have seen it decolorize Ferric salt solutions and deactivate bleaches.
Can it have any effect on B&W developer ingredients that we should be aware of? Any potential interactions with the fixer if we don't rinse well enough after dev? Does Dequest also catch other ions like calcium, manganese or copper or whatever may show up as impurity in the raw chems and bite our precious dev?


Perhaps it's the same stuff. I noticed that the decahydrate that I used is also written as Na2*B2*O4*4H2O, which merely doubles everything, and might be what you have. Here's a data-sheet showing both formulas: http://www.borax.com/pdfs/dist/DataSheet.Borates.SodiumMetaborate4Mol2010.pdf
The problem is that metaborate comes with different (http://www.chemblink.com/products/7775-19-1.htm) amounts of (http://www.borax.com/pdfs/dist/Profile_Sodium_Metaborate_4_Mol.pdf) water (http://www.borax.com/pdfs/dist/MSDS_Sodium_Metaborate_8_Mol.pdf) so there was no way to be sure. There was a procedure for producing crystalline sodium metaborate (http://www.apug.org/forums/viewpost.php?p=1157109) but again, no indication was given how much water is bound per molecule or how one would influence that amount. It looks like I should use Mike Wilde's recipe (http://www.apug.org/forums/viewpost.php?p=755930) as it seems the best option for me right now.

I will be in the dark room this wednesday and let you all know whether I got reasonable looking images out of that roll of film with scanned print samples. Judging shadow details is only marginally informative if one doesn't know the light level of these shadows.

albada
01-16-2012, 03:46 PM
I made up the developer above, call it D316 after the post number.It could be made by heating to 70C in a water bath.The 45g/L sulfite I weighed out is about 4 heaped teaspoons.The measured pH was 8.1.
HP5+ was developed in D316 for 2x the Xtol 1+0 time.
HP5+ for comparison was developed Xtol 1+1.
The EI I would use for sun/shade conditions, average metering, was D316=EI 320, Xtol 1+1 = EI 400.
Attached scans are of 0.1 inch square sections of negative scanned on an Epson V700 at nominal 4800dpi, sharpened equally.

Conclusions:
Xtol 1+1 gives finer grain and slightly higher speed.
D316 wrt its concentrate composition and dilution is practical and economical, probably near optimal.
Concentrate is a good developer but cannot be made so as to give as fine grain as Xtol,though close.

I appreciate your doing this, as it's always good to have reviewers check one's work. Some questions:

* How do the densities of the two negatives compare? My goal was twice XTOL's dev-time, and I'm wondering how close I got for a conventional grain film.

* Could you compare grain by viewing the neg's directly with a loupe? I've found that even a dedicated film-scanner as good as my Nikon Coolscan IV ED does not reliably show grain due to focus-variation, so I trust direct viewing in a loupe or microscope more. Hmm, I guess a couple of carefully-focused extreme enlargements (projecting onto the floor?) would also clearly show the grain-difference.

* I notice that the area under the bumper is darker in the Xtol-scan, indicating a difference in black-point and/or gamma in the scans. How did you set these in your scanning software?

My goal is to get XTOL's grain in a concentrate, and I'll keep hammering at it. Feedback like this is good.

Mark Overton

Photo Engineer
01-16-2012, 03:48 PM
Dequest has no interaction with any B&W chemical AFAIK.

PE

Alan Johnson
01-16-2012, 04:35 PM
I appreciate your doing this, as it's always good to have reviewers check one's work. Some questions:

* How do the densities of the two negatives compare? My goal was twice XTOL's dev-time, and I'm wondering how close I got for a conventional grain film.

* Could you compare grain by viewing the neg's directly with a loupe? I've found that even a dedicated film-scanner as good as my Nikon Coolscan IV ED does not reliably show grain due to focus-variation, so I trust direct viewing in a loupe or microscope more. Hmm, I guess a couple of carefully-focused extreme enlargements (projecting onto the floor?) would also clearly show the grain-difference.

* I notice that the area under the bumper is darker in the Xtol-scan, indicating a difference in black-point and/or gamma in the scans. How did you set these in your scanning software?

My goal is to get XTOL's grain in a concentrate, and I'll keep hammering at it. Feedback like this is good.

Mark Overton
(1)The density with D316 was very slightly higher than Xtol 1+1.You did a great job in formulating this concentrate,the pH was near enough spot on and you managed to dissolve a lot of AA by using the metaborate first.
(2)IMO the most reliable way to assess grain is with an enlarger,which I don't have time to do.However I know my V700 will easily pick up the difference between Perceptol and Xtol.I would be surprised if my conclusions are wrong.
(3)Good spot. But I might get cast into the outer darkness for answering that on APUG.
(4)I did wonder if you could make a very strong concentrate that would give a working solution closer in composition to Xtol ,which working solution could be re-useable by throwing out and replenishing 70ml each time.
But already the solubility limits are approached.

albada
01-16-2012, 07:05 PM
(...) and you managed to dissolve a lot of AA by using the metaborate first.

You are perceptive! Yes, I noticed that more AA would dissolve into PG if I first dissolved metaborate, which converts some of the AA. You're onto my tricks. :)


(3)Good spot. But I might get cast into the outer darkness for answering that on APUG.

We hate to see you weeping and gnashing your teeth, so we'll drop that.


(4)I did wonder if you could make a very strong concentrate that would give a working solution closer in composition to Xtol ,which working solution could be re-useable by throwing out and replenishing 70ml each time. But already the solubility limits are approached.

Which gets back to my original goal: Make a concentrate that gives XTOL's image-quality, with sulfite added separately (for now). I even tested a concentrate that copied XTOL closely, and it worked well. I won't post it here because that was before I had the pH-meter, and I want to measure and perhaps adjust the pH.

But then I tried to cut the sulfite in half and double the dev-time because I'm disappointed at the great quantity of sulfite that gets poured into developers. This half-and-double developer works great for TMY-2, but with your input, I'll try it with HP5+ and Tri-X. I like it because it saves chemistry and gives a high concentration, but if I can't get it to work well with a variety of films, then it'll just be for t-grain or just TMY-2. And I'm thinking I should complete the original goal before pursuing this half/double idea further.

Mark Overton

albada
01-17-2012, 08:53 PM
Mark, It's been a long time and I can't find my recipe (...)

Jerry, your formula with half-TEA and half-PG was in my notes! You posted it to the pure-silver list long ago. I've done a lot of researching, and now I'm forgetting what all I've found. Anyway, for the record and for the sake of search-engines, here is improved PC-TEA by Gerald Koch:


TEA ....................... 50 ml
Propylene glycol ....... 50 ml
Ascorbic acid ........... 9.0 g
Dimezone S ............. 0.3 g
Potassium bromide .... 0.2 g (or 0.25)

Use 1+50 (about 9 min) as with PC-TEA. Works well: Low fog, correct contrast, very fine grain.



Mark Overton

Ryuji
01-18-2012, 05:29 AM
Does it make it worse because the iron bound by it is still or even more chemically active (like it is supposed to be in Ammonium-Ferric-EDTA) ? Or are there other effects I have not thought/learned about?

Would Dequest 2010 be better? I have a possible source for it here in Europe (Tronds knows about this).


In presence iron-EDTA complex is more active redox catalyst than iron itself. Well known and documented in electrochemistry literature.

Keep in mind that iron exists mostly in ferrous form in developer solutions, and ascorbate itself also forms complex with iron and gets destroyed very quickly.

Again, I am not allowed to comment on the works of gentleman from upstate New York. It should also be noted that he is not supposed to talk about my work or statements, at all.

In general, a certain pH-specific blend of amines plus salicylic acid was effective enough that I could keep concentrated developers for months, even when I intentionally mixed impurities and some molecular oxygen and/or peroxide. However, I wasnít satisfied enough to stop looking. Now I have another solution that is much simpler and more effective, but the ingredient is not available from any laboratory reagent supply house (in other words, if you want to adapt this solution, you need to get the stuff from me).

Either way, denial or ignorance is not the answer.

Ryuji
01-18-2012, 05:48 AM
For reference on basic industrial chemistry (such as buffers and solvents) Ullmann's encyclopedia is always a very good start (and usually a good end as well). It's not cheap - get connected with a very good library. Your local university library may have electronic subscription. If not, as librarian for a good alternative reference.

http://onlinelibrary.wiley.com/book/10.1002/14356007

If I were to suggest just one book on general photographic chemistry written in English language, I'd say one by Keller. Each section is written by AGFA experts. It is more updated than Haist, gives more broad coverage, and offers less obsoleted, now-rejected or now-irrelevant information. Very concise so you need to read each sentence very carefully, but it is a good book. If you want to get a glance of existing body of knowledge on theory, the book by T. H. James is probably still the best in English language. Make sure to get the latest edition. Earlier one had a lot of theories/models that became obsolete/irrelevant/wrong.

But nothing is better than reading original peer reviewed papers... though you need to have a very clear bigger map before getting to appreciate details.

Then, in order to really understand the developer chemistry, you should also understand the mechanism of photosensitivity. That is, the theory of emulsion chemistry. This part changed SO MUCH MORE than the developer formulation in the past 100 years. Since the goal of any developer is to exploit latent image centers created by photosensitivity, you should have good understanding of your enemy to fight for the goal well. But I'd start with Ullman and Keller.

That said, there is an excellent book written in Japanese language, more updated than Haist and James combined, and written by mostly Fuji, Konica, and University of Chiba people. It's probably still the latest single book that is comprehensive.

Rudeofus
01-18-2012, 03:38 PM
That said, there is an excellent book written in Japanese language, more updated than Haist and James combined, and written by mostly Fuji, Konica, and University of Chiba people. It's probably still the latest single book that is comprehensive.

You are not by any chance talking about this book (http://www.amazon.com/Organic-Chemistry-Photography-Shinsaku-Fujita/dp/3642059023/ref=sr_1_1?ie=UTF8)?

Ryuji
01-18-2012, 07:46 PM
You are not by any chance talking about this book (http://www.amazon.com/Organic-Chemistry-Photography-Shinsaku-Fujita/dp/3642059023/ref=sr_1_1?ie=UTF8)?

Nope. There are very few people who understand the entire book, and majority of the authors don't write in English, so there is very little chance that such a book gets translated.

Here's some reading list for you. I have a copy of Keller in reprints (as well as electronic subscription) so I didn't include in this shot. The top book is the Japanese book I'm talking about. You could ask the head office of Society of Photographic Science and Technology of Japan, located in Tokyo Polytechnic University (Tokyo kougei university) but I doubt they have anything about this book in English.

The second one from the top is Photographic Sensitivity written by Tani. He recently published another book. He is very smart guy and has deep insight and broad areas of specialty. His books are usually very difficult to comprehend but it is very rewarding to digest one paragraph at a time. Tani was head of Fuji's research lab for years, and also a part of the management team.

Mitchellís Photographic Science is a more accessible, upper level college science elective level treatment of photographic sensitivity and samples science from photography. Mitchell himself is also a research physicist who was active in theories of photographic sensitivity.

The next two volumes are Haist. These are reprinted versions, purchased directly from Grant Haist.

The second from bottom is James 4th edition. Not an easy book to understand, but it is like a giant collection of extensive review papers. If you donít understand relevant chapters of this book, you are a fake photographic engineer. I think it is fair to say that.

The bottom one is the last edition of Nebletteís Handbook, edited byb Sturge. Many best scientists and engineers from Eastman Kodak, Polaroid, 3M, Du Pont de nemours, and others contributed to various editions of Nebletteís. Some of the earlier ones are of historic significance but this last edition is pretty good as a somewhat current knowledge of this broad and deeply integrated field.

Donít jump on difficult books first. I guess that helps you realize how little you know, if that motivates you to study hard. But I think most people find Keller to be a good ďtextbookĒ to start with.

Ryuji
01-18-2012, 07:57 PM
The author of the book you linked, Shinsaku Fujita, is an organic chemist.

His home page:
http://homepage3.nifty.com/xymtex/fujitas/fujitae.html

albada
01-20-2012, 09:23 PM
Does the choice of alkali have much effect on activity if pH is the same?

I modified my half-and-double developer (here: http://www.apug.org/forums/forum37/98430-improved-version-ds-10-ryuji-suzuki-32.html (http://www.apug.org/forums/forum37/98430-improved-version-ds-10-ryuji-suzuki-32.html)) to use potassium sulfite+TEA instead of sodium sulfite+sodium metaborate. With the same pH, I get much higher activity with the PS+TEA brew. Any idea why? To get comparable density, I had to reduce the phenidone by 40%.

Also, in The Film Developing Cookbook, Anchell and Troop state "Potassium sulfite is occasionally used in highly concentrated formulas such as Rodinal. We do not recommend its use elsewhere, except where it is unavoidable." Why are they opposed to it? I'm using the 45% solution of potassium sulfite sold by PhotoFormulary, and it works fine and is convenient. I see nothing against it.

Mark Overton