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Shelf Life for Metol
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Ken Smith - 21 Dec 2005 00:28 GMT Anyone know the shelf life for Metol.? I just got some mush from D76H the other day, and it got me wondering if a year from the Formulary might be too long. Mixed fresh that day. I've used it and sworn by it for HP5 sheets for a while now, since dropping pyro. Xtol also seems to not shine for HP5. Anyone confer?
seog - 21 Dec 2005 16:00 GMT > Anyone know the shelf life for Metol.? > I just got some mush from D76H the other day, and it got me wondering > if a year from the Formulary might be too long. Mixed fresh that day. My Kodak Elon lasted at least 15 years, maybe 20 before it went bad.
Natural Light Black and White Photography http://mysite.verizon.net/vze76ane/ -George-
Ken Smith - 21 Dec 2005 18:36 GMT seog Dec 21, 9:00 am show options
Newsgroups: rec.photo.darkroom From: "seog" <n...@none.com> - Find messages by this author Date: Wed, 21 Dec 2005 16:00:46 GMT Local: Wed, Dec 21 2005 9:00 am Subject: Re: Shelf Life for Metol Reply | Reply to Author | Forward | Print | Individual Message | Show original | Report Abuse
"Ken Smith" <aldenph...@aol.com> wrote in message
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> Anyone know the shelf life for Metol.? > I just got some mush from D76H the other day, and it got me wondering > if a year from the Formulary might be too long. Mixed fresh that day. My Kodak Elon lasted at least 15 years, maybe 20 before it went bad.
Natural Light Black and White Photography http://mysite.verizon.net/vze76ane/-George-
Go figure. I put some packaged D-76 against my homebrew and found better contrast and acutance in the packaged form. My homebrew is D-76H, which is essentially D-23 with less metol, but I don't recall this level of softness before, which really stands out with a grain focuser. I use the developer 1:1 . I know the camera is not at fault because I shot some new tests and got the same result. Lower contrast and less acutance with homebrew. Strange.
Richard Knoppow - 21 Dec 2005 22:41 GMT > seog > Dec 21, 9:00 am show options [quoted text clipped - 38 lines] > Lower contrast > and less acutance with homebrew. Strange. D-76H is D-76 with no Hydroquinone and slightly increased Metol, it does have Borax in it as the accelerator. D-23 does not have Borax, it is Metol and Sulfite only with the amount of Metol increased to 7.5 grams. D-76 without Hydroquinone performs much like D-76 but has less capacity because it does not have the regeneration effect that Metol and Hydroquinone have on each other. Packaged D-76 is similar to published formula D-76d, which is buffered to prevent a slow increase in activity characteristic of the original D-76 and which is due to a slow reaction between the hydroquinone and the sulfite which produces a small amount of Sodium Hydroxide. The buffered version of the developer was announced in a paper [1] by Carlton and Crabtree, of Kodak Labs, published in 1929. This paper also showed about 30 variations of D-76 including one without the Hydroquinone and showed the effect of leaving it out. In the same journal two researchers from Dupont published [2] another variation without Hydroquinone shown below. This might be worth experimenting with. The formula you are using, without the Borax, will be significantly less active than D-76, hense the lower contrast.
Dupont Negative Developer
Water 750.0 ml Metol 2.5 grams Sodium Sulfite, dessicated 75.0 grams Borax, granulated 5.0 grams Water to make 1.0 liter
This formula can also be used diluted 1:1
Another veriation of D-76 is the Kodak D-96, intended for machine processing of motion picture film. The Potassium bromide can probably be left out.
Kodak D-96 Water 750.0 ml Metol 1.5 grams Sodium Sulfite 75.0 grams Hydroquinone 1.5 grams Potassium bromide 0.4 grams Borax, granular decahydrate 4.5 grams Water to make 1.0 liter
The optimum amount of Sulfite for developers of this type seems to be about 75 grams per liter for best combination of speed and grain.
1, "Some Properties of Fine-Grain Developers for Motion Picture Film" H.C.Carlton and J.I.Crabtree, _Transactions of the Society of Motion Picture Engineers_ Vol. XIII, No.38, 1929 p406. 2, "Borax Developer Characteristics" H.W.Moyse and D.R.White, loc sit, p.445
 Signature --- Richard Knoppow Los Angeles, CA, USA dickburk@ix.netcom.com
Ken Smith - 22 Dec 2005 15:21 GMT seog
> Dec 21, 9:00 am show options
> Newsgroups: rec.photo.darkroom > From: "seog" <n...@none.com> - Find messages by this [quoted text clipped - 5 lines] > Message | Show > original | Report Abuse
> "Ken Smith" <aldenph...@aol.com> wrote in message
> news:1135124922.709932.110280@g49g2000cwa.googlegroups.com...
>> Anyone know the shelf life for Metol.? >> I just got some mush from D76H the other day, and it got >> me wondering >> if a year from the Formulary might be too long. Mixed >> fresh that day.
> My Kodak Elon lasted at least 15 years, maybe 20 before it > went bad.
> Natural Light Black and White Photography > http://mysite.verizon.net/vze76ane/-George->
> Go figure. I put some packaged D-76 against my homebrew > and found [quoted text clipped - 9 lines] > Lower contrast > and less acutance with homebrew. Strange. D-76H is D-76 with no Hydroquinone and slightly increased Metol, it does have Borax in it as the accelerator. D-23 does not have Borax, it is Metol and Sulfite only with the amount of Metol increased to 7.5 grams. D-76 without Hydroquinone performs much like D-76 but has less capacity because it does not have the regeneration effect that Metol and Hydroquinone have on each other. Packaged D-76 is similar to published formula D-76d, which is buffered to prevent a slow increase in activity characteristic of the original D-76 and which is due to a slow reaction between the hydroquinone and the sulfite which produces a small amount of Sodium Hydroxide. The buffered version of the developer was announced in a paper [1] by Carlton and Crabtree, of Kodak Labs, published in 1929. This paper also showed about 30 variations of D-76 including one without the Hydroquinone and showed the effect of leaving it out. In the same journal two researchers from Dupont published [2] another variation without Hydroquinone shown below. This might be worth experimenting with. The formula you are using, without the Borax, will be significantly less active than D-76, hense the lower contrast.
Dupont Negative Developer
Water 750.0 ml Metol 2.5 grams Sodium Sulfite, dessicated 75.0 grams Borax, granulated 5.0 grams Water to make 1.0 liter
This formula can also be used diluted 1:1
Another veriation of D-76 is the Kodak D-96, intended for machine processing of motion picture film. The Potassium bromide can probably be left out.
Kodak D-96 Water 750.0 ml Metol 1.5 grams Sodium Sulfite 75.0 grams Hydroquinone 1.5 grams Potassium bromide 0.4 grams Borax, granular decahydrate 4.5 grams Water to make 1.0 liter
The optimum amount of Sulfite for developers of this type seems to be about 75 grams per liter for best combination of speed and grain.
1, "Some Properties of Fine-Grain Developers for Motion Picture Film" H.C.Carlton and J.I.Crabtree, _Transactions of the Society of Motion Picture Engineers_ Vol. XIII, No.38, 1929 p406. 2, "Borax Developer Characteristics" H.W.Moyse and D.R.White, loc sit, p.445
-- --- Richard Knoppow Los Angeles, CA, USA dickb...@ix.netcom.com
Thank You Mr. Knoppow, always a pleasure. Your posts fill my Word file to the brim.
I'm curious why D76H uses less metol than D23? What is acheived by decreasing the metol?
Also, my experiments with packaged D76 vs. D76H showed me that I needed a whopping three minutes more for similar contrast from the D76H to match the package, when aimimg for normal development.
The acutance, I couldn't really say. I think my seeing no snap with a grain focuser was probably only a contrast issue, although there truely was a lack of edge to anything. I know D76H ( any version really ) is fully sound and capable of crisp negatives, so I'll have to search further for answers to why things went soft. It was not at the camera.
dan.c.quinn@att.net - 23 Dec 2005 00:20 GMT > D-76H is D-76 with no Hydroquinone and slightly increased > Metol. It does have Borax in it as the accelerator. D-23 does > not have Borax, it is Metol and Sulfite only with the amount > of Metol increased to 7.5 grams. "It does have Borax in it as the accelerator" Borax is in no way an accelerator in ANY D-76. Borax is a mild alkali and has a ph easily less than sulfite. If there were 100 grams of borax and 2 grams of sulfite in D-76 then borax would be the accelerator. You are not the only one by any means that refers to borax as an accelerator, and call it that even when in the presence of a preponderante amount of some other chemical even more alkaline. I've been studying Mr. Anneman's patent for XR-1. He mentiones a 1/2 gram of borax as being the accelerator in a liter of developer containing 30 grams of sulfite. D-76H, without hydroquinone, has no reason for borax. There is no buffering against ph rise to be done. I'd call it D-23 dilution 1:2. Dan
Jean-David Beyer - 23 Dec 2005 00:51 GMT >> D-76H is D-76 with no Hydroquinone and slightly increased >>Metol. It does have Borax in it as the accelerator. D-23 does [quoted text clipped - 4 lines] > Borax is in no way an accelerator in ANY D-76. Borax is > a mild alkali and has a ph easily less than sulfite. Borax in water gives a pH of 9.2. I could not find the pH of Na2SO3 in water, so I mixed up a little bit and tested it with some pH paper and it comes in between about 8 to 9. I could not read that accurately enough to say which is more basic, but they are pretty close.
I am not sure if it is really proper to call anything D-76 that does not have both metol and hydroquinone in it, and some sulphite and an accelerator (either borax, or boric acid and sodiim metaborate), but YMMV.
> If there > were 100 grams of borax and 2 grams of sulfite in D-76 [quoted text clipped - 9 lines] > There is no buffering against ph rise to be done. I'd call it > D-23 dilution 1:2. Dan
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dan.c.quinn@att.net - 23 Dec 2005 01:20 GMT > Borax in water gives a pH of 9.2. > I could not find the pH of Na2SO3 in water, so I mixed up a > little bit and tested it with some pH paper and it comes in > between about 8 to 9. I could not read that accurately > enough to say which is more basic, Your value of 9.2 for borax does agree with values I've read. Your values for sulfite are very low. I've not read of any value less than 9.5. The range from one major supplier is from 9.5 to 10.5.
Not that I'm conciding for one instant sulfite's ph being higher than that of borax's but what of that 1:49 ratio borax to sulfite? Were it lye for that matter. Dan
Ken Smith - 23 Dec 2005 02:04 GMT > > Borax in water gives a pH of 9.2. > > I could not find the pH of Na2SO3 in water, so I mixed up a [quoted text clipped - 10 lines] > higher than that of borax's but what of that 1:49 ratio > borax to sulfite? Were it lye for that matter. Dan Do either of you gents have any idea why there is so much more metol in D23 than D76H, or any general statement about the action of metol? What is the metol doing exactly, if its the sulfite that reduces the silver halides? And yes, I'm out of my depth, so any basic comment would be of interest.
Jean-David Beyer - 23 Dec 2005 04:00 GMT >>>Borax in water gives a pH of 9.2. >>>I could not find the pH of Na2SO3 in water, so I mixed up a >>>little bit and tested it with some pH paper and it comes in >>>between about 8 to 9. I could not read that accurately >>>enough to say which is more basic, I found another table in L.P.Clerc, ¶589.
Buffer Mixture pH Sodium sulphite - sodium metabisulphite 6.5 to 8.0 Boric Acid - borax 6.8 to 9.2 Sodium Carbonate - sodium bicarbonate 9.0 to 11.0 Borax - sodium hydroxide 9.2 to 11.0 Sodium carbonate - sodium hydroxide 10.5 to 12.0 Disodium hydrogen phosphate - sodium hydroxide 11.0 to 12.0 Trisodium phosphate - sodium hydroxide 12.0 to 13.0 Sodium hydroxide above 12.0
>> Your value of 9.2 for borax does agree with values I've >>read. Your values for sulfite are very low. I've not read [quoted text clipped - 10 lines] > halides? And yes, I'm out of my depth, so any basic comment would be of > interest. No! No! The sulphite does not reduce the halides to silver. It may dissolve a bit of the silver grains, but that is about it.
In D-23, the metol is 7.5 grams/litre and the sulphite is 100 grams/litre.
In D-76, the metol is 2.0 grams/litre and the sulphite is 100 grams/litre, but there is also 5 grams/litre of hydroquinone and 2 grams/litre of borax.
In D-76d, the metol is 2 grams/litre and the sulphite is 100 grams/litre, and there is also 5 grams/litre of hydroquinone, but the accelerator is 8 grams/litre of borax and 8 grams/litre of boric acid. The borax-boric-acid mixture is a better buffer than straight borax.
In DK-76, the metol is 2.0 grams/litre and the sulphite is 100 grams/litre and 5 grams/litre of hydroquinone, and 2 grams/litre of sodium metaborate.
I do not know the formula for D76h
If you want an esoteric developer to amaze your friends, be the first on your block to try this one:
Titanium trichloride (20% solution) 75ml EDTA (tetra sodium salt) 100gram Potassium bromide 4gram water to 1000ml Hydrochloric acid to pH 4.0
No metol, no phenidone, no hydroquinone, no sulphite, no base at all; it is a somewhat acid solution.
Try developing for 5 minutes at 20°C. This is not a joke.
Now as to why there is so much more metol in D-23, my guess is that it is there for longer, more stable, life. Without the synergy of the metol and hydroquinone together, where one tends to regenerate the other, you need more of the reducing agent. But as I said, this is just my guess.
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Richard Knoppow - 23 Dec 2005 06:49 GMT >> > Borax in water gives a pH of 9.2. >> > I could not find the pH of Na2SO3 in water, so I mixed [quoted text clipped - 22 lines] > comment would be of > interest. I think I used to know but can't remember now. Once a certain level of Metol is present increasing it does not increase the activity of the developer. I think around 2.5 grams is already enough. It may be a capacity issue.
 Signature --- Richard Knoppow Los Angeles, CA, USA dickburk@ix.netcom.com
Richard Knoppow - 23 Dec 2005 06:50 GMT >> > Borax in water gives a pH of 9.2. >> > I could not find the pH of Na2SO3 in water, so I mixed [quoted text clipped - 22 lines] > comment would be of > interest. I meant to add that "Nailer" seems to have a good knowledge of this stuff and perhaps will reply.
 Signature --- Richard Knoppow Los Angeles, CA, USA dickburk@ix.netcom.com
Ken Smith - 23 Dec 2005 15:00 GMT I'm sorry who is "Nailer" What I'm a bit confused about is the fact that some refer to D23 as a compensating developer, diluted or not, yet Adams laid claim to its tendencies to block highlkights, and went eventually to HC-110. I worked for years using HC-110 with the landscape, made plenty of great images, but never was happy with it in strong light. Extreme dilutions, N- defvelopment, and increased film speed still looked harsh or dull. HC-110 is called a low contrast developer and I have to wonder why Adams, and Barbaum prefer it. I had better luck with Rodinal 1:100 for strong light. Now I just prefer D-76 1:1. The D76H however, which Dan calls D23 1:2 seems to be a different animal. I have to increase times for contrast, but I still see/feel that a certain snap/ acutance seems to be missing. Perhaps D76H should be used straight.
Richard Knoppow - 23 Dec 2005 21:46 GMT > I'm sorry who is "Nailer" > What I'm a bit confused about is the fact that some refer [quoted text clipped - 20 lines] > acutance seems > to be missing. Perhaps D76H should be used straight. Nailer follows this list and is evidently a graduate chemist with an excellent knowledge of photo chemistry. The term low contrast developer generally means that it takes that developer longer to obtain the same contrast as a more active developer. There are specialized developers for extreme contrast conditions. For instance lighographic developers. These are extremely active developers with large amounts of restrainer in them. They tend to go from not developing a halide crystal to full development over a very short range of exposure. There are also very low contrast developers, for instance POTA or Technidol, which are designed to produce low contrast from inherently high contrast materials. They are slow, and will not achieve "normal" contrast even with extended time, but are produce a "normal" curve shape and are more like "normal" developers than a lith developer. D-76 and D-23 have both been called low contrast developers but are simply slow to build contrast in comparison to developers like Kodak D-60a, or D-61, once commonly used for photo-finishing and press work. I have no idea of what Adam's experience was with specific developers but some of them don't seem to make sense. D-23 can be a "compensating" developer when used at high dilutions. Compensating means that a developer creates a shoulder on the characteristic curve, or, in other words, lowers the contrast of highlights. At normal strength D-23 should not do this. Blocking of highlights means that there is no detail in them. That can happen because there is no detail in the negative or because the negative contains highlights which are beyond the ability of the printing paper to reproduce them. The latter problem can be solved by burning in because the detail is there. Blocking on negatives was a problem in the distant past but modern films have very great overexposure latitude and can record highlights much beyond what can be printed simutaneously with normal mid-tones. Kodak has published curves for a few films done with different developers. It seem to me that HC-110 does produce a slight shoulder when compared to developers like T-Max. I don't think this accounts for your experience. I don't have Grant Haist's book at hand so I can't look up the authentic D-76H. However, A Borax developer with characteristics very similar to D-76 can be made up without the Hydroquinone. At the relatively low pH of D-76 the Hydroquinone is virtually inactive as a developing agent. It probably has a regenerating effect on the Metol. The so-called superadditive effect is not present because the Metol only version produces just about the same densitys in about the same time as the M-H version. The amount of Metol is increased for reasons I don't fully understand. I rather think that extreme dilutions of any developer will produce distorted tone rendition. Over a wide range its possible to vary the overall contrast of negatives by varying the development time. The exposure must be varied also to maintain a constant range of density, but in general, the shape of the curve will not be much affected. To a great degree varying negative contrast and varying paper contrast, by choice of grade or filter, will produce identical results although the _shape_ of the paper characteristic tends to change more than film. Remember that the range of brightness which can be reproduced on a reflection print is only a fraction of what can be recorded on film or what is in many original scenes. Another important factor when deciding on contrast is the perception of the eye. The eye expects to see approximately normal contrast in mid-tones and is not too sensitive to clipping of shadows or highlights. Bright highlights, generally from specular reflections, don't have much detail to begin with. Unless they are presented as large areas of no detail, most viewers will not be disturbed. If contrast is compressed so that a wide brightness range scene can be reproduced on paper the resulting image will look flat and unnatural to the eye. About the only way around this is burning and dodging, which, if done carefully, will result in greater detail in selected shadows and highlights while maintaning a relatively normal gray scale. I will add only that there are no magic developers. There are only a few developing agents in common use and those are the ones that have survived a century of competition. Excellent developers for most B&W uses can be made with Metol and Hydroquinone or the more modern Phenidone and Ascorbic acid. Color developers must react with the color couplers to produce dye so other developing agents are found in them. My standard developer is D-76 mostly diluted 1:1. It has been reliable and long lived and works with most films.
 Signature --- Richard Knoppow Los Angeles, CA, USA dickburk@ix.netcom.com
Ken Smith - 24 Dec 2005 00:05 GMT Thank You RK. Into the word file again. I have settled on D-76 1:1 as well, although still hashing out the difference between some of the variations. While I don't believe in the magic bullet developers, tried pyro for a year or so, I do find that things can sure can go wrong easy enough. Holding tones as the eye sees them, or rather getting as close as you can is all I'm trying to do. The shadow is full, the sky has clouds.Even though some will argue the eye is scanning for this information, nevertheless it's my pictorial goal. The zone system has appealed to me less and less, as I find time and again that I am not willing to favor one area over another in an interpretation of the scene. I can practically take an incident reading, or spot a middle grey, then develop the negative for normal contrast, and make out better, time and again, than plus this and minus that. These are reserved for specific uses where I am willing to sacrifice, say dark hills for brilliant clouds, or settle for white skies for full luminous shadows. Reading Adams one can get the impression that average handling means average pictures, and a real photographer is supposed to shake things up, and give his name to something. Again I just want a print to come as close to what I'm looking at, The modern films do hold alot of the extremes, but the papers don't and burning just means unnaturally dark tree tops, or some such. I find you practically have to compose the image with these materials and their limitations in mind. That addition to the bag of tricks is a very smart one. Since I'm rambling, one more note, I've mentioned it before on this site, but no one seems to have looked. William Wylie's book Riverwalk, get an interlibrary loan, has accomplished a tonal range that is remarkable. Full shadows and natural looking skies, and a clean vivid contrast, all at the same time. Masking? I don't know, but glorious prints. He just received a Guggenheim. We may be seeing more of him in the future. Thanks much, Ken Smith
dan.c.quinn@att.net - 26 Dec 2005 00:53 GMT > What I'm a bit confused about is the fact that some > refer to D23 as a compensating developer, diluted or not, By compensating do you mean a developer which will favor a more full development in less exposed and a less full development in more exposed areas of the film? D23 I suppose could be thought of as compensating. Most consider it a low contrast developer. FX-1, Beutler's, Ethol TEC, and Rodinal are more thought of as being compensating. Characteristic of those three is their high ph and very dilute nature. D23 may make a good low contrast compensating developer. Now and then I mix up an 8 - 80 grams D23, 1 - 10 grams at a time. That goes into 500 ml of solution. The result is 1/2 liter of an 8 - 80 D23 1:3. That developes one 120 roll of film. I've recently decided I should give 1:7 and 1:15 dilutions a try. At those dilutions, in 500 ml of solution, there would be 0.5 - 5 and 0.25 - 2.5 grams respectively. A metol - sulfite developer with low contrast and compensating charater should result.
Back to that sulfite ph matter. The range of ph given by manufacturers and other sources is quite great. Many give a range within a ph of 9 to 10.5. IIRC, at least three give a specific ph AND range for photo grade sulfite. My point is this. As users of sulfite we should not assume from purchase to purchase we have the same stuff in hand. We all know how shifts in ph will affect the activity of a developer. Dan
,
Richard Knoppow - 23 Dec 2005 06:47 GMT >> D-76H is D-76 with no Hydroquinone and slightly >> increased [quoted text clipped - 22 lines] > it > D-23 dilution 1:2. Dan I don't know what definition of "accelerator" with reference to developers you are using but, traditionally, its anything which raises the pH. Borax certainly fits this definition. Metol is acid and needs something to neutralize it. Since it will develop, albeit weakly, even in slightly acid solution, it makes an active developer with sulfite alone. It is more active if the pH is increased. Borax produces a higher pH than sulfite alone but not so high as Sodium carbonate or Sodium metaborate.Anything which ionizes the developing agent can be called an accelerator. Simply put the developer works faster (or at all) with it than without it. There is also a fog consideration. At the pH of sulfite or Borax Metol produces only a little fog and does not need a fog suppressor. With carbonates it does produce enough fog to require the restrainer. The Borax in D-76 is not there to buffer the production of Hydroxide, in fact, its not a good enough buffer to do that. It serves to increase the activity of the developer At the time D076 was devised it was a rather low activity developer. An even less active developer, like D-23, would not have been acceptable for the films of the time, which had very much longer development times than modern films. Kodak lists target pH for several developers. D-76, by memory, is around pH 8.7. I don't have the target for D-23 but its probably around 8.3. D-25 is pH 7.
 Signature --- Richard Knoppow Los Angeles, CA, USA dickburk@ix.netcom.com
dan.c.quinn@att.net - 23 Dec 2005 23:21 GMT > I don't know what definition of "accelerator" with > reference to developers you are using but, traditionally, > its anything which raises the pH. Borax certainly fits this > definition. Sodium sulfite fits the definition even more so as it's ph is higher than that of borax. Last night I reviewed, via Google, S. sulfite's ph and solubility. Integrating the range of ph for both, I'd place the ph of sulfite above that of borax by 0.2. For photo grade sodium sulfite I've read ph 9.3 and 9.6; those two from suppliers. I'm not going to argue the matter any further. Although the extreme values of ph for the two can overlap, it is only the lowest values for sulfite and the highest values for borax which do so. So why the borax? For no good reason according to Mr. M. Merhar. So he and a few fellows experimenting with D-76 replaced the 2 grams of borax with 3 grams of S. bisulfite and 9.6 grams of S. carbonate; ph 8.6. D-76X was born. May work like a charm. But. But I don't agree with Mr. Merhar reason for faulting borax. He attributes the D-76 rise in ph to it's hydrolisis. I think otherwise. I subscribe to the formation of hydroxyl ion theory. Within that context a small amount of borax does fit and should work to maintain a more constant ph. Borax is a least hydrated salt. With an increase in ph, OH radical, the borax hydrates and converts to the metaborate. Although metaborate is more alkaline than S. sulfite it is not so much so as would be an unconstrained build up of OH radical. At least by my reasoning there is some reason for that pinch of borax in D-76. Perhaps someone with more of an understanding of the reactions involved will contribute. Dan
PATRICK GAINER - 24 Dec 2005 18:26 GMT > > [quoted text clipped - 35 lines] > > I am of the opinion that aerial oxidation of Metol in the presence of sulfite also produces the monosulfonate and hydroxide, as does p-aminophenol. Metol can be used to formulate a Rodinal "expedient" with sulfite and hydroxide, and an excess of Metol produces a precipitate which I think improves the resistance to aerial oxidation of the stock. Add 63 grams of Metol to 28.6 grams of sodium hydroxide and 150 grams of sodium hydroxide in water to make a liter and see what happens.
Richard Knoppow - 24 Dec 2005 18:47 GMT >>> I don't know what definition of "accelerator" with >>>reference to developers you are using but, traditionally, [quoted text clipped - 56 lines] > sodium hydroxide in water to make a liter and see what > happens. A very old Agfa booklet on developing mentions that there was a Metol equivalent to Rodinal. However, while the suggested dilution for Rodinal was 1:20 the dilution for the Metol developer was 1:4. I think the reason p-aminophenol was used in Rodinal instead of Metol was its much higher solubility. The two reducers are related chemically.
 Signature --- Richard Knoppow Los Angeles, CA, USA dickburk@ix.netcom.com
PATRICK GAINER - 25 Dec 2005 20:26 GMT > > [quoted text clipped - 77 lines] > > That's interesting. I have been using 63 grams/liter of Metol, which I reckon to be about equal to 40 grams/liter of p-aminophenol or 50 grams of p-aminophenol.HCl. It takes considerably more hydroxide because of the hydrosulfate. I calculated that about 3 grams/liter of the Metol base would precipitate, and that appears to be about right. The developing times for 1+25 dilution are very much like those for Rodinal at 1+25. I could see that if I were to use the same weights, there would be a considerable difference in activity. As it is, the H&D curves for my version of sodium Rodinal and the Metol equivalent at 1+25 dilution , 8 minutes, 68 F coincide for practical purposes.
Both the p-aminophenol base and the Metol base (4 methyl-amino phenol) are practically insoluble. The active compound in Rodinal appears to be the potassium salt of p-aminophenol. I use the sodium salt, warnings to the contrary notwithstanding.
Mike King - 27 Dec 2005 13:37 GMT I see sodium hydroxide listed twice in your formula Patrick, correct me if I'm wrong (won't be the first time) but did you mean 28.6 grams sodium sulfite and 150 grams sodium hydroxide?
 Signature darkroommike
dan.c.quinn@att.net wrote: RE:Richard Knoppow wrote:
I don't know what definition of "accelerator" with reference to developers you are using but, traditionally, its anything which raises the pH. Borax certainly fits this definition.
Sodium sulfite fits the definition even more so as it's ph is higher than that of borax. Last night I reviewed, via Google, S. sulfite's ph and solubility. Integrating the range of ph for both, I'd place the ph of sulfite above that of borax by 0.2. For photo grade sodium sulfite I've read ph 9.3 and 9.6; those two from suppliers. I'm not going to argue the matter any further. Although the extreme values of ph for the two can overlap, it is only the lowest values for sulfite and the highest values for borax which do so. So why the borax? For no good reason according to Mr. M. Merhar. So he and a few fellows experimenting with D-76 replaced the 2 grams of borax with 3 grams of S. bisulfite and 9.6 grams of S. carbonate; ph 8.6. D-76X was born. May work like a charm. But. But I don't agree with Mr. Merhar reason for faulting borax. He attributes the D-76 rise in ph to it's hydrolisis. I think otherwise. I subscribe to the formation of hydroxyl ion theory. Within that context a small amount of borax does fit and should work to maintain a more constant ph. Borax is a least hydrated salt. With an increase in ph, OH radical, the borax hydrates and converts to the metaborate. Although metaborate is more alkaline than S. sulfite it is not so much so as would be an unconstrained build up of OH radical. At least by my reasoning there is some reason for that pinch of borax in D-76. Perhaps someone with more of an understanding of the reactions involved will contribute. Dan
I am of the opinion that aerial oxidation of Metol in the presence of sulfite also produces the monosulfonate and hydroxide, as does p-aminophenol. Metol can be used to formulate a Rodinal "expedient" with sulfite and hydroxide, and an excess of Metol produces a precipitate which I think improves the resistance to aerial oxidation of the stock. Add 63 grams of Metol to 28.6 grams of sodium hydroxide and 150 grams of sodium hydroxide in water to make a liter and see what happens.
PATRICK GAINER - 28 Dec 2005 17:15 GMT >I see sodium hydroxide listed twice in your formula Patrick, correct me if >I'm wrong (won't be the first time) but did you mean 28.6 grams sodium >sulfite and 150 grams sodium hydroxide? > OOPS! No, it's 28.6 grams of sodium hydroxide and 150 grams of sodium sulfite. You can dissolve those in a liter of water and add Metol or p-aminophenol until you get a precipitate. In this case, it does no harm to overshoot because the excess precipitates and cannot affect development as long as it remains in the bottom of the stock bottle. However, if you overshoot too much too fast, the hydroxide might, in the case of Metol, convert it all to the insoluble base. 28.6 grams of sodium hydroxide are enough to precipitate the Metol base out of 63 grams of Metol and to make the sodium salt out of most of the precipitate, leaving some for the protection process. At least, that is my theory. The Metol variation is almost as active in 1 + 50 dilution as Rodinal is in 1 + 25.
Richard Knoppow - 24 Dec 2005 20:02 GMT >> I don't know what definition of "accelerator" with >> reference to developers you are using but, traditionally, [quoted text clipped - 41 lines] > understanding of the reactions involved will contribute. > Dan You must consider the pH of the complete developer, not just the pH of a solution of a salt in water. For instance, the pH of Borax varies from 9.26 at a concentration of 0.1% to 9.32 at saturation. However, the target pH for D-76, full strength, is 8.5. Sulfite pH varies from 8.5 to 10 depending on concentration, but this is in the absense of other substances. In D-23 the sulfite must neutralize the Metol resulting in a lower pH. There are other factors beside pH. One of them is the ionization factor pKa and pKb, which may be more important than pH alone in describing the action of a particular alkali in a developer. Mr. Merhar, whoever he is, is wrong about the mechanism for pH rise in D-76. It has nothing to do with hydrolization of anything. The correct analysis has been known for a very long time. I must say that I don't consider myself even an amateur chemist and have discovered many lacks in my knowledge of chemistry. It is not, for me at any rate, a very intuitive subject. For one thing, some of the older books on photography have gross oversimplifications of chemical processes which can mis-lead as much as otherwise. There is a certain amount of information on the web, but, like web data often is, its incomplete. One can learn more about what pH and ionization factors are with a little searching. One thing I can say is that the chemistry of photography will get one very deeply into advanced chemistry very quickly. I am not sure that one can learn just a little of this without being mislead pretty seriously in places. I have a love for accurate knowledge. That is one reason I respond less and less to questions here; plainly, I have an increasing mistrust of my own knowlege and tend to refrain from responding unless I am pretty certain that what I know is correct.
 Signature --- Richard Knoppow Los Angeles, CA, USA dickburk@ix.netcom.com
Roman J. Rohleder - 24 Dec 2005 09:00 GMT "seog" <no@none.com> schrieb:
>"Ken Smith" <aldenphoto@aol.com> wrote in message
>> Anyone know the shelf life for Metol.?
>> I just got some mush from D76H the other day, and it got me wondering >> if a year from the Formulary might be too long. Mixed fresh that day. A year is well within the boundaries the producers of commercial developers quote as "use before" dates for their materials.
>My Kodak Elon lasted at least 15 years, maybe 20 before it went bad. I´m currently using both "fresh" (bought in 2003) and "old" (a batch of 2kg Metol made in the mid 1980s that were given as a gift to me) and both are fine.
The old Metol is hardly to discern visually from the fresh one, the powder isn´t caked, the color the same very pale yellow/grey. It was stored in the original HDPE bottles the maker (IIRC it was Fluka) packed them in.
>-George- Gruss, Roman
 Signature "Ich fuehle Portraits. ich schmecke Landschaften. Frei von Belichtungsmesser, und Tiefenschaerfe." (aus "Pecker")
Ken Smith - 24 Dec 2005 15:17 GMT Thank You, I almost forgot the original question. But I still can't figure out why one session of 12 4x5's looked like it had no edge sharpness when developed in D76H 1:2, and another session of 24 4x5's developed half store bought D76, and half D76H, both at 1:1 looked good except that the D76H had less contrast and needed a few more minutes to reach the store bought formula. Just another photo mystery to keep one on their toes.
Richard Knoppow - 24 Dec 2005 19:42 GMT > Thank You, I almost forgot the original question. But I > still can't [quoted text clipped - 9 lines] > to keep one > on their toes. Well, acutance is due to effects at the boundaries of high and low density regions. These effects are usually attributed to local exhaustion of the developer but are actually more complicated and vary with the developing agents used, the formulation of the developer, the concentration of the developer, agitation methods, and other factors. The effect of the edge/border effect is to increase the contrast at the transition. It is something like drawing lines around objects in the image. Acutance is a term originated by Kodak to describe this effect. The eye interprets edge contrast as sharpness, so, an image with high edge sharpness may appear sharper than one which has higher resolution but is has less edge contrast. In fact, the edge effects tend to reduce actual resolution. The effects which produce acutance are of fixed scale. This means that they are much more apparent on small than large format negatives.
I can't explain why some of your films had less apparent sharpness than the others. There are too many unknown variations possible.
 Signature --- Richard Knoppow Los Angeles, CA, USA dickburk@ix.netcom.com
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