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Photo Forum / Film Photography / Darkroom / December 2005

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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

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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
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"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
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.

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---
Richard Knoppow
Los Angeles, CA, USA
dickburk@ix.netcom.com

 
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