Metabisulfite in PMK?

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hkcs

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I plan to give a try to the PMK-pyro developer that uses sodium bisulfite as preservative. I would soup the dev of raw chemicals. The thing is that I don't have sodium bisulfite, but have potassium metabisulfite on hand. Many places I've read that sodium bisulfite can be sibstituted for sodium metabisulfite weight for weight, but what about potassium? Does anyone know anything about it? Can I use what I have, and if so, what is the ratio?

Thanks in advance!

Krisztian
 

Murray Kelly

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I read here, somewhere, that the metabisulfite on dissolving turns immediately to the bisulfite. The weight used, for exactness' sake is about 9.1g meta for 10g of bisulfite.
Having said that the potassium salt has a slightly greater molar mass (222 v 190 for the sodium salt).
Plugging that together, I suggest that 10g of sodium bisulfite would need 10.6g of the potassium metabisulfite.
I don't know if the difference would be noticeable but then I've never made up PMK.
 

john_s

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Ryuji Suzuki used to have an informative article on the confusion between metabisulphite and bisulphite. His site seems to have been streamlined. Below is a paste of what I copied from there. Incidentally, Murray has this right. The potassium salt is heavier than the sodium one, so you need a bit more.
<start quote>

Bisulfite
From Silvergrain Labs
(Redirected from Metabisulfite)

Sodium bisulfite, NaHSO3, and sodium metabisulfite, Na2S2O5

Sodium bisulfite and sodium metabisulfite are different chemicals. When metabisulfite is dissolved in water at a reasonably low concentration, one mole of metabisulfite and one mole of water form two moles of bisulfite. Therefore, they are functionally very similar. The difference is the weight they should be substituted at. The difference is small, and is usually nothing to worry about in photographic chemistry. However, in some sensitive developers, this may make sizable difference in pH.

Pure sodium bisulfite is rarely traded for industrial or photographic purposes in dry form, because pure dry form is unstable. However, there is a supplier who sells it in expensive analytical reagent grade in dry form. There are also many suppliers who sell mixture of sodium bisulfite and metabisulfite. The ratio varies across suppliers, but usually about half-half. Sodium bisulfite can be kept in dry form if blended with metabisulfite. Both sodium bisulfite and sodium metabisulfite are most commonly available in anhydrous forms.

Michael Gudzinowicz pointed out that Kodak sells sodium metabisulfite as sodium bisulfite under their label. Kodak's MSDS confirms this. Therefore, when Eastman Kodak Company calls for sodium bisulfite, they mean sodium metabisulfite. If you are buying chemicals from Photographer's Formulary, Johnny Deiure, Digitaltruth or other chemical suppliers, I suggest not to bother with higher priced sodium bisulfite, and purchase sodium metabisulfite. If you publish your formula, it is my opinion that correct name for the chemical you employed, sodium metabisulfite or Na2S2O5, is much preferred to avoid further confusion. (at the expense of four more letters)

Richard Knoppow took his effort and found what we think is Kodak researcher's reasoning for this substitution. Crabtree and Mathews (1938) stated as follows: "Ordinary sodium bisulphite has been shown by analysis to consist chiefly of metabisulphite which is converted into tbisulphite when dissolved in water. Sodium bisulphite may be substituted weight for weight for potasssium metabisulphite. Either chemical is equally satisfactory but the former is usually prefered since it costs from one-third to one-half the prince of teh altter and is available on the American market, at least, in a very pure form." (Ch VII, p.117) They further proceeded to say as follows. "The Preservative. -- It is now customary to substitute sodium bisulphite for potassium metabisulphite weight for weight in either developer of fixing bath formulas. According to Harrison and Carrol(1) the stability of commercial sodium bisulphite is a function of its crystaline structure and also of its lack of moisture content. Furthermore, these authors have proved by analysis that there is very little actual sodium hydrogen sulphite present in commercial sodium bisulphite; the major portion of the sample consisting of sodium metabisulphite. Commercially dry sodium bisulphite of satisfactory quality is now obtainaboe and may be used in mixing formulas calling for either the metabisulphite or the bisulphite. A very intersting discussion of the comparitive properties of the sulphites, maetbisulphites, and acid sulphites has been published by Wall (2)." (Ch. X, p.215)

Crabtree, J. I. and Mathews, G. E. 1938. Photographic Chemicals and Solutions, Boston: American Photographic Book Publishing Co.

Harrison, J. B. P. and Carrol, M. F. 1925. "The Composition and Evaluation of Commercial Sodium Bisulphite," J. Soc. Chem. Ind., 44, 127.

Wall, E. J. 1927. "Sulphites, Metabisulphites, and Acid Sulphite," American Photography, 16, 127
 

Ian Grant

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The difference between Sodium Bisulphite and Sodium Metabisulphite is mainly putity, Metabisulphite has a far greater anti oxidising potential. It also seems to be down to how it's manufactured, the UK/EU sell mainly Metabisulphite whereas the US sells Bisulpite.

In the food industry Metabisulpite is a more effective preservative than Bisulphite and is widely used in the wine trade where all wild yeasts need to be killed before controlled fermentation.

Yes substitutions are possible but what ever the form it should always be relatively fresh and have a strong SO2 smell. In a developer like PMK or Pyrocat HD that freshness and SO2 content has a marked effect on longevity/storage.

Ian
 

Ian Grant

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I should add that as John-s says Ruyuki mentioned Bisulphite and Metabisulphite are different, but Kodak Bisulphite is not 100% Metabisulphite it's a mix of both with quite a possible variation which in most Kodak formulae using Bisulpite is not critical.

However Kodak where aware of the differences by the 1940's and published some data based on the subject, that was after the publications John-s cites.

Ian
 

RalphLambrecht

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... Incidentally, Murray has this right. The potassium salt is heavier than the sodium one, so you need a bit more. ...

Makes sense, it's a mistake in The Darkroom Cookbook on page 330:

If the formula specifies: sodium metabisulfite
and you have: potassium metabisulfte
multiply by: 0.855


it should read:

If the formula specifies: sodium metabisulfite
and you have: potassium metabisulfte
multiply by: 1.17
 
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Murray Kelly

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In the cold light of day I do believe I got that upside down. Well it is the Land Down Under:laugh:.

Looking at the 3 molar masses I think now it should be 9.1g Sodium bisulphite = 10g of Sodium metabisulphite. And as noted, 11.7g Potassium meta for 10g of Sodium meta.

Whew!
 
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Makes sense, it's a mistake in The Darkroom Cookbook on page 330:

If the formula specifies: sodium metabisulfite
and you have: potassium metabisulfte
multiply by: 0.855


it should read:

If the formula specifies: sodium metabisulfite
and you have: potassium metabisulfte
multiply by: 1.17
I'm sure that Steve Anchell would like to be informed of this error if he hasn't been told already.
 

Murray Kelly

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At risk of sounding silly, I just checked on the 'net and I was right the first time. 91.g of meta = 10g of bisulfite (sodium salts). The 9.1g takes up with a molecule of water to make the bisulfite. Hence the result is heavier. Ergo #2 above is OK.
 
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RalphLambrecht

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I'm sure that Steve Anchell would like to be informed of this error if he hasn't been told already.

Keith

I'll send him an email and also mention the mistake on page 189 where it says potassium metabisulfite replaces sodium bisulfite weight for weight. I think, it's a 1.17 to 1 replacement instead if you guys agree.
 
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