greybeard
Member
gainer: What soluble compound of calcium or magnesium might be in water? The hydroxide is somewhat soluble. The carbonate is formed in caves when water containing some of the hydroxide comes in contact with CO2 in the atmosphere. Over years, stalactites and stalagmites are formed out of limestone. When you mix carbonate developers with hard water, you get cloudy developer from the calcium and magnesium hydroxides. You will see it very soon after mixing...
This is close, but maybe not quite right---limestone is calcium carbonate, essentially. Carbon dioxide from or decaying vegetation (or other sources, such as volcanoes) dissolves in water to form carbonic acid, which dissolves calcium carbonate by converting it to calcium bicarbonate, a substance that is much more soluble. In caves, the lower carbon dioxide concentration in the air allows the reaction to go the other way, releasing carbon dioxide and precipitating the carbonate as limestone again. Calcium in water is usually due to a high bicarbonate concentration, which is why boiling it causes a precipitate of calcium carbonate to drop out (the so-called temporary hardness). Calcium hydroxide is much more soluble than the carbonate, but reacts with carbon dioxide until the carbonate/bicarbonate equilibrium is reached; this is the basis for the "limewater" test for carbon dioxide (make limewater by saturating water with calcium hydroxide; bubble your breath through it and the carbon dioxide will cause calcium carbonate to precipitate out)
Magnesium sulfite seems to be reasonably soluble, but the sulfate (Epsom salts) and chloride are very soluble. Of all the possible culprits, it seems that calcium sulfite would be the only thing that could arise from well water and not be soluble in acetic acid; it seems that Bethe's problem might be sulfur caused by bad chemistry, or some sort of soap formed by organics in the water, alkali from the developer, and calcium or magnesium. What is odd is that most of the potential culprits should form precipitates in the solutions, and not streaks on the film at the drying stage. The metallic soap (aka scum) idea is motivated in part because it would probably adhere preferentially to naturally hydrophobic surfaces, like the non-emulsion side of the film.
We really need a photographic chemist in this discussion!
This is close, but maybe not quite right---limestone is calcium carbonate, essentially. Carbon dioxide from or decaying vegetation (or other sources, such as volcanoes) dissolves in water to form carbonic acid, which dissolves calcium carbonate by converting it to calcium bicarbonate, a substance that is much more soluble. In caves, the lower carbon dioxide concentration in the air allows the reaction to go the other way, releasing carbon dioxide and precipitating the carbonate as limestone again. Calcium in water is usually due to a high bicarbonate concentration, which is why boiling it causes a precipitate of calcium carbonate to drop out (the so-called temporary hardness). Calcium hydroxide is much more soluble than the carbonate, but reacts with carbon dioxide until the carbonate/bicarbonate equilibrium is reached; this is the basis for the "limewater" test for carbon dioxide (make limewater by saturating water with calcium hydroxide; bubble your breath through it and the carbon dioxide will cause calcium carbonate to precipitate out)
Magnesium sulfite seems to be reasonably soluble, but the sulfate (Epsom salts) and chloride are very soluble. Of all the possible culprits, it seems that calcium sulfite would be the only thing that could arise from well water and not be soluble in acetic acid; it seems that Bethe's problem might be sulfur caused by bad chemistry, or some sort of soap formed by organics in the water, alkali from the developer, and calcium or magnesium. What is odd is that most of the potential culprits should form precipitates in the solutions, and not streaks on the film at the drying stage. The metallic soap (aka scum) idea is motivated in part because it would probably adhere preferentially to naturally hydrophobic surfaces, like the non-emulsion side of the film.
We really need a photographic chemist in this discussion!