I have no doubt that many of the instances of unusually rapid corrosion of lead by water, such as that mentioned by Dr. Wall [p. [410]] are really owing, not to the simple action of water, but to an action excited obscurely in one or other of the ways now mentioned.
Of the Action of Acidulous Fluids on Lead and its Oxide.
Water acidulated with various acids acts on lead with different degrees of rapidity.
The effect of acidulation with carbonic acid has not yet been accurately ascertained. The effect of sulphuric acid is peculiar. Distilled water feebly acidulated with that acid acts much less rapidly on lead than when quite pure. Thus I have found that, if it contained a 4000th or even only a 7000th of sulphuric acid, fifty grains of lead kept in it for thirty-two days gained a seventh or a twelfth of a grain in weight, and were covered with beautiful crystals of sulphate of lead. A minute trace of lead could be detected in the water. Hydrochloric acid is somewhat more active as a solvent. Distilled water containing a 3000th of that acid acquired in thirty-two days a sweetish taste, and yielded by evaporation a considerable quantity of muriate of lead, while the lead rods lost weight, and were covered with acicular crystals of the same salt.
It is much more important, however, to consider the effects of the vegetable acids on lead and its oxide, because their solvent power is a fruitful source of the accidental as well as intentional adulteration of many articles of food and drink.
Acetic acid in the form of common vinegar, even when much diluted, attacks and dissolves metallic lead, if by exposing the surface of the fluid to the air, a constant supply of oxygen be maintained to produce oxidation. The citric acid will attack it under the same circumstances, but acts more slowly. In a solution of five grains of citric acid in twenty-four parts or two drachms of water, three lead rods lost two grains in weight in nine weeks. The greater part of the citrate of lead separated slowly in white powdery crystals; but a small portion was dissolved by the excess of acid, and imparted to the fluid a pleasant sweetness. Tartaric acid acts much less energetically. In a comparative experiment with the last, the lead gained nearly half a grain in weight by acquiring a crystalline coat of tartrate of lead. But I could not detect any lead in solution; and there was no loose powder. The tartrate of lead is very sparingly soluble in an excess of its acid, so that a sweet taste cannot be communicated by it to a fluid acidulated with tartaric acid. Malic acid, according to MM. Chevallier and Ollivier, acts so quickly as a solvent, that if a solution be kept in a lead vessel for three hours, the metal may be detected in the fluid by any of its ordinary tests.[[1260]]
The acids act with greater rapidity on the protoxide of lead than on the metal; and the presence of air is of course not required to enable them to effect its solution.
The solvent power of the acids is liable to be counteracted by various substances; the operation of which, however, has not been well ascertained. It appears that substances containing gallic acid or tannin throw down the lead; and on this account various adulterations which would otherwise take place are either prevented or corrected. It has been also ascertained by Proust, that the vegetable acids do not attack lead when it is alloyed with tin. For as the latter metal has a stronger attraction than the former for acids, no lead can be oxidated before the tin undergoes that change.[[1261]]
From what has been said of the action of the vegetable acids, it follows that the preparation or preservation of articles of food and drink in leaden vessels is fraught with danger. For, if they contain a vegetable acid, more particularly the acetic, as many of them do, and if they are allowed to remain in the vessel for a moderate length of time, they will be apt to be impregnated with the metal. In this way lead has been often insidiously introduced into the food of man.
Thus milk has been poisoned by being kept in leaden troughs. An instance of the kind has been related by Dr. Darwin. A farmer’s daughter used to wipe the cream from the edge of the milk which was kept in leaden cisterns, and being fond of cream, had a habit of licking it from her finger. She was seized in consequence with the symptoms of lead colic, afterwards with paralytic weakness of the hands, and she died of general exhaustion.[[1262]] The circumstances under which the lead is acted on have not been carefully examined. It appears to be sometimes used with safety. It will of course be dissolved, if the milk should become sour.