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Cadmium Suboxide

There is good evidence for the existence of Cd4O as an amorphous green powder, and of Cd2O both as an amorphous green powder and as small yellow crystals.

March and obtained a green product, which he regarded as Cd2O, by heating cadmium oxalate to the melting-point of lead. Since dilute acetic acid dissolved part of it and left a residue of metallic cadmium, subsequent workers regarded his product as a mixture of cadmium and its normal oxide, CdO.

According to Tanatar, amorphous green Cd4O is formed when cadmium oxalate is carefully heated in an atmosphere of dry carbon dioxide, which is converted into a yellowish-brown mixture of cadmium and cadmic oxide by heating to the melting-point of the metal. Denham says that if the metallic cadmium, which is always formed during the reaction, is distilled off in vacuo, green amorphous Cd4O is obtained, but it never amounts to more than 4 per cent, by weight of the original oxalate.

Tanatar and Levin obtained dark green Cd3O2 and Cd2O by heating cadmium oxalate and cadmic oxide in appropriate proportions. Either oxide, when heated in the absence of air, was converted into a mixture of metal and normal oxide. Denham, using this method and finally distilling off metallic cadmium under reduced pressure, obtained some homogeneous green Cd2O.

Hydrogen reduces heated cadmium oxide either to metal or to metal containing unchanged oxide.

When cadmium oxide is reduced by carbon monoxide in the heat, there is a distinct lessening of the velocity of reduction at a point corresponding to the formation of Cd2O, but the lower oxide could not be isolated from this reaction.

When the compounds Cd4Cl7, Cd4Br7, or Cd12I23 are treated with water, the normal halogen compounds and cadmous hydroxide, CdOH, are produced. Minute yellow translucent crystals of Cd2O are obtained by heating this cadmous hydroxide in a current of dry nitrogen. When strongly heated it gives a green mixture of cadmium and cadmic oxide, and it acts as a strong reducing agent towards acids. Denham could not convert more than 5 per cent, of the original chloride into suboxide.

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