The tri-iodide, AsI3 prepared by subliming arsenic and iodine together in a retort, by leading arsine into an alcoholic iodine solution, or by boiling powdered arsenic and iodine with water, filtering and evaporating, forms brick-red hexagonal tables, of specific gravity 4.39, soluble in alcohol, ether and benzene, and in a large excess of water; in the presence of a small quantity of water, it is decomposed with formation of hydriodic acid and an insoluble basic salt of the composition 4AsOI.
White arsenic exists in two crystalline forms (octahedral and prismatic) and one amorphous form; the octahedral form is produced by the rapid cooling of arsenic vapour, or by cooling a warm saturated solution in water, or by crystallization from hydrochloric acid, and also by the gradual transition of the amorphous variety, this last phenomenon being attended by the evolution of heat.
Brandt showed that white arsenic was the calx of this element, and after the downfall of the phlogiston theory the views concerning the composition of white arsenic were identical with those which are now held, namely that it is an oxide of the element.
An alloy made by addition of about 6th of arsenic has been used for making shot.
The oxide known as white arsenic is mentioned by the Greek alchemist Olympiodorus, who obtained it by roasting arsenic sulphide.
The chlorides AsCl2CH3 and AsCl(CH3)2 as well as As(CH3)3 are capable of combining with two atoms of chlorine, the arsenic atom apparently changing from the tri- to the penta-valent condition, and the corresponding oxygen compounds can also be oxidized to compounds containing one oxygen atom or two hydroxyl groups more, forming acids or oxides.
The ore is treated as described in the cyanide method until the copper precipitated by the aluminium foil has been washed and dissolved in 5 cc. of nitric acid; then 0.25 gramme of potassium chlorate is added, and the solution boiled nearly dry to oxidize any arsenic present to arsenic acid.
Pliny mentions it under the name of minium, but it was confused with cinnabar and the red arsenic sulphide; Dioscorides mentions its preparation from white lead or lead carbonate.
Gowland has shown that, whatever may have been the practice of Japanese bronze makers in ancient and medieval eras, their successors in later days deliberately introduced arsenic and antimony into the compound in order to harden the bronze without impairing its fusibility, so that it might take a sharper impression of the mould.
Distinct crystals are rarely met with; these are rhombohedral and isomorphous with arsenic and bismuth; they have a perfect cleavage parallel to the basal plane, c (111), and are sometimes twinned on a rhombohedral plane, e (1 ro).