A Comprehensive Treatise on Inorganic and Theoretical Chemistry

292 INORGANIC AND THEORETICAL, CHEMISTRY
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§ 22. Platinum Tetrachloride
Li. Pigeon 1 observed that only a very small yield of anhydrous platinic chloride*
or platinum tetrachloride, PtCl4, is obtained by passing chlorine over heated,
finely-divided platinum. At 360° di- and tetra-chlorides are formed, but a considerable
proportion of the metal is not attacked. C. Nogareda found that the
tetrachloride is formed between 600° and 850°. A. Gutbier and F. Heinrich added
that the yield is not much better if platinum be heated with arsenic trichloride in
a sealed tube. L. Pigeon recommended the following process :
Finely-divided, spongy platinum mixed with somewhat less than its own weight of
selenium is placed in a stout glass tube one-third filled with arsenic trichloride, and a
current of chlorine is passed in, the tube being gradually heated until the liquid boils.
The platinum is rapidly and completely dissolved, and the tube is then sealed and heated
at 250° for several hours. After cooling, the tube contains a pale yellow liquid, orangeyellow
crystals, and also, if the selenium is in excess, colourless crystals. The crystals
are separated and heated in vacuo at 110°. They then consist of platinum tetrachloride
and selenium tetrachloride, and are heated at 360° in a current of chlorine, when selenium
chloride sublimes and anhydrous platinum tetrachloride remains as a brown, very hygroscopic
powder. At 440°, it is converted into the dichloride. If platinum selenide is used
instead of a mixture of platinum and selenium, no action takes place even at 300° ; if
selenium is omitted altogether, the platinum is not completely attacked, but the action
becomes complete if selenium is added.
H. Precht removed nitric acid by repeatedly evaporating the soln. of platinum
in aqua regia alternately with hydrochloric acid and water. H. B. North obtained
the tetrachloride by heating platinum wire with sulphury! chloride in a sealed tube
for many days at 150°. The anhydrous salt can be obtained by dehydrating the
hydrated tetrachloride, or hydrochloroplatinic acid. Thus, Ei. Pigeon heated the