| 摘要 |
<p>889,639. Preparing phosphine electrolytically. ALBRIGHT & WILSON (MFG.) Ltd. July 26, 1960 [July 31, 1959], No. 26293/59. Class 41. Phosphine is made by passing an electric current through an aqueous electrolyte e.g. H3PO4 or H2SO4, using as cathode a metal having a hydrogen over-voltage, preferably mercury, in contact with white phosphorus preferably in molten state. The electrolyte is agitated to make contact with the cathode which may be Hg, Zn, Fe, Ni, Co, Ag, Cu, Cd, Al, Bi or Sn. Alternatively if an inert metal cathode is used, a metal salt e.g. PbSo4 is added to the electrolyte and the metal plated out on the cathode. A suitable apparatus consists of a glass vessel 10, Fig. 1, mercury cathode 11 with a supernatant layer of molten white phosphorus 13 which is agitated by a stirrer 15 to bring the mercury in contact with the aqueous electrolyte 14. Anode 17 is mounted in a glass tube 18 having a sintered glass separator 20, thus preventing phosphine from entering the anode compartment, where oxygen may be generated when a metal anode is used. A carbon anode generates Co2 when a separator is not essential. A solid metal cathode may be used, which projects through the aqueous electrolyte into the molten phosphorus which creeps up the outer surface of the electrode. As electrolyte, mineral acids, strong organic acids, or a salt e.g. alkali metal salt is specified for example phosphoric acid, containing a small amount of lead acetate or barium chloride. In examples, lead, an alloy of Ni, Cu, Cr and Fe, used as cathodes and lead peroxide, platinum, or an alloy of Sn and Bi as anode. U.S.A. Specification 1,375,819 is referred to.</p> |
