GERMANIUM.¹ I. EXTRACTION FROM GERMANIUM-BEARING ZINC OXIDE. NON-OCCURRENCE IN SAMARSKITE.

Abstract

No. IO. THE. JOURNAL OF THE. American C h e m i c a l Society with which has been incorporated the American Chemical Journal (Founded by Ire K e m n ) (COSTRIi3UTION FROM TI16 DEPARTMENT OF CIIEMIISTRY OF CORSE1.L UNIVIIRSITY. ] GERMANIUM.' I. EXTRACTION FROM GERMANIUM-BEARING ZINC OXIDE. NON-OCCURRENCE IN SAMARSKITE. 1 3~ I,. >I. DIINNIS A N D JACOB I J~~~~~~~.

Analytical Methods for Germanium

“…Sele-nium present in the distillate is removed by precipitation with hydroxylamine hydrochloride (12,73) or with sulfur dioxide (107). Separation of the germanium from the arsenic is effected by distillation of germanium(IV) chloride from concentrated hydrochloric acid solution containing an oxidant, preferably a stream of chlorine, to keep the arsenic in the nonvolatile quinquevalent state (17,18,32,107). This procedure will detect 0.5 mg. of germanium dioxide in 100 grams of arsenic trioxide.…”

“…Germanium(IV) sulfide is converted to the dioxide by7 direct ignition, but this procedure is unsatisfactory7, because the formation of volatile germanium(II) oxide causes indeterminate losses (61). Direct oxidation with nitric acid is generally unsatisfactory, being subject to mechanical losses by spattering and the formation of volatile germanium(II) oxide (32,110,111).…”

“…(U) Fusion with potassium nitrate and potassium hydroxide, followed by leaching with water. Precipitation as germanium(IV) sulfide from sulfuric acid solution Composition: 7CuS.FeS.GeS2 with varying amounts of (1, 58, 100) arsenic, zinc, lead, and gallium Heating in nitrogen followed by reduction to volatile ger- (88,54) manium(II) sulfide with ammonia Roasting followed by oxidation to germanium dioxide by (85) nitric-sulfuric acid mixture Direct chlorination, then fractional distillation of chloride (79) and hydrolysis to dioxide Treatment with sodium hydroxide, followed by oxidation (91) with nitric acid, precipitation with ammonia, and dehydration with concentrated sulfuric acid to obtain dioxide Electrolysis of alkaline extract using copper or nickel (60) cathode Distillation from hydrochloric acid solution in a stream of (19, 20, 31, chlorine, followed by precipitation as disulfide and con- 32,52,66) version to dioxide Roasting, followed by sintering with salt to obtain chloride, (74) then distillation in hydrochloric acid and hydrolysis to dioxide Digest in concentrated sulfuric acid, convert to sulfide with (102) sodium sulfide, and oxidize to dioxide with nitric acid Remove silicon as tetrafluoride, then distill germanium(IV) The thiodigermanate is oxidized with an excess of standard iodine solution and back-titrated with thiosulfate solution. High concentrations of chloride ion and the presence of strong electrolytes cause appreciable error (109).…”

Germanium and its Inorganic Compounds.

“…The mineral argyrodite, 4AgS • GeS2, from which germanium was first chained (208), contains from 5 to 7 per cent of germanium, but this mineral is comparatively rare and is not an important source. Another sulfide mineral, germanite, 7CuS-FeS-GeS2, found in southwest Africa, contains about 6 per cent of germanium (44), but its value as a source of commercial quantities of germanium is still in doubt.…”

Electrodeposition and Electrowinning of Germanium

“…Several methods have been reported for recovering the metal: distillation of the finely ground germanium-containing ore with hydrochloric acid to produce GeC14 contaminated with arsenic (12,13,14); reduction of germanium dioxide with hydrogen at 540~ (16) to produce a powder which is melted under fused NaCl; reduction of the germanium dioxide with carbon or a mixture of carbon and potassium cyanide (18,10); reaction between zinc and germanium tetrachloride at 930~ to yield germanium metal containing 0.2 per cent zinc (19).…”