The Hydrogenation of Ethylene at Surfaces of Certain Oxides. II

The Hydrogenation of Ethylene at Surfaces of Certain Oxides. II. Molybdenum Oxide Compounds. John F. Woodman, Hugh S. Taylor, and John Turkevich...
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June, 1940

HYDROGENATION OF ETHYLENE ON MOLYBDENUM OXIDESURFACES [CONTRIBUTION FROM

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1397

FRICK CHEMICAL LABORATORY, PRINCETON UNIVERSITY ]

The Hydrogenation of Ethylene at Surfaces of Certain Oxides. 11. Molybdenum Oxide Compounds BY JOHN F. WOODMAN, HUGHS. TAYLOR AND JOHN TURKEVICH Following the study of the activity of zinc oxide and zinc chromite surfaces described in the preceding paper,' a series of experiments was carried out to test the activity of some molybdenum compounds, in view of the well-known industrial applications of the oxides and sulfides of this element in hydrogenation and cracking of oils and tars. Catalytic masses were prepared by decomposition and reduction of ammonium phosphomolybdate, ammonium paramolybdate, and ammonium nickel molybdate. Suspicion of the presence of metallic nickel in extremely active catalysts produced by reduction of the nickel compounds suggested tests of the efficiency of hydrogen sulfide as a poison for these surfaces and measurements of the magnetic susceptibilities of the materials. Experimental Details Apparatus and Procedure.-The catalytic system was the same a s that used in the static experiments on zinc oxide.' The magnetic susceptibilities were determined by the were carried out with ~ method of G o ~ y .Measurements magnetic fields up to about 4800 gausses, the magnet current being increased from.zero to 12 amp. in steps of about 2 amp., then reduced again to zero in the same manner, with the change in weight of the sample determined a t each step. For purposes of calculation, the results were plotted against current and values taken from the smooth curve a t intervals of 2 amp. The relationship between current and field strength was established by calibration with Mohr salt, for which x, the specific susceptibility, cgsm. unit a t 2 2 O . 3 was taken a s 32.1 X The finely divided samples were contained in uniform 5 mm. Pyrex tubes, each filled to a depth of 12.2 cm. Reduced samples were filled into the tubes under vacuum and sealed off without access to air. Measurements were corrected for the small diamagnetic effect of the tubes. During measurements the sample tube hung freely in a Pyrex jacket through which dry nitrogen gas had been passed for one-half to one hour. Only the measurements a t room tem3erature are reported; others at 0, -80 and -190' gave similar results. Materials.-Ammonium phosphomolybdate, 3(SH&O. P206.24MoO3.6H20, was prepared following the analytical ~rocedure.~ The yellow product was dried a t 120'. (1) Woodman and Taylor, THISJ O W R K A L , 62, 1393 (1940). ( 2 ) Gouy, Compl. r e n d . , 109, 935 (1889): see also Klemm, "htagnrtochemie," I.eipzig, 1936, pp. 50-52. (3) Jackson. Phil. 7'voirs. R o y . S u c . (London), A224, 1 (1!)23). ( 4 ) l'rradwrll :III