Reactions between Deuterium and Olefins in the Liquid Phase on Platinum Oxide Catalysts
The liquid phase deuterogenation of 1-hexane, DELTA 1,9- and DELTA 9,10-octalin on platinum oxide catalysts was investigated at room temperatures in the liquid phase. The deuterogenation of 1-hexane is accompanied by isomerization to cis- and trans-2-hexene at a rate 3% of that of deuterogenation and by formation of deuteriated hexene of which 90% is 1-hexene at a rate 30% of that of deuterogenation. Most of the saturated product consists of hexane-d/sub o/to -d-6 with dav about 2.0. Similar isotopic distribution appears in the decalins produced from DELTA 1,9-octalin (54% cis-, 46% transdecalin). Exchanged DELTA1,9-octalin is formed but no isomerized octalins. These data appear consistent with adsorption of olefin as a vic-diadsorbed species, conversion to mono-adsorbed alkane followed by alternation between mono- and diadsorbed alkane. Isotopic exchange between surface H-atoms and gas phase deuterium is slow relative to desorption of monoadsorbed alkane. DELTA 9,10-Octalin can be hydrogenated only by adding acetic acid or by prereducing the catalyst in dilute acid. In thc latter case the product is 61% cis- and 39% trans-decalin, reaction is slow and d-av is nearly 3.0. In all of the trans- and 85% of the cis-decalin, at least three hydrogen atoms were equilibrated with the surface H,D-atom pool in contrast to the situation with DELTA 1,9-octalin where only two hydrogen atoms were equilibrated in 75% of the product decalins. Most of the cis-and all of the trans-decalin produced from DELTA 9,10-octalin appear to be derived from a common intermediate in which three hydrogen atoms are equilibrated, possibly DELTA 1,9-9-octalin-10-d.
- Research Organization:
- Northwestern Univ., Evanston, Ill.
- Sponsoring Organization:
- USDOE
- NSA Number:
- NSA-16-013044
- OSTI ID:
- 4797029
- Journal Information:
- Journal of the American Chemical Society, Vol. 84, Issue 6; Other Information: Orig. Receipt Date: 31-DEC-62; ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- Country unknown/Code not available
- Language:
- English
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