Reactions between Deuterium and Olefins in the Liquid Phase on Platinum Oxide Catalysts

Journal Article · Thu Mar 01 04:00:00 EST 1962 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/ja00865a010· OSTI ID:4797029

Smith, Gerard V.; Burwell, Robert L.

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 d_av about 2.0. Similar isotopic distribution appears in the decalins produced from DELTA ^1,9-octalin (54% cis-, 46% transdecalin). Exchanged DELTA^1,9-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, Journal Name: Journal of the American Chemical Society Journal Issue: 6 Vol. 84; ISSN 0002-7863
• Publisher: American Chemical Society (ACS)
• Country of Publication: Country unknown/Code not available
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ACETIC ACID
ACIDITY
ADSORPTION
ALKENES
ATOMS
CATALYSIS
DEUTERIUM COMPOUNDS
DISTRIBUTION
FUELS
HEXANE
HYDROGEN
ISOMERS
ISOTOPIC EXCHANGE
LIQUIDS
NAPHTHALENE
PHASE DIAGRAMS
PLATINUM OXIDES
STABILITY
SURFACES
TEMPERATURE