Reactions between hydrocarbon and an oxygen covered palladium surface

• Isothermic desorption studies where an oxygen covered polycrystalline Pd surface (T = 325–575 K) is exposed to small unsaturated hydrocarbons have been performed. The studied gases were acetylene, propene, propadiene, propyne, butene, butadiene, butyne, and also for comparison hydrogen. Electron energy loss spectroscopy (EELS) was available for adsorbate studies and a hydrogen sensitive Pd-MOS structure was used as a sample. The temperature limit for total dissociation is observed to decrease slightly for an oxygen covered surface compared to the clean surface. On an oxygen covered surface the dissociation is complete above 400 K and the reaction products are H2O, CO2, and adsorbed C. Varying the adsorption temperature, the carbon dioxide production is not detectable at room temperature, where all carbon is adsorbed and only water is formed, but increases to reach a constant level above 475 K. For temperatures above 400 K the licking coefficient is close to unity and there is no blocking due to preadsorbed oxygen (as there is for H2). Both the water and carbon dioxide formations are of Langmuir-Hinshelwood type but while the H2O desorption rate is found to depend only on impinging hydrocarbon flux the CO2 desorption rate depends also on the oxygen coverage.

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