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rdf:type
lifeskim:mentions
pubmed:issue
6
pubmed:dateCreated
2006-7-20
pubmed:abstractText
The kinetics for the complete combustion of methane was studied on a Pd foil in the regions where the oxide and then the metal were the bulk stable phases. The use of a model catalyst allowed the kinetics to be studied at higher temperatures than are possible on supported catalysts since heat and mass transport limitations could be avoided for this nonporous model catalyst. For all reaction conditions, CH4 and O2 reaction orders remained the same at about 0.7 and 0, respectively. With PdO as the stable phase, the water reaction order increased from -1 to 0 and the apparent activation energy (Ea) decreased from 125 to 30 kJ mol(-1) as the reaction temperature increased from 600 to 880 K. We propose that as the temperature is increased water desorbs from the sites responsible for combustion and as a result water inhibition and Ea decrease. To investigate the rate of reaction on Pd versus PdO, the rates were measured around the Pd-PdO transition temperature. The turnover rate decreased from 3.0 s(-1) to 0.3 s(-1) at the transition temperature (907 K with 1.5 Torr O2 and 0.30 Torr CH4) when PdO decomposed to Pd metal, showing that PdO was more active than Pd metal for methane oxidation at this temperature. The reaction orders for Pd metal in the range of 933-1003 K were 0.7, 0, and 0 for methane, water, and O2, respectively, with an apparent activation energy of 125 kJ mol(-1). Thus, the turnover rate and Ea changes suggest that the reaction mechanism for methane oxidation on Pd is different from the one on PdO.
pubmed:language
eng
pubmed:journal
pubmed:status
PubMed-not-MEDLINE
pubmed:month
Feb
pubmed:issn
1520-6106
pubmed:author
pubmed:issnType
Print
pubmed:day
17
pubmed:volume
109
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
2331-7
pubmed:year
2005
pubmed:articleTitle
Temperature dependence of the kinetics for the complete oxidation of methane on palladium and palladium oxide.
pubmed:affiliation
School of Chemical Engineering, Purdue University, 480 Stadium Mall Drive, West Lafayette, Indiana 47907-2100, USA.
pubmed:publicationType
Journal Article