The oxidative dehydrogenation and cracking of ethane and propane over LiDyM
g mixed oxides is reported. High yields of olefins and only moderate format
ion of carbon oxides was observed. Both are primary products that hardly in
terconvert under the reaction conditions used. Addition of chloride increas
es the rate of reaction, while slightly decreasing the selectivity to olefi
ns. The addition of carbon dioxide strongly decreases the rate of reaction,
the negative order of 0.5 indicating that two active Li+ sites are blocked
by the adsorption of one CO2 molecule. The reaction proceeds at low oxygen
pressure primarily via elimination of dihydrogen, while at higher oxygen p
artial pressure the hydrogen elimination occurs via water formation. It is
speculated that dehydrogenation and cracking involve Li+ and a rather nucle
ophilic oxygen site.