Homogeneous gas‐phase pyrolyses with a wall‐less reactor. III. The oxygen–ethane reaction. A double reversal in oxygen and surface effects

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Abstract
The impact of surface and oxygen on the oxidative pyrolysis of ethane at temperatures above 590°C was studied using a wall‐less reactor. At very low conversions under homogeneous conditions, ethene formation begins at the same temperature regardless of whether oxygen is present or absent. Between 0.00 and 0.13% conversion (592–632°C), the rate with oxygen is actually less than the rate in the absence of oxygen. A reversal occurs at about 633°C above which oxygen has a promoting effect. It is concluded that under homogeneous conditions the initiation step in the oxygen‐promoted pyrolysis is the same as in the oxygen‐free pyrolysis; therefore, initiation by direct attack of oxygen on ethane does not make an important contribution. The decrease in rate observed upon addition of oxygen implies the formation of the relatively unreactive HO2 · radical. As conversion of the HO2 · radical to the more reactive HO · radical becomes significant, the reaction is highly accelerated. If a stainless steel surface is added, the reaction is inhibited at higher conversions in the presence of oxygen. Again at low conversions, a second reversal occurs, and the stainless steel surface acts as a promoter below 649°C. The rate of surfacecatalyzed ethene formation at 590°C equals the rate of homogeneous ethene formation at 630°C.