Kinetics and mechanisms of the pyrolysis of diethyl ether I. The uninhibited reaction

Abstract
The uninhibited thermal decomposition of diethyl ether was studied from 560 to 620 °C and at pressures ranging from 15 to 320 mmHg . The order of the overall reaction was between 1 and 3/2, the order being greater the higher the pressure. Analytical and kinetic data provide strong evidence that there is a molecular split of diethyl ether into ethanol and ethylene. The reaction leading to acetaldehyde and ethane, on the other hand, is concluded to be almost entirely a free-radical chain process. A detailed chain mechanism is postulated, involving first-order initiation and the reaction between C2H5 and CH2CH2OC2H5 as the chain-ending step. This mechanism is shown to give a steady-state rate equation which leads to first-order kinetics at lower ether pressures and three-halves-order kinetics at higher ones. The kinetic results lead to activation energies which are in satisfactory agreement with values calculated on the basis of the elementary reactions.

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