KINETICS AND MECHANISMS OF THE THERMAL DECOMPOSITION OF PROPIONALDEHYDE: PART I. THE UNINHIBITED REACTION

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Abstract
The propionaldehyde pyrolysis was studied in the temperature range 520–560 °C and at pressures from 20 to 360 mm Hg. The reaction was followed by pressure change and by gas chromatography. The overall order was between 1.25 and 1.30 over the whole range of temperatures and pressures studied. Inert gases have no effect on the rates of formation of the products of reaction. The results are consistent with a mechanism consisting of first-order initiation, C2H5CHO → C2H5 + CHO, and second-order termination, C2H5 + C2H5 → C4H10 or C2H6 + C2H4. The overall rate can be expressed as v = k[C2H5CHO]3/2 + k′[C2H5CHO]1/2. The molecular reaction, C2H5CHO → C2H6 + CO, appears to be of minor importance. The reaction C2H5 → C2H4 + H was found to take place in its first-order high-pressure region under the conditions of the present investigations.

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