STUDIES ON HOMOGENEOUS FIRST ORDER GAS REACTIONS: V. THE DECOMPOSITION OF PARACETALDEHYDE AT HIGH PRESSURES

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Abstract
The homogeneous first order gaseous decomposition of paraldehyde to acetaldehyde has been studied at temperatures from 230 to 254 °C. up to pressures at which the liquid phase makes its appearance, i.e., 12 atm. at 230° and 18 atm. at 254 °C. Over-all velocity constants for the homogeneous reaction in the heterogeneous liquid-vapor system have been determined from these pressures up to the critical point. The data confirm results already published. It is found that in the purely gaseous system increase of pressure tends to diminish the reaction velocity. That the specific reaction velocity in the liquid phase is greater than that in the vapor phase is shown by the fact that the velocity constants of the heterogeneous systems increase progressively with the liquid-vapor ratio. Extrapolation to 100% of liquid gives velocity constants about five times as great as those characteristic of the vapor phase. Peculiarities in the behavior of the system at the critical point and preliminary measurements of the velocity of the trimolecular reverse reaction are described.

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