Intramolecular hydrogen isotope effect in the pyrolysis of diethyl carbonate‐1,1,1,2,2‐d₅

Abstract

The thermal unimolecular decomposition of diethyl carbonate-1,1,1,2,2-d5 has been examined in the high-pressure-limiting region. The observed chemistry is consistent with a simple, competitive two-channel model:The intramolecular isotope effect k H / k D has been determined, and the relative Arrhenius parameters for the two channels are given byover the temperature range of 540-620 K. These Arrhenius parameters predict an isotope effect k~/ k~ = 5.4 at 300 K.