Abstract
Carbon-13 fractionation observed in the course of carbon monoxide formation in the reaction of phenylacetylene with the large excess of liquid formic acid in the temperature interval 20–100°C has been investigated and compared with the13C fractionation in the dehydration of pure liquid formic acid. The anomalous temperature dependence of the13C fractionation has been interpreted as caused by the change of the kinetics and of the mechanism of CO formation from the one involving13C−H bond rupture rate determining step (operating in the presence of phenylacetylene) to the mechanism according to which HCOOH decarbonylates in liquid state. No large increase of the13C fractionation with rising of the reaction temperature from 70 to 134°C has been found in the case of decarbonylation of F.A. in the presence of large excess of phenylacetylene. The13C KIE was of 1.020 in the temperature interval 90–133.7°C in this case.
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