Abstract
The13C kinetic isotope effect (K.I.E.) in the decarbonylation of formic acid of natural isotopic composition in 85% orthophosphoric acid, in 100% H3PO4, and in pyrophosphoric acid has been measured in different temperature intervals ranging from 19 to 133 °C. In 85% H3PO4 the carbon-13 K.I.E. is determined by the fractionation of carbon isotopes expected for C−O bond rupture (k 12/k 13=1.0531 at 70°C). In 100% H3PO4 the13C K.I.E. indicates that C−H bond rupture is the major component of the reaction coordinate motion (thek 12/k 13 lay in the range of 1.026–1.017 over the range 30–70 °C). In pyrophosphoric acid the fractionation factor for13C equals 1.010 at 19 °C. Activation parameters for the decarbonylation of H12COOH in phosphoric acid media have been determined also and suggestions concerning the intimate mechanisms of decarbonylation of formic acid in dilute and concentrated phosphoric acids are made.
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Zieliński, M., Zielińska, A. & Papiernik-Zielińska, H. Carbon-13 kinetic isotope effects in the decarbonylation of formic acid of natural isotopic composition in phosphoric acid media. Journal of Radioanalytical and Nuclear Chemistry, Articles 183, 301–311 (1994). https://doi.org/10.1007/BF02037999
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DOI: https://doi.org/10.1007/BF02037999