Carbon-13 fractionation in the oxidation of propionate of natural isotopic composition with permanganate and manganate

Carbon-13 fractionation in the oxidation of sodium propionate of natural isotopic composition with permanganate in water solution and with manganate in alkaline solution has been investigated and compared with carbon-14 kinetic isotope effects in the oxidation of (3-14C) – and (2-14C) propionate with permanganate. The experimental carbon-13 isotope ratios, R(13C/12C)cumul., corrected for dilution of R(13C/12C)a by carbon dioxide derived from all external sources and by carbon dioxide derived from (C-1) and from (C-3) of propionate at its complete and partial oxidations, used for calculation of 13C alfa KIE, provided the carbon-13 isotope effects corresponding to initial oxidation of alpha carbon, which correlate well with (2-14C) KIE determined previously, (k12/k13 -1)?100 ? 1/2(k12/k14 -1)?100 ? 1/2(4.6š0.3) at 373 K. The possibility of extension of isotope ratio measurements, using modern double collector mass spectrometers, from geochemical, biomedical, agriculture and environmental research to carbon-13 isotope effects studies in chemical organic reactions is briefly discussed.