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Carbon-13 fractionation observed in thermal decarboxylation of pure phenylpropiolic acid (PPA) dissolved in phenylacetylene

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Abstract

The determinations of the 13C fractionation in the decarboxylation of pure phenylpropiolic acid (PPA) above its melting point has been extended to higher degrees of decomposition of PPA by carrying out two-step decarboxylations to establish the maximum possible yield of carbon dioxide in the temperature interval of 423-475 K (58%). The result was compared with the yields of CO2 for decarboxylation of PPA in phenylacetylene solvent (PA) (much smaller, temperature dependent, and equal to 11% at 406 K). The ratios of carbon isotope ratios, R so/R pf, all smaller than 1.009 in the temperature interval 405-475 K, have been analyzed formally within the branched decomposition scheme of PPA, providing carbon dioxide and a decarboxylation resistant solid chemical compound enriched in 13C with respect to CO2. A general discussion of the 13C fractionation in the decarboxylation of pure PPA and PPA dissolved in PA is supplemented by the model calculation of the maximized skeletal 13C KIEs, in the linear chain propagation of the acetylene polymerization process. Further studies of the 13C fractionation in condensed phases and in different hydrogen defficient and hydrogen rich media have been suggested.

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  1. Faculty of Chemistry, Jagiellonian University, 30-060, Krakow, Ingardena 3, Poland

    A. Zielinska, M. Zielinski & H. Papiernik-Zielinska

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Zielinska, A., Zielinski, M. & Papiernik-Zielinska, H. Carbon-13 fractionation observed in thermal decarboxylation of pure phenylpropiolic acid (PPA) dissolved in phenylacetylene. Journal of Radioanalytical and Nuclear Chemistry 257, 337–346 (2003). https://doi.org/10.1023/A:1024787914102

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