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Issue 24, 2012
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Radical kinetics in sub- and supercritical carbon dioxide: thermodynamic rate tuning

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Abstract

We report rate constants for muonium addition to 1,1-difluoroethylene (vinylidene fluoride) in CO2 at 290–530 K, 40–360 bar, and 0.05–0.90 g cm−3. Rate constants are mapped against their thermodynamic conditions, demonstrating the kinetic tuning ability of the solvent. The reaction exhibits critical slowing near conditions of maximum solvent isothermal compressibility, where activation volumes of unprecedentedly large magnitudes on the order of ±106 cm3 mol−1 are observed. Such values are suggestive of pressure being a significant parameter for tuning fluorolkene reactivity.

Graphical abstract: Radical kinetics in sub- and supercritical carbon dioxide: thermodynamic rate tuning

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Publication details

The article was received on 12 Apr 2012, accepted on 02 May 2012 and first published on 02 May 2012


Article type: Communication
DOI: 10.1039/C2CP41170A
Citation: Phys. Chem. Chem. Phys., 2012,14, 8502-8505
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    Radical kinetics in sub- and supercritical carbon dioxide: thermodynamic rate tuning

    K. Ghandi, R. M. L. McFadden, P. J. Cormier, P. Satija and M. Smith, Phys. Chem. Chem. Phys., 2012, 14, 8502
    DOI: 10.1039/C2CP41170A

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