title: Radical kinetics in sub- and supercritical carbon dioxide: thermodynamic rate tuning.
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 ±10(6) cm(3) mol(-1) are observed. Such values are suggestive of pressure being a significant parameter for tuning fluorolkene reactivity.
authors.affiliation: Department of Chemistry & Biochemistry, Mount Allison University, 63C York Street, Sackville, NB E4L 1G8, Canada. kghandi@mta.ca.
authors.forename: Khashayar
authors.initials: K
authors.lastname: Ghandi
authors.forename: Ryan M L
authors.initials: RM
authors.lastname: McFadden
authors.forename: Philip J
authors.initials: PJ
authors.lastname: Cormier
authors.forename: Paras
authors.initials: P
authors.lastname: Satija
authors.forename: Marisa
authors.initials: M
authors.lastname: Smith