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

被引：8

作者：

Ghandi, Khashayar ^{[1
]}

McFadden, Ryan M. L. ^{[1
]}

Cormier, Philip J. ^{[1
]}

Satija, Paras ^{[1
]}

Smith, Marisa ^{[1
]}

机构：

[1] Mt Allison Univ, Dept Chem & Biochem, Sackville, NB E4L 1G8, Canada

来源：

PHYSICAL CHEMISTRY CHEMICAL PHYSICS | 2012年 / 14卷 / 24期

关键词：

CHEMICAL-REACTIONS; CRITICAL-POINTS; MUONIUM; CO2; CHEMISTRY; WATER; POLYMERIZATION; FLUORIDE; SOLVENTS; ISOTOPE;

D O I：

10.1039/c2cp41170a

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

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.

引用

页码：8502 / 8505

页数：4

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