Rate coefficient for the reaction FCO+FC(O)O2→2FC(O)O at 296 K

被引：19

作者：

Badenes, MP ^{[1
]}

Castellano, E ^{[1
]}

Cobos, CJ ^{[1
]}

Croce, AE ^{[1
]}

Tucceri, ME ^{[1
]}

机构：

[1] Natl Univ La Plata, Fac Ciencias Exactas, Inst Invest Fisicoquim Teor & Aplicadas, Dept Quim, RA-1900 La Plata, Argentina

来源：

CHEMICAL PHYSICS LETTERS | 1999年 / 303卷 / 5-6期

关键词：

D O I：

10.1016/S0009-2614(99)00221-3

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：

The kinetics of the reaction FCO + FC(O)O-2 --> 2FC(O)O has been studied. The reactants were generated by KrF excimer laser flash photolysis of mixtures of (FCO)(2) and O-2 in excess of M = SF6 at 296 K. The three radicals were monitored by absorption spectroscopy. Assuming that the reaction proceeds through a complex-forming process, the measured rate coefficient, (2.1 +/- 0.5) X 10(-11) cm(3) molecule(-1) s(-1), agrees with that predicted by a simplified version of the statistical adiabatic channel model using a ratio alpha/beta = 0.50 between the looseness and the Morse parameters. A rate coefficient of (3.7 +/- 0.2) X 10(-12) cm(3) molecule(-1) s(-1) was determined for the FC(O)O + FC(O)O-2 + M --> (FCO)(2)O-3 + M reaction. Employing isodesmic reaction schemes at the B3LYP/6-311 + + G(d,p) level of theory, the enthalpy of formation of FC(O)O-2 and (FCO)(2)O-2 are calculated to be -76.1 +/- 4 and -202.9 +/- 4 kcal mol(-1), respectively. (C) 1999 Elsevier Science B.V. All rights reserved.

引用

页码：482 / 488

页数：7

共 33 条

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