Atmospheric Chemistry of Isoflurane, Desflurane, and Sevoflurane: Kinetics and Mechanisms of Reactions with Chlorine Atoms and OH Radicals and Global Warming Potentials

作者：Andersen Mads P Sulbaek; Nielsen Ole J; Karpichev Boris; Wallington Timothy J; Sander Stanley P

来源：Journal of Physical Chemistry A, 2012, 116(24): 5806-5820.

DOI：10.1021/jp2077598

The smog chamber/Fourier-transform infrared spectroscopy (FTIR) technique was used to measure the rate coefficients k(Cl + CF3CHClOCHF2, isoflurane) = (4.5 +/- 0.8) x 10(-15), k(Cl + CF3CHFOCHF2, desflurane) = (1.0 +/- 0.3) x 10(-15), k(Cl + (CF3)(2)CHOCH2F, sevoflurane) = (1.1 +/- 0.1) x 10(-13), and k(OH + (CF3)(2)CHOCH2F) = (3.5 +/- 0.7) x 10(-14) cm(3) molecule(-1) in 700 Torr of N-2/air diluent at 295 +/- 2K. An upper limit of 6 x 10(-17) cm(3) molecule(-1) was established for k(Cl + (CF3)(2)CHOC(O)F). The laser photolysis/laser-induced fluorescence (LP/LIF) technique was employed to determine hydroxyl radical rate coefficients as a function of temperature (241-298 K): k(OH + CF3CHFOCHF2) = (7.05 +/- 1.80) x 10(-13) exp[-(1551 +/- 72)/T] cm(3) molecule(-1); k(296 +/- 1 = (3.73 +/- 0.08) x 10(-15) cm(3) molecule(-1), and k(OH + (CF3)(2)CHOCH2F) = (9.98 +/- 3.24) x 10(-13) exp[-(969 +/- 82)/T] cm(3) molecule(-1); k(298 +/- 1K) = (3.94 +/- 0.30) x 10(-14) cm(3) molecule(-1). The rate coefficient of k(OH + CF3CHClOCHF2, 296 +/- 1 = (1.45 +/- 0.16) x 10(-14) cm(3) molecule(-1) was also determined. Chlorine atoms react with CF3CHFOCHF2 via H-abstraction to give CF3CFOCHF2 and CF3CHFOCF2 radicals in yields of approximately 83% and 17%. The major atmospheric fate of the CF3C(O)FOCHF2 alkoxy radical is decomposition via elimination of CF3 to give FC(O)OCHF2 and is unaffected by the method used to generate the CF3C(O)FOCHF2 radicals. CF3CHFOCF2 radicals add O-2 and are converted by subsequent reactions into CF3CHFOCF2O alkoxy radicals, which decompose to give COF2 and CF3CHFO radicals. In 700 Torr of air 82% of CF3CHFO radicals undergo C-C scission to yield HC(O)F and CF3 radicals with the remaining 18% reacting with O-2 to give CF3C(O)F. Atmospheric oxidation of (CF3)(2)CHOCH2F gives (CF3)(2)CHOC(O)F in a molar yield of 93 +/- 6% with CF3C(O)CF3 and HCOF as minor products. The IR spectra of (CF3)(2)CHOC(O)F and FC(O)OCHF2 are reported for the first time. The atmospheric lifetimes of CF3CHClOCHF2, CF3CHFOCHF2, and (CF3)(2)CHOCH2F (sevoflurane) are estimated at 3.2, 14, and 1.1 years, respectively. The 100 year time horizon global warming potentials of isoflurane, desflurane, and sevoflurane are 510, 2540, and 130, respectively. The atmospheric degradation products of these anesthetics are not of environmental concern.

• 出版日期2012-6-21