화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.115, No.38, 10539-10549, 2011
Atmospheric Chemistry of (Z)-CF3CH=CHCF3: OH Radical Reaction Rate Coefficient and Global Warming Potential
Rate coefficients, k, for the gas-phase reaction of the OH radical with (Z)-CF3CH-CH=CF3 (cis-1,1,1,4,4,4-hexafluoro-2-butene) were measured under pseudo-first-order conditions in OH using pulsed laser photolysis (PLP) to produce OH and laser-induced fluorescence (LIF) to detect it. Rate coefficients were measured over a range of temperatures (212-374 K) and bath gas pressures (20-200 Torr; He, N-2) and found to be independent of pressure over this range of conditions. The rate coefficient has a non-Arrhenius behavior that is well-described by the expression k(1)(T) = (5.73 +/- 0.60) x 10(-19) x T-2 x exp[(678 +/- 10)/T] cm(3) molecule(-1) s(-1) where k(1)(296 K) was measured to be (4.91 +/- 0.50) x 10(-13) cm(3) molecule(-1) s(-1) and the uncertainties are at the 2 sigma level and include estimated systematic errors. Rate coefficients for the analogous OD radical reaction were determined over a range of temperatures (262-374 K) at 100 Torr (He) to be k(2)(T) = (4.81 +/- 0.20) x 10(-19) x T-2 x exp[(776 +/- 15)/T], with k(2)(296 K) = (5.73 +/- 0.50) x 10(-13) cm(3) molecule(-1) s(-1). OH radical rate coefficients were also measured at 296, 345, and 375 K using a relative rate technique and found to be in good agreement with the PLP-LIF results. A room-temperature rate coefficient for the O-3 + (Z)-CF3CH-CH=CF3 reaction was measured using an absolute method with O-3 in excess to be <6 x 10(-21) cm(3) molecule(-1) s(-1). The atmospheric lifetime of (Z)-CF3CH-CHCF3 due to loss by OH reaction was estimated to be similar to 20 days. Infrared absorption spectra of (Z)-CF3CH-CH=CF3 measured in this work were used to determine a (Z)-CF3CH-CH=CF3 global warming potential (GWP) of similar to 9 for the 100 year time horizon. A comparison of the OH reactivity of (Z)-CF3CH-CHCF3 with other unsaturated fluorinated compounds is presented.