Spectroscopic and kinetic study of the gas-phase CH3I-Cl and C2H5I-Cl adducts.
Time-resolved UV-visible absorption spectroscopy has been coupled with UV laser flash photolysis of Cl2/RI/N2/X mixtures (R = CH3 or C2H5; X = O2, NO, or NO2) to generate the RI-Cl radical adducts in the gas phase and study the spectroscopy and reaction kinetics of these species. Both adducts were found to absorb strongly over the wavelength range 310-500 nm. The spectra were very similar in wavelength dependence with lambda(max) approximately 315 nm for both adducts and sigma(max) = (3.5 +/- 1.2) x 10(-17) and (2.7 +/- 1.0) x 10(-17) cm(2) molecule(-1) (base e) for CH3I-Cl and C2H5I-Cl, respectively (uncertainties are estimates of accuracy at the 95% confidence level). Two weaker bands with lambda max approximately 350 and 420 nm were also observed. Over the wavelength range 405-500 nm, where adduct spectra are reported both in the literature and in this study, the absorption cross sections obtained in this study are a factor of approximately 4 lower than those reported previously [Enami et al. J. Phys. Chem. A 2005, 109, 1587 and 6066]. Reactions of RI-Cl with O2 were not observed, and our data suggest that upper limit rate coefficients for these reactions at 250 K are 1.0 x 10(-17) cm(3) molecule(-1) s(-1) for R = CH3 and 2.5 x 10(-17) cm(3) molecule(-1) s(-1) for R = C2H5. Their lack of reactivity with O2 suggests that RI-Cl adducts are unlikely to play a significant role in atmospheric chemistry. Possible reactions of RI-Cl with RI could not be confirmed or ruled out, although our data suggest that upper limit rate coefficients for these reactions at 250 K are 3 x 10(-13) cm(3) molecule(-1) s(-1) for R = CH3 and 5 x 10(-13) cm(3) molecule(-1) s(-1) for R = C2H5. Rate coefficients for CH3I-Cl reactions with CH3I-Cl (k9), NO (k22), and NO2 (k24), and C2H5I-Cl reactions with C2H5I-Cl (k14), NO (k23), and NO2 (k25) were measured at 250 K. In units of 10(-11) cm(3) molecule(-1) s(-1), the rate coefficients were found to be 2k9 = 35 +/- 12, k22 = 1.8 +/- 0.4, k24 = 3.3 +/- 0.6, 2k14 = 40 +/- 16, k23 = 1.8 +/- 0.3, and k25 = 4.0 +/- 0.9, where the uncertainties are estimates of accuracy at the 95% confidence level.
School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, Georgia 30332, USA.
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Dookwah-Roberts
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Nicovich
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Wine
D000042:Absorption; D005609:Free Radicals / Q000737:chemistry; D006843:Hydrocarbons, Chlorinated / Q000737:chemistry*; D006847:Hydrocarbons, Iodinated / Q000737:chemistry*; D007700:Kinetics; D044367:Phase Transition; D010782:Photolysis; D013056:Spectrophotometry, Ultraviolet
D005609:Free Radicals; D006843:Hydrocarbons, Chlorinated; D006847:Hydrocarbons, Iodinated; C521551:iodoethane; C014055:methyl iodide