- Capture of the Sulfur Monoxide-Hydroxyl Radical Complex
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The elusive hydrogen-bonded sulfur monoxide-hydroxyl radical complex (?OH···OS), a missing intermediate in the atmospheric chemistry of SO2, was generated in the 266 nm laser photolysis of the sulfinyl radical HOSO?in cryogenic Ar-matrixes. In addition to the IR spectroscopic characterization with deuteration, its thermal conversion to HOSO?with an activation barrier of 0.33 ± 0.11 kcal mol-1 (calcd 0.32 kcal mol-1, CCSD(T)-F12a/AVTZ) in the temperature range of 15.0-21.0 K and a H/D kinetic isotope effect of 2.4 at 16.0 K have been observed.
- Chen, Changyun,Lu, Bo,Zhao, Xiaofang,Qian, Weiyu,Liu, Jie,Trabelsi, Tarek,Francisco, Joseph S.,Qin, Jie,Li, Jun,Wang, Lina,Zeng, Xiaoqing
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supporting information
p. 2175 - 2179
(2020/03/03)
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- Reaction of Atmospheric Ions with Selected Hydrofluorocarbons
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Selected atmospheric ions have been studied for reactivity with the hydrofluorocarbons (HFC's) CF3CH2F, CF3CHFCF3, and CF3CHFCHF2 and with CHBrF2; the reactant ions chosen for study are O+, O2+, O-, O2-, H3O+, H3O+*H2O, H3O+*(H2O)2, NO3-, and NO3-*HNO3.Rate constants and product branching fractions for these ion-molecule reactions were measured using a selected ion flow tube (SIFT) instrument operated at 300 K.The ions O+ and O- reacted at the collisional rates, forming a number of ionic products in most cases.Most of the other reactions studied were found to be inefficient.The ions H3O+ and NO3- reacted inefficiently by association in all cases.The solvated ions H3O+*H2O, H3O+*(H2O)2, and NO3-*HNO3, which are representative of the abundant ionic species in the lower atmosphere, were unreactive with the compounds investigated; we conclude from this that atmospheric ion chemistry is not a significant sink for these HFC's.The observation of proton transfer from CF3CHFCF3 and CF3CHFCHF2 to O- allows a lower bound to the gas-phase acidities of these HFC's to be assigned: ΔHacid(CF3CHFCF3) and ΔHacid(CF3CHFCHF2) -1.
- Morris, Robert A.,Viggiano, A. A.,Arnold, Susan T.,Paulson, J. F.,Liebman, Joel F.
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p. 5992 - 5999
(2007/10/02)
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