TY - JOUR
T1 - Reactions of O(3P) with alkyl iodides
T2 - Rate coefficients and reaction products
AU - Gilles, Mary K.
AU - Turnipseed, Andrew A.
AU - Talukdar, Ranajit K.
AU - Rudich, Yinon
AU - Villalta, Peter W.
AU - Huey, L. Gregory
AU - Burkholder, James B.
AU - Ravishankara, A. R.
PY - 1996/8/15
Y1 - 1996/8/15
N2 - The rate coefficients for the reactions of O(3P) with CF3I (1) and CH3I (2) were measured between 213 and 364 K to be: k1(T) = (7.9 ± 0.8) × 10-12 exp[-(175 ± 40)/T] and k2(T) = (1.0 ± 0.2) × 10-11 exp[(160 ± 50)/T] cm3 molecule-1 s-1. The rate coefficients for the reaction of O(3P) with CD3I, (CH3)2CHCH2I, (CH3)2-CHI, CF3CH2I, CF3CHFI, and CF3CF2I at 298 K were also measured. The yields of the IO and CF3O products in reaction 1 at 298 K were found to be 0.83 ± 0.09 and <0.01, respectively. Product yields of reaction 2 at 298 K were measured to be IO (0.44 ± 0.04), OH (0.16 ± 0.05), H (0.07 ± 0.02), CH3O (<0.03), and HI (<0.05). IG, OH, and CH3O were detected via laser-induced fluorescence, O and H atoms via resonance fluorescence, and IO, CF3O, and HI by chemical ionization mass spectrometry. The IO yield from reactions 1 and 2 showed a slight positive temperature dependence. Within our experimental error the OH yield from reaction 2 was temperature independent. An upper limit for the enthalpy of formation of IO, ΔfHo(298.15 K)(IO) <28.8 kcal mol-1, was obtained from an interpretation of our data.
AB - The rate coefficients for the reactions of O(3P) with CF3I (1) and CH3I (2) were measured between 213 and 364 K to be: k1(T) = (7.9 ± 0.8) × 10-12 exp[-(175 ± 40)/T] and k2(T) = (1.0 ± 0.2) × 10-11 exp[(160 ± 50)/T] cm3 molecule-1 s-1. The rate coefficients for the reaction of O(3P) with CD3I, (CH3)2CHCH2I, (CH3)2-CHI, CF3CH2I, CF3CHFI, and CF3CF2I at 298 K were also measured. The yields of the IO and CF3O products in reaction 1 at 298 K were found to be 0.83 ± 0.09 and <0.01, respectively. Product yields of reaction 2 at 298 K were measured to be IO (0.44 ± 0.04), OH (0.16 ± 0.05), H (0.07 ± 0.02), CH3O (<0.03), and HI (<0.05). IG, OH, and CH3O were detected via laser-induced fluorescence, O and H atoms via resonance fluorescence, and IO, CF3O, and HI by chemical ionization mass spectrometry. The IO yield from reactions 1 and 2 showed a slight positive temperature dependence. Within our experimental error the OH yield from reaction 2 was temperature independent. An upper limit for the enthalpy of formation of IO, ΔfHo(298.15 K)(IO) <28.8 kcal mol-1, was obtained from an interpretation of our data.
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U2 - 10.1021/jp960688v
DO - 10.1021/jp960688v
M3 - Article
AN - SCOPUS:33748510810
SN - 0022-3654
VL - 100
SP - 14005
EP - 14015
JO - Journal of physical chemistry
JF - Journal of physical chemistry
IS - 33
ER -