| Abstract
| - The title reactions were studied using laser flash photolysis/laser-induced-fluorescence (FP-LIF) techniques.The two spin−orbit states, Cl*(2P1/2) and Cl(2P3/2), were detected using LIF at 135.2 and 134.7 nm, respectively.Measured reaction rate constants were as follows (units of cm3 molecule-1 s-1): k(Cl(2P3/2)+CH3OH) =(5.35 ± 0.24) × 10-11, k(Cl(2P3/2)+C2H5OH) = (9.50 ± 0.85) × 10-11, k(Cl(2P3/2)+n-C3H7OH) = (1.71 ±0.11) × 10-10, and k(Cl(2P3/2)+i-C3H7OH) = (9.11 ± 0.60) × 10-11. Measured rate constants for total removalof Cl*(2P1/2) in collisions with CH3OH, C2H5OH, n-C3H7OH, and i-C3H7OH were (1.95 ± 0.13) × 10-10,(2.48 ± 0.18) × 10-10, (3.13 ± 0.18) × 10-10, and (2.84 ± 0.16) × 10-10, respectively; quoted errors aretwo-standard deviations. Although spin−orbit excited Cl*(2P1/2) atoms have 2.52 kcal/mol more energy thanCl(2P3/2), the rates of chemical reaction of Cl*(2P1/2) with CH3OH, C2H5OH, n-C3H7OH, and i-C3H7OH areonly 60−90% of the corresponding Cl(2P3/2) atom reactions. Under ambient conditions spin−orbit excitedCl* atoms are responsible for 0.5%, 0.5%, 0.4%, and 0.7% of the observed reactivity of thermalized Clatoms toward CH3OH, C2H5OH, n-C3H7OH, and i-C3H7OH, respectively.
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