Kinetics of the reactions of Cl*(2P1/2) and Cl(2P3/2) atoms with CH3OH, C2H5OH, n-C3H7OH, and i-C3H7OH at 295 K

The title reactions were studied using laser flash photolysis/laser-induced-fluorescence (FP-LIF) techniques. The two spin-orbit states, Cl*(P-2(1/2)) and CI(P-2(3/2)), were detected using LIF at 135.2 and 134.7 nm, respectively. Measured reaction rate constants were as follows (units of cm(3) molecule(-1) s(-1)): k(Cl(P-2(3/2)) + CH3OH) (5.35 +/- 0.24) x 10(-11), k(Cl(P-2(3/2)) + C2H5OH) = (9.50 +/- 0.85) x 10(-11) k(Cl(P-2(3/2)) + n-C3H7OH) = (1.71 +/- 0.11) x 10(-10), and k(Cl(P-2(3/2)) + i-C3H7OH) = (9.11 +/- 0.60) x 10-11. Measured rate constants for total removal of Cl*(P-2 (1/2)) in collisions with CH3OH, C2H5OH, n-C3H7OH, and i-C3H7OH were (1.95 +/- 0.13) x 10(-11), (2.48 +/- 0.18) x 10(-10), (3.13 +/- 0.18) x 10(-10), and (2.84 +/- 0.16) x 10(-10), respectively; quoted errors are two-standard deviations. Although spin-orbit excited Cl*(P-2(1/2)) atoms have 2.52 kcal/mol more energy than Cl(P-2(3/2)), the rates of chemical reaction of Cl*(P-2(1/2)) with CH3OH, C2H5OH, n-C3H7OH, and i-C3H7OH are only 60-90% of the corresponding Cl(P-2(3/2)) atom reactions. Under ambient conditions spin-orbit excited Cl* atoms are responsible for 0.5%, 0.5%, 0.4%, and 0.7% of the observed reactivity of thermalized Cl atoms toward CH3OH, C2H5OH, n-C3H7OH, and i-C3H7OH, respectively.