화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.119, No.39, 10060-10066, 2015
Rate Constant for the OH plus CO Reaction at Low Temperatures
Rate constants for the reaction of OH + CO -> products (1) have been measured using laser photolysis/laser-induced fluorescence (LP/LIF) over the temperature range 193-296 K and at pressures of 50-700 Torr of Ar and N-2. The reaction was studied under pseudo-first-order conditions, monitoring the decay of OH in the presence of a large excess of CO. The rate constants can be expressed as a combination of bimolecular and termolecular components. The bimolecular component was found to be temperature-independent with an expression given by k(bi)(T) = (1.54 +/- 0.14) x 10(-13)[e(-(13)+/-(17)/T)] cm(3) molecule(-1) s(-1), with an error of one standard deviation. The termolecular component was fitted to the expression, k(ter) = k(0)(T)[M]/[1 + (k(0)(T)[M]/k(infinity)(T)] x 0.6(10)({1+[log)((k0(T)[M]/k infinity(T))]2}-1) where k(0)(T) = k(0)(300)(T/300)(-n) and k(infinity)(T) = k(infinity)(300)(T/300)(-m). The parameters for k(0)(T) were determined to be k(0)(300) = (6.0 +/- 0.5) X 10(-33) cm(6) molecule(-2) s(-1) in N-2 and k(0)(300) = (3.4 +/- 0.3) x 10(-33) cm(6) molecule(-2) s(-1) in Ar, with n = 1.9 +/- 0.5 and 2.0 +/- 0.4 in N-2 and Ar, respectively. These parameters were determined using k(0)(T) and m from the NASA kinetics data evaluation (JPL Publication No. 10-6) since the experimental pressure range was far from the high-pressure limit. Addition of low concentrations of O-2 had no discernible effect on the mechanism of the OH + CO reaction but resulted in secondary reactions which regenerated OH.