Abstract. The absolute rate constant for the reaction that is the major source of stratospheric NOx, O(1D)+N2O → products, has been determined in the temperature range 227 K to 719 K, and, in the temperature range 248 K to 600 K, the fraction of the reaction that yields O(3P). Both the rate constants and product yields were determined using a recently-developed chemiluminescence technique for monitoring O(1D) that allows for higher precision determinations for both rate constants, and, particularly, O(3P) yields, than do other methods. We found the rate constant, kR1, to be essentially independent of temperature between 400 K and 227 K, having a value of (1.37±0.11)×10−10 cm3 s−1, and for temperatures greater than 450 K a marked decrease in rate constant was observed, with a rate constant of only (0.94±0.11)×10−10 cm3 s−1 at 719 K. The rate constants determined over the 227 K–400 K range show very low scatter and are significantly greater, by 20% at room temperature and 15% at 227 K, than the current recommended values. The fraction of O(3P) produced in this reaction was determined to be 0.002±0.002 at 250 K rising steadily to 0.010±0.004 at 600 K, thus the channel producing O(3P) can be entirely neglected in atmospheric kinetic modeling calculations. A further result of this study is an expression of the relative quantum yields as a function of temperature for the chemiluminescence reactions (kCL1)C2H + O(1D) → CH(A) + CO and (kCL2)C2H + O(3P) → CH(A) + CO, both followed by CH(A) → CH(X) + hν, as kCL1(T)/kCL2(T)=(32.8T−3050)/(6.29T+398).
Absolute rate constant for the reaction of atomic chlorine with hydrogen peroxide vapor over the temperature range 265–400 K