Rate Constants for Reactions between Atmospheric Reservoir Species. 1. HCl

Article abstract of DOI:10.1021/j100352a026

The kinetics of the reactions of HCl with ClONO2, N2O5, O3, and HO2NO2 have been investigated by using a large-volume static reactor and a Fourier transform spectrometer (FTIR) at 296 K.The upper limits for the homogenous gas-phase reaction rates of the ClONO2 + HCl, N2O5 + HCl, O3 + HCl, and HO2NO2 + HCl reactions were found to be 8.4 x 10^-21, 8.4 x 10^-21, 4.7 x 10^-24, and 9.0 x 10^-22 (all in unit of cm³ s^-1), respectively.The heterogeneous nature of the ClONO2 + HCl and N2O5 + HCl reactions are characterized in terms of the Langmuir-Rideal mechanism.The yields of HNO3 were be observed to be 0.94 +/- 0.14 and 1.10 +/- 0.12 for the ClONO2 + HCl and N2O5 + HCl reactions, respectively, and the yield of ClNO2 was found to be 0.84 +/- 0.10 for the N2O5 + HCl reaction.The quoted errors represent one standard deviation of the measurement.In addition, an upper limit of 1.6 x 10^-19 cm³ s^-1 at 296 K for the reaction of NO3 with HCl was also obtained in this study.These results may be important in the elucidation of the role played by heterogeneous reactions in the development of the springtime Antarctic ozone depletion over the past decade.