KINETICS OF THE REACTION BRO+NO2+M-]BRONO2+M IN THE TEMPERATURE-RANGE 263-343-K

The rate constant of the reaction BrO+NO2+M→BrONO2+M (M=O2) has been measured at low pressure, P <12 Torr, and as a function of temperature from 263 to 343 K. The rate expression obtained is k1(0)=(4.2±0.8)×10-31(T/298)-2.0±0.5 with Fc=exp(-T/325). This expression was obtained by using for k1(∞) the reported expression k1(∞)=2.0×10-11(T/298)-1. A theoretical analysis of this reaction, using both RRKM and Troe's simplified calculations, accounts correctly for the temperature dependence but not for the absolute value of k1(0). These results are discussed in connection with previous findings concerning equivalent reactions of halogen oxides. © 1990.