KINETICS OF THE REACTION OF CHLORINE ATOMS WITH DIMETHYLNITRAMINE

The kinetics of the reaction Cl + (CH3)2NNO2 --> HCl + CH2N(CH3)NO2 have been studied over the temperature range 273-353 K by using the very low pressure reactor technique. The absolute rate constant at 303 K was found to be k = (1.86 +/- 0.54) x 10(-11) cm3 molecule-1 s-1, and from the range of temperature measurements (273-353 K), k = 1.44(-0.76)+1.04 x 10(-10) exp(-1200 +/- 370/RT) cm3 molecule-1 s-1 (R expressed in cal mol-1 K-1). Transition-state (TS) models of the reaction rule out a TS geometry with collinear Cl-H-C bonds in favor of a bent TS geometry, and the estimated A factor was in excellent agreement with the experimental value 10(-9.84) cm3 molecule-1 s-1.