Journal of Physical Chemistry, Vol.99, No.42, 15678-15685, 1995
Gas-Phase Reactions of Cl2O with No- (X=2,3)-Center-Dot(D2O)(N=0-2) and Cl-Center-Dot(D2O)(N=0-2)
The results of laboratory measurements are reported for the reactions of Cl2O with NO2-.(D2O)(n=0-2), NO3-.(D2O)(n=0-2), and Cl-.(D2O)(n=0-2). These were studied using a flow-tube apparatus at several temperatures within the range 168-298 K and at a helium buffer gas pressure of 0.30+/-0.02 Torr. Rate constants for primary reactions and product ions observed in various reaction sequences are reported, along with a discussion of possible reaction mechanisms. The findings contribute to a further mechanistic understanding of ionic reactions as well as other heterogeneous ones involving chlorine-containing molecules. Interestingly, evidence for a water-catalyzed reaction between Cl2O and Cl-/NO3- was obtained, Also, the present findings suggest that several ionic reactions may lead to the formation of ClONO2 as a neutral product, Finally, limits on the electron affinity of Cl2O are determined to be 2.52 eV less than or equal to EA(Cl2O) less than or equal to 3.617 eV.