Journal of Physical Chemistry, Vol.100, No.18, 7488-7493, 1996
Gas-Phase Reactions of Dno3 with X(-)Center-Dot(D2O)(N), X=o, OD, O-2, Do2, and O-3
The gas-phase reactions of DNO3 with anions X(-).(D2O)(n less than or equal to 3), where X = O, OD, O-2, and O-3, in helium at several temperatures within the range 185-298 K have been studied using a fast-flow apparatus operated at 0.28 Torr. At room temperature the ions O-.(D2O)(n=1,2), OD-.(D2O)(n=1,2), O-2(-).(D2O)(n=0,1),DO2-.(D2O)(n=0,1), and O-3(-) react rapidly with DNO3 to form mainly bare product ion NO3-. At low temperatures, in the presence of larger hydrates of the reactant ions, the hydrated species, NO3-. D2O, as well as the (O-2 . DNO3)(-) and (DO2 . DNO3)(-) product ions from the O-2(-).(D2O)(n=1,2)/DNO3 and DO2-.(D2O)(n=1,2)/DNO3 systems, respectively, were seen to be efficiently produced in primary reactions. These ions react further with DNO3 to form (NO3DNO3)(-). Rate constants for the observed reactions were determined. The measured rate coefficient for the association reaction of NO3- with DNO3 shows a temperature dependence and can be represented by the expression k(T) = k(298)(298/T)(3.7+/-0.4). The implications of the present experimental results to atmospheric ion chemistry are briefly discussed.
Keywords:PROTONATED WATER CLUSTERS;ION-MOLECULE ASSOCIATION;NITRIC-ACID;CHEMISTRY;OZONE;HNO3;STRATOSPHERE;WINTER;ACETONITRILE;DEPLETION