A DENSITY-FUNCTIONAL THEORY AND AB-INITIO STUDY OF THE HYDROLYSIS OF DINITROGEN PENTOXIDE

The density functional theory and ab initio methods are used to study two minimum energy pathways for the hydrolysis of N2O5 to form nitric acid, one involving a single water molecule and the other involving tw o water molecules, Both of the reactions are initiated by the nucleoph ilic attack on N2O5 by water while the additional water in the two-wat er reaction acts as a polar solvent to stabilize the ion pair resulted from the nucleophilic attack. The activation energy is 20 kcal/mol fo r the one-water reaction and it is reduced by half for the two-water r eaction. The study suggests that the heterogeneous hydrolysis of N2O5 is likely more favorable than the homogeneous process. (C) 1998 Publis hed by Elsevier Science B.V.