REACTIONS OF NAPHTHALENE IN N2O5-NOO-NO2-AIR MIXTURES

The reactions of naphthalene in N2O5NO3NO2N2O2 reactant mixtures have been investigated over the temperature range 272–297 K at ca. 745 torr total pressure and at 272 K and ca. 65 torr total pressure using long pathlength Fourier transform infrared absorption spectroscopy. 2,3‐Dimethyl‐2‐butene was added to the reactant mixtures at 272 K to rapidly scavenge the NO3 radicals both initially present in the added N2O5 and formed from the thermal decomposition of N2O5 during the reactions. The data obtained in the presence and absence of added 2,3‐dimethyl‐2‐butene showed that napthalene undergoes initial reaction with the NO3 radical to form an NO3‐naphthalene adduct, which either rapidly decomposes back to the reactants (at a rate of ca. 5 × 105 s−1 at 298 K) or reacts exclusively with NO2 to form products. When NO3 radicals, N2O5 and NO2 are in equilibrium, this overall process is kinetically equivalent to reaction of naphthalene with N2O5, and previous kinetic and product studies have indeed assumed the reactions of naphthalene and alkyl‐substituted naphthalenes in N2O5NO3NO2air mixtures to be with N2O5, and not with NO3 radicals. Copyright © 1990 John Wiley & Sons, Inc.