Journal of Physical Chemistry, Vol.99, No.43, 15890-15898, 1995
Selected-Ion Flow Drift-Tube Studies of the Reactions of S+(S-4) with CH4, C2H2, C2H4, and C3H8
The reaction rate coefficients, k, and the product distributions for the reactions of ground-state S+(S-4) with small hydrocarbon molecules CH4, C2H2, C2H4, and C3H8 have been measured as a function of reactant ion/ reactant neutral average center-of-mass kinetic energy, KE(CM), in a selected ion flow drift tube (SIFDT) apparatus. The measurements have been performed at a temperature 298 +/- 2 K with helium as a buffer gas. The values k of the studied reactions have pronounced negative energy dependencies. For some reactions k decreases by about one order of magnitude when KE(CM) is increasing from near thermal values to a few electronvolts. This is interpreted in terms of a simple model assuming the reactions to proceed via the formation of long-lived complexes. The lifetimes of these intermediate complexes against decomposition back to reactants and forward to products (or corresponding unimolecular rate coefficients k(-1) and k(2)) govern the overall rate of the reactions. It is found from the kinetics of the studied reactions that a power law of the form k(-1)/k(2) = const(KE(CM))(m), where m is a constant parameter, can be used to describe the energy dependencies of the overall reaction rate coefficients of studied reactions.
Keywords:TERNARY ASSOCIATION REACTIONS;DENSE INTERSTELLAR CLOUDS;N = 0-4;ENERGY-DEPENDENCE;POSITIVE-IONS;CHEMISTRY;CH3+;S+;TEMPERATURE;GAS