Nitrogen-15 Kinetic Isotope Effects in the Decomposition of Nitric Oxide on Copper

Isotopic rate constant ratios, k14/k15, have been determined for the decomposition of nitric oxide over copper wire at initial NO pressures 40-60 kPa over temperature range 725-825 K. They were interpreted using the Bigeleisen formalism. Under these experimental conditions the reaction was found to be second order in NO. On the basis of the temperature independence, k14/k15 = 1.010 š 0.001 at all temperatures studied, a cis ONNO transition state was shown to account satisfactorily for the experimental k14/k15 values.