Kinetics of the Reaction of Nitric Oxide with Molecular Oxygen

Details Kinetics of the Reaction of Nitric Oxide with Molecular Oxygen Kinetics of the Reaction of Nitric Oxide with Molecular Oxygen

Feb 1966

adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=1966natur.209..706s&link_type=abstract

Nature, Volume 209, Issue 5024, pp. 706 (1966).

Computer Science

Scientific paper

THE results of detailed kinetic investigations of the reaction of nitric oxide with oxygen at a temperature of 25° C and partial gas pressures of 1-50 mm mercury demonstrate that this reaction does not exactly follow an equation of third order1. The formal third-order rate constant kexp = (d[NO2]/dt)/[NO]2.[O2] calculated from reaction rates near the starting point of the reaction ([O2], [NO]>>[NO2]) depends on the composition of the sytesm: it follows from experimental data that kexp does not depend only on the concentration of nitric oxide ([NO]) or that of oxygen [O2], but on their ratio [O2]/[NO] (Fig. 1). The relation kexp = kexp ([O2]/[NO]) decreases monotonously: within [O2]/[NO] values of three orders dkexp/d([O2]/[NO]) < 0, that is, ∂kexp/∂[O2] < 0 and ∂kexp/∂[NO] > 0, which formally corresponds with a reaction order higher than 2 with respect to the concentration of nitric oxide and lower than 1 with respect to that of oxygen. This conclusion is in qualitative agreement with the results published by Treacy and Daniels2. For [O2]/[NO] << 1, the limiting Value of kexp of 1.48 (+/- 0.05) × 104 l.2/mol2 sec was found; for [O2]/[NO] >> 1 this value is 0.80 (+/- 0.05) × 104 l.2/mol2 sec.

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