Journal of the Chemical Society - Faraday Transactions p. 4377 - 4384 (1996)
Update date:2022-08-02
Topics:
Campbell, Mark L.
The gas-phase reactivity of Ru(a 5F5) with N2O and O2 in the temperature range 296-623 K is reported. Ruthenium atoms were produced by the photodissociation of ruthenocene and detected by laser-induced fluorescence. The reaction rate of the ground a 5F5 state with N2O is very slow and temperature dependent. The bimolecular rate constant exhibits marked non-Arrhenius behaviour. The rate constants are described by the empirical relation ln(k) = (-54.4 ± 0.2) + (3.95 ± 0.04)ln T or, alternatively, by the biexponential relation k(T) = (1.3 ± 0.3) × 10-12 exp(-11.1 ± 0.5 kJ mol-1/RT) + (1.9 ± 1.9) × 10-10 exp(-37.8 ± 5.7 kJ mol-1/RT) cm3 s-1 where the uncertainties are ±σ. The disappearance rates in the presence of N2O are independent of buffer gas identity (Ar or N2) and total pressure indicating a bimolecular abstraction mechanism. The reaction rate of the a 5F5 state with O2 is pressure dependent and decreases with increasing temperature indicating adduct formation. The limiting low-pressure third-order, k0, and limiting high-pressure second-order, k∞, room-temperature rate constants in argon buffer are (5.2 ± 0.7) × 10-29 cm6 s-1 and (2.8 ± 0.2) × 10-11 cm3 s-1, respectively. In N2, k0 and k∞ are (1.1 ± 0.2) × 10-28 cm6 s-1 and (6.3 ± 0.3) × 10-11 cm3 s-1, respectively. An upper limit of 498 kJ mol-1 is established for the bond energy of RuO(g) based on the lack of a bimolecular reaction for Ru(g) with O2.
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