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Kinetic investigation of the reactions of NCO radicals with alkanes in the temperature range 294 to 1113 K

✍ Scribed by Alexander Schuck; Hans-Robert Volpp; Jürgen Wolfrum

Publisher
Elsevier Science
Year
1994
Tongue
English
Weight
523 KB
Volume
99
Category
Article
ISSN
0010-2180

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✦ Synopsis

Absolute rate coefficients for the reaction of NCO radicals with methane (k 1 ), ethane (k2), and propane (k 3) were measured as a function of temperature in a heatable quartz reactor by means of the laser photolysis/laser-induced fluorescence (LP/LIF) pump-probe technique. NCO radicals were produced by the fast precursor reaction NH(aaA) + HNCO ~ NH 2 + NCO, following the 193-nm photolysis of isocyanic acid. The measured rate coefficients can be described by the following expressions: k1(512 < T < 1113 K) = 1012"995-0.12 X exp(--34.0 _+ 1.8 kJ mol -I/RT) cm 3 mol-1 s-t

(1) k2(296 < T < 922 K) = 10821 × (T/298 K) c6"89+°°2) × exp(12.2 _+ 0.5 kJ mol 1/RT) cm 3 tool-1 s 1,

(2) ks(300 < T < 849 K) = 1011"49 × (T/298 K) ~2A5+°°2) × exp( -1.8 +_ 0.4 kJ tool t/RT) cm 3 tool i s-t.

(3)

A comparison with the corresponding reactions of CN, CI, and OH radicals with alkanes suggests that all these title reactions also proceed predominantly via a hydrogen atom abstraction mechanism to form HNCO.

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