Kinetic investigation of the reactions of NCO radicals with alkanes in the temperature range 294 to 1,113 K

Conference · Thu Dec 01 04:00:00 EST 1994 · Combustion and Flame; (United States)

OSTI ID:6627681

Schuck, A; Volpp, H R; Wolfrum, J ^[1]

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1. Univ. of Heidelberg (Germany). Physikalisch-Chemisches Inst.

Absolute rate coefficients for the reaction of NCO radicals with methane (k[sub 1]), ethane (k[sub 2]), and propane (k[sub 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(a[sup 1] [Delta]) + HNCO [yields] NH[sub 2] + NCO, following the 193-nm photolysis of isocyanic acid. The measure rate coefficients can be described by the following expressions: k[sub 1](512 < T < 1,113 K) = 10[sup 12.99 [+-] 0.12] [times] exp(-34.0[+-]1.8 kJ/mol/RT) cm[sup 3]/mol s; k[sub 2](296 < T < 922 K) = 10[sup 8.21] [times] (T/298 K)[sup (6.89[+-]0.02)] [times] exp(12.2[+-]0.5 kJ/mol/RT)cm[sup 3]/mol s; and k[sub 3](300 < T < 849 K) = 10[sup 11.49] [times] (T/298 K)[sup (2.15[+-]0.02)] [times] exp(-1.8[+-]0.4 kJ/mol/RT)cm[sup 3]/mol s. A comparison with the corresponding reactions of CN, Cl, and OH radicals with alkanes suggests that all these title reactions also proceed predominantly via a hydrogen atom abstraction mechanism to form HNCO.

• OSTI ID: 6627681
• Report Number(s): CONF-940711--
• Conference Information: Journal Name: Combustion and Flame; (United States) Journal Volume: 99:3-4
• Country of Publication: United States
• Language: English

Related Subjects

02 PETROLEUM
025000 -- Petroleum-- Combustion
03 NATURAL GAS
034000 -- Natural Gas-- Combustion
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400800* -- Combustion
Pyrolysis
&amp; High-Temperature Chemistry
ACTIVATION ENERGY
AIR POLLUTION CONTROL
ALKANES
CHALCOGENIDES
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
COMBUSTION KINETICS
CONTROL
DIAGNOSTIC TECHNIQUES
ENERGY
ETHANE
FUELS
HYDROCARBONS
ISOCYANATES
KINETICS
METHANE
NITROGEN COMPOUNDS
NITROGEN OXIDES
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
POLLUTION CONTROL
PROPANE
REACTION KINETICS
YIELDS