Kinetics of the CN + HCNO Reaction

Abstract

The kinetics of the CN + HCNO reaction were studied using laser-induced fluorescence and infrared diode laser absorption spectroscopy. The total rate constant was measured to be k(T) = (3.95 +/- 0.53) x 10(-11) exp[(287.1 +/- 44.5)/T] cm3 molec(-1) s(-1), over the temperature range 298-388 K, with a value of k1 = (1.04 +/- 0.1) x 10(-10) cm3 molec(-1) s(-1) at 298 K. After detection of products and consideration of secondary chemistry, we conclude that NO + HCCN is the only major product channel.

Product Channels of the CN + HCNO Reaction

“…No experimental data has previously been reported for these reactions. We obtained upper limits for the 298 K rate constants of reactions 10−13 using standard pseudofirst order kinetics techniques, similar to our previous reports of the kinetics of HCNO with OH, 11 CN, 12 and NCO 13 radicals. For the NH + HCNO reaction, we used laser induced fluorescence (LIF) at 336 nm to monitor the decay of NH radicals produced by 266 nm Nd:YAG laser photolysis of HN 3 precursor molecules.…”

“…Many product channels are thermodynamically possible: Thermochemical information has been obtained from standard tables 24 as well as other literature for the heats of formation of HCNO, NCO, 25 HCNN, 26 HCCO, 27 NCCO, 28 and CCO. 29 In our previous experiment, 12 we detected NO products, presumably from channel 1a, and upon the addition of NO reagent, we detected CO, CO 2 , and N 2 O secondary products, which we attributed to the following secondary chemistry:…”

Theoretical studies and topological analysis of the electron density of clusters of O3 with HNCO and HCNO

“…Several experimental and computational studies on the kinetics of HCNO have been reported [16][17][18][19][20][21][22][23]. Despite the potential importance of O 3 , HNCO and HCNO we could not find neither experimental nor theoretical report on O 3 -HNCO or O 3 -HCNO interactions.…”

Product channels in the 193-nm photodissociation of HCNO (fulminic acid)

“…HCNO (fulminic acid) is the less stable isomer of isocyanic acid; the kinetics of several reactions involving HCNO has only recently been studied [3][4][5][6][7]. There is only one previous study of the photochemistry of HCNO, an infrared laser spectroscopic study from our laboratory that identified five separate photolysis channels in the 248 nm photodissociation of this molecule [8].…”