Product Channels of the HCCO + NO Reaction

Abstract

The product branching ratio of the HCCO + NO reaction was investigated using the laser photolysis/infrared absorption technique. Ethyl ethynyl ether (C(2)H(5)OCCH) was used as the HCCO radical precursor. Transient infrared detection of CO, CO(2), and HCNO products was used to determine the following branching ratios at 296 K: phi(CO+HCNO) = 0.78 +/- 0.04 and phi(CO(2)+HCN) = 0.22 +/- 0.04. These values are in good agreement with some recent ab initio calculations.

Modeling nitrogen chemistry in combustion

“…has been characterized experimentally in a number of studies [312314,324328] and both the overall rate constant and the branching fraction is fairly well established. Measurements of the branching fraction indicate that the HCNO + CO channel (R91) dominates, with reported yields of 64-88% [313,314,326,327]. We have combined the total rate coecient measurement of Carl et al [312] with the reported branching fraction, which appears to be independent of temperature [313,314], to arrive at the rate coecients used in the present work.…”

A density functional investigation of the reaction mechanism of H2O + HCNO

“…of Path P 6 . Therefore, the pathway P 6 can proceed much more easily than P 6 , to be considered as a major product channel.…”

“…The PES in Figure 5 shows that the pathway P 6 takes the common division R → d as starting step Path P 6 : where the CO molecule keeps unchanged in the sub process 1 → P 6 The pathway R(0.0) → e(−27.2) to products P 6 involves a very high-energy transition state f/1 as is therefore not expected to be important. An alternative pathway is suggested: Path P 6 :…”

“…As shown in PES in Figure 5, there is a possible way involving a few steps, i.e., through the pathway P 6 , across the transition state P 6 /P 2 and down to the product P 2 (CO + NH 2 + OH), such that Path P 2 where the notation R → P 6 stands for the pathway P 6 for convenience. The energy of this subprocess of Path P 6 possesses enough energy to cross the transition state P 6 /P 2 to produce the product P 2 (CO + NH 2 + OH).…”

“…HCNO is formed in combustion primarily by the CH 2 + NO [2][3][4][5] and HCCO + NO [6][7][8][9][10][11] reactions, and can be synthesized by vacuum pyrolysis of 3-phenyl-4-oximinoisoxazol-5(4H)-one [12][13][14]. Several experimental [15][16][17][18] and computational studies [19][20][21] on the kinetics of HCNO have been reported.…”