Kinetics of the reaction CH + N2 rarr;[M]?[M] products in the range 10-620 torr and 298-1059 K

The CH + N2 Association Reaction at Low Temperatures: Ab Initio MO/VRRKM-Theory Analysis of Temperature and Pressure Effects

“…As one can see, at 100 Torr there are experimental measurements by four groups [2,[4][5][6] that agree quite well with one another. This agreement becomes illuminated when theory is invoked.…”

“…These results have since been corroborated by several independent studies [3][4][5][6][7][8][9][10], including the recent very low temperature measurement by Smith and co-workers [7,10] employing a CRESU (Reaction Kinetics under Uniform Supersonic Flow) system. The HCNN adduct has been commonly considered as the precursor of the HCN + N( 4 S) products first proposed by Fenimore in 1971 to be a potential source of "prompt NO" in hydrocarbon combustion [11].…”

“…4). At 20 Torr the theoretical estimate is about a factor of 3 lower than Becker's [5] data which, in addition, starts to curve up too early compared with the theoretical expectation. In fact, a similar relation between the Becker's data and the theory can be found on the 100 Torr graph; however, because of more available data at 100 Torr the overall agreement seems almost quantitative.…”

“…Plot of the pressure dependence of the CH + N 2 association rate constant for temperatures of 52-54 K and 294-300 K. The solid curves denote VRRKM result at the E, J -resolved level; the dotted curve corresponds to VRRKM result at the E-resolved level. Experimental data: open circles, [5]; filled circles, [6]; crosses, [2]; open squares, [8]; filled squares, [9]; open triangles, [4]; stars, [10]; open diamonds, [29].…”

HNNC Radical and Its Role in the CH + N2 Reaction

“…[1][2][3][4] At the high temperatures of combustion environments, the reaction is believed to be dominated by pathways that lead to the production of the "prompt" NO seen in flames. 5 Initially, a spin-forbidden pathway in which HCN (X 1 Σ + ) + N( 4 S) are produced had been postulated, [6][7][8][9][10][11][12][13][14] whereas more recently, Lin and co-workers 15 proposed that the dominant route in combustion produces H + NCN ( 3 Σ -g ) in a spin-allowed process that passes through an HNCN intermediate. Further theoretical and experimental studies have supported the spin-allowed pathway.…”