The “point source” technique using upstream sampling for rate constant determinations in flame gases

Quasi-classical trajectory calculations in asymmetrically substituted polyatomic systems of the type A + CX3Y → products: the H + CH3Cl hydrogen abstraction reaction channel

“…which have very different thermochemical and kinetic properties. In our earlier paper 6 we performed several tests of consistency of the new PES, observing that they reproduce the available experimental [7][8][9][10][11][12] and theoretical [12][13][14][15] kinetics information. Firstly, high-level electronic structure calculations were performed to estimate the barrier heights of the H-and Cl-abstraction channels, (R1) and (R2) respectively, which are used as targets in the calibration process.…”

Perturbation of Moist CO Oxidation by Trace Quantities of CH3Cl

“…However, due to large disagreements between the reported values, no recommendation was made. In addition to disagreements in the overall reaction rate of CH 3CI and H, the branching factor is not well defined (Westenberg and deHaas, 1975;Hart et al, 1974). Recently, Tsang (1990) has argued that the contribution from the H 2 product channel could be significant.…”

“…In a recent survey (Senkan, 1993), a three parameter rate expression has been suggested for reaction (1) in order to fit the lower temperature data (326-652 K) of Downloaded by [McGill University Library] at 00:43 21 November 2014 Aders et al (1975) and the higher temperature data (870-1088 K) of Hart et al (1974). The present detailed kinetic mechanism uses the rate expression from Hart et al (1974) for reaction (1) and specifies a backward estimated rate constant for reaction (2).…”

“…The present detailed kinetic mechanism uses the rate expression from Hart et al (1974) for reaction (1) and specifies a backward estimated rate constant for reaction (2). Hence the rate constant of reaction (2) is calculated from the principles of detailed balancing.…”

“…Reactions from the CO/H20/OdHCI subset were assumed to form a validated and unchangeable set based on previous work (Roesler et al,I992b). The rate expression for reaction (I) obtained by Aders et al (1975) was fit with a three parameter expression by using a pre-exponential temperature dependency ofT"o, such that the total rate of CH 3Cl + H -> products matched the rate expression obtained by Hart et al (1974) at 1000 K. The three parameter rate expression for reaction (4) was modified by adjusting the pre-exponential factor and activation energy to fit the data of Jeong et al (1984) from 247 to 483 K, while maintaining a pre-exponential temperature dependency of T'·6. The pre-exponential factor in the rate expression for reaction (9) was decreased by a factor 2.5 to compensate for the change in reaction time generated by the previous alterations, and also to reduce the production of formaldehyde.…”