Statistical-theoretical investigation of the thermal rate coefficient and branching ratio for the reaction O + HCN. -->. products

Journal Article · Thu Jul 17 04:00:00 EDT 1986 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100406a008· OSTI ID:5584352

Miller, J A; Parrish, C; Brown, N J

Using the BAC-MP4 potential surface parameters of Melius and Binkley, we have predicted the thermal rate coefficients for the two reactions: O + HCN ..-->.. NCO + H (a) and O + HCN ..-->.. NH + CO (b). Several levels of approximation are used in the theoretical treatment: a, canonical theory; b, canonical theory with Wigner tunneling correction; c, microcanonical theory (energy conserving); d, microcanonical/J-conservative theory (conserves both energy and angular momentum); e, microcanonical/J-conservative theory with one-dimensional tunneling. At high temperature the available experimental results are predicted accurately by even the crudest theoretical treatment (canonical theory). At lower temperature the theoretical predictions using the basic BAC-MP4 parameters are too low. However, adjustments to the BAC-MP4 energy barriers within their stated error limits lead to satisfactory agreement with experiment over the entire temperature range where experimental results are available (500 to 2500 K). The most important results of the investigation concern the dependence of the predictions on the level of approximation. Each successive refinement in the theory produces larger values of k/sub b/. The details of the theoretical treatment and comparisons with experiment are described in detail.

• Research Organization: Sandia National Labs., Livermore, CA
• DOE Contract Number: AC03-76SF00098
• OSTI ID: 5584352
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 90:15; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
CYANIDES
DATA
ELEMENTS
HIGH TEMPERATURE
HYDROCYANIC ACID
HYDROGEN COMPOUNDS
INFORMATION
INORGANIC ACIDS
KINETICS
MATHEMATICAL MODELS
NONMETALS
NUMERICAL DATA
OXYGEN
REACTION KINETICS
STATISTICAL MODELS
THEORETICAL DATA
VERY HIGH TEMPERATURE
YIELDS