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Pressure and temperature dependence of reactions proceeding via a bound complex. An approach for combustion and atmospheric chemistry modelers. Application to HO + CO → [HOCO] → H + CO 2
Author(s) -
Larson C. W.,
Stewart P. H.,
Golden D. M.
Publication year - 1988
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550200105
Subject(s) - chemistry , reaction rate constant , thermodynamics , combustion , equilibrium constant , kinetics , atmospheric pressure , constant (computer programming) , computational chemistry , meteorology , classical mechanics , physics , computer science , programming language
Elementary bimolecular processes that involve formation of a chemically activated intermediate species are common. We address the general problem of modeling these processes and describe the necessary and sufficient information that must be specified to assure that a kinetics model will extrapolate the rate constants for those reactions over wide ranges of temperature and pressure. The approach is illustrated for the system centered around the HOCO intermediate. Here, specification of the temperature and pressure dependence of three rate constants, k ( T , P ) and the temperature dependence of two equilibrium constants, K ( T ), is necessary and sufficient, viz:Rate constants are cast in the form of an analytical expression, suggested by Troe, and appropriate parameters are tabulated.