A computational analysis of a chemical switch mechanism. Catalysis-inhibition on effects in a copper surface-catalyzed oxidation
A reaction scheme was designed for the tert.-butyl hydroperoxide-initiated autoxidation of hexadecane at 100/sup o/C, which was inhibited by small amounts of copper and accelerated by copper in excess of a critical ratio of initial hydroperoxide concentration to copper surface area. The model consisted of a homogeneous reaction set of 53 steps based on well-known free-radical oxidation, and a surface reaction set of 34 steps based on a proposed competition for trapping of hydroperoxide at inhibition and catalysis surface sites. A computational procedure for numerical solution of the mass-action differential equations by the Gear integration technique was used. The homogeneous mechanism correctly predicted the observed oxidation rates and insensitivity to initial hydroperoxide concentrations in the absence of copper. The surface mechanism, tested with various initial conditions and rate parameters, gave results in agreement with experiment for the following phenomna: location of the switch point of the mechanism, the shape of the reaction curve, and the insensitivity of the rate to the hydroperoxide concentration above the switch point. Graphs, tables, and 15 references.
- Research Organization:
- Bell Lab.
- OSTI ID:
- 5641507
- Report Number(s):
- CONF-770301-
- Journal Information:
- J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 81:25; ISSN JPCHA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
CATALYSIS
CATALYSTS
CATALYTIC EFFECTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COPPER
CORROSION
DIFFERENTIAL CALCULUS
ELEMENTS
HYDROCARBONS
INHIBITION
INTEGRAL CALCULUS
KINETICS
MATHEMATICS
METALS
ORGANIC COMPOUNDS
OXIDATION
RADICALS
REACTION KINETICS
SURFACE PROPERTIES
TRANSITION ELEMENTS