Cobalt bromide catalysis of the oxidation of organic compounds. II. Chain propagation reactions involving cobaltous ions
Oxygen absorption and chemiluminescence kinetic data were used to study the contribution of reactions of peroxide radicals with cobaltous ions RO/sub 2/ + Co(II)/sup H+/ ROOH + Co(III) in chain propagation upon the oxidation of alkylaromatic hydrocarbons with a cobalt bromide catalyst. (RO/sub 2/) increases linearly with an increase in (Co(II)). Comparison of the rate of formation of ROOH and the rate of O/sub 2/ absorption showed the formation of ROOH in the reactions of RO/sub 2/ with Co(II). The dependences of WO/sub 2/ on (Co(II)), (NaBr), and temperature in the range from 40 to 90/sup 0/C gave the rate constants for the reactions of RO/sub 2/ with Co(OAc)/sub 2/ and with CoOAcBr: 1 x 10/sup 7/ exp(-31 kJ/RT) liters/mole x sec and 2.5 x 10/sup 6/ exp(-16 kJ/RT) for ethylebenzene, 1.3 x 10/sup 9/ exp(-41 kJ/RT), and 3.8 x 10/sup 6/ exp(-21 kJ/RT) for p-xylene, and 1.5 x 10/sup 9/ exp(-42 kJ/RT) and 3.3 x 10/sup 6/ exp(-21 kJ/RT) for toluene. Reactions of RO/sub 2/ species with Co(OAc)/sub 2/ occur in the absence of bromide ions in the initial, non-steady-state oxidation step.
- OSTI ID:
- 5886775
- Journal Information:
- Kinet. Catal. (Engl. Transl.); (United States), Journal Name: Kinet. Catal. (Engl. Transl.); (United States) Vol. 27:5; ISSN KICAA
- Country of Publication:
- United States
- Language:
- English
Similar Records
Temperature-dependent rate constants for the reactions of gas-phase lanthanides with O{sub 2}
Kinetics of the high temperature reaction of CO with N/sub 2/O
Related Subjects
400201* -- Chemical & Physicochemical Properties
ACTIVATION ENERGY
AROMATICS
BROMIDES
BROMINE COMPOUNDS
CATALYSIS
CATALYSTS
CATALYTIC EFFECTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMILUMINESCENCE
COBALT BROMIDES
COBALT COMPOUNDS
ELEMENTS
ENERGY
HALIDES
HALOGEN COMPOUNDS
HOMOGENEOUS CATALYSIS
HYDROGEN COMPOUNDS
HYDROGEN PEROXIDE
KINETICS
LUMINESCENCE
NONMETALS
ORGANIC COMPOUNDS
OXIDATION
OXIDIZERS
OXYGEN
OXYGEN COMPOUNDS
PEROXIDES
PEROXY RADICALS
QUANTITY RATIO
RADICALS
REACTION KINETICS
REDOX POTENTIAL
REDUCTION
TRANSITION ELEMENT COMPOUNDS
VALENCE