Reduction of dimensionality in radical decay kinetics induced by micellar systems. [Electron pulse radiolysis; cetyltrimethylammonium bromide; examination and separation of bulk vs surface diffusion]
The dismutation reaction of Br/sub 2//sup -/ ion radicals in aqueous solution was studied in the presence of micellar cetyltrimethylammonium bromide (CTAB) by pulse radiolysis technique. Two kinetic processes involving the Br/sub 2//sup -/ radicals were identified: two-dimensional intramicellar surface diffusion and three-dimensional intermicellar (or solution bulk type) diffusion with respective rate constants of 2.1 x 10/sup 6/ s/sup -1/ and 1.46 x 10/sup 9/ M/sup -1/ s/sup -1/. The CTAB/Br/sub 2//sup -/ system represents the first example in which two kinetic components of a diffusion-controlled reaction differing in dimensionality of reaction space can be distinguished. Reduction of dimensionality dramatically increases the probability of reaction. Random-walk theory for two- and three-dimensional lattices with traps is invoked to explain these results.
- Research Organization:
- Univ. of Notre Dame, IN
- OSTI ID:
- 7185322
- Journal Information:
- J. Am. Chem. Soc.; (United States), Vol. 98:11
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
BROMINE
CHEMICAL REACTION KINETICS
MICELLAR SYSTEMS
CATALYTIC EFFECTS
QUATERNARY COMPOUNDS
RADIOLYSIS
SODIUM BROMIDES
ANIONS
AQUEOUS SOLUTIONS
CATALYSTS
DECAY
DIFFUSION
ALKALI METAL COMPOUNDS
AMINES
AMMONIUM COMPOUNDS
BROMIDES
BROMINE COMPOUNDS
CHARGED PARTICLES
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
CHEMISTRY
DECOMPOSITION
DISPERSIONS
ELEMENTS
HALIDES
HALOGEN COMPOUNDS
HALOGENS
IONS
KINETICS
MIXTURES
NONMETALS
ORGANIC COMPOUNDS
RADIATION CHEMISTRY
RADIATION EFFECTS
REACTION KINETICS
SODIUM COMPOUNDS
SOLUTIONS
400600* - Radiation Chemistry