Photohydration of styrenes and phenylacetylenes. General acid catalysis and Broensted relationships
Journal Article
·
· J. Am. Chem. Soc.; (United States)
The acid-catalyzed photohydrations of a series of substituted styrenes and phenylacetylenes have been investigated in aqueous buffer solutions. General acid catalysis was clearly detected in five cases with a range of catalysts, and approximately linear Broensted plots gave ..cap alpha.. values in the range 0.14-0.18. The rate enhancements caused by excitation from S/sub 0/ to S/sub 1/ were estimated from comparisons with thermal hydration data to be in the 10/sup 11/-10/sup 15/ range. Treatment of the dependence of the rate constants for general acid catalysis (k/sub HA/) on the buffer pK/sub HA/ values with multiple regression analysis suggests that the Broensted plots are smoothly curved, as predicted by Eigen and by the Marcus equation. However, reliable values of the Broensted curvature could not be established. The possible catalytic reactivity of analogous triplet states was examined with a series of nitrosubstituted analogues, but no general acid catalysis could be detected. The factors controlling the detection of general acid catalysis in these photoreactions are discussed.
- Research Organization:
- Univ. of Toronto, Ontario
- OSTI ID:
- 5953024
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 109:19; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
ABSORPTION SPECTROSCOPY
ALKYLATED AROMATICS
AQUEOUS SOLUTIONS
AROMATICS
BROENSTED ACIDS
CATALYSIS
CATALYSTS
CATALYTIC EFFECTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMISTRY
DATA
DISPERSIONS
ENERGY LEVELS
EXCITED STATES
EXPERIMENTAL DATA
HYDRATION
HYDROCARBONS
HYDROGEN COMPOUNDS
INFORMATION
INORGANIC ACIDS
KINETICS
MIXTURES
NUMERICAL DATA
ORGANIC COMPOUNDS
PH VALUE
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
REACTION KINETICS
SOLUTIONS
SOLVATION
SPECTRA
SPECTROSCOPY
STYRENE
TOLAN
ULTRAVIOLET SPECTRA
400500* -- Photochemistry
ABSORPTION SPECTROSCOPY
ALKYLATED AROMATICS
AQUEOUS SOLUTIONS
AROMATICS
BROENSTED ACIDS
CATALYSIS
CATALYSTS
CATALYTIC EFFECTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMISTRY
DATA
DISPERSIONS
ENERGY LEVELS
EXCITED STATES
EXPERIMENTAL DATA
HYDRATION
HYDROCARBONS
HYDROGEN COMPOUNDS
INFORMATION
INORGANIC ACIDS
KINETICS
MIXTURES
NUMERICAL DATA
ORGANIC COMPOUNDS
PH VALUE
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
REACTION KINETICS
SOLUTIONS
SOLVATION
SPECTRA
SPECTROSCOPY
STYRENE
TOLAN
ULTRAVIOLET SPECTRA