pK estimates for weak CH acids from the electrochemical reduction rate constants of their radicals to carbanions
Laser-pulse electron photoemission was used to measure the rate constants, W/sub 3/(E), of one-electron reduction of methyl radicals and their halide derivatives (CH/sub 3/, CH/sub 2/Cl, CHF/sub 2/, CHFCl, CHCl/sub 2/, CF/sub 3/, CF/sub 2/Cl, CFCl/sub 2/, and CCl/sub 3/) to the carbanions at mercury as functions of electrode potential. The functions W/sub 3/(E) are characterized by similar transfer coefficients (0.45 +/- 0.05); the range of E-values where identical W/sub 3/-values are found within the region of 10/sup 3/-10/sup 5/ sec/sup -1/ extends from -1.7 to 0 V. Assuming equal changes in the values of equilibrium potential and of E the pK values were calculated for the series listed, and found to be 47, 39, 37, 32, 31, 30, 23, 20, and 15 for the CH acids of the corresponding carbanions.
- Research Organization:
- Institute of Chemical Physics, Moscow (USSR)
- OSTI ID:
- 7005236
- Journal Information:
- Sov. Electrochem. (Engl. Transl.); (United States), Journal Name: Sov. Electrochem. (Engl. Transl.); (United States) Vol. 23:6; ISSN SOECA
- Country of Publication:
- United States
- Language:
- English
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400201* -- Chemical & Physicochemical Properties
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75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY
ALKYL RADICALS
ANIONS
CARBANIONS
CARBOXYLIC ACIDS
CATALYSIS
CATALYSTS
CATALYTIC EFFECTS
CHARGED PARTICLES
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
CHLORINATED ALIPHATIC HYDROCARBONS
ELECTROCATALYSTS
ELECTROLYSIS
ELECTROMAGNETIC RADIATION
ELECTRON EMISSION
ELECTRON TRANSFER
ELEMENTS
EMISSION
EQUILIBRIUM
FLUORINATED ALIPHATIC HYDROCARBONS
HALOGENATED ALIPHATIC HYDROCARBONS
HETEROGENEOUS CATALYSIS
IONS
KINETICS
LASER RADIATION
LASERS
LYSIS
MERCURY
METALS
METHYL RADICALS
NEODYMIUM LASERS
ORGANIC ACIDS
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC FLUORINE COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
PHOTOEMISSION
RADIATIONS
RADICALS
REACTION KINETICS
REDUCTION
SECONDARY EMISSION
SOLID STATE LASERS
YIELDS