Pulse radiolysis of aqueous solutions of benzyltrialkylammonium cations: reactions with the primary transients from water radiolysis

Journal Article · Thu Feb 19 04:00:00 EST 1981 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j150604a016· OSTI ID:6507518

Bobrowski, K

The primary reactions of hydrogen atoms, hydrated electrons, hydroxyl radicals, and oxide radical ions with benzyltrimethylammonium cations in aqueous solutions have been studied by the technique of pulse radiolysis. Hydrogen atoms react with the rate constant (2.0 +- 0.1) x 10/sup 9/ M/sup -1/ s/sup -1/. The cyclohexadienyl-type radical decayed in a second-order process with a rate constant 2k = (4.8 +- 0.2) x 10/sup 9/ M/sup -1/ s/sup -1/. Hydrated electrons react with a rate constant (4.3 +- 0.2) x 10/sup 9/ M/sup -1/ s/sup -1/ to form benzyl radical. It has been concluded that irradation of benzyltrimethylammonium cations results in deamination brought about by hydrated electrons. Hydroxyl radicals react with benzyltrimethylammonium cation with a rate constant (5.0 +- 0.6) x 10/sup 9/ M/sup -1/ s/sup -1/ to form the cyclohexadienyl-type radical HOC/sub 6/H/sub 5/CH/sub 2/N/sup +/(CH/sub 3/)/sub 3/ (approx. 65%) and C/sub 6/H/sub 5/CHN/sup +/(CH/sub 3/)/sub 3/ (approx. 35%) radicals. The cyclohexadienyl radical has a broad absorption maximum at 325 nm (epsilon approx. = 3300 M/sup -1/ cm/sup -1/). Oxide radical ions react with the rate constant (5.9 +- 0.5) x 10/sup 8/ M/sup -1/ s/sup -1/ to form C/sub 6/H/sub 5/CHN/sup +/(CH/sub 3/)/sub 3/ with absorption maxima at 260 and 305 nm. With the increasing chain length of the alkyl substituent (as in the benzyltri-n-butylammonium cation) the reaction of hydrogen abstraction from the alkyl groups becomes more important.

• Research Organization: Univ. of Notre Dame, IN
• OSTI ID: 6507518
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 85:4; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400600* -- Radiation Chemistry
AMINES
AMMONIUM COMPOUNDS
AQUEOUS SOLUTIONS
CHALCOGENIDES
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
CHEMISTRY
DATA
DECOMPOSITION
DISPERSIONS
ELECTRONS
ELEMENTARY PARTICLES
EXPERIMENTAL DATA
FERMIONS
HYDROGEN COMPOUNDS
HYDROXYL RADICALS
INFORMATION
IRRADIATION
KINETICS
LEPTONS
MIXTURES
NUMERICAL DATA
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PULSED IRRADIATION
QUATERNARY COMPOUNDS
RADIATION CHEMISTRY
RADIATION EFFECTS
RADICALS
RADIOLYSIS
REACTION KINETICS
SOLUTIONS
WATER