Pulse Radiolysis Studies. XVI. Kinetics of the Reaction of Gaseous Hydrogen Atoms with Molecular Oxygen by Fast Lyman-α Absorption Spectrophotometry

Abstract

The pulse radiolysis method has been used to produce ground-state hydrogen atoms in gaseous hydrogen and has been combined with fast Lyman-α absorption spectrophotometry to observe these atoms directly with microsecond time resolution. The technique has been used to study the kinetics of the reaction H + O2 + M = HO2 + M, where M is H2. The rate constant for this reaction was found to have the value (1.7 ± 0.4) × 1010M−2·sec−1 at 298°K. This value, together with earlier data for Ar as third body, gives kH2 / kAr = 2.0 at 298°K for the ratio of the efficiencies of H2 and Ar as third body in this reaction.

Applications of Pulse Radiolysis to Protein Chemistry

“…The early instrumentation has been described by McCarthy & MacLachlan (i960), Boag (1963), Dorfman (1963), and Keene (1964). Technical improvements have resulted in increased time resolution from the initial microsecond to the pico-second range (Hunt & Thomas, 1967;Hunt, Greenstock & Bronskill, 1972;Bronskill et al 1970) and in detection devices for other than the visible spectral region -the vacuum ultraviolet (Bishop & Dorfman, 1970), and ultraviolet (Gordon, Hart & Thomas, 1964); the infrared (Dorfman, Jou & Wageman, 1971); electron spin resonance (Fessenden, 1964;and Smaller, Remko & Avery, 1968); and solution conductivity (Schmidt & Buck, 1966).…”

Application of pulse radiolysis methods to study the reactions and structure of biomolecules

“…Continuing technical advances, especially the development of solid-state photodetectors, limit the value of a more extensive description of the performance of optical detection systems currently being used to study the formation and behaviour of radiation-induced transients. The wavelength range which has been utilised covers the vacuum ultraviolet, 122 nm for gas-phase work (Bishop and Dorfman 1970) through 2 188 nm for solutions (Nielsen et a1 1976) to -5 pm in the infrared in a recent study of gas-phase hydration of protons (Schwarz et a1 1977). I n the near-infrared a variety of detectors have been used with varying degrees of sensitivity and time response (Richards and Thomas 1970, Michael et a1 1971, Klassen et al 1972, Baxendale and Wardman 1973, Seddon et a1 1973, Jou and Dorfman 1973, Baxendale et a1 1974a, Teather et a1 1976, Hunt 1976, Beck 1976).…”

Pulse Radiolysis Studies. XX. Kinetics of Some Addition Reactions of Gaseous Hydrogen Atoms by Fast Lyman-α Absorption Spectrophotometry

“…This method, fully described in our earlier report! on the reaction H+02+H2=H02+H2, (1) has now been extended to an investigation of the reactions H+CO+M=HCO+M,…”