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Studies of the reactions of hydrogen atoms by time-resolved E. S. R. spectroscopy

Abstract

Time-resolved e.s.r. spectroscopy has been used to follow directly the reactions of H atoms produced by pulse radiolysis of acid solutions. Detailed analysis of the time profile of the e.s.r. signal was carried out by means of modified Bloch equations. The increased signal found when a scavenger for OH such as t-butyl alcohol is present is shown to be mainly the result of slower H atom decay by radical-radical reaction. The reaction H + OH does not appear to produce any signal polarization. The decay curves observed in the presence of solute are readily accounted for by the treatment, and good plots of pseudo first-order rate constant against solute concentration are obtained. The absolute rate constants for reaction with H atoms are for methanol 2.5 x10/sup 6/, for ethanol 2.1 X 10/sup 7/, for isopropanol 6.8 x 10/sup 7/, and for succinic acid 3.0 x 10/sup 6/ dm/sup 3/ mol/sup -1/s/sup -1/. These values are in good agreement with the earlier chemical measurements.
Authors:
Fessenden, R W; Verma, N C [1] 
  1. Carnegie-Mellon Univ., Pittsburgh, Pa. (USA). Dept. of Chemistry
Publication Date:
Jan 01, 1977
Product Type:
Journal Article
Reference Number:
AIX-09-357147; EDB-78-033241
Resource Relation:
Journal Name: Faraday Discuss. Chem. Soc.; (United Kingdom); Journal Volume: 63
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; HYDROGEN; ELECTRON SPIN RESONANCE; INORGANIC ACIDS; RADIOLYSIS; AQUEOUS SOLUTIONS; BLOCH EQUATIONS; BUTANOLS; CHEMICAL REACTION KINETICS; DECAY; ELECTRONS; ETHANOL; METHANOL; PROPANOLS; RADICALS; SCAVENGING; SUCCINIC ACID; ALCOHOLS; CARBOXYLIC ACIDS; CHEMICAL RADIATION EFFECTS; CHEMICAL REACTIONS; CHEMISTRY; CRYOGENIC FLUIDS; DECOMPOSITION; DICARBOXYLIC ACIDS; DISPERSIONS; ELEMENTARY PARTICLES; ELEMENTS; EQUATIONS; FERMIONS; FLUIDS; HYDROGEN COMPOUNDS; HYDROXY COMPOUNDS; KINETICS; LEPTONS; MAGNETIC RESONANCE; MIXTURES; NONMETALS; ORGANIC ACIDS; ORGANIC COMPOUNDS; RADIATION CHEMISTRY; RADIATION EFFECTS; REACTION KINETICS; RESONANCE; SOLUTIONS; 400600* - Radiation Chemistry
OSTI ID:
5311329
Country of Origin:
United Kingdom
Language:
English
Other Identifying Numbers:
Journal ID: CODEN: FDCSB
Submitting Site:
INIS
Size:
Pages: 104-111
Announcement Date:

Citation Formats

Fessenden, R W, and Verma, N C. Studies of the reactions of hydrogen atoms by time-resolved E. S. R. spectroscopy. United Kingdom: N. p., 1977. Web. doi:10.1039/dc9776300104.
Fessenden, R W, & Verma, N C. Studies of the reactions of hydrogen atoms by time-resolved E. S. R. spectroscopy. United Kingdom. doi:10.1039/dc9776300104.
Fessenden, R W, and Verma, N C. 1977. "Studies of the reactions of hydrogen atoms by time-resolved E. S. R. spectroscopy." United Kingdom. doi:10.1039/dc9776300104. https://www.osti.gov/servlets/purl/10.1039/dc9776300104.
@misc{etde_5311329,
title = {Studies of the reactions of hydrogen atoms by time-resolved E. S. R. spectroscopy}
author = {Fessenden, R W, and Verma, N C}
abstractNote = {Time-resolved e.s.r. spectroscopy has been used to follow directly the reactions of H atoms produced by pulse radiolysis of acid solutions. Detailed analysis of the time profile of the e.s.r. signal was carried out by means of modified Bloch equations. The increased signal found when a scavenger for OH such as t-butyl alcohol is present is shown to be mainly the result of slower H atom decay by radical-radical reaction. The reaction H + OH does not appear to produce any signal polarization. The decay curves observed in the presence of solute are readily accounted for by the treatment, and good plots of pseudo first-order rate constant against solute concentration are obtained. The absolute rate constants for reaction with H atoms are for methanol 2.5 x10/sup 6/, for ethanol 2.1 X 10/sup 7/, for isopropanol 6.8 x 10/sup 7/, and for succinic acid 3.0 x 10/sup 6/ dm/sup 3/ mol/sup -1/s/sup -1/. These values are in good agreement with the earlier chemical measurements.}
doi = {10.1039/dc9776300104}
journal = {Faraday Discuss. Chem. Soc.; (United Kingdom)}
volume = {63}
journal type = {AC}
place = {United Kingdom}
year = {1977}
month = {Jan}
}