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Title: Rates and mechanism of the reactions of hydroxyl radicals with acetic, deuterated acetic, and propionic acids in the gas phase

Abstract

Rate constants for the reactions of hydroxyl radicals with the monomer and dimer of acetic acid, deuterated acetic acids, and propionic acid have been determined by a laser photolysis-resonance absorption technique. Hydroxyl radicals were generated by photolysis of the acids at 222 nm with a KrCl laser and their decay was followed by time-resolved resonance absorption. The monomers of acetic and deuterated acetic acids reacted with OH much faster than the dimers, whereas the monomer and dimer of propionic acid reacted with about equal rate constants. A primary isotope effect was observed when carboxylic but not alkyl hydrogen was substituted by deuterium in acetic acid. The results are entirely consistent with the two-channel mechanism that we proposed for the reaction of OH with formic acid. The results are interpreted in terms of the variations in C-H bond strengths and in equilibrium constants for adduct formation of the acids studied.

Authors:
; ;  [1]
  1. (National Research Council of Canada, Ottawa, Ontario (Canada))
Publication Date:
OSTI Identifier:
6724126
Alternate Identifier(s):
OSTI ID: 6724126
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of the American Chemical Society; (USA); Journal Volume: 111:14
Country of Publication:
United States
Language:
English
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; HYDROXYL RADICALS; CHEMICAL REACTIONS; ACETIC ACID; CALCULATION METHODS; DATA ANALYSIS; DEUTERIUM COMPOUNDS; EXPERIMENTAL DATA; GAS ANALYSIS; MEASURING INSTRUMENTS; MEASURING METHODS; PROPIONIC ACID; CARBOXYLIC ACIDS; DATA; HYDROGEN COMPOUNDS; INFORMATION; MONOCARBOXYLIC ACIDS; NUMERICAL DATA; ORGANIC ACIDS; ORGANIC COMPOUNDS; RADICALS 400600* -- Radiation Chemistry

Citation Formats

Singleton, D.L., Paraskevopoulos, G., and Irwin, R.S.. Rates and mechanism of the reactions of hydroxyl radicals with acetic, deuterated acetic, and propionic acids in the gas phase. United States: N. p., 1989. Web. doi:10.1021/ja00196a035.
Singleton, D.L., Paraskevopoulos, G., & Irwin, R.S.. Rates and mechanism of the reactions of hydroxyl radicals with acetic, deuterated acetic, and propionic acids in the gas phase. United States. doi:10.1021/ja00196a035.
Singleton, D.L., Paraskevopoulos, G., and Irwin, R.S.. Wed . "Rates and mechanism of the reactions of hydroxyl radicals with acetic, deuterated acetic, and propionic acids in the gas phase". United States. doi:10.1021/ja00196a035.
@article{osti_6724126,
title = {Rates and mechanism of the reactions of hydroxyl radicals with acetic, deuterated acetic, and propionic acids in the gas phase},
author = {Singleton, D.L. and Paraskevopoulos, G. and Irwin, R.S.},
abstractNote = {Rate constants for the reactions of hydroxyl radicals with the monomer and dimer of acetic acid, deuterated acetic acids, and propionic acid have been determined by a laser photolysis-resonance absorption technique. Hydroxyl radicals were generated by photolysis of the acids at 222 nm with a KrCl laser and their decay was followed by time-resolved resonance absorption. The monomers of acetic and deuterated acetic acids reacted with OH much faster than the dimers, whereas the monomer and dimer of propionic acid reacted with about equal rate constants. A primary isotope effect was observed when carboxylic but not alkyl hydrogen was substituted by deuterium in acetic acid. The results are entirely consistent with the two-channel mechanism that we proposed for the reaction of OH with formic acid. The results are interpreted in terms of the variations in C-H bond strengths and in equilibrium constants for adduct formation of the acids studied.},
doi = {10.1021/ja00196a035},
journal = {Journal of the American Chemical Society; (USA)},
number = ,
volume = 111:14,
place = {United States},
year = {Wed Jul 05 00:00:00 EDT 1989},
month = {Wed Jul 05 00:00:00 EDT 1989}
}