Absolute and relative rate constants for the reactions of hydroxyl radicals and chlorine atoms with a series of aliphatic alcohols and ethers at 298 K

✍ Scribed by Linda Nelson; Oliver Rattigan; Ruaidhri Neavyn; Howard Sidebottom; Jack Treacy; Ole John Nielsen

• Publisher: John Wiley and Sons
• Year: 1990
• Tongue: English
• Weight: 906 KB
• Volume: 22
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550221102

✦ Synopsis

Abstract

Rate constants for the gas‐phase reactions of hydroxyl radicals and chlorine atoms with aliphatic alcohols and ethers have been determined at 298 ± 2 K and at a total pressure of 1 atmosphere. The OH radical rate data were obtained using both the absolute technique of pulse radiolysis combined with kinetic UV spectroscopy and a conventional photolytic relative rate method. The Cl atom rate constants were measured using only the relative rate method. Values of the rate constants in units of 10^−12^ cm^3^ molecule^−1^ s^−1^ are:
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The above relative rate constants are based on the values of 𝓀(OH + c‐C~6~H~12~) = 7.49 × 10^−12^ cm^3^ molecule^−1^ s^−1^ and 𝓀(Cl + c‐C~6~H~12~) = 311 × 10^−12^ cm^3^ molecule^−1^ s^−1^. Attempts to corre late the trends in the rate constant data in terms of the bond dissociation energies and inductive effects are discussed.