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

TY - JOUR

T1 - 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

AU - Nelson, Linda

AU - Rattigan, Oliver

AU - Neavyn, Ruaidhri

AU - Sidebottom, Howard

AU - Treacy, Jack

AU - Nielsen, Ole John

PY - 1990/1/1

Y1 - 1990/1/1

N2 - 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 cm3 molecule−1 s−1 are: (Formula Presented.) The above relative rate constants are based on the values of 퓀(OH + c‐C6H12) = 7.49 × 10−12 cm3 molecule−1 s−1 and 퓀(Cl + c‐C6H12) = 311 × 10−12 cm3 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.

AB - 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 cm3 molecule−1 s−1 are: (Formula Presented.) The above relative rate constants are based on the values of 퓀(OH + c‐C6H12) = 7.49 × 10−12 cm3 molecule−1 s−1 and 퓀(Cl + c‐C6H12) = 311 × 10−12 cm3 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.

UR - http://www.scopus.com/inward/record.url?scp=0025509979&partnerID=8YFLogxK

U2 - 10.1002/kin.550221102

DO - 10.1002/kin.550221102

M3 - Journal article

AN - SCOPUS:0025509979

SN - 0538-8066

VL - 22

SP - 1111

EP - 1126

JO - International Journal of Chemical Kinetics

JF - International Journal of Chemical Kinetics

IS - 11

ER -