Rate constants for the gas-phase reaction of OH with amines: Tert-butyl amine, 2,2,2-trifluoroethyl amine, and 1,4-diazabicyclo[2.2.2]octane
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Rate constants for the gas-phase reaction of OH with amines : Tert-butyl amine, 2,2,2-trifluoroethyl amine, and 1,4-diazabicyclo[2.2.2]octane. / Koch, Robert; Krüger, Heinz-Ulrich; Elend, Manfred et al.
in: International Journal of Chemical Kinetics, Jahrgang 28, Nr. 11, 1996, S. 807-815.Publikation: Beiträge in Zeitschriften › Zeitschriftenaufsätze › Forschung › begutachtet
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TY - JOUR
T1 - Rate constants for the gas-phase reaction of OH with amines
T2 - Tert-butyl amine, 2,2,2-trifluoroethyl amine, and 1,4-diazabicyclo[2.2.2]octane
AU - Koch, Robert
AU - Krüger, Heinz-Ulrich
AU - Elend, Manfred
AU - Palm, W. U.
AU - Zetzsch, Cornelius
PY - 1996
Y1 - 1996
N2 - The title compounds were selected to test the current predictions of OH reaction rate constants. The reactions are studied employing flash photolysis/resonance fluorescence in 130 mbar He at room temperature and up to 420 K. Experimental difficulties were encountered due to the polar and hygroscopic properties of the compounds. The rate constants obtained at 298 K, 12, 0.9, and 22 · 10-12 cm3/s for tert-Butyl amine (TBA), 2,2,2-Trifluoroethyl amine (TFEA), and 1.4-Diazabicyclo[2.2.2]octane (DABCO®), respectively, are much lower (up to a factor > 20) than calculated with the incremental system devised by Atkinson, indicating that electronic and steric effects should not be neglected. Activation energies are slightly negative for TBA and DABCO and some +450 K for TFEA. The reactivity of TFEA was also determined (as 1.2 · 10-12cm3/s) relative to a set of hydrocarbons employing continuous photolysis of H2O2 in a glass chamber.
AB - The title compounds were selected to test the current predictions of OH reaction rate constants. The reactions are studied employing flash photolysis/resonance fluorescence in 130 mbar He at room temperature and up to 420 K. Experimental difficulties were encountered due to the polar and hygroscopic properties of the compounds. The rate constants obtained at 298 K, 12, 0.9, and 22 · 10-12 cm3/s for tert-Butyl amine (TBA), 2,2,2-Trifluoroethyl amine (TFEA), and 1.4-Diazabicyclo[2.2.2]octane (DABCO®), respectively, are much lower (up to a factor > 20) than calculated with the incremental system devised by Atkinson, indicating that electronic and steric effects should not be neglected. Activation energies are slightly negative for TBA and DABCO and some +450 K for TFEA. The reactivity of TFEA was also determined (as 1.2 · 10-12cm3/s) relative to a set of hydrocarbons employing continuous photolysis of H2O2 in a glass chamber.
KW - Chemistry
UR - http://www.scopus.com/inward/record.url?scp=0030286117&partnerID=8YFLogxK
U2 - 10.1002/(SICI)1097-4601(1996)28:11<807::AID-KIN3>3.0.CO;2-R
DO - 10.1002/(SICI)1097-4601(1996)28:11<807::AID-KIN3>3.0.CO;2-R
M3 - Journal articles
AN - SCOPUS:0030286117
VL - 28
SP - 807
EP - 815
JO - International Journal of Chemical Kinetics
JF - International Journal of Chemical Kinetics
SN - 0538-8066
IS - 11
ER -