First rate constants reactions of OH radicals with amides
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in: International Journal of Chemical Kinetics, Jahrgang 29, Nr. 2, 1997, S. 81-87.
Publikation: Beiträge in Zeitschriften › Zeitschriftenaufsätze › Forschung › begutachtet
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TY - JOUR
T1 - First rate constants reactions of OH radicals with amides
AU - Koch, Robert
AU - Palm, Wolf-Ulrich
AU - Zetzsch, Cornelius
PY - 1997
Y1 - 1997
N2 - Rate constants have been measured for the reaction of OH radicals with four amides, R1N(CH3)-C(O)R2 (R1 = H or Methyl, R2 = Methyl or Ethyl), at 300 and 384 K using flash photolysis/resonance fluorescence. Reactants are introduced under slow flow conditions and are controlled by two independent methods, gas saturation and continuous injection. It turns out that the reactivities of the amides are considerably lower than those of the corresponding amines. The pattern of rate constants obtained at 300 K: 14, 21, 5.2, and 7.6 · 10-12 cm3/s for N,N-Dimethylacetamide (dmaa), N,N-Dimethylpropionamide (dmpa), N-Methylacetamide (maa), and N-Methylpropionamide (mpa), respectively, indicates a single, dominating reaction center and strong electronic effects of the substituents at both sides of the amide function. Correspondingly, the observed negative temperature dependence (E/R= - 400 to - 600 K) excludes a direct abstraction mechanism.
AB - Rate constants have been measured for the reaction of OH radicals with four amides, R1N(CH3)-C(O)R2 (R1 = H or Methyl, R2 = Methyl or Ethyl), at 300 and 384 K using flash photolysis/resonance fluorescence. Reactants are introduced under slow flow conditions and are controlled by two independent methods, gas saturation and continuous injection. It turns out that the reactivities of the amides are considerably lower than those of the corresponding amines. The pattern of rate constants obtained at 300 K: 14, 21, 5.2, and 7.6 · 10-12 cm3/s for N,N-Dimethylacetamide (dmaa), N,N-Dimethylpropionamide (dmpa), N-Methylacetamide (maa), and N-Methylpropionamide (mpa), respectively, indicates a single, dominating reaction center and strong electronic effects of the substituents at both sides of the amide function. Correspondingly, the observed negative temperature dependence (E/R= - 400 to - 600 K) excludes a direct abstraction mechanism.
KW - Chemistry
UR - http://www.scopus.com/inward/record.url?scp=0031078701&partnerID=8YFLogxK
U2 - 10.1002/(sici)1097-4601(1997)29:2<81::aid-kin1>3.0.co;2-g
DO - 10.1002/(sici)1097-4601(1997)29:2<81::aid-kin1>3.0.co;2-g
M3 - Journal articles
AN - SCOPUS:0031078701
VL - 29
SP - 81
EP - 87
JO - International Journal of Chemical Kinetics
JF - International Journal of Chemical Kinetics
SN - 0538-8066
IS - 2
ER -