21576-64-7Relevant articles and documents
Rate constant measurements for the overall reaction of OH + 1-butanol → products from 900 to 1200 K
Pang, Genny A.,Hanson, Ronald K.,Golden, David M.,Bowman, Craig T.
experimental part, p. 2475 - 2483 (2012/05/19)
The rate constant for the overall reaction OH + 1-butanol → products was determined in the temperature range 900 to 1200 K from measurements of OH concentration time histories in reflected shock wave experiments of tert-butyl hydroperoxide (TBHP) as a fast source of OH radicals with 1-butanol in excess. Narrow-linewidth laser absorption was employed for the quantitative OH concentration measurement. A detailed kinetic mechanism was constructed that includes updated rate constants for 1-butanol and TBHP kinetics that influence the near-first-order OH concentration decay under the present experimental conditions, and this mechanism was used to facilitate the rate constant determination. The current work improves upon previous experimental studies of the title rate constant by utilizing a rigorously generated kinetic model to describe secondary reactions. Additionally, the current work extends the temperature range of experimental data in the literature for the title reaction under combustion-relevant conditions, presenting the first measurements from 900 to 1000 K. Over the entire temperature range studied, the overall rate constant can be expressed in Arrhenius form as 3.24 × 10-10 exp(-2505/T [K]) cm3 molecule-1 s-1. The influence of secondary reactions on the overall OH decay rate is discussed, and a detailed uncertainty analysis is performed yielding an overall uncertainty in the measured rate constant of ±20% at 1197 K and ±23% at 925 K. The results are compared with previous experimental and theoretical studies on the rate constant for the title reaction and reasonable agreement is found when the earlier experimental data were reinterpreted.
Absolute Rate Constants for the Addition of Hydroxymethyl Radicals to Alkenes in Methanol Solution
Wu, J. Q.,Fischer, H.
, p. 167 - 180 (2007/10/02)
Absolute rate constants and their temperature dependencies were determined for the addition of hydroxymethyl radicals (.CH2OH) to 20 mono- or 1,1-disubstituted alkenes (CH2 = CXY) in methanol by time-resolved electron spin resonance spectroscopy.With the alkene substituents the rate constants at 298 K (k298) vary from 180 M-1s-1 (ethyl vinylether) to 2.1*106 M-1s-1 (acrolein).The frequency factors obey log A/M-1s-1 = 8.1 +/- 0.1, whereas the activation energies (Ea) range from 11.6 kJ/mol (methacrylonitrile) to 35.7 kJ/mol (ethyl vinylether).As shown by good correlations with the alkene electron affinities (EA), log k298/M-1s-1 = 5.57 + 1.53 * EA/eV (R2 = 0.820) and Ea = 15.86 - 7.38 * EA/eV (R2 = 0.773), hydroxymethyl is a nucleophilic radical, and its addition rates are strongly influenced by polar effects.No apparent correlation was found between Ea or log k298 with the overall reaction enthalpy.
