Experimental and theoretical studies of the kinetics of the reactions of OH and OD with acetone and acetone-d6 at low pressure

Davis, Maxine E.; Drake, W. V.; Vimal, D.; Stevens, P. S.

doi:10.1016/j.jphotochem.2005.08.030

Cited by 12 publications

(41 citation statements)

References 37 publications

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“…The overall rate constant for the latter reaction, along with its temperature dependence, has been the subject of much experimental work. [1][2][3][4][5][6][7][8] There is good agreement among all the results as shown in Fig. 1 where symbols are experimental results.…”

Section: Introductionmentioning

confidence: 56%

“…As indicated in the introduction, large primary kinetic isotope effect (KIE) was observed experimentally [5][6][7][8] and therefore needs to be considered. KIE is defined as the ratio of reaction rate constant for the hydrogen-containing species relative to that of the isotopically substituted species.…”

Section: Kinetic Isotope Effectmentioning

confidence: 99%

“…It is now experimentally well established that the yield of acetic acid is negligible, [10][11][12][13] the major channel being the production of acetonyl radicals. The kinetic isotope effect in the title reaction was also thoroughly explored [5][6][7][8] demonstrating a large primary effect. Experimental Arrhenius plots for both OH + acetone and OH + acetone-d6 reactions are shown in Fig.…”

Section: Introductionmentioning

confidence: 99%

“…11,12 It is now qualitatively established that substantial quantum mechanical tunneling is likely to account for this behavior. 5,6,8,10 The purpose of this work is to quantitatively verify the tunneling hypothesis now that the requisite primary data are available. The microcanonical rate constants for reactions involving H-atom transfer through energy barriers will be obtained using semi-classical WKB 17 approximation for calculating the tunneling probability.…”

Section: Introductionmentioning

confidence: 99%

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Tunneling in the reaction of acetone with OH

Caralp

Forst

Hénon

et al. 2006

Phys. Chem. Chem. Phys.

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Based on recent detailed quantum mechanical computations of the mechanism of the title reaction and, this paper presents kinetics analysis of the overall rate constant and its temperature dependence, for which ample experimental data are available for comparison. The analysis confirms that the principal channel is the formation of acetonyl radical + H(2)O, while the channel leading to acetic acid is of negligible importance. It is shown that the unusual temperature dependence of the overall rate constant, as observed experimentally, is well accounted for by standard RRKM treatment that includes tunneling. This treatment is applied at the microcanonical level, with chemically activated distribution of entrance species, i.e. using a stationary rather than a thermal distribution that incorporates collisional energy transfer and competition between the redissociation and exit channel. A similar procedure is applied to the isotopic reaction acetone-d6 + OH with equally satisfying results, so that the experimental temperature dependence of the KIE (kinetic isotope effect) is perfectly reproduced. This very good agreement between calculation and experiment is obtained without any fitting to experimental values and without any adjustment of the parameters of calculation.

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Section: Introductionmentioning

confidence: 56%

Section: Kinetic Isotope Effectmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Tunneling in the reaction of acetone with OH

Caralp

Forst

Hénon

et al. 2006

Phys. Chem. Chem. Phys.

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“…The addition of oxygen appears to reduce the reagent-catalyzed loss of OH by inhibiting active wall sites. 30,33,36,37 Pseudo-first-order conditions were maintained during all experiments, and the OH concentrations were kept below 3 × 10 11 molecules cm -3 . 1,3-Butadiene (Sigma-Aldrich, 99%) was used to prepare reagent mixtures (0.08-0.4% of 1,3-butadiene) in approximately 760 Torr of helium using either a 5.5 or 10 L calibrated reservoir fitted with a capacitance manometer.…”

Section: Methodsmentioning

confidence: 99%

Experimental and Ab Initio Dynamical Investigations of the Kinetics and Intramolecular Energy Transfer Mechanisms for the OH + 1,3-Butadiene Reaction between 263 and 423 K at Low Pressure

et al. 2008

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The rate constants for the reaction of the OH radical with 1,3-butadiene and its deuterated isotopomer has been measured at 1-6 Torr total pressure over the temperature range of 263-423 K using the discharge flow system coupled with resonance fluorescence/laser-induced fluorescence detection of OH. The measured rate constants for the OH + 1,3-butadiene and OH + 1,3-butadiene-d 6 reactions at room temperature were found to be (6.98 ( 0.28) × 10 -11 and (6.94 ( 0.38) × 10 -11 cm 3 molecule -1 s -1 , respectively, in good agreement with previous measurements at higher pressures. An Arrhenius expression for this reaction was determined to be k 1 II (T) ) (7.23 ( 1.2) ×10 -11 exp [(664 ( 49)/T] cm 3 molecule -1 s -1 at 263-423 K. The reaction was found to be independent of pressure between 1 and 6 Torr and over the temperature range of 262-423 K, in contrast to previous results for the OH + isoprene reaction under similar conditions. To help interpret these results, ab initio molecular dynamics results are presented where the intramolecular energy redistribution is analyzed for the product adducts formed in the OH + isoprene and OH + butadiene reactions.

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Features of the potential energy surface for the reaction of HO₂ radical with acetone

Cours

Canneaux

Bohr

2006

Int J of Quantum Chemistry

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ABSTRACT:The mechanism of the reaction of acetone with HO 2 has been studied by quantum chemical computations. Different stationary points on the potential energy surface (PES) of the reaction have been characterized. These stationary points are the reactants, products, molecular complexes, and transition states. Three pathways have been studied: two H-abstraction channels and one HO 2 -addition channel. The MP2 level of theory with the 6-311G(d,p) basis set was employed for geometry optimization. The electronic energies was obtained at the PMP2, PMP4, and CCSD(T) level of theory with the 6-311G(d,p) basis set on the computed geometries. The addition pathway is clearly the more favorable, contrary to the acetone ϩ OH system. The pre-reactive hydrogenbonded complexes have been characterized and show a large red shift between the OOH stretching frequency in the HO 2 radical and the one in the HO 2 fragment of intermolecular complexes. Our addition rate constant k ϩ at T ϭ 298 K (3.49 ϫ 10 Ϫ16 cm 3 s Ϫ1 ) is consistent with previous experimental results (giving an upper limit of the rate constant of 6 ϫ 10 Ϫ16 cm 3 s Ϫ1 at 298 K).

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Experimental and theoretical studies of the kinetics of the reactions of OH and OD with acetone and acetone-d6 at low pressure

Cited by 12 publications

References 37 publications

Tunneling in the reaction of acetone with OH

Tunneling in the reaction of acetone with OH

Experimental and Ab Initio Dynamical Investigations of the Kinetics and Intramolecular Energy Transfer Mechanisms for the OH + 1,3-Butadiene Reaction between 263 and 423 K at Low Pressure

Features of the potential energy surface for the reaction of HO₂ radical with acetone

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Experimental and theoretical studies of the kinetics of the reactions of OH and OD with acetone and acetone-d6 at low pressure

Cited by 12 publications

References 37 publications

Tunneling in the reaction of acetone with OH

Tunneling in the reaction of acetone with OH

Experimental and Ab Initio Dynamical Investigations of the Kinetics and Intramolecular Energy Transfer Mechanisms for the OH + 1,3-Butadiene Reaction between 263 and 423 K at Low Pressure

Features of the potential energy surface for the reaction of HO2 radical with acetone

Contact Info

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Features of the potential energy surface for the reaction of HO₂ radical with acetone