Kinetics and thermochemistry of the reaction atomic chlorine + cyclopropane .dblarw. hydrochloric acid + cyclopropyl. Heat of formation of the cyclopropyl radical

Baghal-Vayjooee, Mohammad H.; Benson, Sidney W.

doi:10.1021/ja00505a005

Cited by 55 publications

(40 citation statements)

References 3 publications

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“…The C 3 H 5 -H BDE derived from reaction 10 using the MP2 and ZPE corrected energies is 102.1 kcal mol -1 (Table 3), or 4.2 kcal mol -1 less than that derived from the reaction 1 equilibrium. 18 Chlorination of the cyclopropyl radical produces chlorocyclopropane (reaction 4), and the calculated scaled vibrational spectrum agrees well with the experimentally observed spectrum ( Figure 5D). As described above, further chlorination can produce up to three possible dichlorocyclopropane isomers.…”

Section: Computational Study Of Hydrogen Abstractionsupporting

confidence: 80%

Kinetics of Elementary Reactions in the Chain Chlorination of Cyclopropane

Hurley¹,

Schneider²,

Wallington³

et al. 2003

J. Phys. Chem. A

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The kinetics of elementary reactions involved in the chain chlorination of cyclopropane are examined using a combination of absolute and relative rate constant measurements and first principles electronic structure calculations. Relative rate methods are used in a smog chamber FTIR apparatus to determine k(Cl + c-C 3 H 6 ) ) (1.15 ( 0.17) × 10 -13 and k(Cl + c-C 3 H 5 Cl) ) (1.06 ( 0.18) × 10 -12 cm 3 molecule -1 s -1 in 10-700 Torr of air, or N 2 , diluent at 296 K. Absolute rate coefficients for the reaction of Cl with cyclopropane are measured between 293 and 623 K by a laser-photolysis/CW infrared absorption method. The data can be represented in Arrhenius form as k(Cl + c-C 3 H 6 ) ) ((1.8 ( 0.3) × 10 -10 cm 3 molecule -1 s -1 )e -(2150(100)/T . To support the experimental investigations, first principles electronic structure calculations are performed. Vibrational spectra of c-C 3 H 5 Cl, c-C 3 H 4 Cl 2 , and c-C 3 H 3 Cl 3 are calculated and are presented. gem-C 3 H 4 Cl 2 is calculated to be the kinetically and thermodynamically most favored dichlorocyclopropane. The experimental observations are consistent with the computational findings.

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Section: Computational Study Of Hydrogen Abstractionsupporting

confidence: 80%

Kinetics of Elementary Reactions in the Chain Chlorination of Cyclopropane

Hurley¹,

Schneider²,

Wallington³

et al. 2003

J. Phys. Chem. A

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“…The reaction enthalpy for the cyclopropyl to the allyl ring opening based on experimental data is Ϫ26.1 kcal/mol. 40 The present calculated value of Ϫ32 kcal/mol is significantly lower, but in agreement with other ab initio calculations. 41,42 Potential energy surfaces relevant to DCPK photodissociation are shown in Fig.…”

Section: E Electronic Structure Calculationssupporting

confidence: 91%

Photodissociation dynamics of dicyclopropyl ketone at 193 nm: Isomerization of the cyclopropyl ligand

Clegg

Parsons

Klippenstein

et al. 2003

The Journal of Chemical Physics

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The photodissociation dynamics of dicyclopropyl ketone are investigated using time-resolved Fourier transform infrared spectroscopy and photofragment ion imaging spectroscopy. The photodissociation products are C3H5+CO+C3H5, and the isomerization dynamics of C3H5 are the focus of this paper. Electronic structure calculations are used to define the potential energy surface, while a two-step phase space theory model predicts excitation in the CO product. The vibrational energy distribution of the CO product is not described by this statistical distribution, and is more excited than that observed in the analogous dissociation of acetone. The translational energy distribution of CO indicates an exit barrier on the potential energy surface. Contrary to expectations based on the photodissociation of other aliphatic ketones, the hydrocarbon products are not cyclopropyl radicals. Instead, the excited dicyclopropyl ketone undergoes a ring-opening isomerization to form diallyl ketone, followed by dissociation producing allyl radicals and carbon monoxide. Some of the allyl radicals have sufficient internal energy to decompose to allene+H.

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“…H bond lengths to be 1. 47 and 0.92 A, respectively, and the angle between them, 0". The other C-H bonds were found to be 1.08 A, negligibly different from the value of 1.093 in unperturbed CH4.…”

Section: Methodsmentioning

confidence: 99%

The use of transition‐state theory to extrapolate rate coefficients for reactions of H atoms with alkanes

Cohen

1991

Int J of Chemical Kinetics

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The thermochemical kinetics formulation of conventional transition state theory has been applied to metathesis reactions of H atoms with a series of alkanes in order to provide a sound framework for the intercomparison of experimental data, and also to extrapolate rate coefficients to temperature regimes that may lie beyond the range of experiments. The calculations require a value for the rate coefficient at some temperature, necessitating a discussion of the extant experimental data and their reliability. The procedures are described, the results of the calculations are presented, and their agreement with experimental data (for methane, ethane, propane, butane, pentane, isobutane, cyclopropane, cyclohexane, neopentane, neooctane, and 2,2,3-trimethylbutane) is discussed. A general expression for reactions of H with large (more than 4 carbons) alkanes is proposed: K(T) = 5.4 x 103n,TZ0 exp(-3540/T) + 4.7 x 103nsTZZ exp(-2640/T) + 3.7 x 103n,TZ0 exp(-970/T), where n,,, ns, and n, are the numbers of primary, secondary, and tertiary H atoms available for abstraction.

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Kinetics and thermochemistry of the reaction atomic chlorine + cyclopropane .dblarw. hydrochloric acid + cyclopropyl. Heat of formation of the cyclopropyl radical

Cited by 55 publications

References 3 publications

Kinetics of Elementary Reactions in the Chain Chlorination of Cyclopropane

Kinetics of Elementary Reactions in the Chain Chlorination of Cyclopropane

Photodissociation dynamics of dicyclopropyl ketone at 193 nm: Isomerization of the cyclopropyl ligand

The use of transition‐state theory to extrapolate rate coefficients for reactions of H atoms with alkanes

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