Reply to the comment of L. G. Piper on “Determination of the rate constants of the reactions of N3 and NCl free radicals using a simulation technique”

Jourdain, J. L.; Bras, G. Le; Poulet, G.; Combourieu, J.

doi:10.1016/0010-2180(80)90053-x

Cited by 14 publications

(25 citation statements)

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“…Our corrected value also exhibits good agreement with the previous value measured by Jourdain et al 15 using the same experimental method but with no explicit account for variation of Cl concentration along the reaction distance.…”

Section: Resultssupporting

confidence: 89%

Rate Coefficients of the Reactions of Chlorine Atoms with Haloethanes of Type CH₃CCl₃_-_xF_x(x= 0, 1, and 2): Experimental and ab Initio Theoretical Studies

Talhaoui¹,

Louis²,

Devolder³

et al. 1996

J. Phys. Chem.

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The absolute rate coefficients for the hydrogen abstraction reactions from CH 3 CCl 3 (k 1 ), CH 3 CCl 2 F (k 2 ), and CH 3 CClF 2 (k 3 ) by chlorine atoms in gas phase have been measured as a function of temperature using the discharge flow/mass spectrometric technique (DF/MS). The reactions were investigated under pseudo-firstorder conditions with Cl atoms in large excess with respect to the haloethanes. The temperature dependence of the rate coefficients is expressed in the Arrhenius form:) × 10 -12 exp-[-(2420 ( 400)/T]. The units of the rate constants are cm 3 molecule -1 s -1 , and the quoted uncertainties are (2σ. For understanding the reaction path mechanism of the chlorination of the studied halogen-substituted ethanes, ab initio molecular orbital calculations were performed. Transition state structures were determined. These calculations lead to predictions of preexponential factors in the same order of magnitude of measured values. The ab initio energetics of the reactions were corrected using the ISO-M method, a mixing of isodesmic reactions for obtaining reaction enthalpies and concept of intrinsic energy of Marcus to deduce activation energies. A reasonably good agreement with the experimental values were found.

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Section: Resultssupporting

confidence: 89%

Rate Coefficients of the Reactions of Chlorine Atoms with Haloethanes of Type CH₃CCl₃_-_xF_x(x= 0, 1, and 2): Experimental and ab Initio Theoretical Studies

Talhaoui¹,

Louis²,

Devolder³

et al. 1996

J. Phys. Chem.

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“…For CHF 2 Cl, the reference rate constant has been measured using absolute rate techniques by Sawerysyn et al [26] and by Jourdain et al [27]. These two studies agree very well, and the rate constant from Sawerysyn et al is used as the reference value in this work.…”

Section: Resultsmentioning

confidence: 92%

Kinetic studies of Cl-atom reactions with selected aromatic compounds using the photochemical reactor-FTIR spectroscopy technique

Shi

Bernhard

1997

Int. J. Chem. Kinet.

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Relative rate constant measurements have been carried out on the Cl-atom reactions with benzene, chlorobenzene, toluene, xylene, and styrene in 740 torr of air at room temperature (295 K), using the photochemical reactor-FTIR spectroscopy technique. The Cl atoms were generated by the UV photolysis of Cl 2 , and the reference compounds were CHF 2 Cl for benzene and chlorobenzene and isobutane for toluene, xylene, and styrene. Using the absolute rate constants for these two reference compounds reported in the literature, the following kinetic data were obtained for the study compounds (in units of cm 3 s Ϫ1 ).The quoted error bars are for Ϯ 2. The present kinetic results are compared with available literature data to update and expand the kinetics database for Cl-atom reactions of organic compounds. The results are also analyzed to provide insights into the reaction mechanism for the Cl-atom initiated oxidation of benzene under atmospheric conditions.

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“…Our data, similar data from Henshaw et al, 18a and laser-induced fluorescence experiments 9 that monitored [N 3 ] decay vs [Cl] all favor a k 1 value of in the range (3 ( 1) × 10 -11 cm 3 s -1 . Jourdain and co-workers 26 assigned a k 1 value of (0.75-1.5) × 10 -11 cm 3 s -1 based on modeling the Cl + ClN 3 reaction system. The (3 ( 1) × 10 -11 cm 3 s -1 value is an order of magnitude smaller than an early report, 7 which also was based upon the reduction in [NF(a)] when Cl atoms were generated in the flow reactor.…”

Section: Discussionmentioning

confidence: 99%

Kinetics of NCl(aΔ and b¹Σ⁺) Generation: The Cl + N₃ Rate Constant, the NCl(a¹Δ) Product Branching Fraction, and Quenching of NCl(a¹Δ) by F and Cl Atoms

Manke

Setser

1998

J. Phys. Chem. A

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The quenching rate constants for NCl(a1Δ) by F and Cl atoms have been measured at room temperature to be (2.2 ± 0.7) × 10-11 and (1.0 + 1.0/−0.5) × 10-12 cm3 s-1, respectively, by adding F and Cl atoms to a flow reactor containing NCl(a1Δ). With knowledge of these quenching rate constants, the kinetics for the formation of NCl(a1Δ) from the Cl + N3 reaction could be investigated in the F/Cl/HN3 reaction system. The reduction in NF(a1Δ) yield from adding Cl atoms to the reactor containing F and HN3 and the relative NF(a1Δ) and NCl(a1Δ) yields for known concentrations of F and Cl atoms in this reaction system favor a total Cl + N3 rate constant of 3 ± 1 × 10-11 cm3 s-1 with a branching fraction for NCl(a1Δ) formation of ≳ 0.5. The branching fraction was deduced from comparing the relative intensities of the NCl(a−X) and NF(a−X) transitions using a lower limit to the NCl(a) radiative lifetime of 2 s. The direct formation of NCl(b1Σ+) from Cl + N3 is a minor channel; however, NCl(b1Σ+) is formed by bimolecular energy pooling of NCl(a1Δ) molecules with a rate constant of ≈1.5 × 10-13 cm3 s-1 and by energy transfer between NCl(a1Δ) and HF(v ≥ 2). The bimolecular energy-pooling process is a small fraction of the total bimolecular self-destruction rate for NCl(a1Δ).

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Reply to the comment of L. G. Piper on “Determination of the rate constants of the reactions of N3 and NCl free radicals using a simulation technique”

Cited by 14 publications

References 0 publications

Rate Coefficients of the Reactions of Chlorine Atoms with Haloethanes of Type CH₃CCl₃_-_xF_x(x= 0, 1, and 2): Experimental and ab Initio Theoretical Studies

Rate Coefficients of the Reactions of Chlorine Atoms with Haloethanes of Type CH₃CCl₃_-_xF_x(x= 0, 1, and 2): Experimental and ab Initio Theoretical Studies

Kinetic studies of Cl-atom reactions with selected aromatic compounds using the photochemical reactor-FTIR spectroscopy technique

Kinetics of NCl(aΔ and b¹Σ⁺) Generation: The Cl + N₃ Rate Constant, the NCl(a¹Δ) Product Branching Fraction, and Quenching of NCl(a¹Δ) by F and Cl Atoms

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Reply to the comment of L. G. Piper on “Determination of the rate constants of the reactions of N3 and NCl free radicals using a simulation technique”

Cited by 14 publications

References 0 publications

Rate Coefficients of the Reactions of Chlorine Atoms with Haloethanes of Type CH3CCl3-xFx(x= 0, 1, and 2): Experimental and ab Initio Theoretical Studies

Rate Coefficients of the Reactions of Chlorine Atoms with Haloethanes of Type CH3CCl3-xFx(x= 0, 1, and 2): Experimental and ab Initio Theoretical Studies

Kinetic studies of Cl-atom reactions with selected aromatic compounds using the photochemical reactor-FTIR spectroscopy technique

Kinetics of NCl(aΔ and b1Σ+) Generation: The Cl + N3 Rate Constant, the NCl(a1Δ) Product Branching Fraction, and Quenching of NCl(a1Δ) by F and Cl Atoms

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Rate Coefficients of the Reactions of Chlorine Atoms with Haloethanes of Type CH₃CCl₃_-_xF_x(x= 0, 1, and 2): Experimental and ab Initio Theoretical Studies

Rate Coefficients of the Reactions of Chlorine Atoms with Haloethanes of Type CH₃CCl₃_-_xF_x(x= 0, 1, and 2): Experimental and ab Initio Theoretical Studies

Kinetics of NCl(aΔ and b¹Σ⁺) Generation: The Cl + N₃ Rate Constant, the NCl(a¹Δ) Product Branching Fraction, and Quenching of NCl(a¹Δ) by F and Cl Atoms