Reaction of acetonitrile and chlorine atoms

Olbregts, Jean; Brasseur, G.; Arijs, E.

doi:10.1016/0047-2670(84)80013-1

Cited by 14 publications

(19 citation statements)

References 16 publications

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“…However, the data at 296 K are in agreement with those found here. There is no evidence in our data for the curvature in the temperature dependence observed by Poulet et al 11 The competitive chlorination experiments of Olbregts et al 9 yielded values for k 1 at 370 and 413 K. They measured Cl + CHCl 3 f HCl + CCl 3 (15)…”

Section: Discussionmentioning

confidence: 69%

“…When N 2 was used as the bath gas, only a short chain decomposition was observed, consistent with the observations of Olbregts at higher temperature. 9 This observation implies that the reaction of CH 2 CN with Cl 2 (5) is very slow, as is also the case for other methyl radicals with electronegative substituent groups (e.g., CH 2 F, CF 3 , etc). 24…”

Section: A Relative Rate Studies Of the Reactions Of CL And F Atoms mentioning

confidence: 93%

“…The reaction between chlorine atoms and acetonitrile (1) has been studied several times before. − Olbregts et al performed a competitive chlorination experiment at 370 and 413 K, using chloroform as the reference gas. Poulet et al measured absolute values of k 1 between 295 and 723 K using a discharge flow tube, with chlorine atoms in excess, and mass spectroscopic detection of acetonitrile.…”

Section: Introductionmentioning

confidence: 99%

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Kinetics of the Reactions of Acetonitrile with Chlorine and Fluorine Atoms

Tyndall

Wallington

Sehested³

et al. 1996

J. Phys. Chem.

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The rate coefficients for the reactions of chlorine and fluorine atoms with acetonitrile have been measured using relative and direct methods. In the case of chlorine atoms the rate coefficient k 1 was measured between 274 and 345 K using competitive chlorination and at 296 K using laser flash photolysis with atomic resonance fluorescence. The rate coefficient measured at ambient temperature (296 ( 2 K) is (1.15 ( 0.20) × 10 -14 cm 3 molecule -1 s -1 , independent of pressure between 5 and 700 Torr (uncertainties are 2 standard deviations throughout). This result is a factor of 6 higher than the currently accepted value. The results from the three independent determinations reported here yield the Arrhenius expression k 1 ) (1.6 ( 0.2) × 10 -11 exp [-(2140 ( 200)/T] cm 3 molecule -1 s -1 . Product studies show that the reaction of Cl atoms with CH 3 CN proceeds predominantly, if not exclusively, by hydrogen abstraction at 296 K. The rate coefficient for the reaction of fluorine atoms with acetonitrile was measured using both the relative rate technique and pulse radiolysis with time-resolved ultraviolet absorption spectroscopy. The rate coefficient for the reaction of F atoms with CH 3 -CN was found to be dependent on total pressure. The observed rate data could be fitted using the Troe expression with F c ) 0.6, k 0 ) (2.9 ( 2.1) × 10 -28 cm 6 molecule -2 s -1 , and k ∞ ) (5.8 ( 0.8) × 10 -11 cm 3 molecule -1 s -1 , with a zero pressure intercept of (0.9 ( 0.4) × 10 -11 cm 3 molecule -1 s -1 . The kinetic data suggest that the reaction of F atoms with CH 3 CN proceeds via two channels: a pressure-independent H atom abstraction mechanism and a pressure-dependent addition mechanism. Consistent with this hypothesis, two products were observed using pulsed radiolysis with detection by UV absorption spectroscopy. As part of the product studies, relative rate techniques were used to measure k(Cl+CH 2 ClCN) ) (2.8 ( 0.4) × 10 -14 and k(F+CH 2 FCN) ) (3.6 ( 0.2) × 10 -11 cm 3 molecule -1 s -1 .

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Section: Discussionmentioning

confidence: 69%

Section: A Relative Rate Studies Of the Reactions Of CL And F Atoms mentioning

confidence: 93%

Section: Introductionmentioning

confidence: 99%

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Kinetics of the Reactions of Acetonitrile with Chlorine and Fluorine Atoms

Tyndall

Wallington

Sehested³

et al. 1996

J. Phys. Chem.

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“…The recommendation is based on results of the study of Tyndall et al [1353]. The results of this study, using both relative and absolute methods and measured over a wide range of experimental conditions are preferred over the results of earlier studies of Kurylo and Knable [756], Poulet et al [1071], and Olbregts et al [1009]. Product studies reported by Tyndall et al show that reaction proceeds predominantly by hydrogen atom abstraction.…”

Section: -81mentioning

confidence: 74%

Environmental effects of large igneous province magmatism: a Siberian perspective

Black

Lamarque

Shields

et al. 2015

Volcanism and Global Environmental Change

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“…Furthermore, high sensitivity for chlorine detection is possible if a photochemical reaction of chlorine is sensed. [26][27][28][29][30][31] In this study, we proposed a new method for detecting temporarily solvated chlorine gas in a polar aprotic solvent, and for detecting chlorine molecules based on an anodic oxidation reaction. Among the various solvents available, we selected acetonitrile (AN) (donor number 14.1; acceptor number 18.9; relative permittivity 35.9) and dimethyl sulfoxide (DMSO) (donor number 29.8; acceptor number 19.3; relative permittivity 46.5).…”

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confidence: 99%

Detection of Chlorine in a Non-aqueous Solution via Anodic Oxidation and a Photochemical Reaction

2018

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In this study, we developed a new chlorine gas detection method using anodic oxidation and a photochemical reaction. Chlorine gas was temporarily solvated with an aprotic polar solvent having an extensive potential range in the positive direction, and the solvated chlorine molecule was detected by an anodic oxidation reaction. In addition, when combined with ultraviolet light irradiation, we could detect high sensitivity using the photochemical reaction.

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Reaction of acetonitrile and chlorine atoms

Cited by 14 publications

References 16 publications

Kinetics of the Reactions of Acetonitrile with Chlorine and Fluorine Atoms

Kinetics of the Reactions of Acetonitrile with Chlorine and Fluorine Atoms

Environmental effects of large igneous province magmatism: a Siberian perspective

Detection of Chlorine in a Non-aqueous Solution via Anodic Oxidation and a Photochemical Reaction

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