Kinetic and Spectroscopic Studies of the Reaction of CF<sub>2</sub> with H<sub>2</sub> in Shock Waves

Cobos, Carlos; Knight, Gary; Sölter, L.; Tellbach, E.; Troe, J.

doi:10.1021/acs.jpca.7b05859

Cited by 11 publications

(25 citation statements)

References 22 publications

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“…We furthermore inspected absorption signals from C 2 radicals, formed in secondary high-temperature reaction. 18 Wavelengths between 350 and 390 nm were particularly suitable for this purpose. Here, absorptions from neither CF nor from CF 2 perturb the observation of C 2 formation and dissociation.…”

Section: Experimental Techniquementioning

confidence: 99%

High-Temperature Fluorocarbon Chemistry Revisited

Cobos

Hintzer²,

Sölter

et al. 2021

J. Phys. Chem. A

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The thermal dissociation reactions of C 2 F 4 and C 2 F 6 were studied in shock waves over the temperature range 1000−4000 K using UV absorption spectroscopy. Absorption cross sections of C 2 F 4 , CF 2 , CF, and C 2 were derived and related to quantum-chemically modeled oscillator strengths. After confirming earlier results for the dissociation rates of C 2 F 4 , CF 3 , and CF 2 , the kinetics of secondary reactions were investigated. For example, the reaction CF 2 + CF 2 → CF + CF 3 was identified. Its rate constant of 10 10 cm 3 mol −1 s −1 near 2400 K is markedly larger than the limiting high-pressure rate constant of the dimerization CF 2 + CF 2 → C 2 F 4 , suggesting that the reaction follows a different path. When the measurements of the thermal dissociation CF 2 (+Ar) → CF + F (+Ar) are extended to temperatures above 2500 K, the formation of C 2 radicals was shown to involve the reaction CF + CF → C 2 F + F (modeled rate constant 8.0 × 10 12 (T/3500 K) 1.0 exp(−4400 K/T) cm 3 mol −1 s −1 ) and the subsequent dissociation C 2 F (+Ar) → C 2 + F + (Ar) (modeled limiting low-pressure rate constant 3.0 × 10 16 (T/3500 K) −4.0 exp(−56880 K/T) cm 3 mol −1 s −1 ). This mechanism was validated by monitoring the dissociation of C 2 at temperatures close to 4000 K. Temperature-and pressure-dependences of rate constants of reactions involved in the system were modeled by quantum-chemistry based rate theory.

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Section: Experimental Techniquementioning

confidence: 99%

High-Temperature Fluorocarbon Chemistry Revisited

Cobos

Hintzer²,

Sölter

et al. 2021

J. Phys. Chem. A

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“…Next, a detection method for SiF 2 had to be chosen. As the UV absorption of CF 2 has been found useful to study hightemperature fluorocarbon chemistry, [9][10][11] one may try to employ the analogous spectrum of SiF 2 to investigate reactions of the latter. At room temperature, SiF 2 has a band spectrum which is similarly structured and intense as that of CF 2 .…”

Section: Introductionmentioning

confidence: 99%

Shock wave and modelling study of the unimolecular dissociation of Si(CH₃)₂F₂: an access to spectroscopic and kinetic properties of SiF₂

Cobos

Sölter

Tellbach

et al. 2021

Phys. Chem. Chem. Phys.

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“…ref. [12][13][14][15][16]. Mixtures of (C 2 F 5 ) 3 N (from Fluorochem, purity 96%) and Ar (from Air Liquide, purity 99.9999%) were prepared in mixing vessels outside the shock tube and then introduced into the tube.…”

Section: Experimental Technique and Resultsmentioning

confidence: 99%