Kinetics of the shock wave pyrolysis of pentafluoroethane

Tschuikow‐Roux, E.; Millward, G.E.; Quiring, W. J.

doi:10.1021/j100692a001

Cited by 23 publications

(16 citation statements)

References 1 publication

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“…In an examination of the results of Cadman and coworkers, Tsang [13] argues that this approach may also lead to rate constant data with acceptable error limits provided the uncertainty in the temperature does not exceed f30°K. Despite this conclusion, the rate constants for the thermally induced dehydrofluorination of 1,l-difluoroethane and l,l,l-trifluoroethane differed by an order of magnitude from those reported by Tschuikow-Roux and coworkers [14,15]. Tsang [13] has demonstrated that the differences are mostly due to the abnormally high reflected shock temperatures calculated by Cadman and coworkers [l I].…”

Section: Introductionmentioning

confidence: 89%

A comparison of two single‐pulse shock‐tube techniques: The thermal decomposition of ethyl chloride and n‐propyl chloride

Evans

Ichimura

Tschuikow‐Roux

1978

Int J of Chemical Kinetics

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This investigation presents a detailed examination of the relative reliability of the comparative and absolute rate methods as they are applied to kinetic studies in the single-pulse shock tube. For this purpose two previously studied reactions, the thermal elimination of HCI from ethyl chloride and n-propyl chloride, were selected and mixtures of these compounds were shock heated to temperatures in the range of 960"-1100"K. The experimental results were analyzed by both methods and the rate constants obtained from these analyses are compared with those of previous studies. The advantages and shortcomings of both methods are noted and it is concluded that reliable kinetic data can be obtained by the absolute rate (isolation technique) method with careful examination of the gas-dynamic flow conditions and taking cognizance of the incident shock deceleration. The limitations of the comparative rate technique encountered in the present study were similar to those detailed in previous investigations.

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Section: Introductionmentioning

confidence: 89%

A comparison of two single‐pulse shock‐tube techniques: The thermal decomposition of ethyl chloride and n‐propyl chloride

Evans

Ichimura

Tschuikow‐Roux

1978

Int J of Chemical Kinetics

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“…Experimental studies have shown that the ground state dissociates both to C 2 F 4 ϩHF ͑the lowest-energy channel͒ and to CHF 2 ϩCF 3 , with the latter channel dominating when sufficient energy is available for it to proceed. 37,38 We would therefore expect dissociation via coupling to the ground state mostly to produce CHF 2 ϩCF 3 .…”

Section: B Electron-impact Excitationmentioning

confidence: 99%

Low-energy electron scattering by C2HF5

Bettega

Winstead

McKoy

2001

The Journal of Chemical Physics

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We report elastic and electronically inelastic cross sections for low-energy electron scattering by pentafluoroethane, C 2 HF 5 . Our calculations were performed using the Schwinger multichannel method. For elastic scattering, we calculated integral, differential, and momentum transfer cross sections for energies from 5 to 50 eV. In the inelastic case, we obtained integral and differential cross sections for electron-impact excitation of the 1 1,3AЈ and 2 1,3 AЈ excited states at the three-channel level of approximation. At higher energies, the elastic differential cross sections are quite similar to existing theoretical results for C 2 F 6 . Limited electronic-structure calculations were carried out to explore the dissociation behavior of the excited states.

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“…This value falls within the uncertainty in the experimental value of 12.7 f 0.5. It may be noted that the latter value is significantly less than the observed A-factor in (16) CF3CH3 -+ CFzCHz + H F for which log ( A , sec-l) = 14.0 f 0.4 [19]. While part of the difference2 may be ascribed as due to the higher reaction path degeneracy, g = 9, and lower barrier to internal rotation in CF3CH3 (V = 3.5 kcal/mole [16,25]), it cannot account for a factor of -20.…”

Section: )/Rt]mentioning

confidence: 73%

“…(13), m = (dT5/dt)i is the initial cooling rate (Fig. 1); 2"s is the reflected shock temperature; 5 = is a cut-off parameter [19]; and E, is the activation energy obtained to a first approximation from a plot of log k versus 1/T5. An iterative procedure involving several cycles was used to evaluate the true activation energy, and computations were terminated at E N E,.…”

Section: Analysis and Discussionmentioning

confidence: 99%

The Competitive dehydrohalogenation of 1,1,1‐trifluoro‐2‐chloroethane in reflected shock waves

Millward

Tschuikow‐Roux

1972

Int J of Chemical Kinetics

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The thermal decomposition of 1,1,1 -trifluoro-2-chloroethane has been investigated in the single-pulse shock tube between 11 20" and 1300°K at total reflected shock pressures from -2610 to 3350 torr. Under these conditions, the major reaction is the a,a-elimination of hydrogen chloride, CF,CH&I A CFZCHF + HCI with log (k?, sec-l) = 13.3 f 0.4 -(65.5 f 2.2 kca1)/2.303RT C F 3 C H 2 C l A CFZCHCl + H F The decomposition also involves the slower a,@-elimination of hydrogen fluoride, with the first-order rate constant given by log (k?, sec-I) = 12.7 f 0.5 -(67.6 f 2.7 kca1)/2.303RT At temperatures above 1270"K, two additional minor products were observed. These were identified as CFZCFCI and CF3CHC12 and suggest C-Cl rupture as a third reaction channel leading to complicated kinetics.

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Kinetics of the shock wave pyrolysis of pentafluoroethane

Cited by 23 publications

References 1 publication

A comparison of two single‐pulse shock‐tube techniques: The thermal decomposition of ethyl chloride and n‐propyl chloride

A comparison of two single‐pulse shock‐tube techniques: The thermal decomposition of ethyl chloride and n‐propyl chloride

Low-energy electron scattering by C2HF5

The Competitive dehydrohalogenation of 1,1,1‐trifluoro‐2‐chloroethane in reflected shock waves

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