Rates of reactions of cyclopropane, cyclobutane, cyclopentene,and cyclohexene in the presence of boron trichloride

Lewis, David; Bergmann, J.; Manjoney, R.; Paddock, Robert L.; Kalra, Bansi L.

doi:10.1021/j150662a051

Cited by 42 publications

(41 citation statements)

References 2 publications

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“…Cyclopentene, in any case, would preferentially undergo the well-studied conversion to cyclopentadiene rather than reform 1,2-pentadiene. That process is also too slow to be important, however, in agreement with the literature data [20] and the absence of this species in the product spectrum.…”

Section: Rate Expressions For Elementary Processessupporting

confidence: 90%

“…However, the proposed transition states both involve carbene insertions and it is not clear how these structures may be so different. We have investigated the possibility that secondary decomposition of cyclopentene to form cyclopentadiene [20] could be perturbing our derived rate expression for cyclopentene formation. The published rate constants are not large enough to make a significant contribution, however, and it is not obvious what other reaction could play a role.…”

Section: Mechanism Of Isomerizationmentioning

confidence: 99%

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1,2‐Pentadiene decomposition

Herzler

Manion

Tsang

2001

Int J of Chemical Kinetics

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1,2-Pentadiene has been decomposed in single pulse shock tube experiments. There appear to be a large number of parallel decomposition and isomerization channels. The following rate expressions for isomerization in the temperature range 1100-1250 K and pressures between 200 and 300 kPa have been obtainedOverall, we estimate the 2σ uncertainty in the absolute rate constants to be about 30%. From detailed balance the rate expression for 1,3 to 1,2-pentadiene isomerization has been found to be k(1,3-pentadiene → 1,2-pentadiene) = 1.2 × 10 15 exp(−42070 ± 900 K/T ) s −1The significance of the 1,3 to 1,2 isomerization process as a bridge between the two-carbon and three-carbon species in high temperature hydrocarbon decomposition systems is discussed. The decomposition processes involve bond breaking and retroene reactions. The rate expression for the latter has been found to be k(1,2-pentadiene → propyne + ethylene) = 6.6 × 10 12 exp(−29240 ± 900 K/T ) sThe rate constants for fission of the C 3 C 4 and C 4 C 5 bonds appear to be close to each other. Our results indicate that the resonance energy of the 1,3-butadiene-2-yl radical is smaller than that of allyl radical by an amount equal to the π bond conjugation energy of butadiene. C 2001

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Section: Rate Expressions For Elementary Processessupporting

confidence: 90%

Section: Mechanism Of Isomerizationmentioning

confidence: 99%

1,2‐Pentadiene decomposition

Herzler

Manion

Tsang

2001

Int J of Chemical Kinetics

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“…Several groups have studied cyclohexene decomposition [13][14][15][16][17][18][19] and the rate expressions obtained are in good agreement over a wide range of experimental conditions. Kiefer et al [13] have developed an RRKM model for R 3 and from this model an expression for the high-pressure limit rate coefficient has been obtained…”

Section: Cyclohexenementioning

confidence: 83%

Calibration of reaction temperatures in a very high pressure shock tube using chemical thermometers

Tranter

Sivaramakrishnan

Srinivasan

et al. 2001

Int J of Chemical Kinetics

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Two chemical thermometers, 1,1,1-trifluoroethane and cyclohexene, have been used to calibrate the temperatures behind reflected shock waves, T 5real , in a unique highpressure, single-pulse shock tube. Experiments with 1,1,1-trifluoroethane were performed at nominal postshock pressures of 5000 psi and 9000 psi, and T 5real was calculated from the extent of the reaction and literature values for k ∞ . Both parent molecule decomposition and product formation were used to calculate the extent of reaction. At each pressure the two methods of calculating T 5real are in excellent agreement. The values for T 5real obtained from the cyclohexene experiments are in good agreement with those from 1,1,1-trifluoroethane. The range of the temprature calibration is 1050-1350 K. No discernable pressure dependence between the two sets of experiments was observed for the calculated values of T 5real . The effect of a 10% rise in pressure during the residence time on the calculated temperatures was also examined and is found to give rise to only small errors in T 5real .

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“…The thermal decomposition of the C-H bond in cyclopentane was written in the exothermic recombination direction, and the recommended rate constants of Allara and Shaw [32] were used. Finally, rate coefficients from Lewis et al [33] were used for H2 elimination from cyclopentene (included in the mechanism, but not shown in Figure 1).…”

Section: Unimolecular Decompositionmentioning

confidence: 99%

Cyclopentane combustion chemistry. Part I: Mechanism development and computational kinetics

Rashidi

Mehl

Pitz

et al. 2017

Combustion and Flame

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CitationAl Rashidi MJ, Mehl M, Pitz WJ, Mohamed S, Sarathy SM (2017) Cyclopentane combustion chemistry. Part I: Mechanism development and computational kinetics. Combustion and Flame 183: 358-371. Available: http://dx. AbstractCycloalkanes are significant constituents of conventional fossil fuels, in which they are one of the main contributors to soot formation, but also significantly influence the ignition characteristics below ~900 K. This paper discusses the development of a detailed high-and low-temperature oxidation mechanism for cyclopentane, which is an important archetypical cycloalkane. The differences between cyclic and non-cyclic alkane chemistry, and thus the inapplicability of acyclic alkane analogies, required the detailed theoretical investigation of the kinetics of important cyclopentane oxidation reactions as part of the mechanism development. The cyclopentyl + O2 reaction was investigated at the UCCSD(T)-F12a/cc-pVTZ-F12//M06-2X/6-311++G(d,p) level of theory in a timedependent master equation framework. Comparisons with analogous cyclohexane or noncyclic alkane reactions are presented. Our study suggests that beyond accurate quantum chemistry the inclusion of pressure dependence and especially that of formally direct kinetics is crucial even at pressures relevant for practical application. KeywordsCyclopentane, detailed mechanism, computational kinetics, pressure-dependent rate constants IntroductionCycloalkanes are important constituents of petroleum-derived liquid fuels. They make up ~40 wt% of diesel [1,2], ~20 wt% of kerosene [3,4], and ~10 to 15 wt% of gasoline [5]. Some studies have shown that at high temperatures, cycloalkanes may contribute to the production of soot by means of de-hydrogenation reactions [6]. Generally, cycloalkanes exhibit less low-temperature reactivity than their non-cyclic counterparts due to the conformational inhibition of the alkylperoxyhydroperoxyalkyl isomerization, an important low-temperature chain branching pathway. Yang et al. [7,8] have shown that in the case of cyclohexane, the suppression of low-temperature isomerization renders the HO2-elimination pathway more important. This leads to higher concentrations of olefins, which reduces reactivity, delays ignition and also promotes soot formation [7]. The ring strain energy changes the oxidation kinetics, particularly for the ring-opening reactions, which also involve significant change in entropy [8].Furthermore, unlike in n-alkanes, methyl substitution in cycloalkanes increases lowtemperature reactivity [9] for reasons that are not well known on the molecular level.Therefore, more detailed kinetic research is needed to better explain the observed trends, and to enable accurate predictive modeling of cycloalkane-containing fuels.Due to their simplicity and abundance, particularly in shale-and oil sand-derived fuels [10], cyclohexane and cyclopentane are often used to represent the naphthenic fraction in surrogate fuels. While models for cyclohexane [11][12][13][14] cover a wide temperature range, the cyclop...

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Rates of reactions of cyclopropane, cyclobutane, cyclopentene,and cyclohexene in the presence of boron trichloride

Cited by 42 publications

References 2 publications

1,2‐Pentadiene decomposition

1,2‐Pentadiene decomposition

Calibration of reaction temperatures in a very high pressure shock tube using chemical thermometers

Cyclopentane combustion chemistry. Part I: Mechanism development and computational kinetics

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