Shock tube and modeling study of propene pyrolysis

Hidaka, Yoshiaki; Nakamura, Takuji; Tanaka, Hiroya; Jinno, A.; Kawano, Hiroyuki; Higashihara, Tetsuo

doi:10.1002/kin.550240902

Cited by 67 publications

(43 citation statements)

References 41 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…7) is another evidence for its molecular origin. This result does not disagree with those obtained by Hidaka et al [31]. They could not identify this molecular source of allene because radical routes are probably important at Instead, they 1200 -1800 K. identified a molecular elimination of methane: which might be in competition with (m 1 ) at 800 K. We failed to detect any trace of acetylene even though this hydrocarbon should be very easily detected; this suggests that Hidaka's activation energy for may k 109 be too low, or that extrapolation of their data to is impossible.…”

supporting

confidence: 71%

Kinetics and modeling of the thermal reaction of propene at 800 K. Part iii. Propene in the presence of small amounts of oxygen

Barbè¹,

Baronnet²,

Martin³

et al. 1998

Int. J. Chem. Kinet.

View full text Add to dashboard Cite

The thermal reaction of propene was examined around in the presence of 800 K less than 20% oxygen. At initial time, the production of H 2 , CH 4 , C 2 H 4 , C 2 H 6 , allene, C 3 H 8 , 1,3-butadiene, butenes, 3-and 4-methylcyclopentene, a mixture of 1,4-and 1,5-hexadienes, methylcyclopentane (or dimethylcyclobutane), 4-methylpent-1-ene, and hex-1-ene, was observed along with hydrogen peroxide, CO, and small quantities of ethanal and CO 2 . Oxygen increases the initial production of hydrogen and of most hydrocarbons and, particularly, that of C 6 dienes and of cyclenes. However, the production of allene, methylcyclopentane (or dimethylcyclobutane), and 4-methylpent-1-ene is practically not affected. A kinetic study confirms the mechanism proposed for the thermal reaction of propene. Formation of allene, thus, involves a four-center-unimolecular dehydrogenation of propene, that of 4-methylpent-1-ene is explained by an ene bimolecular reaction while methylcyclopentane (or dimethylcyclobutane) probably arises from a bimolecular process involving a biradical intermediate. Other products arise from a conventional chain radical mechanism.A kinetic scheme is proposed in which chains are primarily initiated by the bimolecular step:which competes with the second-order initiation of propene pyrolysis. Since allene production is not affected by oxygen, it is concluded that allyl radicals are not dehydrogenated by oxygen; but they oxidize in a branching step involving allylperoxyl radicals; r. radicals other than methyl, and allyl are dehydrogenated according to the conventional process:r· ϩ O !: unsaturated ϩ HO · 2 2

show abstract

supporting

confidence: 71%

Kinetics and modeling of the thermal reaction of propene at 800 K. Part iii. Propene in the presence of small amounts of oxygen

Barbè¹,

Baronnet²,

Martin³

et al. 1998

Int. J. Chem. Kinet.

View full text Add to dashboard Cite

show abstract

“…Hidaka et al [3] investigated the thermal decomposition of propene behind reflected shock waves over a temperature range of 1200-1800 K, measuring the product distribution using infrared laser absorption spectroscopy and gas chromatography. The authors reported species profiles for C 3 H 6 , C 2 H 2 , C 4 H 6 , C 3 H 4 , and C 6 H 6 .…”

Section: Introductionmentioning

confidence: 99%

An experimental and modeling study of propene oxidation. Part 2: Ignition delay time and flame speed measurements

Burke

Donagh

et al. 2015

Combustion and Flame

288

208

View full text Add to dashboard Cite

Experimental data obtained in this study (Part II) complement the speciation data presented in Part I, but also offer a basis for extensive facility cross-comparisons for both experimental ignition delay time (IDT) and laminar flame speed (LFS) observables.To improve understanding of the ignition characteristics of propene, a series IDT experiments were performed in six different shock tubes and two rapid compression machines (RCMs) under conditions not previously studied. This study is the first of its kind to directly compare ignition in several different shock tubes over a wide range of conditions. For common nominal reaction conditions among these facilities, cross-comparison of shock tube IDTs suggests 20-30% reproducibility (2σ) for the IDT observable. The combination of shock tube and RCM data greatly expands the data available for validation of propene oxidation models to higher pressures (2-40 atm) and lower temperatures (750-1750 K).Propene flames were studied at pressures from 1-20 atm and unburned gas temperatures of 295-398 K for a range of equivalence ratios and dilutions in different facilities. The present propene-air LFS results at 1 atm were also compared to LFS measurements from the literature. With respect to initial reaction conditions, the present experimental LFS cross-comparison is not as comprehensive as the IDT comparison; however, it still suggests reproducibility limits for the LFS observable. For the LFS results, there was agreement between certain data sets and for certain equivalence ratios (mostly in the lean region), but the remaining discrepancies highlight the need to reduce uncertainties in laminar flame speed experiments amongst different groups and different methods. Moreover, this is the first study to investigate the burning rate characteristics of propene at elevated pressures (> 5 atm).IDT and LFS measurements are compared to predictions of the chemical kinetic mechanism presented in Part I and good agreement is observed.

show abstract

“…Note also that trans-cyclopropane-d, isomerizes to 1-d, (33). A possible explanation, put forward by Bernardi et al (34) is that "It is conceivable that the structural isomerization proceeds by a path not involving trimethylene, and hence may not be pertinent to the [1,2] shift transition state." Clearly more experimental work is needed on this problem which we are currently investigating by theoretical methods.…”

Section: Photochemical Reactions Ofmentioning

confidence: 99%

“…Pour des longueurs de liaison 1. Introduction Propene (1) has been the object of many investigations of its thermal (1)(2)(3)(4)(5)(6)(7)(8) and photochemical reactions (9)(10)(11)(12)(13)(14)(15)(16)(17)(18)(19), but the overall reaction mechanisms are still not fully elucidated. An important reason is the large number of products at lower pyrolysis temperatures: for instance Kallend et al (8) identified 26 products, many of which are more reactive than 1.…”

mentioning

confidence: 99%

“…The minimal levels necessary for the GVB-PP and MCSCF calculations to obtain satisfactory results were determined, not only for the C-H reaction coordinate in ethylene, but also for H-X reaction coordinates where X = CH3, OH, and F (25). 1 have not yet been determined experimentally but the participation of H e C H -C H 3 radicals of undefined geometry in its shock tube pyrolysis has been proposed by Hidaka et al (1).…”

mentioning

confidence: 99%

See 1 more Smart Citation

Ab initio study of C—H bond breaking in olefins. II. GVB computations on propene ↔ H + cis- or trans-propen-1-yl

Maré¹,

Evleth²,

Poirier³

et al. 1994

Can. J. Chem.

View full text Add to dashboard Cite

. Can. J. Chem. 72, 1230Chem. 72, (1994.The Generalized-Valence-Bond-Perfect-Pairing (GVB-PP) method has been used to investigate the structural behaviour, energy, and dipole moment along the reaction coordinates for propene tt H + cis-or trans-propen-1-yl. Geometry optimizations were carried out at the GVB(9)lSTO-3G level (complete valence shell) for the minimum energy propene structure (complete optimization) and for numerous structures up to r(C-H) = 10 A (only the elongated C-H distance kept fixed). The dissociation curves are smooth, without a maximum, and yield predicted dissociation energies of propene to H + cis-propen-1-yl and H + trans-propen-1-yl of 555.8 and 554.8 kJ mol-', respectively. These values are within several percent of those obtained for C-H bond rupture in ethylene using GVB and MCSCF methods with the same basis set. They are obviously too high but they confirm that removal of a hydrogen atom from the CH? moiety in propene requires about the same energy as removal of a hydrogen atom from ethylene. GVB(7)/6-31GllGVB(9)/STO-3G computations lower the predicted dissociation energies of propene + H + cis-propen-1-yl and H + trans-propen-1 -yl to 448.2 and 448.6 kJ mol-', respectively. The reduced energy concept (ER = (E, -E,)lDe) is applied to the reaction coordinates. Linear behaviour for In ER versus bond length is observed at long bond distances. At r(C-H) = 3 A, the values of the slopes, d(ln ER)ldr(C-H), which are related to the effective Morse constant B are -3.73 and -3.74 (GVB(9)lSTO-3G) and -2.75 and -2.8 1 (GVB(7)/6-3 1 GllGVB(9)lSTO-3G) for the H + cis-and H + trans-propen-1-yl reaction coordinates, respectively. On a utilisC la mCthode de l'appariement parfait de la liaison de valence gCnCraliste (GVB-PP) pour Ctudier le comportement structurel, 1'Cnergie et le moment dipolaire le long des coordonnCes de la rCaction propene tt H +cis-ou trans-propCn-1-yle. On a effectuC les optimisations de gtomCtrie au niveau GVB(9)lSTO-3G (couche de valence complete) pour la structure du propkne 2 Cnergie minimale (optimisation complkte) et pour de nombreuses structures jusqu'2 r(C-H) = 10 A (seule la distance C-H allongee est maintenue constante). Les courbes de dissociation sont lisses, sans un maximum, et elles conduisent 2 prCdire des Cnergies de dissociation pour les rCactions du propkne en H + cis-propen-1-yle et en H + trans-propCn-1-yle de 555,8 i t 554,8 kJ1 mol respectivement. Ces valeurs sont 2 1'intCrieur des limites de quelques pour-cent de celles obtenues pour la rupture de la liaison C-H dans 1'Cthylkne lorsque des calculs ont Cte effectuees par les mCthodes GVB et MCSCF, avec le mCme ensemble de base. Ces valeurs sont Cvidemment trop ClevCes, mais elles confirment que l'enlkvement d'un atome d'hydrogkne a partir de la portion CH, du propkne nCcessite approximativement la mCme Cnergie que l'enlkvement d'un atome d'hydrogkne a partir de 1'Cthylkne. Des calculs au niveau GVB(7)16-3 1GllGVB(9)lSTO-3G abaissent les valeurs des Cnergies de dissociation des rtactions du propkne en H + ...

show abstract

Shock tube and modeling study of propene pyrolysis

Cited by 67 publications

References 41 publications

Kinetics and modeling of the thermal reaction of propene at 800 K. Part iii. Propene in the presence of small amounts of oxygen

Kinetics and modeling of the thermal reaction of propene at 800 K. Part iii. Propene in the presence of small amounts of oxygen

An experimental and modeling study of propene oxidation. Part 2: Ignition delay time and flame speed measurements

Ab initio study of C—H bond breaking in olefins. II. GVB computations on propene ↔ H + cis- or trans-propen-1-yl

Contact Info

Product

Resources

About