The rate of dissociation of allyl iodide in shock waves

Maloney, K.L.; Palmer, Howard B.; Seery, D.J.

doi:10.1002/kin.550040108

Cited by 7 publications

(6 citation statements)

References 15 publications

(6 reference statements)

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“…The LS experiments overlap with the highest temperature experiments of Maloney et al who studied allyl iodide decomposition in a shock tube over 169–1429 Torr and 740–1070 K. Maloney et al did not observe a pressure dependence, although there is considerable scatter in their data. The RRKM calculations from the current work predict a high pressure limit that is 3.6 times greater than k 2a from Maloney et al, which was assumed to be within 20% of the high pressure limit. Butler and Polanyi measured the dissociation of allyl iodide in a flow reactor at a pressure of 6 Torr and temperatures between 569 and 767 K. The 6 Torr results of the present Gorin model calculations are actually in fair agreement with their results, indicating that Butler and Polanyi’s measurements are also far from the high pressure limit.…”

Section: Resultssupporting

confidence: 53%

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Recombination of Allyl Radicals in the High Temperature Fall-Off Regime

et al. 2013

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The recombination of allyl radicals (C3H5), generated from the dissociation of 1,5-hexadiene or allyl iodide dilute in krypton, has been investigated in a diaphragmless shock tube using laser schlieren densitometry, LS, (900-1700 K, 10 ± 1, 29 ± 3, 57 ± 3, and 120 ± 4 Torr). The LS density gradient profiles were simulated and excellent agreement was found between simulations and experimental profiles. Rate coefficients for C3H5I → C3H5 + I and C3H5 + C3H5 → C6H10 were obtained and showed strong fall-off. Second order rate coefficients for allyl radical recombination were determined as k(1a,124Torr) = (2.6 ± 0.8) × 10(55)T( -12.995) exp(-8426/T), k(1a,57Torr) = (1.7 ± 0.5) × 10(60)T( -14.49) exp(-9344/T), and k(1a,30Torr) = (7.5 ± 2.3) × 10(66)T( -15.935) exp(-10192/T) cm(3) mol(-1)s(-1). The contribution of a disproportionation channel in allyl radical reactions was assessed, and the best agreement was obtained with no more than 5% disproportionation. Notably, because both the forward and back reactions of C6H10 ⇌ C3H5 + C3H5 were measured, utilizing two different precursors, the equilibrium constant of this reaction could be found, suggesting an entropy of formation of 1,5-hexadiene, 87.3 cal mol(-1 )K(-1), which is significantly smaller than that group additivity predicts, but larger than other reference literature values.

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Section: Resultssupporting

confidence: 53%

“…Dissociation of allyl iodide has been investigated by a number of groups for T < 1070 K, ,, and the results were assumed to be at or close to the high pressure limit. LS experiments have an observation period of <10 μs and thus are typically conducted at higher temperatures than other techniques.…”

Section: Introductionmentioning

confidence: 99%

Recombination of Allyl Radicals in the High Temperature Fall-Off Regime

et al. 2013

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“…An activation energy E a = 75 kJ/mol was extracted from the data. This is significantly lower than the C-I bond dissociation energy (E 0 = 178 kJ/mol) and also lower than the activation energy E a = 173 kJ/mol reported by Maloney et al [39] based on shock tube measurements performed at temperatures T = 742 − 1068 K and total pressures around p ≈ 1 bar. Obviously, our low E a value indicates that the unimolecular allyliodide decomposition took place in the fall-off range under our experimental conditions.…”

Section: Methodscontrasting

confidence: 61%

The Products of the Reactions of o-Benzyne with Ethene, Propene, and Acetylene: A Combined Mass Spectrometric and Quantum Chemical Study

Friedrichs¹,

Goos²,

Gripp³

et al. 2009

Zeitschrift Für Physikalische Chemie

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The primary products of the bimolecular reactions of ortho-benzyne, o-C6H4 (1,2-dehydrobenzene), with ethene, propene, and acetylene have been detected by molecular beam mass spectrometry at a combustion relevant temperature of T = 1475 K. o-Benzyne was produced by flash pyrolysis of phthalic anhydride in the absence and presence of the respective reactant. Potential reaction pathways of the addition reactions were investigated by quantum chemical calculations. Channels with biradical intermediates were found to be energetically more favorable than alternative quasi-concerted [2+1] cycloaddition and concerted H-transfer pathways. Bicyclic benzocyclobutene and benzocyclobutadiene were identified as the main products of the reactions with C2H4 and C2H2, respectively. At combustion temperatures, however, these cyclic products are likely to undergo sequential ring opening. In the case of propene, the presence of an allylic H atom initiates a favorable ene-type reaction sequence yielding the open-chain product allylbenzene. Overall, hydrocarbon reactivity was found to increase in the order C2H2, C2H4 to 3H8. The range of the estimated bimolecular rate constants is comparable to the rate constants of the corresponding phenyl radical reactions and hence point out a potentially important role of o-C6H4 reactions in flame and soot formation chemistry.

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“…To within the precision of the velocity measurements, attenuation in the shock velocities was nil; from this an upper limit can be estimated of about 1% per meter of travel. Previous experience with the same shock tube [7] suggests that the actual attenuation may have been of the order of 0.5% per meter. Associated effects on shock properties in the time-distance regions in which kinetic measurements were performed were estimated to be negligible under all of our conditions.…”

Section: Apparatusmentioning

confidence: 96%

“…Previous experience with the same shock tube [7] suggests that the actual attenuation may have been of the order of 0.5% per meter. Associated effects on shock properties in the time-distance regions in which kinetic measurements were performed were estimated to be negligible under all of our conditions.…”

Section: Apparatusmentioning

confidence: 96%

Shock‐tube studies of the reactions of NO₂ with NO₂, SO₂, and CO

Freund

Palmer

1977

Int J of Chemical Kinetics

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The thermal decomposition of NO2 and its atom-transfer reactions with SO2 and CO have been studied behind incident shock waves using photometric detection methods. From the decomposition study it is possible to obtain information on the rate of the reaction 2N02 -antisynmetric-NOS + NO. The results on the reaction, NO2 + SO2 -NO + SO3 extend the earlier work of Armitage and Cullis to about 2000'K. The reaction with CO [NO2 + CO -NO + COs] a t shock temperatures is somewhat faster than predicted from available low-temperature data and provides a modification of the rate-constant expression that is applicable over a wide temperature range.

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The rate of dissociation of allyl iodide in shock waves

Cited by 7 publications

References 15 publications

Recombination of Allyl Radicals in the High Temperature Fall-Off Regime

Recombination of Allyl Radicals in the High Temperature Fall-Off Regime

The Products of the Reactions of o-Benzyne with Ethene, Propene, and Acetylene: A Combined Mass Spectrometric and Quantum Chemical Study

Shock‐tube studies of the reactions of NO₂ with NO₂, SO₂, and CO

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The rate of dissociation of allyl iodide in shock waves

Cited by 7 publications

References 15 publications

Recombination of Allyl Radicals in the High Temperature Fall-Off Regime

Recombination of Allyl Radicals in the High Temperature Fall-Off Regime

The Products of the Reactions of o-Benzyne with Ethene, Propene, and Acetylene: A Combined Mass Spectrometric and Quantum Chemical Study

Shock‐tube studies of the reactions of NO2 with NO2, SO2, and CO

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Shock‐tube studies of the reactions of NO₂ with NO₂, SO₂, and CO