Pressure dependence of the rate constants for the reactions of ethene and propene with hydroxyl radicals at 295 K

Klein, Th.; Barnes, Ian; Becker, Karl‐Heinz; Fink, E.H.; Zabel, F.

doi:10.1021/j150665a046

Cited by 48 publications

(82 citation statements)

References 14 publications

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“…The room temperature relative rate data of Atkinson et al (1983a), , Behnke et al (1987Behnke et al ( , 1988 and McLoughlin et al (1993), which are not shown in the Arrhenius plot in Fig. 11, are also in good agreement with these data of Atkinson et al (1982a), Klein et al (1984), Donahue et al (1998) and DeMore and Bayes (1999). However, as shown by the dashed line in the Arrhenius plot (Fig.…”

Section: Oh+n-hexanesupporting

confidence: 73%

“…The available rate data are listed in Table 28, and to date only two absolute rate studies have been carried out, that of Koffend and Cohen (1996) at 962 K and that of over the temperature range 300-390 K. Furthermore, the only temperature-dependent studies are the absolute rate study of Donahue et al (1998) (300-390 K) and the relative rate study of DeMore and Bayes (1999) (292-397 K), with no rate constants having been measured below 290 K. Figure 11 shows an Arrhenius plot of the absolute rate constants of Koffend and Cohen (1996) and Klein et al (1984) and DeMore and Bayes (1999). In the temperature range 292-390 K the agreement between the absolute and relative rate studies is good.…”

Section: Oh+n-hexanementioning

confidence: 99%

“…11), a least-squares analysis of the rate constants from the studies of Atkinson et al (1982a), Klein et al (1984), Koffend and Cohen (1996), Donahue et al (1998) and DeMore and Bayes (1999) using the expression k=AT 2 e −B/T leads to a rate constant expression of k(n-hexane)=1.82×10 −17 T 2 e 361/T cm 3 molecule −1 s −1 over the temperature range 290-970 K, which does not fit the data particularly well. A least-squares analysis of the rate constants in the temperature range 292-390 K of Atkinson et al (1982a), Klein et al (1984), Donahue et al (1998) and DeMore and Bayes (1999) using the Arrhenius expression k=Ae −B/T leads to k(n−hexane)=2.29×10 −11 e −(442±52)/T cm 3 molecule −1 s −1 , where the indicated error in the value of B is two leastsquares standard deviations, and k(n−hexane)=5.20×10 −12 cm 3 molecule −1 s −1 at 298 K.…”

Section: Oh+n-hexanementioning

confidence: 99%

“…A least-squares analysis of the rate constants of Atkinson et al (1982a), Klein et al (1984), Koffend and Cohen (1996), Donahue et al (1998) and DeMore and Bayes (1999) with an estimated overall uncertainty at 298 K of ±20%. This expression is shown as the solid line in Fig.…”

Section: Oh+n-hexanementioning

confidence: 99%

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Kinetics of the gas-phase reactions of OH radicals with alkanes and cycloalkanes

2003

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Abstract. The available database concerning rate constants for gas-phase reactions of the hydroxyl (OH) radical with alkanes through early 2003 is presented over the entire temperature range for which measurements have been made (∼180-2000 K). Measurements made using relative rate methods are re-evaluated using recent rate data for the reference compound (generally recommendations from this review). In general, whenever more than one study has been carried out over an overlapping temperature range, recommended rate constants or temperature-dependent rate expressions are presented. The recommended 298 K rate constants, temperature-dependent parameters, and temperature ranges over which these recommendations are applicable are listed in Table 1.

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Section: Oh+n-hexanesupporting

confidence: 73%

Section: Oh+n-hexanementioning

confidence: 99%

Section: Oh+n-hexanementioning

confidence: 99%

Section: Oh+n-hexanementioning

confidence: 99%

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Kinetics of the gas-phase reactions of OH radicals with alkanes and cycloalkanes

2003

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“…Near room temperature the high-pressure limit is approached at pressures of about 1 atm. 36,37,51 The high-pressure addition rate constant for C 2 H 4 + OH was generally found to decrease slightly with increasing temperature in the 100-600 K range, with measured Arrhenius activation energies ranging from -2.3 to 0.0 kcal/ mol. 23,31,36,43,51,53 Lower-temperature studies have been limited to Leone and co-workers' 53 study over the temperature range from 96 to 296 K using the pulsed Laval nozzle technique.…”

Section: Introductionmentioning

confidence: 99%

A Two Transition State Model for Radical−Molecule Reactions: Applications to Isomeric Branching in the OH−Isoprene Reaction

et al. 2007

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A two transition state model is applied to the study of the addition of hydroxyl radical to ethylene. This reaction serves as a prototypical example of a radical-molecule reaction with a negative activation energy in the high-pressure limit. The model incorporates variational treatments of both inner and outer transition states. The outer transition state is treated with a recently derived long-range transition state theory approach focusing on the longest-ranged term in the potential. High-level quantum chemical estimates are incorporated in a variational transition state theory treatment of the inner transition state. Anharmonic effects in the inner transition state region are explored with direct phase space integration. A two-dimensional master equation is employed in treating the pressure dependence of the addition process. An accurate treatment of the two separate transition state regions at the energy and angular momentum resolved level is essential to the prediction of the temperature dependence of the addition rate. The transition from a dominant outer transition state to a dominant inner transition state is predicted to occur at about 130 K, with significant effects from both transition states over the 10 to 400 K temperature range. Modest adjustment in the ab initio predicted inner saddle point energy yields theoretical predictions which are in quantitative agreement with the available experimental observations. The theoretically predicted capture rate is reproduced to within 10% by the expression [4.93 × 10 -12 (T/298) -2.488 exp(-107.9/RT) + 3.33 × 10 -12 (T/298) 0.451 exp(117.6/RT); with R ) 1.987 and T in K] cm 3 molecules -1 s -1 over the 10-600 K range.

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The High Pressure Range of the Addition of OH to C₂H₂ and C₂H₄

Fülle

Hamann

Hippler

et al. 1997

Ber Bunsenges Phys Chem

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The kinetics of the bimolecular reactions OH+C 2H2+M ... C 2H20H+M (I) and OH+C 2H4+M ... C 2H40H + M (2) have been investigated over an extended pressure (1-130 bar) and temperature (300-800 K) range. The OH radicals have been generated by laser flash photolysis of suited precursors and their decays have been measured by saturated laser-induced fluorescence (SLIF) under pseudo-first-order conditions. The pressure dependences have been analyzed by constructing falloff curves at fixed temperatures leading to reliable extrapolations towards the high pressure limiting rate constants k co' In the given temperature range these rate constants are represented as k l • co = 3.8xlO-11 exp(-910KIT)cm 3 molecule-I S-I and as k 2.co = 1.0xlO-11 em? molecule -I s -I . At temperatures above 700 K biexponential decay curves have been obtained. The chemical equilibria of reactions (1) and (2)

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Pressure dependence of the rate constants for the reactions of ethene and propene with hydroxyl radicals at 295 K

Cited by 48 publications

References 14 publications

Kinetics of the gas-phase reactions of OH radicals with alkanes and cycloalkanes

Kinetics of the gas-phase reactions of OH radicals with alkanes and cycloalkanes

A Two Transition State Model for Radical−Molecule Reactions: Applications to Isomeric Branching in the OH−Isoprene Reaction

The High Pressure Range of the Addition of OH to C₂H₂ and C₂H₄

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Pressure dependence of the rate constants for the reactions of ethene and propene with hydroxyl radicals at 295 K

Cited by 48 publications

References 14 publications

Kinetics of the gas-phase reactions of OH radicals with alkanes and cycloalkanes

Kinetics of the gas-phase reactions of OH radicals with alkanes and cycloalkanes

A Two Transition State Model for Radical−Molecule Reactions: Applications to Isomeric Branching in the OH−Isoprene Reaction

The High Pressure Range of the Addition of OH to C2H2 and C2H4

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The High Pressure Range of the Addition of OH to C₂H₂ and C₂H₄