Rate coefficients and mechanistic analysis for the reaction of hydroxyl radicals with 1,1-dichloroethylene and trans-1,2-dichloroethylene over an extended temperature range

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Article on rate coefficients and mechanistic analysis for the reaction of hydroxyl radicals with 1,1-dichloroethylene and trans-1,2-dichloroethylene over an extended temperature range.

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10 p.

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Yamada, Takahiro; El-Sinawi, Abdulaziz; Siraj, Mohammad Masud, 1972-; Taylor, Philip H.; Peng, Jingping; Hu, Xiaohua et al. July 17, 2001.

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Article on rate coefficients and mechanistic analysis for the reaction of hydroxyl radicals with 1,1-dichloroethylene and trans-1,2-dichloroethylene over an extended temperature range.

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10 p.

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Abstract: Rate coefficients are reported for the gas-phase reaction of the hydroxyl radical (OH) with 1,1-dichloroethylene (k1) and trans-1,2-dichloroethylene (k2) over an extended temperature range at 740 ± 10 Torr in a He bath gas. Absolute rate measurements were obtained using a laser photolysis/laser-induced fluorescence (LP/LIF) technique under slow flow conditions. Rate measurements for k1 exhibited complex behavior with negative temperature dependence at temperatures below 640 K, a rapid falloff in rate between 650 and 700 K, and positive temperature dependence from 700 to 750 K. The simple Arrhenius equation adequately describes the data below 640 K and above 700 K and is given (in units of cm3 molecule-1 s-1) by k1(291−640 K) = (1.81 ± 0.36) × 10-12 exp(511 ± 71)/T and k1(700−750 K) = 3.13 × 10-10 exp(−5176/T). Rate measurements for k2 also exhibited complex behavior with a near-zero or slightly negative temperature dependence below 500 K and a near-zero or slightly positive temperature dependence above 500 K. The modified Arrhenius equation adequately describes all of the data and is given (in units of cm3 molecule-1 s-1) by k2(293−720 K) = (9.75 ± 1.14) × 10-18 T1.73± 0.05 exp(727 ± 46)/T. Error limits are 2σ values. The room-temperature values for k1 and k2 are within ±2σ of previous data using different techniques. The rate measurements were modeled using QRRK theory. OH addition to the unsubstituted carbon followed by adduct stabilization describes the low-temperature measurements for k1. Analysis of equilibration in this system yields a C−O bond dissociation enthalpy of 32.8 ± 1.5 kcal mol-1 at 298 K, a value confirmed by ab initio calculations. OH addition followed by Cl elimination described the experimental data for k2. Ab initio based transition state calculations for the H atom abstraction channel indicated that this mechanism is consistent with the rate measurements for k1 above 700 K. The H abstraction channel for k2 could not be observed because of the presence of a more rapid Cl elimination channel at elevated temperatures. H abstraction is predicted to be the dominant reaction channel for both k1 and k2 at flame temperatures.

Reprinted with permission from the Journal of Physical Chemistry A. Copyright 2001 American Chemical Society.

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  • Journal of Physical Chemistry A, 2001, Washington D.C.: American Chemical Society, pp. 7588-7597

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  • Publication Title: Journal of Physical Chemistry A
  • Volume: 105
  • Issue: 32
  • Page Start: 7588
  • Page End: 7597
  • Pages: 10
  • Peer Reviewed: Yes

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  • July 17, 2001

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  • March 17, 2015, 10:38 a.m.

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Yamada, Takahiro; El-Sinawi, Abdulaziz; Siraj, Mohammad Masud, 1972-; Taylor, Philip H.; Peng, Jingping; Hu, Xiaohua et al. Rate coefficients and mechanistic analysis for the reaction of hydroxyl radicals with 1,1-dichloroethylene and trans-1,2-dichloroethylene over an extended temperature range, article, July 17, 2001; [Washington, D.C.]. (digital.library.unt.edu/ark:/67531/metadc501404/: accessed October 18, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.