PLP–LIF study of the reactions of chlorine atoms with C2H2, C2H4, and C3H6 in 2–100 Torr of N2 diluent at 295 K

Iwasaki, Erika; Chiba, Hitoshi; Nakayama, Tomoki; Matsumi, Yutaka; Wallington, Timothy J.

doi:10.1016/j.cplett.2010.06.034

Cited by 5 publications

(5 citation statements)

References 38 publications

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“…Reaction R8 has been studied by direct time resolved methods by observing the decay of Cl atoms in the presence of excess ethene, but such studies are costly. Iwasaki et al [44] have produced an elegant study where reaction R8 has been studied by direct techniques and the results are in good agreement with the much simpler relative rate method. In a relative rate method a pair of hydrocarbons (the test reagent, SH, and a reference compound, RH) are reacted with the radical species, X.…”

Section: CLmentioning

confidence: 53%

A brief review of the use of environmental chambers for gas phase studies of kinetics, chemical mechanisms and characterisation of field instruments

Seakins

2010

EPJ Web of Conferences

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Abstract. This introductory review considers the role of environmental chambers in atmospheric chemistry, emphasising the importance of being able to carry out studies in controlled conditions. The advantages and disadvantages of different types of chambers are discussed and compared. Examples of the use of chambers for kinetic and mechanistic studies are presented. The final section of this brief review considers the use of chambers in providing a well defined environment for calibrating and investigating the performance of field instruments.

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Section: CLmentioning

confidence: 53%

A brief review of the use of environmental chambers for gas phase studies of kinetics, chemical mechanisms and characterisation of field instruments

Seakins

2010

EPJ Web of Conferences

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“…To check the consistency of the results the relative rates of the reference reactions were determined. Based on literature data the expected ratio k (C2H6+Cl) / k (C2H2+Cl) is 1.1 ± 0.1. , In experiments performed with C 2 H 6 and C 2 H 2 , the relative rate ratios 1.22 and 1.10 were obtained.…”

Section: Resultsmentioning

confidence: 84%

“…Based on literature data the expected ratio k (C2H6+Cl) /k (C2H2+Cl) is 1.1 ± 0.1. 33,34 In was used as a reference in 2(5H)-F measurements. The relative rate plots for the OD reactions of GVL are shown in Figure 3.…”

Section: Resultsmentioning

confidence: 99%

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Reactions of Three Lactones with Cl, OD, and O₃: Atmospheric Impact and Trends in Furan Reactivity

et al. 2017

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Lactones, cyclic esters of hydroxycarboxylic acids, are interesting biofuel candidates as they can be made from cellulosic biomass and have favorable physical and chemical properties for distribution and use. The reactions of γ-valerolactone (GVL), γ-crotonolactone (2(5H)-F), and α-methyl-γ-crotonolactone (3M-2(5H)-F) with Cl, OD, and O were investigated in a static chamber at 700 Torr and 298 ± 2 K. The relative rate method was used to determine k = (4.56 ± 0.51) × 10, k = (2.94 ± 0.41) × 10, k = (2.94 ± 0.41) × 10, k = (4.06 ± 0.073) × 10, k = (16.1 ± 1.8) × 10, and k = (12.6 ± 0.52) × 10, all rate coefficients in units of cm molecule s. An absolute rate method was used to determine k = (6.73 ± 0.18) × 10 and k = (5.42 ± 1.23) × 10 in units of cm molecule s. Products were identified for reactions of the lactones with Cl. In the presence of O the products are formic acid (HCOOH), formyl chloride (CHClO), and phosgene (CClO), and also maleic anhydride (CH(CO)O) for 2(5H)-F. In addition both reactions produced a number of unidentified products that likely belong to molecules with the ring-structure intact. A review of literature data for reactions of other furans show that the reactivity of the lactones are generally lower compared to that of corresponding compounds without the carbonyl group.

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“…where we carry out calculations for the condition where the pressure is high enough that the kinetics is in the pressureindependent second-order regime. The temperature and pressure dependence of reaction 1 have been studied both experimentally (28)(29)(30)(31)(32)(33)(34)(35)(36) and theoretically (36,37). Experimental measurements of association rate constants generally do not go to high enough pressure to measure the high-pressure equilibrium limit directly, and this limit is obtained by theory-guided extrapolation.…”

mentioning

confidence: 99%

Association of Cl with C ₂ H ₂ by unified variable-reaction-coordinate and reaction-path variational transition-state theory

Zhang

Truhlar

Sun

2020

Proc. Natl. Acad. Sci. U.S.A.

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Barrierless unimolecular association reactions are prominent in atmospheric and combustion mechanisms but are challenging for both experiment and kinetics theory. A key datum for understanding the pressure dependence of association and dissociation reactions is the high-pressure limit, but this is often available experimentally only by extrapolation. Here we calculate the high-pressure limit for the addition of a chlorine atom to acetylene molecule (Cl + C2H2→C2H2Cl). This reaction has outer and inner transition states in series; the outer transition state is barrierless, and it is necessary to use different theoretical frameworks to treat the two kinds of transition state. Here we study the reaction in the high-pressure limit using multifaceted variable-reaction-coordinate variational transition-state theory (VRC-VTST) at the outer transition state and reaction-path variational transition state theory (RP-VTST) at the inner turning point; then we combine the results with the canonical unified statistical (CUS) theory. The calculations are based on a density functional validated against the W3X-L method, which is based on coupled cluster theory with single, double, and triple excitations and a quasiperturbative treatment of connected quadruple excitations [CCSDT(Q)], and the computed rate constants are in good agreement with some of the experimental results. The chlorovinyl (C2H2Cl) adduct has two isomers that are equilibrium structures of a double-well C≡C–H bending potential. Two procedures are used to calculate the vibrational partition function of chlorovinyl; one treats the two isomers separately and the other solves the anharmonic energy levels of the double well. We use these results to calculate the standard-state free energy and equilibrium constant of the reaction.

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PLP–LIF study of the reactions of chlorine atoms with C2H2, C2H4, and C3H6 in 2–100 Torr of N2 diluent at 295 K

Cited by 5 publications

References 38 publications

A brief review of the use of environmental chambers for gas phase studies of kinetics, chemical mechanisms and characterisation of field instruments

A brief review of the use of environmental chambers for gas phase studies of kinetics, chemical mechanisms and characterisation of field instruments

Reactions of Three Lactones with Cl, OD, and O₃: Atmospheric Impact and Trends in Furan Reactivity

Association of Cl with C ₂ H ₂ by unified variable-reaction-coordinate and reaction-path variational transition-state theory

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PLP–LIF study of the reactions of chlorine atoms with C2H2, C2H4, and C3H6 in 2–100 Torr of N2 diluent at 295 K

Cited by 5 publications

References 38 publications

A brief review of the use of environmental chambers for gas phase studies of kinetics, chemical mechanisms and characterisation of field instruments

A brief review of the use of environmental chambers for gas phase studies of kinetics, chemical mechanisms and characterisation of field instruments

Reactions of Three Lactones with Cl, OD, and O3: Atmospheric Impact and Trends in Furan Reactivity

Association of Cl with C 2 H 2 by unified variable-reaction-coordinate and reaction-path variational transition-state theory

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Reactions of Three Lactones with Cl, OD, and O₃: Atmospheric Impact and Trends in Furan Reactivity

Association of Cl with C ₂ H ₂ by unified variable-reaction-coordinate and reaction-path variational transition-state theory