Kinetics and mechanism of the tropospheric reaction of tetrahydropyran with Cl atoms

Ballesteros, Bernabé; Ceacero-Vega, Antonio A.; Garzón, Andrés; Jiménez, Elena; Albaladejo, José

doi:10.1016/j.jphotochem.2009.09.014

Cited by 22 publications

(33 citation statements)

References 43 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The rate coefficient of the reaction of the Cl atom with cycloheptene is (5.32 ± 0.57) × 10 −10 cm 3 molecule −1 s −1 [12]. Although the absence of heterogeneous chemistry cannot be completely ruled out in the present experimental conditions, the major products observed here match very well with those reported for THP in a 200 L Teflon bag [16], namely tetrahydro-4H-pyran-4-ol, tetrahydro-4H-pyran-4-one, tetrahydro-2H-pyran-2-one, 2-methyl tetrahydrofuran, tetrahydro-2-furanone, and ring-opened product 3-chloropropyl formate. Similar products, formed by H atom abstraction, are also observed in the case of Cl-initiated oxidation of THF.…”

Section: Resultssupporting

confidence: 83%

“…These cyclic ethers are known to react very fast with OH radicals, their reactivity being higher than that of the corresponding hydrocarbons. The recent relative rate measurements of the rate coefficients of the reactions of Cl atoms with THP [16,17] and THF [17] show the reactivity of THP to be lower than that of THF in spite of the increased number of CH 2 groups, and no clear trend is observed in the reactivity of Cl atoms with respect to the corresponding hydrocarbons. In the present study, the rate coefficients for the reaction of Cl atoms with THF and THP are measured at 298 K along with that of dihydrofurans, namely 2,5-dihydrofuran (2,5-DHF, also known as 3-oxolene) and 2,3-dihydrofuran (2,3-DHF or 2-oxolene), to see the effect of unsaturation.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Rate Coefficients for the Gas‐Phase Reactions of Chlorine Atoms with Cyclic Ethers at 298 K

Alwe

Walawalkar

Sharma

et al. 2013

Int J of Chemical Kinetics

View full text Add to dashboard Cite

Rate coefficients of reactions of Cl atoms with cyclic ethers, tetrahydropyran (THP), tetrahydrofuran (THF), and dihydrofurans (2,5-DHF and 2,3-DHF) have been measured at 298 K using a relative rate method. The relative rate ratios for THP and THF are 0.80 ± 0.05 and 0.80 ± 0.08, respectively, with n-hexane as the reference molecule. The relative rate ratios for THF and 2,5-DHF with n-pentane as the reference molecule are 0.95 ± 0.07 and 1.73 ± 0.06, respectively, and for 2,5-DHF with 1-butene as reference is 1.38 ± 0.05. The average values of the rate coefficients are (2.52 ± 0.36), (2.50 ± 0.39), and (4.48 ± 0.59) × 10 −10 cm 3 molecule −1 s −1 for THP, THF, and 2,5-DHF, respectively. The errors quoted here for relative rate ratios are 2σ of the statistical variation in different sets of experiments. These errors, combined with the reported errors of the reference rate coefficients using the statistical error propagation equation, are the quoted errors for the rate coefficients. In the case of 2,3-DHF, after correcting for the dark reaction with CH 3 COCl and assuming no interference from other radical reactions, a relative rate ratio of 0.85 ± 0.16 is obtained with respect to cycloheptene, corresponding to a rate coefficient of (4.52 ± 0.99) × 10 −10 cm 3 molecule −1 s −1 . Unlike cyclic hydrocarbons, there is no increase with increasing number of CH 2 groups in these cyclic ethers whereas there is an increase in the rate coefficient with unsaturation in the ring. An attempt is also made to correlate the rate coefficients of cyclic hydrocarbons and ethers with the molecular size as well as HOMO energy. C 2013 Wiley Periodicals, Inc. Int J Chem Kinet 45: [295][296][297][298][299][300][301][302][303][304][305] 2013

show abstract

Section: Resultssupporting

confidence: 83%

Section: Introductionmentioning

confidence: 99%

Rate Coefficients for the Gas‐Phase Reactions of Chlorine Atoms with Cyclic Ethers at 298 K

Alwe

Walawalkar

Sharma

et al. 2013

Int J of Chemical Kinetics

View full text Add to dashboard Cite

show abstract

“…[10][11][12][13][14] A brief description is provided below. Prior to performing the kinetic experiments, the analysis of CF 3 (CH 2 ) x CH 2 OH samples was carried out by static headspace gas chromatography/mass spectrometry (GC-MS) at room temperature to detect any impurity that could affect the determined rate coefficients.…”

Section: Methodsmentioning

confidence: 99%

“…In this work, S int was obtained from the linear leastsquares analysis of the plots of the integrated absorbance A int versus the HFA concentration [Eq. (14)]:…”

mentioning

confidence: 99%

Atmospheric Lifetimes and Global Warming Potentials of CF₃CH₂CH₂OH and CF₃(CH₂)₂CH₂OH

et al. 2010

View full text Add to dashboard Cite

A comprehensive study of several atmospheric degradation routes for two hydrofluoroalcohols, CF(3)(CH(2))(x=1,2)CH(2)OH, is presented. The gas-phase kinetics of their reactions with hydroxyl radicals (OH) and chlorine (Cl) atoms are investigated by absolute and relative techniques, respectively. The room-temperature rate coefficients (±σ, in cm(3) molecule(-1) s(-1)) k(OH) and k(Cl), are respectively (9.7±1.1)×10(-13) and (1.60±0.45)×10(-11) for CF(3)CH(2)CH(2)OH, and (2.62±0.32)×10(-12) and (8.71±0.24)×10(-11) for CF(3)(CH(2))(2)CH(2)OH. Average lifetimes of CF(3)CH(2)CH(2)OH and CF(3)(CH(2))(2)CH(2)OH due to the OH and Cl reactions are estimated to be 12 and 4 days, and greater than 20 and 4 years, respectively. Also, the IR and UV absorption cross sections of CF(3)(CH(2))(x=1,2)CH(2)OH are determined in the spectral ranges of 500-4000 cm(-1) and 200-310 nm. Photolysis of CF(3)(CH(2))(x=1,2)CH(2)OH in the actinic region (λ≥290 nm) is negligible compared to their homogeneous removal. Additionally, computational IR spectra are consistent with the experimental ones, thus giving high confidence in the obtained results. The lifetimes of CF(3)(CH(2))(x=1,2)CH(2)OH and IR spectra reported herein allow the calculation of the direct global warming potential of these hydrofluoroalcohols. The contribution of CF(3)(CH(2))(x)CH(2)OH to radiative forcing of climate change will be negligible.

show abstract

“…Although the kinetics of the OH reactions with cyclic ethers has been investigated in detail, [3,4] mechanistic studies have only been reported for 1,4-dioxane, [5,6] 1,3-dioxolane, [7] 1,3,5-trioxane [8] and tetrahydrofuran. [2] Ballesteros et al [9] have also investigated the kinetics and mechanisms for the reaction of chlorine (Cl) atoms with tetrahydropyran. The aim of this work is to investigate the atmospheric oxidation mechanism for another cyclic ether, 1,3-dioxane.…”

Section: Introductionmentioning

confidence: 99%

Product Study of the OH Radical and Cl Atom Initiated Oxidation of 1,3‐Dioxane

2010

View full text Add to dashboard Cite

The products of the hydroxyl (OH) radical and chlorine (Cl) atom initiated oxidation of 1,3-dioxane are determined under various reaction conditions in a 50 L teflon reaction chamber using FTIR spectroscopy for analysis. The major products detected in all experiments are (2-oxoethoxy)methyl formate, formic acid and methylene glycol diformate with average molar yields of 0.50±0.05, 0.41±0.02 and 0.03±0.01 respectively for the OH initiated oxidation in the presence of NO(x). The yields of these products do not vary significantly with O(2) partial pressure or oxidising agent (OH or Cl). However, the yield of formic acid decreased by at least a factor of two in the absence of NO(x). The results of these experiments are used to elucidate a simplified gas-phase atmospheric degradation scheme for 1,3-dioxane and also provide valuable information on the atmospheric fate of the cyclic and linear alkoxy radicals produced in these and similar reactions. The available experimental data suggests that the relative importance of the competing pathways (reaction with O(2) and ring opening by C-C or C-O bond fission) is a strong function of the ring strain in the cycloalkoxy radicals.

show abstract

Kinetics and mechanism of the tropospheric reaction of tetrahydropyran with Cl atoms

Cited by 22 publications

References 43 publications

Rate Coefficients for the Gas‐Phase Reactions of Chlorine Atoms with Cyclic Ethers at 298 K

Rate Coefficients for the Gas‐Phase Reactions of Chlorine Atoms with Cyclic Ethers at 298 K

Atmospheric Lifetimes and Global Warming Potentials of CF₃CH₂CH₂OH and CF₃(CH₂)₂CH₂OH

Product Study of the OH Radical and Cl Atom Initiated Oxidation of 1,3‐Dioxane

Contact Info

Product

Resources

About

Kinetics and mechanism of the tropospheric reaction of tetrahydropyran with Cl atoms

Cited by 22 publications

References 43 publications

Rate Coefficients for the Gas‐Phase Reactions of Chlorine Atoms with Cyclic Ethers at 298 K

Rate Coefficients for the Gas‐Phase Reactions of Chlorine Atoms with Cyclic Ethers at 298 K

Atmospheric Lifetimes and Global Warming Potentials of CF3CH2CH2OH and CF3(CH2)2CH2OH

Product Study of the OH Radical and Cl Atom Initiated Oxidation of 1,3‐Dioxane

Contact Info

Product

Resources

About

Atmospheric Lifetimes and Global Warming Potentials of CF₃CH₂CH₂OH and CF₃(CH₂)₂CH₂OH