Atmospheric Chemistry of Tetrahydrofuran, 2-Methyltetrahydrofuran, and 2,5-Dimethyltetrahydrofuran: Kinetics of Reactions with Chlorine Atoms, OD Radicals, and Ozone

Christina Andersen; Ole John Nielsen; Freja F. Østerstrøm; Stina Ausmeel; Elna J.K. Nilsson; Mads P. Sulbaek Andersen

doi:10.1021/acs.jpca.6b06618

Atmospheric Chemistry of Tetrahydrofuran, 2-Methyltetrahydrofuran, and 2,5-Dimethyltetrahydrofuran: Kinetics of Reactions with Chlorine Atoms, OD Radicals, and Ozone

Christina Andersen, Ole John Nielsen, Freja F. Østerstrøm, Stina Ausmeel, Elna J.K. Nilsson, Mads P. Sulbaek Andersen^*

^*Corresponding author for this work

Environment and Geography

Research output: Contribution to journal › Article › peer-review

Abstract

FTIR smog chamber techniques were used to study the kinetics of the gas-phase reactions of Cl atoms, OD radicals, and O₃ with the five-membered ring-structured compounds tetrahydrofuran (C₄H₈O, THF), 2-methyltetrahydrofuran (CH₃C₄H₇O, 2-MTHF), 2,5-dimethyltetrahydrofuran ((CH₃)₂C₄H₅O, 2,5-DMTHF), and furan (C₄H₄O). The rate coefficients determined using relative rate methods were k_THF+Cl = (1.96 ± 0.24) × 10^-10, k_THF+OD = (1.81 ± 0.27) × 10^-11, k_THF+O₃ = (6.41 ± 2.90) × 10^-21, k_2-MTHF+Cl = (2.65 ± 0.43) × 10^-10, k_2-MTHF+OD = (2.41 ± 0.51) × 10^-11, k_2-MTHF+O₃ = (1.87 ± 0.82) × 10^-20, k_2,5-DMTHF+OD = (4.56 ± 0.68) × 10^-11, k_2,5-DMTHF+Cl = (2.84 ± 0.34) × 10^-10, k_{2,5-DMTHF+O₃} = (4.58 ± 2.18), k_furan+Cl = (2.39 ± 0.27) × 10^-10, and k_furan+O₃ = (2.60 ± 0.31) × 10^-18 molecules cm^-3 s^-1. Rate coefficients of the reactions with ozone were also determined using the absolute rate method under pseudo-first-order conditions. OD radicals, in place of OH radicals, were produced from CD₃ONO to avoid spectral overlap of isopropyl and methyl nitrite with the reactants. The kinetics of OD radical reactions are expected to resemble the kinetics of OH radical reactions, and the rate coefficients of the reactions with OD radicals were used to calculate the atmospheric lifetimes with respect to reactions with OH radicals. The lifetimes of THF, 2-MTHF, and 2,5-DMTHF are approximately 15, 12, and 6 h, respectively.

Original language	English
Pages (from-to)	7320-7326
Number of pages	7
Journal	Journal of Physical Chemistry A
Volume	120
Issue number	37
Early online date	24 Aug 2016
DOIs	https://doi.org/10.1021/acs.jpca.6b06618
Publication status	Published - 22 Sept 2016

Access to Document

10.1021/acs.jpca.6b06618

Cite this

Andersen, C., Nielsen, O. J., Østerstrøm, F. F., Ausmeel, S., Nilsson, E. J. K., & Sulbaek Andersen, M. P. (2016). Atmospheric Chemistry of Tetrahydrofuran, 2-Methyltetrahydrofuran, and 2,5-Dimethyltetrahydrofuran: Kinetics of Reactions with Chlorine Atoms, OD Radicals, and Ozone. Journal of Physical Chemistry A, 120(37), 7320-7326. https://doi.org/10.1021/acs.jpca.6b06618

@article{e9782206b74248b38e8f7343236c3f21,

title = "Atmospheric Chemistry of Tetrahydrofuran, 2-Methyltetrahydrofuran, and 2,5-Dimethyltetrahydrofuran: Kinetics of Reactions with Chlorine Atoms, OD Radicals, and Ozone",

abstract = "FTIR smog chamber techniques were used to study the kinetics of the gas-phase reactions of Cl atoms, OD radicals, and O3 with the five-membered ring-structured compounds tetrahydrofuran (C4H8O, THF), 2-methyltetrahydrofuran (CH3C4H7O, 2-MTHF), 2,5-dimethyltetrahydrofuran ((CH3)2C4H5O, 2,5-DMTHF), and furan (C4H4O). The rate coefficients determined using relative rate methods were kTHF+Cl = (1.96 ± 0.24) × 10-10, kTHF+OD = (1.81 ± 0.27) × 10-11, kTHF+O3 = (6.41 ± 2.90) × 10-21, k2-MTHF+Cl = (2.65 ± 0.43) × 10-10, k2-MTHF+OD = (2.41 ± 0.51) × 10-11, k2-MTHF+O3 = (1.87 ± 0.82) × 10-20, k2,5-DMTHF+OD = (4.56 ± 0.68) × 10-11, k2,5-DMTHF+Cl = (2.84 ± 0.34) × 10-10, k2,5-DMTHF+O3 = (4.58 ± 2.18), kfuran+Cl = (2.39 ± 0.27) × 10-10, and kfuran+O3 = (2.60 ± 0.31) × 10-18 molecules cm-3 s-1. Rate coefficients of the reactions with ozone were also determined using the absolute rate method under pseudo-first-order conditions. OD radicals, in place of OH radicals, were produced from CD3ONO to avoid spectral overlap of isopropyl and methyl nitrite with the reactants. The kinetics of OD radical reactions are expected to resemble the kinetics of OH radical reactions, and the rate coefficients of the reactions with OD radicals were used to calculate the atmospheric lifetimes with respect to reactions with OH radicals. The lifetimes of THF, 2-MTHF, and 2,5-DMTHF are approximately 15, 12, and 6 h, respectively.",

author = "Christina Andersen and Nielsen, {Ole John} and {\O}sterstr{\o}m, {Freja F.} and Stina Ausmeel and Nilsson, {Elna J.K.} and {Sulbaek Andersen}, {Mads P.}",

year = "2016",

month = sep,

day = "22",

doi = "10.1021/acs.jpca.6b06618",

language = "English",

volume = "120",

pages = "7320--7326",

journal = "Journal of Physical Chemistry A",

issn = "1089-5639",

publisher = "American Chemical Society",

number = "37",

}

Andersen, C, Nielsen, OJ, Østerstrøm, FF, Ausmeel, S, Nilsson, EJK & Sulbaek Andersen, MP 2016, 'Atmospheric Chemistry of Tetrahydrofuran, 2-Methyltetrahydrofuran, and 2,5-Dimethyltetrahydrofuran: Kinetics of Reactions with Chlorine Atoms, OD Radicals, and Ozone', Journal of Physical Chemistry A, vol. 120, no. 37, pp. 7320-7326. https://doi.org/10.1021/acs.jpca.6b06618

Atmospheric Chemistry of Tetrahydrofuran, 2-Methyltetrahydrofuran, and 2,5-Dimethyltetrahydrofuran: Kinetics of Reactions with Chlorine Atoms, OD Radicals, and Ozone. / Andersen, Christina; Nielsen, Ole John; Østerstrøm, Freja F. et al.
In: Journal of Physical Chemistry A, Vol. 120, No. 37, 22.09.2016, p. 7320-7326.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Atmospheric Chemistry of Tetrahydrofuran, 2-Methyltetrahydrofuran, and 2,5-Dimethyltetrahydrofuran

T2 - Kinetics of Reactions with Chlorine Atoms, OD Radicals, and Ozone

AU - Andersen, Christina

AU - Nielsen, Ole John

AU - Østerstrøm, Freja F.

AU - Ausmeel, Stina

AU - Nilsson, Elna J.K.

AU - Sulbaek Andersen, Mads P.

PY - 2016/9/22

Y1 - 2016/9/22

N2 - FTIR smog chamber techniques were used to study the kinetics of the gas-phase reactions of Cl atoms, OD radicals, and O3 with the five-membered ring-structured compounds tetrahydrofuran (C4H8O, THF), 2-methyltetrahydrofuran (CH3C4H7O, 2-MTHF), 2,5-dimethyltetrahydrofuran ((CH3)2C4H5O, 2,5-DMTHF), and furan (C4H4O). The rate coefficients determined using relative rate methods were kTHF+Cl = (1.96 ± 0.24) × 10-10, kTHF+OD = (1.81 ± 0.27) × 10-11, kTHF+O3 = (6.41 ± 2.90) × 10-21, k2-MTHF+Cl = (2.65 ± 0.43) × 10-10, k2-MTHF+OD = (2.41 ± 0.51) × 10-11, k2-MTHF+O3 = (1.87 ± 0.82) × 10-20, k2,5-DMTHF+OD = (4.56 ± 0.68) × 10-11, k2,5-DMTHF+Cl = (2.84 ± 0.34) × 10-10, k2,5-DMTHF+O3 = (4.58 ± 2.18), kfuran+Cl = (2.39 ± 0.27) × 10-10, and kfuran+O3 = (2.60 ± 0.31) × 10-18 molecules cm-3 s-1. Rate coefficients of the reactions with ozone were also determined using the absolute rate method under pseudo-first-order conditions. OD radicals, in place of OH radicals, were produced from CD3ONO to avoid spectral overlap of isopropyl and methyl nitrite with the reactants. The kinetics of OD radical reactions are expected to resemble the kinetics of OH radical reactions, and the rate coefficients of the reactions with OD radicals were used to calculate the atmospheric lifetimes with respect to reactions with OH radicals. The lifetimes of THF, 2-MTHF, and 2,5-DMTHF are approximately 15, 12, and 6 h, respectively.

AB - FTIR smog chamber techniques were used to study the kinetics of the gas-phase reactions of Cl atoms, OD radicals, and O3 with the five-membered ring-structured compounds tetrahydrofuran (C4H8O, THF), 2-methyltetrahydrofuran (CH3C4H7O, 2-MTHF), 2,5-dimethyltetrahydrofuran ((CH3)2C4H5O, 2,5-DMTHF), and furan (C4H4O). The rate coefficients determined using relative rate methods were kTHF+Cl = (1.96 ± 0.24) × 10-10, kTHF+OD = (1.81 ± 0.27) × 10-11, kTHF+O3 = (6.41 ± 2.90) × 10-21, k2-MTHF+Cl = (2.65 ± 0.43) × 10-10, k2-MTHF+OD = (2.41 ± 0.51) × 10-11, k2-MTHF+O3 = (1.87 ± 0.82) × 10-20, k2,5-DMTHF+OD = (4.56 ± 0.68) × 10-11, k2,5-DMTHF+Cl = (2.84 ± 0.34) × 10-10, k2,5-DMTHF+O3 = (4.58 ± 2.18), kfuran+Cl = (2.39 ± 0.27) × 10-10, and kfuran+O3 = (2.60 ± 0.31) × 10-18 molecules cm-3 s-1. Rate coefficients of the reactions with ozone were also determined using the absolute rate method under pseudo-first-order conditions. OD radicals, in place of OH radicals, were produced from CD3ONO to avoid spectral overlap of isopropyl and methyl nitrite with the reactants. The kinetics of OD radical reactions are expected to resemble the kinetics of OH radical reactions, and the rate coefficients of the reactions with OD radicals were used to calculate the atmospheric lifetimes with respect to reactions with OH radicals. The lifetimes of THF, 2-MTHF, and 2,5-DMTHF are approximately 15, 12, and 6 h, respectively.

UR - http://www.scopus.com/inward/record.url?scp=84988691023&partnerID=8YFLogxK

U2 - 10.1021/acs.jpca.6b06618

DO - 10.1021/acs.jpca.6b06618

M3 - Article

AN - SCOPUS:84988691023

SN - 1089-5639

VL - 120

SP - 7320

EP - 7326

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

IS - 37

ER -

Atmospheric Chemistry of Tetrahydrofuran, 2-Methyltetrahydrofuran, and 2,5-Dimethyltetrahydrofuran: Kinetics of Reactions with Chlorine Atoms, OD Radicals, and Ozone

Abstract

Access to Document

Other files and links

Cite this