Atmospheric chemistry of 3-methoxy-1-propanol and 3-methoxy-1-butanol: Kinetics with OH radicals and Cl atoms, identification of the end-products in the presence of NO, mechanisms and atmospheric implications

Barrera, Javier; Garavagno, María de los A.; Dalmasso, Pablo R.; Taccone, Raúl A.

doi:10.1016/j.atmosenv.2018.12.056

Cited by 10 publications

(20 citation statements)

References 45 publications

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“…25 Our results are in accordance with the experimental observations. 25 To confirm this claim, we calculated the pseudo-first-order rate coefficients for the IM2 + O 2 reaction shown in Scheme 1 at 298 K and 1 atm pressure utilizing the Mesmer kinetic code. The obtained rate coefficients are found to be 1.37 × 10 5 , 0.83, 3.79 × 10 −3 , 2.18 × 10 3 , and 3.54 × 10 2 s −1 for the formation of P1 + HO 2 , P2 + HO 2 , IM6A, IM6B, and IM6C, respectively.…”

Section: Initial Reactions Of 3m1polsupporting

confidence: 92%

“…Furthermore, our result is in line with the prediction from the experimental study. 25 Past studies have shown that M06-2X is the best method to predict the reaction's thermochemistry and kinetics. 58,59 Then, the geometries of all the species for the HO• + 3M1POL reaction are reoptimized by employing the M06-2X/6-311+ +G(d,p) method.…”

Section: Initial Reactions Of 3m1pol With Ho• Radicalsmentioning

confidence: 99%

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Atmospheric Degradation of 3-Methoxy-1-propanol by Reaction with Hydroxyl Radicals and Chlorine Atoms

Du,

Zhu,

Zhang

2024

ACS Earth Space Chem.

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The BH&HLYP/6-311++G(d,p) level of theory has been employed to investigate the degradation of 3-methoxy-1-propanol (3M1POL) initiated by HO• radicals. Additionally, the CCSD(T)/6-311++G(d,p) method is used to recalculate the single-point energies for each stationary point. For the reaction of 3M1POL + Cl•, the potential energy surface profile has been constructed at the CCSD(T)/cc-pVTZ// MP2/6-311++G(d,p) + 0.95 × ZPE level of theory. The results reveal that the abstractions at three −CH 2 − groups of 3M1POL play an important role in the oxidation mechanisms of 3M1POL with HO• radicals and Cl• atoms, yielding three intermediates:

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Section: Initial Reactions Of 3m1polsupporting

confidence: 92%

Section: Initial Reactions Of 3m1pol With Ho• Radicalsmentioning

confidence: 99%

Atmospheric Degradation of 3-Methoxy-1-propanol by Reaction with Hydroxyl Radicals and Chlorine Atoms

Du,

Zhu,

Zhang

2024

ACS Earth Space Chem.

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“…The rate coefficient for the title reaction at 296 ± 2 K and atmospheric pressure (750 ± 10 Torr) was determined by the conventional relative rate method described in previous works. − …”

Section: Methodsmentioning

confidence: 99%

“…The experimental setup was described in detail previously, and only a brief description will be given here. − The kinetic determinations were made in a collapsible Teflon bag of approximately 80 L. All of the reactants diluted in ultrapure air were left to mix in the reaction chamber for approximately 1 h before the first photolysis. The OH radicals were produced by the UV photolysis of H 2 O 2 at around 254 nm for which the Teflon bag was placed inside a wooden box with six germicidal lamps (Philips 30 W).…”

Section: Methodsmentioning

confidence: 99%

Rate Coefficient and Mechanism of the OH-Initiated Degradation of 1-Chlorobutane: Atmospheric Implications

et al. 2019

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In this work, we investigate the degradation process of 1chlorobutane, initiated by OH radicals, under atmospheric conditions (air pressure of 750 Torr and 296 K) from both experimental and theoretical approaches. In the first one, a relative kinetic method was used to obtain the rate coefficient for this reaction, while the products were identified for the first time (1-chloro-2-butanone, 1-chloro-2-butanol, 4-chloro-2butanone, 3-hydroxy-butanaldehyde, and 3-chloro-2-butanol) using mass spectrometry, allowing suggesting a reaction mechanism. The theoretical calculations, for the reactive process, were computed using the BHandHLYP/6-311++G(d,p) level of theory, and the energies for all of the stationary points were refined at the CCSD(T) level. Five conformers for 1-chlorobutane and 33 reactive channels with OH radicals were found, which were considered to calculate the thermal rate coefficient (as the sum of the site-specific rate coefficients using canonical transition state theory). The theoretical rate coefficient (1.8 × 10 −12 cm 3 molecule −1 s −1 ) is in good agreement with the experimental value (2.22 ± 0.50) × 10 −12 cm 3 molecule −1 s −1 determined in this work. Finally, environmental impact indexes were calculated and a discussion on the atmospheric implications due to the emissions of this compound into the troposphere was given.

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“…Heterogeneous reactions involving sea salt and ozone are also a source of Cl atoms in the marine boundary layer [31,32]. Over the last two decades, although several experimental and theoretical works debated the potential impact of Cl oxidation with numerous VOCs in the tropospheric chemistry [33][34][35][36][37], the reactivity of some unsaturated alcohols is still not well established.…”

Section: Introductionmentioning

confidence: 99%

Kinetic Measurements of Cl Atom Reactions with C5–C8 Unsaturated Alcohols

et al. 2020

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The reactions of five structurally similar unsaturated alcohols, i.e., (Z)-2-penten-1-ol, (E)-2-hexen-1-ol, (E)-3-hexen-1-ol, (Z)-3-hexen-1-ol, and 1-octen-3-ol, with Cl atoms in the gas phase, were investigated at 296 ± 2 K and 1 atm by the relative-rate kinetic technique using a 600-L Teflon reaction chamber. Selected ion flow tube mass spectrometry (SIFT-MS) was used simultaneously to monitor the decay of the alcohols of interest and selected reference compounds. Tetrahydrofuran (THF), propan-1-ol, and octane were used as reference compounds. Chlorine atoms were produced by the photolysis of molecular chlorine (Cl 2 ) using broadband actinic lamps near 365 nm. The estimated rate constant values (in 10 −10 cm 3 ·molecule −1 ·s −1 ) followed the order 2.99 ± 0.53 ((Z)-2-penten-1-ol) < 3.05 ± 0.59 ((E)-3-hexen-1-ol) < 3.15 ± 0.58 ((Z)-3-hexen-1-ol) < 3.41 ± 0.65 ((E)-2-hexen-1-ol) < 4.03 ± 0.77 (1-octen-3-ol). The present work provides the first value of the rate constant for the reaction of 1-octen-3-ol with Cl atoms. The results are discussed and interpreted in relation to other studies where literature data are available. The structure-activity relationship and the atmospheric implications are discussed as well.

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Atmospheric chemistry of 3-methoxy-1-propanol and 3-methoxy-1-butanol: Kinetics with OH radicals and Cl atoms, identification of the end-products in the presence of NO, mechanisms and atmospheric implications

Cited by 10 publications

References 45 publications

Atmospheric Degradation of 3-Methoxy-1-propanol by Reaction with Hydroxyl Radicals and Chlorine Atoms

Atmospheric Degradation of 3-Methoxy-1-propanol by Reaction with Hydroxyl Radicals and Chlorine Atoms

Rate Coefficient and Mechanism of the OH-Initiated Degradation of 1-Chlorobutane: Atmospheric Implications

Kinetic Measurements of Cl Atom Reactions with C5–C8 Unsaturated Alcohols

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