Experimental and theoretical rate coefficients for the gas phase reaction of β-Pinene with OH radical

Dash, Manas Ranjan; Rajakumar, B.

doi:10.1016/j.atmosenv.2013.05.039

Cited by 29 publications

(18 citation statements)

References 48 publications

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“…The equilibrium geometries and harmonic vibrational frequencies of the reactants (cis-CHF=CHCHF 2 , trans-CHF=CHCHF 2 , CF 2 =CHCHF 2, CF 2 =C=CHF and OH), pre-reactive complexes ( RCα , RCβ, RCγ ) for addition reactions, addition transition states (TSα, TSβ, TSγ ), hydrogen abstraction transition states (Ab-TSα, Ab-TSβ, Ab-TSγ ) and products formed in the abstraction and addition reactions of OH radical with title molecules were optimized at M06-2X/6-31+G(d,p) level of theory. M06-2X functional has previously been shown to perform well in predicting the transition state geometries and vibrational frequencies [13][14][15][16]. Truhlar and co-workers [17] concluded that M06-2X functional is highly recommended for the study of main-group thermochemistry, kinetics and also for the prediction of noncovalent interactions.…”

Section: Computational Methodologymentioning

confidence: 99%

Kinetic parameters for the reaction of OH radical with cis-CHFCHCHF2, trans-CHFCHCHF2, CF2CHCHF2 and CF2CCHF: Hybrid meta DFT and CVT/SCT/ISPE calculations

Ramanjaneyulu

Rajakumar

2015

Journal of Fluorine Chemistry

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Section: Computational Methodologymentioning

confidence: 99%

Kinetic parameters for the reaction of OH radical with cis-CHFCHCHF2, trans-CHFCHCHF2, CF2CHCHF2 and CF2CCHF: Hybrid meta DFT and CVT/SCT/ISPE calculations

Ramanjaneyulu

Rajakumar

2015

Journal of Fluorine Chemistry

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“…Also, the ozone formation potential of the test molecule was calculated to be negligibly small (0.229 ppm). The detailed procedure to calculate the ozone formation potential was discussed in our previous publication …”

Section: Resultsmentioning

confidence: 99%

Kinetic Investigations on the Gas Phase Reaction of 2,2,2‐Trifluoroethylbutyrate with OH Radicals: An Experimental and Theoretical Study

2018

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The temperature dependent rate coefficients for the reaction between 2,2,2‐trifluoroethylbutyrate (2,2,2‐TFEB) with OH radicals were measured as a function of temperature (268‐343 K) and pressure (400‐760 Torr; N2 and O2) using relative rate technique. The temperature dependent rate coefficients for the gas phase reaction of 2,2,2‐TFEB + OH were used to deduce the Arrhenius expression: k(268‐343 K) = (2.72 ± 1.3)×10−13 exp{(530± 72)/T}cm3 molecule−1 s−1. At 298 K, the rate coefficient for the title reaction was obtained to be (1.58 ± 0.42) ×10−12 cm3 molecule−1 s−1. Extensive computational calculations were also performed as a complement to the present experimental study using canonical variational transition state theory (CVT) with small curvature tunnelling (SCT) correction in combination with the CCSD(T)/CC‐PVDZ//M062X/6‐31+G(d,p) level of theory. The atmospheric lifetime of the test molecule due to its reaction with OH radical is about 3 days, which is short lived. And therefore, its contribution towards the global warming potentials can be insignificant. The ozone formation potential of the test molecule is calculated to be 0.229 ppm, which is again negligible.

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“…From the slopes of the plots (k SA /k R ) and using known values of the rate coefficients for the reference compounds employed (k R ), the value of the absolute rate coefficient for each saturated alcohol (k SA ) was determined. Rate coefficients of the reactions of reference compounds with Cl atom reactions (in 10 −10 cm 3 molecule −1 s −1 ) were 3.40 ± 0.28 for 2methylpropene, 3.38 ± 0.48 for 1-butene (Ezzel et al, 2002), and 2.23 ± 0.31 for propene (Ceacero-Vega et al, 2009); rate coefficients of the reactions of reference compounds with OH radicals (in 10 −11 cm 3 molecule −1 s −1 ) were 2.66±0.40 for propene (Atkinson and Aschmann, 1989), 6.77 ± 1.69 for cyclohexene (Atkinson and Arey, 2003), 0.51 ± 0.008 for isopropanol (IUPAC http://www.iupac-kinetic.ch.cam.ac.uk, last access: 19 December 2017), and 0.36 ± 0.06 for 2methyl-2-butanol (Jiménez et al, 2005); and rate coefficients of the reactions of reference compounds with NO 3 radicals (in 10 −15 cm 3 molecule −1 s −1 ) were 3.14 ± 0.97 for 1butanol and 2.93 ± 0.92 2-ethyl-1-hexanol (Gallego-Iniesta et al, 2010).…”

Section: Kinetic Studymentioning

confidence: 98%

Atmospheric fate of a series of saturated alcohols: kinetic and mechanistic study

et al. 2020

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Abstract. The atmospheric fate of a series of saturated alcohols (SAs) was evaluated through kinetic and reaction product studies with the main atmospheric oxidants. These SAs are alcohols that could be used as fuel additives. Rate coefficients (in cm3 molecule−1 s−1) measured at ∼298 K and atmospheric pressure (720±20 Torr) were as follows: k1 ((E)-4-methylcyclohexanol + Cl) = (3.70±0.16) ×10-10, k2 ((E)-4-methylcyclohexanol + OH) = (1.87±0.14) ×10-11, k3 ((E)-4-methylcyclohexanol + NO3) = (2.69±0.37) ×10-15, k4 (3,3-dimethyl-1-butanol + Cl) = (2.69±0.16) ×10-10, k5 (3,3-dimethyl-1-butanol + OH) = (5.33±0.16) ×10-12, k6 (3,3-dimethyl-2-butanol + Cl) = (1.21±0.07) ×10-10, and k7 (3,3-dimethyl-2-butanol + OH) = (10.50±0.25) ×10-12. The main products detected in the reaction of SAs with Cl atoms (in the absence/presence of NOx), OH radicals, and NO3 radicals were (E)-4-methylcyclohexanone for the reactions of (E)-4-methylcyclohexanol, 3,3-dimethylbutanal for the reactions of 3,3-dimethyl-1-butanol, and 3,3-dimethyl-2-butanone for the reactions of 3,3-dimethyl-2-butanol. Other products such as formaldehyde, 2,2-dimethylpropanal, and acetone have also been identified in the reactions of Cl atoms and OH radicals with 3,3-dimethyl-1-butanol and 3,3-dimethyl-2-butanol. In addition, the molar yields of the reaction products were estimated. The products detected indicate a hydrogen atom abstraction mechanism at different sites on the carbon chain of alcohol in the case of Cl reactions and a predominant site in the case of OH and NO3 reactions, confirming the predictions of structure–activity relationship (SAR) methods. Tropospheric lifetimes (τ) of these SAs have been calculated using the experimental rate coefficients. Lifetimes are in the range of 0.6–2 d for OH reactions, 7–13 d for NO3 radical reactions, and 1–3 months for Cl atoms. In coastal areas, the lifetime due to the reaction with Cl decreases to hours. The calculated global tropospheric lifetimes, and the polyfunctional compounds detected as reaction products in this work, imply that SAs could contribute to the formation of ozone and nitrated compounds at local, regional, and even global scales. Therefore, the use of saturated alcohols as additives in diesel blends should be considered with caution.

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Experimental and theoretical rate coefficients for the gas phase reaction of β-Pinene with OH radical

Cited by 29 publications

References 48 publications

Kinetic parameters for the reaction of OH radical with cis-CHFCHCHF2, trans-CHFCHCHF2, CF2CHCHF2 and CF2CCHF: Hybrid meta DFT and CVT/SCT/ISPE calculations

Kinetic parameters for the reaction of OH radical with cis-CHFCHCHF2, trans-CHFCHCHF2, CF2CHCHF2 and CF2CCHF: Hybrid meta DFT and CVT/SCT/ISPE calculations

Kinetic Investigations on the Gas Phase Reaction of 2,2,2‐Trifluoroethylbutyrate with OH Radicals: An Experimental and Theoretical Study

Atmospheric fate of a series of saturated alcohols: kinetic and mechanistic study

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