Kinetics of OH radical reaction with allyl alcohol (H2CCHCH2OH) and propargyl alcohol (HCCCH2OH) studied by LIF

Upadhyaya, Hari P.; Kumar, Awadhesh; Naik, Prakash D.; Sapre, A. V.; Mittal, Jai P.

doi:10.1016/s0009-2614(01)01218-0

Cited by 31 publications

(50 citation statements)

References 19 publications

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“…Our rate coefÞcients are consistent with the relative and absolute rate results from Le Person et al [11] and Parker and Espada-Jallad [12]. The pulsed laser photolysis-laser-induced ßuo-rescence (PLP-LIF) measurements by Upadhyaya et al [9] in 10-20 Torr argon give a rate coefÞcient that is approximately 25% lower than our measurement in 700 Torr air. The magnitude of this apparent pressure effect is comparable to that observed in the reaction of OH radicals with propene [24] and presumably reßects the pressure dependence of the addition channel in reaction (1).…”

Section: Kinetics Of the Reactions Of Oh With Unsaturated Alcoholssupporting

confidence: 91%

“…As discussed above, the experiments of Upadhyaya et al [9] were conducted at low pressure and are not appropriate for atmospheric pressure, and the results from Fantechi et al [14] appear to be in error. The remaining absolute and relative rate studies listed in Table I gives lifetimes of approximately 2 h for these small unsaturated alcohols with respect to reaction with OH radicals.…”

Section: Discussionmentioning

confidence: 99%

“…Pfrang et al [24] noted what appeared to be a surprising discrepancy for allyl alcohol with the experimental value based on the measurements by Upadhyaya et al [9] and Papagni et al [7] being substantially lower than that predicted by the SAR. As discussed above, the measurements by Upadhyaya et al [9] were conducted at low pressure and are an underestimate of the rate coefÞcient at atmospheric pressure. The value of k 1 predicted by Pfrang et al [26] from the SAR (5.44 × 10 −11 ) is in good agreement with the value of k 1 = (5.50 ± 0.54) × 10 −11 cm 3 molecule −1 s −1 measured in the present work (see Table I …”

Section: Kinetics Of the Reactions Of Oh With Unsaturated Alcoholsmentioning

confidence: 98%

“…The kinetics of reactions (1)-(3) were measured relative to reactions (8) and (9). OH + C 3 H 6 → Products (8) OH + 1, 3, 5-Trimethylbenzene → Products (9) Figure 1 shows the observed loss of allyl alcohol versus propene and 1,3,5-trimethylbenzene following UV irradiation of allyl alcohol/reference/CH 3 Fig.…”

Section: Kinetics Of the Reactions Of Oh With Unsaturated Alcoholsmentioning

confidence: 99%

“…There have been six studies of reaction (1) (Papagni et al [7], Orlando et al [8], Upadhyaya et al [9], Holloway et al [10], Le Person et al [11], and Parker and Espada-Jallad [12]), and values of k 1 in the range (3.7-6.8) × 10 −11 cm 3 molecule −1 s −1 have been reported at room temperature. There has been one study of reaction (2); Papagni et al [7] measured k 2 = 5.9 × 10 −11 cm 3 molecule −1 s −1 at 296 K. Nine experimental studies of the kinetics of reaction of OH radicals with 2-methyl-3-buten-2-ol have been conducted (Papagni et al [7], Rudich et al [13], Fantechi et al [14], Ferronato et al [15], Alvarado et al [16], Reisen et al [17], Imamura et al [18], Baasandorj and Stevens [19], and Carrasco et al [20]).…”

Section: Introductionmentioning

confidence: 99%

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Kinetics and mechanisms of OH‐initiated oxidation of small unsaturated alcohols

Takahashi

Hurley

Wallington

2010

Int J of Chemical Kinetics

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Smog chamber relative rate techniques were used to measure rate coefficients of (5.00 ± 0.54) × 10 −11 , (5.87 ± 0.63) × 10 −11 , and (6.49 ± 0.82) × 10 −11 cm 3 molecule −1 s −1 in 700 Torr air at 296 ± 1 K for reactions of OH radicals with allyl alcohol, 1-buten-3-ol, and 2-methyl-3-buten-2-ol, respectively; the quoted uncertainties encompass the extremes of determinations using two different reference compounds. The OH-initiated oxidation of allyl alcohol in the presence of NO x gives glycolaldehyde in a molar yield of 0.85 ± 0.08; the quoted uncertainty is two standard deviations. Oxidation of 2-methyl-3-buten-2-ol gives acetone and glycolaldehyde in molar yields of 0.66 ± 0.06 and 0.56 ± 0.05, respectively. The reaction of OH radicals with allyl alcohol, 1-buten-3-ol, and 2-methyl-3-buten-2-ol proceeds predominately via addition to the >C CH 2 double bond with most of the addition occurring to the terminal carbon. C 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: [151][152][153][154][155][156][157][158] 2010

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Section: Kinetics Of the Reactions Of Oh With Unsaturated Alcoholssupporting

confidence: 91%

Section: Discussionmentioning

confidence: 99%

Section: Kinetics Of the Reactions Of Oh With Unsaturated Alcoholsmentioning

confidence: 98%

Section: Kinetics Of the Reactions Of Oh With Unsaturated Alcoholsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Kinetics and mechanisms of OH‐initiated oxidation of small unsaturated alcohols

Takahashi

Hurley

Wallington

2010

Int J of Chemical Kinetics

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Theoretical study on the gas phase reaction of propargyl alcohol with hydroxyl radical

et al. 2014

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The reaction of propargyl alcohol with hydroxyl radical has been studied extensively at CCSD(T)/aug-cc-pVTZ//MP2/cc-pVTZ level. This is the first time to gain a conclusive insight into the reaction mechanism and kinetics for this important reaction in detail. Two reaction mechanisms were revealed, namely addition/elimination and hydrogen abstraction mechanism. The reaction mechanism confirms that OH addition to C≡C triple bond forms the chemically activated adducts, IM1 (·CHCOHCH2OH) and IM2 (CHOH·CCH2OH), and the hydrogen abstraction pathways (-CH2OH bonded to the carbon atom and alcohol hydrogen) may occur via low barriers. Harmonic model of Rice-Ramsperger-Kassel-Marcus theory and variational transition state theory are used to calculate the overall and individual rate constants over a wide range of temperatures and pressures. The calculated rate constants are in good agreement with the experimental data. At atmospheric pressure with Ar as bath gas, IM1 (·CHCOHCH2OH) and IM2 (CHOH·CCH2OH) formed by collisional stabilization are dominant in the low temperature range. The production of CHCCHOH + H2O via hydrogen abstraction becomes dominate at higher temperature. The fraction of IM3 (CH2COHCH2·O) is very significant over the moderate temperature range.

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Gas Phase OH Radical Reaction with 2‐Chloroethyl Vinyl Ether in the 256–333 K Temperature Range: A Combined LP‐LIF and Computational Study

2018

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The absolute rate coefficient for the gas phase reaction of OH radical with 2-chloroethyl vinyl ether (H 2 C = CH-O-CH 2 CH 2 Cl, 2ClEVE) has been measured using the laser photolysis (LP)laser induced fluorescence (LIF) technique. The kinetics measurements were done over the temperature range of 256-333 K. The bimolecular rate coefficients obtained, k(T), showed Arrhenius type behaviour which were fitted to the expression k(T) = (4.18 AE 0.55) 3 10 À12 exp[(700 AE 70)/T] cm 3 molecule À1 s À1 .The room temperature rate coefficient shows pressure independent behaviour in the range of 10-40 Torr. The reaction shows weak negative temperature dependence. A detail computational studies involving the energies and structures of the reactants, transition states and products were performed using Complete Basis Set (CBS) and Quadratic Configuration Interaction with Single and Double substitutions with a Triples contribution to the energy, QCISD(T), method to elucidate the reaction mechanism. The results suggest that the major pathways for the reaction proceeds through addition of OH radical to the C=C double bond and the H atom abstraction from the -O-CH 2 -group and they are competitive in nature. The tropospheric lifetime, radiative efficiency (RE) and the global warming potential (GWP) for 2-chloroethyl vinyl ether (2ClEVE) have been also determined.[a] Dr.

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Kinetics of OH radical reaction with allyl alcohol (H2CCHCH2OH) and propargyl alcohol (HCCCH2OH) studied by LIF

Cited by 31 publications

References 19 publications

Kinetics and mechanisms of OH‐initiated oxidation of small unsaturated alcohols

Kinetics and mechanisms of OH‐initiated oxidation of small unsaturated alcohols

Theoretical study on the gas phase reaction of propargyl alcohol with hydroxyl radical

Gas Phase OH Radical Reaction with 2‐Chloroethyl Vinyl Ether in the 256–333 K Temperature Range: A Combined LP‐LIF and Computational Study

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