Reaction of hydroxymethyl radicals with oxygen, nitric oxide, and nitrogen dioxide at room temperature

Pagsberg, P.; Munk, Jette; Anastasi, Christopher; Simpson, Victoria

doi:10.1021/j100350a028

Cited by 41 publications

(50 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…We confirmed no pressure dependence of the rate constant in the pressure range up to 50 Torr, which is consistent with previous studies. 9,[19][20][21][22][23][24][25] 3.3. Comparison to Previous Studies.…”

Section: Rate Constantsmentioning

confidence: 99%

“…[9][10][11][12][13] Much effort has been made to investigate the kinetics of this reaction. 9,[14][15][16][17][18][19][20][21][22][23][24][25] Table 1 summarizes recent studies, the majority of which report rate constants around room temperature. 9,14,[18][19][20][21][22][23][24][25] The only exceptions to this are the studies of Grotheer et al 9 and Nesbitt et al 22 who reported rate constants at above and below room temperature, respectively.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Kinetics and Rate Constants of the Reaction CH₂OH + O₂→ CH₂O + HO₂in the Temperature Range of 236−600 K

et al. 2007

View full text Add to dashboard Cite

The kinetics and absolute rate constants of the gas-phase reaction of the hydroxymethyl radical (CH2OH) with molecular oxygen have been studied using laser photolysis/near-IR absorption spectroscopy. The reaction was tracked by monitoring the time-dependent changes in the production of the hydroperoxy radical (HO2) concentration. For sensitive detection of HO2, two-tone frequency modulation absorption spectroscopy was used in combination with a Herriott-type optical multipass absorption cell. Rate constants were determined as a function of temperature (236 K

show abstract

Section: Rate Constantsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Kinetics and Rate Constants of the Reaction CH₂OH + O₂→ CH₂O + HO₂in the Temperature Range of 236−600 K

et al. 2007

View full text Add to dashboard Cite

show abstract

“…The hydroxymethyl radical, CH 2 OH, is involved as an intermediate species in many chemical reaction systems, and its study spans a wide range of fields, such as in tropospheric chemistry (Atkinson 1990;Pagsberg et al 1989;Nesbitt et al 1989) and hydrocarbon (e.g. methane and methanol) oxidation processes (Lin et al 1999(Lin et al , 2000Rissanen et al 2013;Rasmussen et al 2008).…”

Section: Introductionmentioning

confidence: 99%

Laboratory detection of the rotational-tunnelling spectrum of the hydroxymethyl radical, CH₂OH

Bermúdez

Bailleux

Cernicharo

2017

A&A

View full text Add to dashboard Cite

Context. Of the two structural isomers of CH 3 O, methoxy is the only radical whose astronomical detection has been reported through the observation of several rotational lines at 2 and 3 mm wavelengths. Although the hydroxymethyl radical, CH 2 OH, is known to be thermodynamically the most stable (by~3300 cm −1 ), it has so far eluded rotational spectroscopy presumably because of its high chemical reactivity. Aims. Recent high-resolution (~10 MHz) sub-Doppler rovibrationally resolved infrared spectra of CH 2 OH (symmetric CH stretching a-type band) provided accurate ground vibrational state rotational constants, thus reviving the quest for its millimeter-wave spectrum in laboratory and subsequently in space. Methods. The search and assignment of the rotational spectrum of this fundamental species were guided by our quantum chemical calculations and by using rotational constants derived from high-resolution IR data. The hydroxymethyl radical was produced by hydrogen abstraction from methanol by atomic chlorine. Results. Ninety-six b-type rotational transitions between the v = 0 and v = 1 tunnelling sublevels involving 25 fine-structure components of Q branches (with K a = 1 ← 0) and 4 fine-structure components of R branches (assigned to K a = 0 ← 1) were measured below 402 GHz. Hyperfine structure alternations due to the two identical methylenic hydrogens were observed and analysed based on the symmetry and parity of the rotational levels. A global fit including infrared and millimeter-wave lines has been conducted using Pickett's reduced axis system Hamiltonian. The recorded transitions (odd ∆K a ) did not allow us to evaluate the Coriolis tunnelling interaction term. The comparison of the experimentally determined constants for both tunnelling levels with their computed values secures the long-awaited first detection of the rotational-tunnelling spectrum of this radical. In particular, a tunnelling rate of 139.73 ± 0.10 MHz (4.6609(32) × 10 −3 cm −1 ) was obtained along with the rotational constants, electron spin-rotation interaction parameters and several hyperfine coupling terms. Conclusions. The laboratory characterization of CH 2 OH by millimeter-wave spectroscopy now offers the possibility for its astronomical detection for the first time.

show abstract

“…Although there has been no direct experimental determination of the branching between channels, theoretical work has predicted branching of 0.67, 0.02, 0.02, and 0.29, respectively, for isomers I, II, III, and IV, 14 with an overall rate of (1.0 ( 0.1) × 10 -10 molecule -1 cm 3 s -1 . [14][15][16][17][18][19] End product analysis studies also suggest that OH addition occurs preferentially at the terminal carbons. 20,21 The radicals formed from OH addition to the terminal carbons react with molecular oxygen under atmospheric conditions to form peroxy radicals, which subsequently react with NO to form alkoxy radicals.…”

Section: Introductionmentioning

confidence: 99%

Isomer-Selective Study of the OH-Initiated Oxidation of Isoprene in the Presence of O₂ and NO: 2. The Major OH Addition Channel

et al. 2010

View full text Add to dashboard Cite

We report the first isomeric-selective study of the dominant isomeric pathway in the OH-initiated oxidation of isoprene in the presence of O 2 and NO using the laser photolysis-laser induced fluorescence (LP-LIF) technique. The photolysis of monodeuterated/nondeuterated 2-iodo-2-methylbut-3-en-1-ol results exclusively in the dominant OH-isoprene addition product, providing important insight into the oxidation mechanism. On the basis of kinetic analysis of OH cycling experiments, we have determined the rate constant for O 2 addition to the hydroxyalkyl radical to be 1.0 -0.5 +1.7 × 10 -12 cm 3 s -1 , and we find a value of 8.1 -2.3 +3.4 × 10 -12 cm 3 s -1 for the overall reaction rate constant of the resulting hydroxyperoxy radical with NO. We also report the first clear experimental evidence of the (E) form of the δ-hydroxyalkoxy channel through isotopic labeling experiments and quantify its branching ratio to be (10 ( 3)%. This puts a rigorous upper limit on the branching of the (E)-δ-hydroxyalkoxy radical channel. Since our measured isomeric-selective rate constants for the dominant outer channel in OH-initiated isoprene chemistry are similar to the overall rate constants derived from nonisomeric kinetics, we predict that the remaining outer addition channel will have similar reactivity.

show abstract

Reaction of hydroxymethyl radicals with oxygen, nitric oxide, and nitrogen dioxide at room temperature

Cited by 41 publications

References 0 publications

Kinetics and Rate Constants of the Reaction CH₂OH + O₂→ CH₂O + HO₂in the Temperature Range of 236−600 K

Kinetics and Rate Constants of the Reaction CH₂OH + O₂→ CH₂O + HO₂in the Temperature Range of 236−600 K

Laboratory detection of the rotational-tunnelling spectrum of the hydroxymethyl radical, CH₂OH

Isomer-Selective Study of the OH-Initiated Oxidation of Isoprene in the Presence of O₂ and NO: 2. The Major OH Addition Channel

Contact Info

Product

Resources

About

Reaction of hydroxymethyl radicals with oxygen, nitric oxide, and nitrogen dioxide at room temperature

Cited by 41 publications

References 0 publications

Kinetics and Rate Constants of the Reaction CH2OH + O2→ CH2O + HO2in the Temperature Range of 236−600 K

Kinetics and Rate Constants of the Reaction CH2OH + O2→ CH2O + HO2in the Temperature Range of 236−600 K

Laboratory detection of the rotational-tunnelling spectrum of the hydroxymethyl radical, CH2OH

Isomer-Selective Study of the OH-Initiated Oxidation of Isoprene in the Presence of O2 and NO: 2. The Major OH Addition Channel

Contact Info

Product

Resources

About

Kinetics and Rate Constants of the Reaction CH₂OH + O₂→ CH₂O + HO₂in the Temperature Range of 236−600 K

Kinetics and Rate Constants of the Reaction CH₂OH + O₂→ CH₂O + HO₂in the Temperature Range of 236−600 K

Laboratory detection of the rotational-tunnelling spectrum of the hydroxymethyl radical, CH₂OH

Isomer-Selective Study of the OH-Initiated Oxidation of Isoprene in the Presence of O₂ and NO: 2. The Major OH Addition Channel