The methylidyne radical + carbon monoxide reaction: rate coefficient for carbon atom exchange at 294 K

Anderson, S. M.; McCurdy, K.E.; Kolb, C. E.

doi:10.1021/j100340a007

Cited by 6 publications

(14 citation statements)

References 1 publication

(1 reference statement)

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“…The rate for carbon-atom exchange was measured previously by Anderson et al using a flow reactor at 2 Torr total pressure of Ar, to be 2.1Ϯ0.3ϫ10 Ϫ12 cm 3 molecule Ϫ1 s Ϫ1 . 28 The present measurements indicate that the exchange rate is somewhat slower, with a rate constant of 1.0Ϯ0.2ϫ10 Ϫ12 cm 3 molecule Ϫ1 s Ϫ1 at 20 Torr total pressure. This is relatively rapid, but is only ϳ1% of the high-pressure limiting rate constant for the reaction.…”

Section: B Carbon-atom Exchange Reactionmentioning

confidence: 50%

“…The calculation of the high-pressure limiting value for the CHϩCO association reaction by Anderson et al is also on the order of 10 Ϫ10 cm 3 molecule Ϫ1 s Ϫ1 . 28 The limited reliability of the extrapolation to k ϱ probably does not allow an accurate estimate to be made on the basis of the present data, since the current measurements do not approach the high-pressure limit. In addition, extrapolations from the falloff region have been found by Brownsword et al to underestimate the high-pressure limit.…”

Section: A Ch؉co Association Reactionmentioning

confidence: 65%

“…Extrapolations of the present data to lower pressure predict much smaller rate constants than those reported by Brownsword et al at 2 and 4 Torr of Ar buffer, but are in good agreement with the 2 Torr determination of Anderson et al using a flow apparatus. 28 Additional lowpressure studies may be needed to resolve this discrepancy.…”

Section: A Ch؉co Association Reactionmentioning

confidence: 99%

“…As Anderson et al note, dominance of the elimination channel in HCCO dissociation would seem to imply a barrier to C-C bonding. 28 Equation ͑14͒ can be used to test the consistence of a qualitative picture of the exchange reaction with the measured kinetic isotope effect. The isotope effect therefore offers the opportunity to distinguish between the possible pathways for exchange.…”

Section: ͑14͒mentioning

confidence: 99%

“…The rate constant for carbon atom exchange in the CHϩCO reaction was measured at 293 K and 2 Torr by Anderson et al using a flow reactor. 28 They reported an exchange rate constant of 2.1Ϯ0.3ϫ10 Ϫ12 cm 3 molecule Ϫ1 s Ϫ1 , indicating that carbon-atom exchange is relatively facile. They postulated two possible mechanisms for the exchange, one involving association followed by isomerization through an oxiryl intermediate and one involving insertion of CH into the C-O bond, followed by elimination or C-C bond fission.…”

Section: Introductionmentioning

confidence: 99%

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Association and isotopic exchange reactions of CH(CD)[X 2Π]+CO

Taatjes

1997

The Journal of Chemical Physics

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Potential energy surface for the CH 3 + HBr → CH 4 + Br hydrogen abstraction reaction: Thermal and stateselected rate constants, and kinetic isotope effectsThe high-pressure range of the reaction CH( 2 Π)+CO+MHCCO+M The reaction rates for 12 CH and 12 CD with normal isotopic abundance CO and 13 CO have been studied at 293 K for pressures between 12.5 and 500 Torr and at 100 Torr for temperatures between 293 and 650 K. The pressure and temperature dependence of the addition reaction of CH with CO have been measured. The addition rate coefficient can be fit to the expression 7.2Ϯ0.3ϫ10 Ϫ12 (T/293) Ϫ2.4Ϯ0.2 cm 3 molecule Ϫ1 s Ϫ1 at 100 Torr total pressure ͑He buffer͒. A fit of the pressure dependence to a Troe expression with F c ϭ0.6 yields a low-pressure rate constant (k 0 ) of 2.4Ϯ0.3ϫ10 Ϫ30 cm 6 molecule Ϫ2 s Ϫ1 . The rate for carbon atom exchange has been measured by comparison of the 13 C labeled and unlabeled reaction rates. The isotopic exchange reaction is 1.0Ϯ0.2ϫ10 Ϫ12 cm 3 molecule Ϫ1 s Ϫ1 at 20 Torr. The deuterium isotope effect on the exchange rate is large, with an inverse kinetic isotope effect ͑k H /k D ͒ϭ0.28Ϯ0.08 at 20 Torr. This inverse isotope effect reflects the competition between collisional stabilization and isomerization, and is a convolution of isotope effects for the isomerization, unimolecular dissociation, and stabilization rates. The experimental results are consistent with a mechanism for exchange that involves isomerization of an HCCO adduct via an oxiryl intermediate, and indicate that insertion into the C-O bond is not important in this reaction.

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Section: B Carbon-atom Exchange Reactionmentioning

confidence: 50%

Section: A Ch؉co Association Reactionmentioning

confidence: 65%

Section: A Ch؉co Association Reactionmentioning

confidence: 99%

Section: ͑14͒mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Association and isotopic exchange reactions of CH(CD)[X 2Π]+CO

Taatjes

1997

The Journal of Chemical Physics

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Rate coefficients for the CH(X2Π) + CHX3 (X = Cl and Br) reactions and the propensity of the reactions of CH with halomethanes

Yoshiki

Sugino

Tendo

et al. 2022

Chemical Physics Letters

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Contribution to the analysis of the predissociated rovibronic structure of the symmetric isotopomers and of ozone near 10,400 cm−1: and

Wannous

Bouvier

Helou

et al. 2004

Spectrochimica Acta Part A: Molecular and Biomolecular Spectros

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The absorption spectrum of ozone was recorded at low temperatures (down to -135 degrees C) by high resolution Fourier transform spectrometry and intra cavity laser absorption spectroscopy (ICLAS) near 10,400 cm-1. A preliminary analysis of the rotational structure of the absorption spectra of 16O3 and 18O3 shows that this spectral region corresponds to a superposition of two different electronic transitions, one with a very broad rotational structure, showing for the first time the asymmetric stretching frequency mode nu3 of the electronic state 3A2, the other formed by a completely diffuse band, probably the 2(1)(0) band of a new transition due to the triplet electronic state 3B2. Predissociation effects induce large broadening of the rotational lines for the transition centered at 10,473 cm-1 identified as the 3(2)(0) band of the 3A2 <-- X1A1 electronic transition. The rotational structure cannot be analyzed directly but instead the band contour method was used to confirm the symmetry of the transition and to estimate the spectroscopic constants for the 16O isotopomer. The origin of the band is at 10,473 +/- 3 cm-1 and the value of the 16O3(3A2) antisymmetric stretching frequency mode is equal to 460 +/- 2 cm-1. We believe that the diffuse band is due to the 3B2 state and is located at about 10,363 +/- 3 cm-1 for 16O3 and 10,354 +/- 3 cm-1 for 18O3. The isotopic rules confirm the different results obtained for 18O3 and 16O3.

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The methylidyne radical + carbon monoxide reaction: rate coefficient for carbon atom exchange at 294 K

Cited by 6 publications

References 1 publication

Association and isotopic exchange reactions of CH(CD)[X 2Π]+CO

Association and isotopic exchange reactions of CH(CD)[X 2Π]+CO

Rate coefficients for the CH(X2Π) + CHX3 (X = Cl and Br) reactions and the propensity of the reactions of CH with halomethanes

Contribution to the analysis of the predissociated rovibronic structure of the symmetric isotopomers and of ozone near 10,400 cm−1: and

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