Infrared chemiluminescence in the reactions of atomic fluorine with ethanol, propanol-(2) and some deuterated analogs

Dill, Bernd; Hildebrandt, Barbara; Vanni, H.; Heydtmann, H.

doi:10.1016/0301-0104(81)80053-5

Cited by 10 publications

(4 citation statements)

References 15 publications

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“…The derived quantity y(HyEt) represents a Boltzmann weighted average of the unknown quantities k2(T) and kfT). with this work, while the measurements of Dill et al 18 disagree by a factor of 2. The stated primary goal of the latter work was to obtain vibrational-state population distributions from chemiluminescence spectra of HF and DF products.…”

Section: Methodsmentioning

confidence: 99%

Ethoxy Radical Yield in the System C2D5OH plus F(2P) plus F2 at P = 1 Torr and T = 223-423 K

Bogan¹,

Nesbitt²

1994

J. Phys. Chem.

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A discharge flow reactor with mass spectrometric detection has been used to determine the fractional yield of ethoxy, Y(EtO), from the reaction of F(2P) with C~D S O H . The chemical titration method that was used depends only upon the occurrence of the fast chain reaction, F2 + C2D40H -C2D40H + F, and the ability to measure relative concentrations of ethoxy radical. Ethoxy concentration was proportional to the detected ion count signal a t m/z 50.[Ethoxy] was titrated to an asymptote with a large excess of F2. The titration removes hydroxyethyl radicals and regenerates F so that, a t the asymptote, each F initially present will have formed one ethoxy radical. The experimental value of Y(Et0) is the ratio of the m / z 50 signal in the absence of F2 to the signal in the presence of F2. The measured values of Y(Et0) f ( l a ) are 0.62 f 0.08 a t 223 K, 0.55 f 0.06 a t 300 K, and 0.39 f 0.02 a t 423 K. An Arrhenius analysis of these data implies that the average activation energy for abstraction a t a C-D bond is about 1 kcal/mol larger than that for abstraction at the 0-H bond. The activation energy for attack a t 0-H is likely to be near zero. Allowing F(2P) to react with large excesses of ethanol and F2 provides a good clean source of ethoxy radical.

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Section: Methodsmentioning

confidence: 99%

Ethoxy Radical Yield in the System C2D5OH plus F(2P) plus F2 at P = 1 Torr and T = 223-423 K

Bogan¹,

Nesbitt²

1994

J. Phys. Chem.

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“…Infrared chemiluminescence has been used to determine the relative rates of hydrogen atom abstraction from ethanol with fluorine atoms. 8 From this study it is expected that the rate constants for formation of CH The aim of this present work was to study the F + CH 3 CH 2 OH reaction using He I photoelectron spectroscopy to observe bands associated with the radicals formed by primary hydrogen atom abstraction. In particular, it was hoped to obtain an improved first adiabatic ionization energy of CH 3 CHOH.…”

Section: Introductionmentioning

confidence: 99%

“…Infrared chemiluminescence has been used to determine the relative rates of hydrogen atom abstraction from ethanol with fluorine atoms . From this study it is expected that the rate constants for formation of CH 3 CHOH and CH 2 CH 2 OH are approximately equal, and greater than the rate constant for formation of CH 3 CH 2 O.…”

Section: Introductionmentioning

confidence: 99%

Study of the CH₃CHOH Radical with Ultraviolet Photoelectron Spectroscopy

et al. 1997

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He I photoelectron spectra have been recorded for the F + C 2 H 5 OH reaction, and a band has been identified associated with the primary reaction product CH 3 CHOH. The first adiabatic and vertical ionization energies of this radical have been measured as (6.64 ( 0.03) and ( 7.29 ( 0.03) eV respectively. The assignment of this band to CH 3 CHOH is supported by ab initio calculations performed at the G2 level of theory. Spectra recorded at different reaction times have demonstrated the short-lived nature of CH 3 CHOH and the major pathway of the F + C 2 H 5 OH reaction. The value measured for the adiabatic ionization energy has allowed the heat of formation of CH 3 CHOH to be derived from the heat of formation of CH 3 CHOH + .

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“…Several measurements on the alkoxy yield from reactions of F with normal and deuterated ethanols and propanols presented similar alkoxy product fractions. 15,22,23 The fraction yielding ethoxy radical is reported to be 0.5 although alkyl hydrogen abstraction is also energetically favored. The probability of attack on the C−H group was found to be five times less than attack on the O−H group for the reactions of F atoms with alcohols.…”

Section: ■ Introductionmentioning

confidence: 99%

H Abstraction Channels in the Crossed-Beam Reaction of F + 1-Propanol, 1-Butene and 1-Hexene by DC Slice Imaging

2016

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We report a crossed molecular beam study of the reaction dynamics of fluorine atom with 1-propanol, 1-butene, and 1-hexene. The product alkoxy and alkenyl radicals were detected via dc slice imaging by 157 nm single photon ionization at collision energies around 10 kcal mol. The analyzed data is interpreted with the aid of theoretical investigation of the relevant potential energy surfaces. The translational energy distribution and center-of-mass angular distribution of F + 1-propanol is quite similar to our previous results for F + n-butane, albeit with an increased fraction of the available energy in translation. In F atom reaction with alkenes, we also detected the HF formation channel. The low translational energy release and presence of significant backward scattering suggests the importance of an addition/elimination mechanism. Our selective single photon ionization probe allows us to examine the dynamics in minor channels in these systems. Although the probe is not sensitive to reaction at vinylic H sites, theoretical calculations consistently suggest a lower barrier from the addition complex to HF elimination involving vinylic H atoms.

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Infrared chemiluminescence in the reactions of atomic fluorine with ethanol, propanol-(2) and some deuterated analogs

Cited by 10 publications

References 15 publications

Ethoxy Radical Yield in the System C2D5OH plus F(2P) plus F2 at P = 1 Torr and T = 223-423 K

Ethoxy Radical Yield in the System C2D5OH plus F(2P) plus F2 at P = 1 Torr and T = 223-423 K

Study of the CH₃CHOH Radical with Ultraviolet Photoelectron Spectroscopy

H Abstraction Channels in the Crossed-Beam Reaction of F + 1-Propanol, 1-Butene and 1-Hexene by DC Slice Imaging

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Infrared chemiluminescence in the reactions of atomic fluorine with ethanol, propanol-(2) and some deuterated analogs

Cited by 10 publications

References 15 publications

Ethoxy Radical Yield in the System C2D5OH plus F(2P) plus F2 at P = 1 Torr and T = 223-423 K

Ethoxy Radical Yield in the System C2D5OH plus F(2P) plus F2 at P = 1 Torr and T = 223-423 K

Study of the CH3CHOH Radical with Ultraviolet Photoelectron Spectroscopy

H Abstraction Channels in the Crossed-Beam Reaction of F + 1-Propanol, 1-Butene and 1-Hexene by DC Slice Imaging

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Study of the CH₃CHOH Radical with Ultraviolet Photoelectron Spectroscopy