Infrared multiphoton absorption and decomposition of ethanol vapour

Back, R. A.; Evans, Douglas E.; McAlpine, Robert D.; Verpoorte, Elisabeth; Ivanco, Mike; Goodale, J. W.; Adams, H. M.

doi:10.1139/v88-148

Cited by 6 publications

(2 citation statements)

References 16 publications

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“…As reported earlier (12), the addition of O2 as a radical scavenger had no effect on the molecular elimination reactions [ l a ] , [ l b ] , or [ I c]; however, it completely suppressed the production of ethane. This indicated that ethane is produced following the radical reaction [Id], which produces CH3.…”

Section: Results and Discussion Ethyl Alcohol Plus Iodinesupporting

confidence: 60%

The mechanism of the infrared laser induced multiphoton decomposition of ethyl alcohol

Goodale¹,

Evans²,

Ivanco³

et al. 1990

Can. J. Chem.

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. Can. J. Chem. 68, 1437 (1990). The infrared laser induced multiphoton decomposition of ethyl alcohol has been studied in experiments with iodine as a radical scavenger and the deuterium substituted form CH3CD20H of the alcohol. These experiments show that the principal product, C2H4, arises from a concerted molecular elimination, as do most of the CH4 and CH3CH0. The C2H6 product results from recombination of the nascent methyl radicals formed in the minor bond breaking channel.Key words: ethyl alcohol, multiphoton decomposition.

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Section: Results and Discussion Ethyl Alcohol Plus Iodinesupporting

confidence: 60%

The mechanism of the infrared laser induced multiphoton decomposition of ethyl alcohol

Goodale¹,

Evans²,

Ivanco³

et al. 1990

Can. J. Chem.

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“…The assumed dissociation channel leading to H 2 O and C 2 H 4 has been confirmed in IR multiphoton excitation experiments of C 2 H 5 OH. 73,74 To our knowledge a deconvoluted dependence of product yields F P upon laser fluence has not yet been published. It would be possible to detect ethylene products by direct IR absorption.…”

Section: E Master Equation Calculations For the Ir Multiphoton Excitmentioning

confidence: 99%

Nonlinear intensity dependence in the infrared multiphoton excitation and dissociation of methanol pre-excited to different energies

Boyarkin

Rizzo

Rueda

et al. 2002

The Journal of Chemical Physics

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We report quantitative dissociation yields for the reaction CH 3 OH (v OH) → nh CH 3 ϩOH induced by infrared multiphoton excitation of methanol pre-excited to various levels of the OH stretching vibration (v OH ϭ0, 1, 3, 5). The yields are measured by detecting OH using laser induced fluorescence. It is demonstrated that for low levels of pre-excitation (v OH ϭ0, 1, 3) there is a substantial nonlinear intensity dependence, as a higher yield is found for self mode-locked CO 2 laser pulses ͑with higher peak intensity͒ as compared to single mode pulses of the same laser fluence, but lower peak intensity. In contrast, at high levels of preexcitation (v OH ϭ5) this nonlinear intensity dependence is absent. Quantitative model calculations are carried out using a case B/case C master equation approach that takes nonlinear intensity dependence into account. The calculations are consistent with the experimental results and confirm the prediction that an important part of the selectivity of the CO 2 laser excitation step in infrared laser assisted photofragment spectroscopy of CH 3 OH is due to this nonlinear intensity dependence. We discuss further consequences of these experimental observations and theoretical predictions, which are also extended to infrared multiphoton excitation of C 2 H 5 OH. Infrared ͑C-O͒ chromophore band strengths are reported for CH 3 OH and C 2 H 5 OH.

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CO₂ laser‐induced decomposition of ethanol

Holbrook¹,

Oldershaw²,

Shaw³

1993

Int J of Chemical Kinetics

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The multiple photon absorption and decomposition of ethanol irradiated by pulsed 9P 18 infrared radiation (1048.7 cm-') from a TEA GO2 laser has been studied in the fluence range 1.5 to 5 J cm-2. The absorption cross-section is pressure-dependent due to rapid collisional rotational hole-filling. At low pressures the only important decomposition channel following absorption is molecular dehydration of ethanol to yield ethene, but at higher pressures hydrogen, methane, carbon monoxide, ethane, and ethyne are also produced. In the irradiation of pure ethanol under 'collision-free' conditions, thermal decomposition following collisional redistribution of energy makes only a small contribution to the overall decomposition yield at fluences above 3.5 J cm-' but may become more significant at lower fluences. Modelling using RRKM calculations has been employed to link measured absorbed energies to extents of decomposition of ethanol. Both these calculations and the absorption measurements indicate that at low pressures only a fraction of the irradiated ethanol molecules absorb the 9P18 radiation. 0

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Infrared multiphoton absorption and decomposition of ethanol vapour

Cited by 6 publications

References 16 publications

The mechanism of the infrared laser induced multiphoton decomposition of ethyl alcohol

The mechanism of the infrared laser induced multiphoton decomposition of ethyl alcohol

Nonlinear intensity dependence in the infrared multiphoton excitation and dissociation of methanol pre-excited to different energies

CO₂ laser‐induced decomposition of ethanol

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Infrared multiphoton absorption and decomposition of ethanol vapour

Cited by 6 publications

References 16 publications

The mechanism of the infrared laser induced multiphoton decomposition of ethyl alcohol

The mechanism of the infrared laser induced multiphoton decomposition of ethyl alcohol

Nonlinear intensity dependence in the infrared multiphoton excitation and dissociation of methanol pre-excited to different energies

CO2 laser‐induced decomposition of ethanol

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CO₂ laser‐induced decomposition of ethanol