The pulse radiolysis of carbon monoxide

Willis, C.; Devillers, C.

doi:10.1016/0009-2614(68)80146-0

Cited by 14 publications

(4 citation statements)

References 7 publications

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“…Our search of the literature (e.g., ref ) suggests that very few neutral, stable C x O y species absorbing light in the visible are known. Among the few that we found are “red graphite” (carbon suboxide polymer, (C 3 O 2 ) n ), , singlet carbon trioxide (CO 3 ), − and ozone (O 3 ). , Most of the other chromophores (for instance, C 2 O( 3 Σ)) can be eliminated on the basis of their short lifetimes and/or low oxidative states. The UV−vis spectrum of “red graphite” 31 has striking resemblance to that of the product.…”

Section: Discussionmentioning

confidence: 90%

Ionic and Neutral Species in Pulse Radiolysis of Supercritical CO₂. 1. Transient Absorption Spectroscopy, Electric Field Effect, and Charge Dynamics

et al. 2002

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Transient absorption spectroscopy was used to study the mechanism for radiolysis of dense, liquidlike supercritical (sc) CO2 (T = 41 °C, ρ = 0.84 g/cm3). The 350−1500 nm spectra are decomposed into the contributions from the solvent radical cation, solvent radical anion, and a long-lived neutral product that we associate with singlet carbon trioxide, CO3(1A1). These three species are characterized by their optical spectra, chemical behavior, kinetics, and the response of these kinetics to external electric field. The following mechanism for radiolysis of sc CO2 is suggested: Ionization of the solvent yields ≈5 pairs per 100 eV. Most of these pairs are comprised of the solvent hole and a thermalized quasifree electron; the prompt yield of CO3 - is <3% of the total ion yield. The electrons are trapped by the solvent in <200 ps. Because of high electron mobility, most of this trapping occurs after the charges escape each other's Coulomb field. Because of cross recombination of the electrons with nongeminate solvent holes, the lifetime of the quasifree electrons is further reduced. A theoretical model that accounts for these dynamics is suggested. It is shown that di- and triatomic molecules donate an electron to the solvent hole, and the resulting solute cations polymerize. Exotic ion species, such as (N2O)2 + and (CO) n +, can be produced this way. Using sc CO2 provides an opportunity to study such multimer cations in liquid solution.

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Section: Discussionmentioning

confidence: 90%

Ionic and Neutral Species in Pulse Radiolysis of Supercritical CO₂. 1. Transient Absorption Spectroscopy, Electric Field Effect, and Charge Dynamics

et al. 2002

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“…The formation of C 2 O in pulsed radiolysis of CO was shown first by Willis and Devillers [47] and they showed that adding CO 2 did not affect the kinetics of C 2 O. Kinetics of this molecule discussed from kinetic analysis of pure CO discharges can then probably be extended to mixtures of CO/CO 2 .…”

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confidence: 91%

Analysis of the C₂ ( d 3 Π g − a 3 Π u ) Swan bands as a thermometric probe in CO₂ microwave plasmas

Carbone

D'Isa

Hecimovic

et al. 2020

Plasma Sources Sci. Technol.

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The optical emission spectra of high pressure CO2 microwave plasmas are usually dominated by the C2 Swan bands. In this paper, the use of the C2 Swan bands for estimating the gas temperature in CO2 microwave plasmas is assessed. State by state fitting is employed to check the correctness of assuming a Boltzmann distribution for the rotational and vibrational distribution functions and, within statistical and systematic uncertainties, the C2 Swan band can be fitted accurately with a single temperature for rotational and vibrational levels. The processes leading to the production of the C2 molecule and particularly its d 3 Π g state are briefly reviewed as well as collisional relaxation times of the latter. It is concluded that its rotational temperature can be associated to the gas temperature of the CO2 microwave plasma and the results are moreover cross-checked by adding a small amount of N2 in the discharge and measuring the CN violet band system. The 2.45 GHz plasma source is analyzed in the pressure range 180–925 mbar, for input microwave powers ranging from 0.9 to 3 kW and with gas flow rates of 5–100 l min−1. An intense C2 Swan bands emission spectrum can be measured only when the plasma is operated in contracted regime. A unique temperature of about 6000 ± 500 K is obtained for all investigated conditions. A spectroscopic database is constructed using the recent compilation and calculations by Brooke et al (2013 J. Quant. Spectrosc. Radiat. Transfer 124 11–20) of the line strengths and molecular constants for the C2 (d 3 Π g −a 3 Π u ) Swan bands system and made available as supplementary material in a format compatible with the open source MassiveOES software.

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“…[?I e + SF,-r SF, [3] Positive ion + SF; -, dissociation products. This leads to the indirect effect of changing the neutralization step to involve c-C4F, as the dominant negative species.…”

Section: Discussionmentioning

confidence: 99%

A Positive-Ion Reaction Mechanism for the Radiation Induced Oxidation of Carbon Monoxide in the High Dose Rate Radiolysis of CO–O₂ Mixtures

Willis¹,

Boyd²,

Bindner³

1972

Can. J. Chem.

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Carbon dioxide and ozone yields have been measured in the irradiation of CO–O2 mixtures with single pulses of electrons. The yields of CO2 at 2 × 1027 ev g−1 s−1 are large G(CO2) = 15 ± 1 from 20–60% O2. These decrease by ∼50% at 1028 eV g−1 s−1. Although the results are somewhat irreproducible the addition of c-C4F8, an electron scavenger, increases these CO2 yields at both dose rates by up to a factor of 15. They are reduced to G(CO2) < 2 by the addition of positive ion scavengers. These results are consistent with a chain reaction similar to that proposed for low dose rate studies involving [Formula: see text], [Formula: see text], and [Formula: see text] as chain carriers.The ozone yields are consistent with a total oxygen atom yield of G(O) = 1.4 in pure CO from neutral processes.

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The pulse radiolysis of carbon monoxide

Cited by 14 publications

References 7 publications

Ionic and Neutral Species in Pulse Radiolysis of Supercritical CO₂. 1. Transient Absorption Spectroscopy, Electric Field Effect, and Charge Dynamics

Ionic and Neutral Species in Pulse Radiolysis of Supercritical CO₂. 1. Transient Absorption Spectroscopy, Electric Field Effect, and Charge Dynamics

Analysis of the C₂ ( d 3 Π g − a 3 Π u ) Swan bands as a thermometric probe in CO₂ microwave plasmas

A Positive-Ion Reaction Mechanism for the Radiation Induced Oxidation of Carbon Monoxide in the High Dose Rate Radiolysis of CO–O₂ Mixtures

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The pulse radiolysis of carbon monoxide

Cited by 14 publications

References 7 publications

Ionic and Neutral Species in Pulse Radiolysis of Supercritical CO2. 1. Transient Absorption Spectroscopy, Electric Field Effect, and Charge Dynamics

Ionic and Neutral Species in Pulse Radiolysis of Supercritical CO2. 1. Transient Absorption Spectroscopy, Electric Field Effect, and Charge Dynamics

Analysis of the C2 ( d 3 Π g − a 3 Π u ) Swan bands as a thermometric probe in CO2 microwave plasmas

A Positive-Ion Reaction Mechanism for the Radiation Induced Oxidation of Carbon Monoxide in the High Dose Rate Radiolysis of CO–O2 Mixtures

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Ionic and Neutral Species in Pulse Radiolysis of Supercritical CO₂. 1. Transient Absorption Spectroscopy, Electric Field Effect, and Charge Dynamics

Ionic and Neutral Species in Pulse Radiolysis of Supercritical CO₂. 1. Transient Absorption Spectroscopy, Electric Field Effect, and Charge Dynamics

Analysis of the C₂ ( d 3 Π g − a 3 Π u ) Swan bands as a thermometric probe in CO₂ microwave plasmas

A Positive-Ion Reaction Mechanism for the Radiation Induced Oxidation of Carbon Monoxide in the High Dose Rate Radiolysis of CO–O₂ Mixtures