Pressure and temperature dependence of the kinetics of the reaction aluminum + carbon dioxide

Garland, Nancy; Douglass, Charles H.; Nelson, H. H.

doi:10.1021/j100200a034

Cited by 20 publications

(15 citation statements)

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“…Garland et al studied the reverse reaction and found that it was bimolecular above 700 K, obtaining k (Al + CO 2 → AlO + CO) = 2.9 × 10 –10 exp(−(26.8 ± 1.7 kJ mol –1 / RT ) cm 3 molecule –1 s –1 . This activation energy is close to our calculated reaction endothermicity of 34 kJ mol –1 at the CBS-QB3 level.…”

Section: Discussionmentioning

confidence: 99%

Kinetic Study of the Reactions of AlO and OAlO Relevant to Planetary Mesospheres

Mangan

Harman-Thomas

Lade

et al. 2020

ACS Earth Space Chem.

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Section: Discussionmentioning

confidence: 99%

Kinetic Study of the Reactions of AlO and OAlO Relevant to Planetary Mesospheres

Mangan

Harman-Thomas

Lade

et al. 2020

ACS Earth Space Chem.

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“…The barrier for the dissociation of the η - AlCO 2 structure into reactants is 15.8 kcal mol –1 relative to η - AlCO 2 , which is 5.3 kcal mol –1 lower in energy than the overall energy needed to pass from η - AlCO 2 to AlO + CO at the W1BD//M11 level. Garland et al reported a consistent result from their experimental study of Al + CO 2 , for temperatures below 700 K, insofar as they suggested Al + CO 2 reacts to form the AlCO 2 complex, which can be stabilized or can dissociate back to reactants or forward to products.…”

Section: Resultsmentioning

confidence: 76%

“…The most favorable saddle point is designated SP1, which connects Al + CO 2 to η-AlCO 2 via a barrier of 0.8 kcal mol –1 . On the basis of their experimental results, Parnis et al and Garland et al reported barriers to complex formation of >1.0 kcal mol –1 and 0.48 ± 0.16 kcal mol –1 , respectively. Our calculated value for SP1 falls between those two experimental values.…”

Section: Resultsmentioning

confidence: 99%

“…Garland et al studied the reaction of Al + CO 2 using laser pump–probe techniques. They reported rate coefficients for total pressures between 10 and 600 Torr and temperatures between 298 and 1215 K. They reported that below 700 K the rate coefficient exhibits a strong pressure dependence, which suggests a complex-formation mechanism, with activation energy 0.48 ± 0.16 kcal mol –1 .…”

Section: Introductionmentioning

confidence: 99%

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Correlated Molecular Orbital Theory Study of the Al + CO₂ Reaction

et al. 2018

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Density functional theory (DFT) and correlated molecular orbital electronic structure calculations were used to study the Al + CO → AlO + CO reaction on the electronic ground-state potential-energy surface (PES). Geometries were optimized using DFT (M11/jun-cc-pV(Q+d)Z) and more accurate energies were obtained using the composite Weizmann-1 theory with Brueckner doubles (W1BD). The results comprise the most complete, most systematic characterization of the Al + CO reaction surface to date and are based on consistent application of high-level methods for all stationary points identified. The pathways from Al + CO to AlO + CO on the electronic ground-state PES all involve formation of one or more stable AlCO complexes denoted η-AlCO, trans-AlCO, and C-AlCO, among which η-AlCO and C-AlCO are the least and most stable, respectively. We report a new minimum-energy pathway for the overall reaction, namely formation of η-AlCO from reactants and dissociation of that same complex to products via a bond-insertion reaction that passes through a fourth (weakly metastable) AlCO complex denoted cis-OAlCO. Natural Bond Orbital analysis was applied to study trends in charge distribution and the degree of charge transfer in key structures along the minimum-energy pathway. The process of aluminum insertion into CO is discussed in the context of analogous processes for boron and first-row transition metals.

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“…While pressure was not varied in the high-temperature experiments the positive activation energies obtained, 160 Ϯ 41 and 36 Ϯ 12 kJ mol Ϫ1 , respectively, strongly indicate at least a major bimolecular component. The Al/CO 2 system has been found to display mainly fall-off behavior at room temperature, with an abstraction component, while in the 750Ϫ1215 K range abstraction dominates [3,48,49]. Competition between termolecular and bimolecular reactions has also been noted in room temperature measurements on the Pt/N 2 O system [50].…”

Section: Discussionmentioning

confidence: 98%

Transitions in Order and Molecularity with Temperature in Gaseous Metal Oxidation Reactions. The Sb-O2 System

Cosic¹,

Fontijn²

2000

Zeitschrift Für Physikalische Chemie

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High Temperature Kinetics / Gas-phase / Molecularity / Metal Atoms / Metal Oxidation / Rate Coefficients / Activation Energies / Sb / As / O 2 / SbO Bond EnergyExamples of reactions which are termolecular near room temperature and gradually switch over to complex-forming bimolecular reactions with increasing temperature are discussed. The Sb/O2 system, which is known from D. Husain's work to be termolecular at 300 K, has been studied here from 1165Ϫ1495 K at 12 to 52 mbar in a high-temperature fast-flow reactor (HTFFR). Sb was vaporized from a crucible and atomic resonance absorption spectrometry was used to measure the rates of Sb consumption. Under these conditions the reaction, identified as Sb ϩ O2 → SbO ϩ O, is pressure-independent with k(T) ϭ 6.3 ϫ10 Ϫ11 exp (Ϫ 9107 K/T) cm 3 molecule Ϫ1 s Ϫ1 . The 2σ precision limits are Ϯ 8% and the corresponding estimated accuracy limits are Ϯ 24%. The results suggest that D 0 (Sb-O) ϭ 444 Ϯ 28 kJ mol Ϫ1 . The results are compared to those of other endothermic metal-atom O 2 abstraction reactions, all of which have pre-exponentials on the order of 10 Ϫ10 cm 3 molecule Ϫ1 s Ϫ1 and activation energies for abstraction close to the endothermicity. This allows assessments of the relative importance of bi-, and ter-molecular kinetics, as illustrated for As ϩ O2.

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Pressure and temperature dependence of the kinetics of the reaction aluminum + carbon dioxide

Cited by 20 publications

References 4 publications

Kinetic Study of the Reactions of AlO and OAlO Relevant to Planetary Mesospheres

Kinetic Study of the Reactions of AlO and OAlO Relevant to Planetary Mesospheres

Correlated Molecular Orbital Theory Study of the Al + CO₂ Reaction

Transitions in Order and Molecularity with Temperature in Gaseous Metal Oxidation Reactions. The Sb-O2 System

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Pressure and temperature dependence of the kinetics of the reaction aluminum + carbon dioxide

Cited by 20 publications

References 4 publications

Kinetic Study of the Reactions of AlO and OAlO Relevant to Planetary Mesospheres

Kinetic Study of the Reactions of AlO and OAlO Relevant to Planetary Mesospheres

Correlated Molecular Orbital Theory Study of the Al + CO2 Reaction

Transitions in Order and Molecularity with Temperature in Gaseous Metal Oxidation Reactions. The Sb-O2 System

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Correlated Molecular Orbital Theory Study of the Al + CO₂ Reaction