Reaction kinetics of Mo(a7S3, a5S2, a5DJ, a5GJ) with O2

Campbell, Mark L.; McClean, Roy E.; Harter, James S.S.

doi:10.1016/0009-2614(95)00165-z

Cited by 33 publications

(35 citation statements)

References 9 publications

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“…Reaction Mechanisms. Gas-phase studies − have found that both ground ( 7 S 3 ) and excited-state Mo and W atoms react with O 2 with nearly gas kinetic rates and no pressure dependence, which suggests that the O−O bond is easily activated. These studies followed the metal atoms and not the products formed; however, MoO and WO have been observed in gas phase. , The growth of MoO 2 and WO 2 on matrix photolysis and the absence of growth on matrix annealing suggest some activation energy for insertion reaction 5: …”

Section: Discussionmentioning

confidence: 99%

Reactions of Laser-Ablated Molybdenum and Tungsten Atoms with Dioxygen. Resolved Infrared Spectra of Natural Molybdenum and Tungsten Isotopic Oxides in Argon Matrices

1998

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Laser-ablated molybdenum and tungsten atoms were reacted with dioxygen and 18O-substituted dioxygen. The products of these reactions were isolated in solid argon matrices at 10 K and studied by matrix infrared spectroscopy. Analysis of spectra enabled identification of reaction products, which included MoO2, (O2)MoO2, MoO3, WO, WO2, (O2)WO2, and WO3. Resolution of isotopic splitting due to natural isotopic abundance of the metal verified the presence of a single metal atom in these molecules and allowed for calculation of bond angles for the molybdenum and tungsten dioxide molecules and their dioxygen complexes.

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Section: Discussionmentioning

confidence: 99%

Reactions of Laser-Ablated Molybdenum and Tungsten Atoms with Dioxygen. Resolved Infrared Spectra of Natural Molybdenum and Tungsten Isotopic Oxides in Argon Matrices

1998

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“…The long-range, ion-induced dipole force makes barriers to bond insertion and rearrangement unusual, whereas barriers are commonplace in condensed phase bond-breaking chemistry. Accordingly, we and others have been studying reactions of neutral metal atoms with alkanes, alkenes, and oxidants. − In our experiments, laser-induced fluorescence (LIF) monitors the decay of ground-state, neutral metal atom density vs calibrated hydrocarbon density in a fast flow reactor at 300 K and 0.5−1.1 Torr of He buffer gas. We obtain ground-state effective bimolecular rate constants from a well-defined, Boltzmann distribution of collision energy and internal hydrocarbon energy.…”

Section: Introductionmentioning

confidence: 99%

Gas Phase Kinetics of Neutral Transition Metal Atoms: Reactions of Hf, Ta, Ir, Pt, and Au with Alkanes and Alkenes

and

Weisshaar

1996

J. Phys. Chem.

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The chemical kinetics of the ground-state, neutral transition metal atoms Hf, Ta, Ir, Pt, and Au with alkanes and alkenes is surveyed. Laser-induced fluorescence measures effective bimolecular rate constants at 300 K in 0.5-1.1 Torr of He buffer gas. Pt(5d 9 6s 1 ) is thus far the only ground-state neutral atom in the entire transition metal block that reacts with methane. It also reacts rapidly with linear alkanes, cyclopropane, and the alkenes. Au(5d 10 6s 1 ) reacts only with the largest alkenes studied, and then very slowly. In spite of their 6s 2 ground-state configurations, Hf(5d 2 6s 2 ), Ta(5d 3 6s 2 ), and Ir(5d 7 6s 2 ) react rapidly with alkenes including ethene; these atoms do not react with methane and the linear alkanes. An attempt is made to interpret the pattern of reactivity in terms of simple chemical bonding concepts, including electron configuration and spin, guided by earlier extensive electronic structure calculations for the 4d series. It appears that the lanthanide contraction of the 6s orbital strongly influences the chemical reactivity of the 5d-series atoms.

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“…character [4]. Experiments with vanadium [6], titanium [3,7], molybdenum [2,17], and niobium [25] have been performed recently which generally support this model.…”

Section: Discussionmentioning

confidence: 61%

“…The experimental apparatus used in these experiments has been discussed in detail previously [1,2] and is only briefly described here. The experiments were performed under pseudo-first-order kinetics ([W] Ͻ Ͻ [Ox]) using a laser-photolysis/laser-induced fluorescence (LIF) technique in an apparatus with slowly flowing gas.…”

Section: Methodsmentioning

confidence: 99%

Depletion kinetics of low-lying states of tungsten in the presence of NO, N2O, and SO2

Harter

Campbell

McClean

1997

Int. J. Chem. Kinet.

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The gas-phase reactivities of W(a 5 D J , a 7 S 3 ) with N 2 O, SO 2 , and NO in the temperature range of 295 -573 K are reported. Tungsten atoms were produced by the photodissociation of W(CO) 6 . The tungsten atoms were detected by a laser-induced fluorescence technique. The removal rate constants for the 6s 2 5d 4 a 5 D J states were found to be J dependent for all of the reactants. Removal rate constants for the 6s 1 5d 5 a 7 S 3 state were found to be fast compared to the a 5 D J states and often approached the gas kinetic rate constant. The reaction rates for all the states were found to be pressure independent with respect to the total pressure. Results are discussed in terms of the different electronic configurations of the states of tungsten.

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Reaction kinetics of Mo(a7S3, a5S2, a5DJ, a5GJ) with O2

Cited by 33 publications

References 9 publications

Reactions of Laser-Ablated Molybdenum and Tungsten Atoms with Dioxygen. Resolved Infrared Spectra of Natural Molybdenum and Tungsten Isotopic Oxides in Argon Matrices

Reactions of Laser-Ablated Molybdenum and Tungsten Atoms with Dioxygen. Resolved Infrared Spectra of Natural Molybdenum and Tungsten Isotopic Oxides in Argon Matrices

Gas Phase Kinetics of Neutral Transition Metal Atoms: Reactions of Hf, Ta, Ir, Pt, and Au with Alkanes and Alkenes

Depletion kinetics of low-lying states of tungsten in the presence of NO, N2O, and SO2

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