Dynamics of the reaction of oxygen atoms with carbon suboxide

D. S.Y. Hsu; Ming-Chang Lin

doi:10.1063/1.435511

Dynamics of the reaction of oxygen atoms with carbon suboxide

D. S.Y. Hsu^*
, Ming-Chang Lin

^*Corresponding author for this work

Department of Applied Chemistry

Research output: Contribution to journal › Article › peer-review

9 Scopus citations

Abstract

The dynamics of the O(³P)+C₃O₂→3CO reaction (ΔH°=-115 kcal/mole) has been investigated by means of a CO laser resonance absorption technique. The reaction mixtures consisted of NO ₂ and C₃O₂, with He or SF₆ dilution. The O(³P) atom was generated by the flash photolysis of the NO ₂ above 300 nm. The three CO's formed in the reaction were found to carry vibrationally about 19% of the total available energy, with an apparent near statistical population distribution. The results of an ¹⁸O- labeled experiment, however, indicate that the two CO's originating from the parent C₃O₂ molecule are vibrationally much colder (〈E_v〉≃ 4.2 kcal/mole) than that from the reaction of the O atom with the center C atom (〈E_v〉≃15 kcal/mole). This result is attributed to the incomplete randomization of the reaction energy in the dissociating C₃O₃ complex. Possible reaction mechanisms are presented.

Original language	English
Pages (from-to)	4347-4351
Number of pages	5
Journal	The Journal of chemical physics
Volume	68
Issue number	10
DOIs	https://doi.org/10.1063/1.435511
State	Published - 1 Jan 1978

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title = "Dynamics of the reaction of oxygen atoms with carbon suboxide",

abstract = "The dynamics of the O(3P)+C3O2→3CO reaction (ΔH°=-115 kcal/mole) has been investigated by means of a CO laser resonance absorption technique. The reaction mixtures consisted of NO 2 and C3O2, with He or SF6 dilution. The O(3P) atom was generated by the flash photolysis of the NO 2 above 300 nm. The three CO's formed in the reaction were found to carry vibrationally about 19\% of the total available energy, with an apparent near statistical population distribution. The results of an 18O- labeled experiment, however, indicate that the two CO's originating from the parent C3O2 molecule are vibrationally much colder (〈Ev〉≃ 4.2 kcal/mole) than that from the reaction of the O atom with the center C atom (〈Ev〉≃15 kcal/mole). This result is attributed to the incomplete randomization of the reaction energy in the dissociating C3O3 complex. Possible reaction mechanisms are presented.",

author = "Hsu, \{D. S.Y.\} and Ming-Chang Lin",

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doi = "10.1063/1.435511",

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TY - JOUR

T1 - Dynamics of the reaction of oxygen atoms with carbon suboxide

AU - Hsu, D. S.Y.

AU - Lin, Ming-Chang

PY - 1978/1/1

Y1 - 1978/1/1

N2 - The dynamics of the O(3P)+C3O2→3CO reaction (ΔH°=-115 kcal/mole) has been investigated by means of a CO laser resonance absorption technique. The reaction mixtures consisted of NO 2 and C3O2, with He or SF6 dilution. The O(3P) atom was generated by the flash photolysis of the NO 2 above 300 nm. The three CO's formed in the reaction were found to carry vibrationally about 19% of the total available energy, with an apparent near statistical population distribution. The results of an 18O- labeled experiment, however, indicate that the two CO's originating from the parent C3O2 molecule are vibrationally much colder (〈Ev〉≃ 4.2 kcal/mole) than that from the reaction of the O atom with the center C atom (〈Ev〉≃15 kcal/mole). This result is attributed to the incomplete randomization of the reaction energy in the dissociating C3O3 complex. Possible reaction mechanisms are presented.

AB - The dynamics of the O(3P)+C3O2→3CO reaction (ΔH°=-115 kcal/mole) has been investigated by means of a CO laser resonance absorption technique. The reaction mixtures consisted of NO 2 and C3O2, with He or SF6 dilution. The O(3P) atom was generated by the flash photolysis of the NO 2 above 300 nm. The three CO's formed in the reaction were found to carry vibrationally about 19% of the total available energy, with an apparent near statistical population distribution. The results of an 18O- labeled experiment, however, indicate that the two CO's originating from the parent C3O2 molecule are vibrationally much colder (〈Ev〉≃ 4.2 kcal/mole) than that from the reaction of the O atom with the center C atom (〈Ev〉≃15 kcal/mole). This result is attributed to the incomplete randomization of the reaction energy in the dissociating C3O3 complex. Possible reaction mechanisms are presented.

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U2 - 10.1063/1.435511

DO - 10.1063/1.435511

M3 - Article

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SN - 0021-9606

VL - 68

SP - 4347

EP - 4351

JO - The Journal of chemical physics

JF - The Journal of chemical physics

IS - 10

ER -

Dynamics of the reaction of oxygen atoms with carbon suboxide

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