The kinetics of the reactions of C2 (a3∏ u) with alcohols

Cunshun Huang; Zhiqiang Zhu; Hailing Wang; Linsen Pei; Yang Chen

doi:10.1021/jp0457390

The kinetics of the reactions of C₂ (a³∏ _u) with alcohols

Cunshun Huang
, Zhiqiang Zhu
, Hailing Wang
, Linsen Pei
, Yang Chen^*

^*Corresponding author for this work

University of Science and Technology of China

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

14 Scopus citations

Abstract

The reactions of C₂ (a³∏_u) radicals with a series of alcohols have been studied at about 6.5 Torr total pressure and room temperature using the pulsed laser photolysis/laser-induced fluorescence technique. The relative concentration of C₂ (a³∏ _u) radicals, which are generated via the photolysis of C ₂Cl₄ with the focused output from the fourth harmonic of a Nd:YAG laser (266 nm), was monitored by laser-induced fluorescence (LIF) in the (0, 0) band of the C₂ (d³∏_g←a ³∏_u) transition at 516.5 nm. Under pseudo-first-order conditions, we measured the time evolution of C₂ (a ³∏_u) and determined the rate constants for reactions of C₂ (a³∏_u) with alcohols. The rate constants increase linearly with the number of C atoms in the alcohols. All of them are larger than those for reactions of C₂ (a³∏ _u) with alkanes (C₂-C₅). Based on the bond dissociation energy and linear free energy correlations, we believe the reactions of C₂ (a³∏_u) with alcohols proceed via the mechanism of hydrogen abstraction. The experimental results show that the H-atom on the C-H bonds is activated at the presence of the OH substituent group in the alcohol molecule. The theoretical calculations for the reaction of C₂ (a³∏_u) with methanol also support these hypotheses.

Original language	English
Pages (from-to)	3921-3925
Number of pages	5
Journal	Journal of Physical Chemistry A
Volume	109
Issue number	17
DOIs	https://doi.org/10.1021/jp0457390
State	Published - 5 May 2005
Externally published	Yes

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title = "The kinetics of the reactions of C2 (a3∏ u) with alcohols",

abstract = "The reactions of C2 (a3∏u) radicals with a series of alcohols have been studied at about 6.5 Torr total pressure and room temperature using the pulsed laser photolysis/laser-induced fluorescence technique. The relative concentration of C2 (a3∏ u) radicals, which are generated via the photolysis of C 2Cl4 with the focused output from the fourth harmonic of a Nd:YAG laser (266 nm), was monitored by laser-induced fluorescence (LIF) in the (0, 0) band of the C2 (d3∏g←a 3∏u) transition at 516.5 nm. Under pseudo-first-order conditions, we measured the time evolution of C2 (a 3∏u) and determined the rate constants for reactions of C2 (a3∏u) with alcohols. The rate constants increase linearly with the number of C atoms in the alcohols. All of them are larger than those for reactions of C2 (a3∏ u) with alkanes (C2-C5). Based on the bond dissociation energy and linear free energy correlations, we believe the reactions of C2 (a3∏u) with alcohols proceed via the mechanism of hydrogen abstraction. The experimental results show that the H-atom on the C-H bonds is activated at the presence of the OH substituent group in the alcohol molecule. The theoretical calculations for the reaction of C2 (a3∏u) with methanol also support these hypotheses.",

author = "Cunshun Huang and Zhiqiang Zhu and Hailing Wang and Linsen Pei and Yang Chen",

year = "2005",

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doi = "10.1021/jp0457390",

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T1 - The kinetics of the reactions of C2 (a3∏ u) with alcohols

AU - Huang, Cunshun

AU - Zhu, Zhiqiang

AU - Wang, Hailing

AU - Pei, Linsen

AU - Chen, Yang

PY - 2005/5/5

Y1 - 2005/5/5

N2 - The reactions of C2 (a3∏u) radicals with a series of alcohols have been studied at about 6.5 Torr total pressure and room temperature using the pulsed laser photolysis/laser-induced fluorescence technique. The relative concentration of C2 (a3∏ u) radicals, which are generated via the photolysis of C 2Cl4 with the focused output from the fourth harmonic of a Nd:YAG laser (266 nm), was monitored by laser-induced fluorescence (LIF) in the (0, 0) band of the C2 (d3∏g←a 3∏u) transition at 516.5 nm. Under pseudo-first-order conditions, we measured the time evolution of C2 (a 3∏u) and determined the rate constants for reactions of C2 (a3∏u) with alcohols. The rate constants increase linearly with the number of C atoms in the alcohols. All of them are larger than those for reactions of C2 (a3∏ u) with alkanes (C2-C5). Based on the bond dissociation energy and linear free energy correlations, we believe the reactions of C2 (a3∏u) with alcohols proceed via the mechanism of hydrogen abstraction. The experimental results show that the H-atom on the C-H bonds is activated at the presence of the OH substituent group in the alcohol molecule. The theoretical calculations for the reaction of C2 (a3∏u) with methanol also support these hypotheses.

AB - The reactions of C2 (a3∏u) radicals with a series of alcohols have been studied at about 6.5 Torr total pressure and room temperature using the pulsed laser photolysis/laser-induced fluorescence technique. The relative concentration of C2 (a3∏ u) radicals, which are generated via the photolysis of C 2Cl4 with the focused output from the fourth harmonic of a Nd:YAG laser (266 nm), was monitored by laser-induced fluorescence (LIF) in the (0, 0) band of the C2 (d3∏g←a 3∏u) transition at 516.5 nm. Under pseudo-first-order conditions, we measured the time evolution of C2 (a 3∏u) and determined the rate constants for reactions of C2 (a3∏u) with alcohols. The rate constants increase linearly with the number of C atoms in the alcohols. All of them are larger than those for reactions of C2 (a3∏ u) with alkanes (C2-C5). Based on the bond dissociation energy and linear free energy correlations, we believe the reactions of C2 (a3∏u) with alcohols proceed via the mechanism of hydrogen abstraction. The experimental results show that the H-atom on the C-H bonds is activated at the presence of the OH substituent group in the alcohol molecule. The theoretical calculations for the reaction of C2 (a3∏u) with methanol also support these hypotheses.

UR - https://www.scopus.com/pages/publications/18844437824

U2 - 10.1021/jp0457390

DO - 10.1021/jp0457390

M3 - 文章

AN - SCOPUS:18844437824

SN - 1089-5639

VL - 109

SP - 3921

EP - 3925

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

IS - 17

ER -

The kinetics of the reactions of C₂ (a³∏ _u) with alcohols

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