Volume 238, 2022

Master equation study of hydrogen abstraction from HCHO by OH via a chemically activated intermediate

Abstract

The abstraction reaction of hydrogen from formaldehyde by OH radical plays an important role in formaldehyde oxidation. The reaction involves a bimolecular association to form a chemically activated hydrogen-bonded reaction complex followed by a unimolecular reaction of the complex to generate the products. The reaction rate is usually considered to be pressure-independent by assuming equilibrium between the reactants and the complex. However, our nonequilibrium calculations based on the chemically significant eigenmode of the master equation, carried out with our recently developed TUMME program, indicate that the reaction complex makes the rate constant dependent on pressure at low temperatures (T < 200 K). The calculations include anharmonicity, variational effects, and multi-dimensional tunneling. We find that the reaction rate constant reaches a low-pressure limit at pressures below 10 Torr over the whole investigated temperature range (20–1800 K), which explains why the available low-temperature experiments, which are for pressures below 2 Torr, did not observe the pressure dependence. A new extension of the TUMME master-equation program is used to explore the time evolutions of the concentrations of the OH radical and the complex under pseudo-first-order conditions. The time-dependent evolution of the concentrations of the complex at a low temperature provide direct evidence for the stabilization of the reaction complex at high pressures, and it shows the negligible role of the stabilized reaction complex at low pressures. The picture that emerges is qualitatively consistent with our previous study of the reaction of methanol with OH in that the tunneling in the unimolecular step from the complex to the products affects the phenomenological reaction rate constants differently at high and low pressures and leads to a significant pressure effect.

Graphical abstract: Master equation study of hydrogen abstraction from HCHO by OH via a chemically activated intermediate

Associated articles

Supplementary files

Article information

Article type
Paper
Submitted
31 яну 2022
Accepted
03 фев 2022
First published
08 фев 2022

Faraday Discuss., 2022,238, 431-460

Author version available

Master equation study of hydrogen abstraction from HCHO by OH via a chemically activated intermediate

R. M. Zhang, W. Chen, D. G. Truhlar and X. Xu, Faraday Discuss., 2022, 238, 431 DOI: 10.1039/D2FD00024E

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements