Issue 16, 2018

Reaction kinetics of hydrogen atom abstraction from isopentanol by the H atom and HO2˙ radical

Abstract

Isopentanol is a potential next-generation biofuel for future applications to Homogeneous Charge Compression Ignition (HCCI) engine concepts. To provide insights into the combustion behavior of isopentanol, especially to its auto-ignition behavior which is linked both to efficiency and pollutant formation in real combustion systems, detailed quantum chemical studies for crucial reactions are desired. H-Abstraction reaction rates from fuel molecules are key initiation steps for chain branching required for auto-ignition. In this study, rate constants are determined for the hydrogen atom abstraction reactions from isopentanol by the H atom and HO2˙ radical by implementing the CBS-QB3 composite method. For the treatment of the internal rotors, a Pitzer–Gwinn-like approximation is applied. On comparing the computed reaction energies, the highest exothermicity (ΔE = −46 kJ mol−1) is depicted for Hα abstraction by the H atom whereas the lowest endothermicity (ΔE = 29 kJ mol−1) is shown for the abstraction of Hα by the HO2˙ radical. The formation of hydrogen bonding is found to affect the kinetics of the H atom abstraction reactions by the HO2˙ radical. Further above 750 K, the calculated high pressure limit rate constants indicate that the total contribution from delta carbon sites (Cδ) is predominant for hydrogen atom abstraction by the H atom and HO2˙ radical.

Graphical abstract: Reaction kinetics of hydrogen atom abstraction from isopentanol by the H atom and HO2˙ radical

Supplementary files

Article information

Article type
Paper
Submitted
01 des. 2017
Accepted
20 feb. 2018
First published
21 feb. 2018

Phys. Chem. Chem. Phys., 2018,20, 10895-10905

Reaction kinetics of hydrogen atom abstraction from isopentanol by the H atom and HO2˙ radical

P. R. Parab, K. A. Heufer and R. X. Fernandes, Phys. Chem. Chem. Phys., 2018, 20, 10895 DOI: 10.1039/C7CP08077H

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