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Issue 16, 2018
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Reaction kinetics of hydrogen atom abstraction from isopentanol by the H atom and HO2˙ radical

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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

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Publication details

The article was received on 01 Dec 2017, accepted on 20 Feb 2018 and first published on 21 Feb 2018


Article type: Paper
DOI: 10.1039/C7CP08077H
Citation: Phys. Chem. Chem. Phys., 2018,20, 10895-10905
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    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

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