| Zugriffsnummer | 41091 |
| Dokumenttyp | Zeitschriftenartikel |
| Peer Review | mit Peer Review |
| Sprache | Englisch |
| Titel | Reaction kinetics of hydrogen atom abstraction from isopentanol by the H atom and HO2· radical |
| Autor(in); Institution |
Parab, Prajakta; RWTH Aachen University, Aachen, Physico Chemical Fundamentals of Combustion, GERMANY
Heufer, Alexander; RWTH Aachen University, Aachen, Physico Chemical Fundamentals of Combustion, GERMANY
Fernandes, Ravi; 3.3, Thermophysikalische Größen, PTB-Braunschweig
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| Quelle/Jahr | Physical Chemistry, Chemical Physics: 20 (2018), 10895 - 10905 |
| ISSN | 1463-9076 (PRINT) ; 1463-9084 (ONLINE) |
| DOI | |
| Verlag | Cambridge: RSC |
| Zusammenfassung | 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. |
| Themenbereich der Metrologie | Metrologie in der Chemie und Stoffeigenschaften |