Automated Reaction Mechanism Generation Including Nitrogen as a Heteroatom
The open source rate-based Reaction Mechanism Generator (RMG) software and its thermochemical and kinetics databases were extended to include nitrogen as a heteroatom. Specific changes to RMG and the mining of thermochemistry and reaction kinetics data are discussed. This new version of RMG has been...
| Main Authors: | , , , |
|---|---|
| Other Authors: | |
| Format: | Article |
| Language: | English |
| Published: |
Wiley
2020
|
| Online Access: | https://hdl.handle.net/1721.1/125783 |
| _version_ | 1811072139465326592 |
|---|---|
| author | Grinberg Dana, Alon Busser, Beat Andreas Merchant, Shamel Sarfaraz Green Jr, William H |
| author2 | Massachusetts Institute of Technology. Department of Chemical Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Chemical Engineering Grinberg Dana, Alon Busser, Beat Andreas Merchant, Shamel Sarfaraz Green Jr, William H |
| author_sort | Grinberg Dana, Alon |
| collection | MIT |
| description | The open source rate-based Reaction Mechanism Generator (RMG) software and its thermochemical and kinetics databases were extended to include nitrogen as a heteroatom. Specific changes to RMG and the mining of thermochemistry and reaction kinetics data are discussed. This new version of RMG has been tested by generating a detailed pyrolysis and oxidation model for ethylamine (EA, CH3CH2NH2) at ∼1400 K and ∼2 bar, and comparing it to recent shock tube studies. Validation of the reaction network with recent experimental data showed that the generated model successfully reproduced the observed species as well as ignition delay measurements. During pyrolysis, EA initially decomposes via a CC bond scission, and the CH2NH2 product subsequently produces the first H radicals in this system via β-scission. As the concentration of H increases, the major EA consuming reaction becomes H abstraction at the α-site by H radicals, leading to a chain reaction since its product generates more H radicals. During oxidation, the dominant N2-producing route is mediated by NO and N2O. The observables were found to be relatively sensitive to the CC and CN EA bond scission reactions as well as to the thermodynamic values of EA; thermodynamic data for EA were computed at the CBS-QB3 level and reported herein. This work demonstrates the ability of RMG to construct adequate kinetic models for nitrogenous species and discusses the pyrolysis and oxidation mechanisms of EA. |
| first_indexed | 2024-09-23T09:01:30Z |
| format | Article |
| id | mit-1721.1/125783 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T09:01:30Z |
| publishDate | 2020 |
| publisher | Wiley |
| record_format | dspace |
| spelling | mit-1721.1/1257832022-09-30T12:53:45Z Automated Reaction Mechanism Generation Including Nitrogen as a Heteroatom Grinberg Dana, Alon Busser, Beat Andreas Merchant, Shamel Sarfaraz Green Jr, William H Massachusetts Institute of Technology. Department of Chemical Engineering The open source rate-based Reaction Mechanism Generator (RMG) software and its thermochemical and kinetics databases were extended to include nitrogen as a heteroatom. Specific changes to RMG and the mining of thermochemistry and reaction kinetics data are discussed. This new version of RMG has been tested by generating a detailed pyrolysis and oxidation model for ethylamine (EA, CH3CH2NH2) at ∼1400 K and ∼2 bar, and comparing it to recent shock tube studies. Validation of the reaction network with recent experimental data showed that the generated model successfully reproduced the observed species as well as ignition delay measurements. During pyrolysis, EA initially decomposes via a CC bond scission, and the CH2NH2 product subsequently produces the first H radicals in this system via β-scission. As the concentration of H increases, the major EA consuming reaction becomes H abstraction at the α-site by H radicals, leading to a chain reaction since its product generates more H radicals. During oxidation, the dominant N2-producing route is mediated by NO and N2O. The observables were found to be relatively sensitive to the CC and CN EA bond scission reactions as well as to the thermodynamic values of EA; thermodynamic data for EA were computed at the CBS-QB3 level and reported herein. This work demonstrates the ability of RMG to construct adequate kinetic models for nitrogenous species and discusses the pyrolysis and oxidation mechanisms of EA. Swiss National Science Foundation (Grant PBEZB2-140081) US Department of Energy, Office of Basic Energy Sciences (Award DE-SC0014901) 2020-06-12T19:18:30Z 2020-06-12T19:18:30Z 2018-02 2017-12 2020-06-08T14:32:32Z Article http://purl.org/eprint/type/JournalArticle 0538-8066 https://hdl.handle.net/1721.1/125783 Dana, Alon Grinberg et al. "Automated Reaction Mechanism Generation Including Nitrogen as a Heteroatom." International Journal of Chemical Kinetics 50, 4 (February 2018) © 2018 Wiley Periodicals, Inc en http://dx.doi.org/10.1002/kin.21154 International Journal of Chemical Kinetics Creative Commons Attribution-Noncommercial-Share Alike http://creativecommons.org/licenses/by-nc-sa/4.0/ application/pdf Wiley Prof. Green via Ye Li |
| spellingShingle | Grinberg Dana, Alon Busser, Beat Andreas Merchant, Shamel Sarfaraz Green Jr, William H Automated Reaction Mechanism Generation Including Nitrogen as a Heteroatom |
| title | Automated Reaction Mechanism Generation Including Nitrogen as a Heteroatom |
| title_full | Automated Reaction Mechanism Generation Including Nitrogen as a Heteroatom |
| title_fullStr | Automated Reaction Mechanism Generation Including Nitrogen as a Heteroatom |
| title_full_unstemmed | Automated Reaction Mechanism Generation Including Nitrogen as a Heteroatom |
| title_short | Automated Reaction Mechanism Generation Including Nitrogen as a Heteroatom |
| title_sort | automated reaction mechanism generation including nitrogen as a heteroatom |
| url | https://hdl.handle.net/1721.1/125783 |
| work_keys_str_mv | AT grinbergdanaalon automatedreactionmechanismgenerationincludingnitrogenasaheteroatom AT busserbeatandreas automatedreactionmechanismgenerationincludingnitrogenasaheteroatom AT merchantshamelsarfaraz automatedreactionmechanismgenerationincludingnitrogenasaheteroatom AT greenjrwilliamh automatedreactionmechanismgenerationincludingnitrogenasaheteroatom |