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Computational study of the unimolecular and bimolecular decomposition mechanisms of propylamine
A detailed computational study of the dehydrogenation reaction of trans-propylamine (trans-PA) in the gas phase has been performed using density functional method (DFT) and CBS-QB3 calculations. Different mechanistic pathways were studied for the reaction of n-propylamine. Both thermodynamic functio...
Autores principales: | , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Publishing Group UK
2020
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7366726/ https://www.ncbi.nlm.nih.gov/pubmed/32678287 http://dx.doi.org/10.1038/s41598-020-68723-7 |
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author | Almatarneh, Mansour H. Al Omari, Rima Omeir, Reema A. Al Khawaldeh, Ahmad Afaneh, Akef T. Sinnokrot, Mutasem Al Akhras, Alaa Marashdeh, Ali |
author_facet | Almatarneh, Mansour H. Al Omari, Rima Omeir, Reema A. Al Khawaldeh, Ahmad Afaneh, Akef T. Sinnokrot, Mutasem Al Akhras, Alaa Marashdeh, Ali |
author_sort | Almatarneh, Mansour H. |
collection | PubMed |
description | A detailed computational study of the dehydrogenation reaction of trans-propylamine (trans-PA) in the gas phase has been performed using density functional method (DFT) and CBS-QB3 calculations. Different mechanistic pathways were studied for the reaction of n-propylamine. Both thermodynamic functions and activation parameters were calculated for all investigated pathways. Most of the dehydrogenation reaction mechanisms occur in a concerted step transition state as an exothermic process. The mechanisms for pathways A and B comprise two key-steps: H(2) eliminated from PA leading to the formation of allylamine that undergoes an unimolecular dissociation in the second step of the mechanism. Among these pathways, the formation of ethyl cyanide and H(2) is the most significant one (pathway B), both kinetically and thermodynamically, with an energy barrier of 416 kJ mol(−1). The individual mechanisms for the pathways from C to N involve the dehydrogenation reaction of PA via hydrogen ion, ammonia ion and methyl cation. The formation of α-propylamine cation and NH(3) (pathway E) is the most favorable reaction with an activation barrier of 1 kJ mol(−1). This pathway has the lowest activation energy calculated of all proposed pathways. |
format | Online Article Text |
id | pubmed-7366726 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | Nature Publishing Group UK |
record_format | MEDLINE/PubMed |
spelling | pubmed-73667262020-07-17 Computational study of the unimolecular and bimolecular decomposition mechanisms of propylamine Almatarneh, Mansour H. Al Omari, Rima Omeir, Reema A. Al Khawaldeh, Ahmad Afaneh, Akef T. Sinnokrot, Mutasem Al Akhras, Alaa Marashdeh, Ali Sci Rep Article A detailed computational study of the dehydrogenation reaction of trans-propylamine (trans-PA) in the gas phase has been performed using density functional method (DFT) and CBS-QB3 calculations. Different mechanistic pathways were studied for the reaction of n-propylamine. Both thermodynamic functions and activation parameters were calculated for all investigated pathways. Most of the dehydrogenation reaction mechanisms occur in a concerted step transition state as an exothermic process. The mechanisms for pathways A and B comprise two key-steps: H(2) eliminated from PA leading to the formation of allylamine that undergoes an unimolecular dissociation in the second step of the mechanism. Among these pathways, the formation of ethyl cyanide and H(2) is the most significant one (pathway B), both kinetically and thermodynamically, with an energy barrier of 416 kJ mol(−1). The individual mechanisms for the pathways from C to N involve the dehydrogenation reaction of PA via hydrogen ion, ammonia ion and methyl cation. The formation of α-propylamine cation and NH(3) (pathway E) is the most favorable reaction with an activation barrier of 1 kJ mol(−1). This pathway has the lowest activation energy calculated of all proposed pathways. Nature Publishing Group UK 2020-07-16 /pmc/articles/PMC7366726/ /pubmed/32678287 http://dx.doi.org/10.1038/s41598-020-68723-7 Text en © The Author(s) 2020 Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/. |
spellingShingle | Article Almatarneh, Mansour H. Al Omari, Rima Omeir, Reema A. Al Khawaldeh, Ahmad Afaneh, Akef T. Sinnokrot, Mutasem Al Akhras, Alaa Marashdeh, Ali Computational study of the unimolecular and bimolecular decomposition mechanisms of propylamine |
title | Computational study of the unimolecular and bimolecular decomposition mechanisms of propylamine |
title_full | Computational study of the unimolecular and bimolecular decomposition mechanisms of propylamine |
title_fullStr | Computational study of the unimolecular and bimolecular decomposition mechanisms of propylamine |
title_full_unstemmed | Computational study of the unimolecular and bimolecular decomposition mechanisms of propylamine |
title_short | Computational study of the unimolecular and bimolecular decomposition mechanisms of propylamine |
title_sort | computational study of the unimolecular and bimolecular decomposition mechanisms of propylamine |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7366726/ https://www.ncbi.nlm.nih.gov/pubmed/32678287 http://dx.doi.org/10.1038/s41598-020-68723-7 |
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