Cato A. R. Pappijn, Ruben Van de Vijver, Marie-Françoise Reyniers, Maarten K. Sabbe, Guy B. Marin and Kevin M. Van Geem
{"title":"通过基团相加性建立含氮化合物热化学模型","authors":"Cato A. R. Pappijn, Ruben Van de Vijver, Marie-Françoise Reyniers, Maarten K. Sabbe, Guy B. Marin and Kevin M. Van Geem","doi":"10.1039/D4CP00727A","DOIUrl":null,"url":null,"abstract":"<p >First-principles based kinetic modeling is essential to gain insight into the governing chemistry of nitrogen-containing compounds over a wide range of technologically important processes, <em>e.g.</em> pyrolysis, oxidation and combustion. It also enables the development of predictive, fundamental models key to improving understanding of the influence of nitrogen-containing compounds present as impurities or process additives, considering safety, operability and quality of the product streams. A prerequisite for the generation of detailed fundamental kinetic models is the availability of accurate thermodynamic properties. To address the scarcity of thermodynamic properties for nitrogen-containing compounds, a consistent set of 91 group additive values and three non-nearest-neighbor interactions has been determined from a dataset of CBS-QB3 calculations for 300 species, including 104 radicals. This dataset contains a wide range of nitrogen-containing functionalities, <em>i.e.</em> imine, nitrile, nitro, nitroso, nitrite, nitrate and azo functional groups. The group additivity model enables the approximation of the standard enthalpy of formation and standard entropy at 298 K as well as the standard heat capacities over a large temperature range, <em>i.e.</em> 300–1500 K. For a test set of 27 nitrogen-containing compounds, the group additivity model succeeds in approximating the <em>ab initio</em> calculated values for the standard enthalpy of formation with a MAD of 2.3 kJ mol<small><sup>−1</sup></small>. The MAD for the standard entropy and heat capacity is lower than 4 and 2 J mol<small><sup>−1</sup></small> K<small><sup>−1</sup></small>, respectively. For a test set of 11 nitrogen-containing compounds, the MAD between experimental and group additivity approximated values for the standard enthalpy of formation amounts to 2.8 kJ mol<small><sup>−1</sup></small>.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":null,"pages":null},"PeriodicalIF":2.9000,"publicationDate":"2024-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Modeling the thermochemistry of nitrogen-containing compounds via group additivity†\",\"authors\":\"Cato A. R. Pappijn, Ruben Van de Vijver, Marie-Françoise Reyniers, Maarten K. Sabbe, Guy B. Marin and Kevin M. Van Geem\",\"doi\":\"10.1039/D4CP00727A\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >First-principles based kinetic modeling is essential to gain insight into the governing chemistry of nitrogen-containing compounds over a wide range of technologically important processes, <em>e.g.</em> pyrolysis, oxidation and combustion. It also enables the development of predictive, fundamental models key to improving understanding of the influence of nitrogen-containing compounds present as impurities or process additives, considering safety, operability and quality of the product streams. A prerequisite for the generation of detailed fundamental kinetic models is the availability of accurate thermodynamic properties. To address the scarcity of thermodynamic properties for nitrogen-containing compounds, a consistent set of 91 group additive values and three non-nearest-neighbor interactions has been determined from a dataset of CBS-QB3 calculations for 300 species, including 104 radicals. This dataset contains a wide range of nitrogen-containing functionalities, <em>i.e.</em> imine, nitrile, nitro, nitroso, nitrite, nitrate and azo functional groups. The group additivity model enables the approximation of the standard enthalpy of formation and standard entropy at 298 K as well as the standard heat capacities over a large temperature range, <em>i.e.</em> 300–1500 K. For a test set of 27 nitrogen-containing compounds, the group additivity model succeeds in approximating the <em>ab initio</em> calculated values for the standard enthalpy of formation with a MAD of 2.3 kJ mol<small><sup>−1</sup></small>. The MAD for the standard entropy and heat capacity is lower than 4 and 2 J mol<small><sup>−1</sup></small> K<small><sup>−1</sup></small>, respectively. For a test set of 11 nitrogen-containing compounds, the MAD between experimental and group additivity approximated values for the standard enthalpy of formation amounts to 2.8 kJ mol<small><sup>−1</sup></small>.</p>\",\"PeriodicalId\":99,\"journal\":{\"name\":\"Physical Chemistry Chemical Physics\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.9000,\"publicationDate\":\"2024-07-02\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Physical Chemistry Chemical Physics\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2024/cp/d4cp00727a\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Physical Chemistry Chemical Physics","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2024/cp/d4cp00727a","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Modeling the thermochemistry of nitrogen-containing compounds via group additivity†
First-principles based kinetic modeling is essential to gain insight into the governing chemistry of nitrogen-containing compounds over a wide range of technologically important processes, e.g. pyrolysis, oxidation and combustion. It also enables the development of predictive, fundamental models key to improving understanding of the influence of nitrogen-containing compounds present as impurities or process additives, considering safety, operability and quality of the product streams. A prerequisite for the generation of detailed fundamental kinetic models is the availability of accurate thermodynamic properties. To address the scarcity of thermodynamic properties for nitrogen-containing compounds, a consistent set of 91 group additive values and three non-nearest-neighbor interactions has been determined from a dataset of CBS-QB3 calculations for 300 species, including 104 radicals. This dataset contains a wide range of nitrogen-containing functionalities, i.e. imine, nitrile, nitro, nitroso, nitrite, nitrate and azo functional groups. The group additivity model enables the approximation of the standard enthalpy of formation and standard entropy at 298 K as well as the standard heat capacities over a large temperature range, i.e. 300–1500 K. For a test set of 27 nitrogen-containing compounds, the group additivity model succeeds in approximating the ab initio calculated values for the standard enthalpy of formation with a MAD of 2.3 kJ mol−1. The MAD for the standard entropy and heat capacity is lower than 4 and 2 J mol−1 K−1, respectively. For a test set of 11 nitrogen-containing compounds, the MAD between experimental and group additivity approximated values for the standard enthalpy of formation amounts to 2.8 kJ mol−1.
期刊介绍:
Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions.
The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.