Ab initio kinetic mechanism of OH-initiated atmospheric oxidation of pyrrole

The comprehensive kinetic mechanism of the OH-initiated gas-phase oxidation of pyrrole is first theoretically reported in a broad range of conditions (T = 200–2000 K &P = 1–7600 Torr). On the potential energy surface constructed at the M06–2X/aug-cc-pVTZ level, the temperature- and pressure-depe...

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Published in:Chemosphere (Oxford) 2021-01, Vol.263, p.127850, Article 127850
Main Authors: Mai, Tam V.-T., Nguyen, Hieu T., Huynh, Lam K.
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Language:English
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And atmospheric chemistry
Atmosphere
Hydroxyl Radical
Kinetics
Master equation
OH radical
Oxidation-Reduction
POPs
Pyrrole
Pyrroles
Rate constants
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description The comprehensive kinetic mechanism of the OH-initiated gas-phase oxidation of pyrrole is first theoretically reported in a broad range of conditions (T = 200–2000 K &P = 1–7600 Torr). On the potential energy surface constructed at the M06–2X/aug-cc-pVTZ level, the temperature- and pressure-dependent behaviors of the title reaction were characterized using the stochastic Rice–Ramsperger–Kassel–Marcus based Master Equation (RRKM-ME) rate model. The corrections of the hindered internal rotation and quantum tunneling treatments were included. The calculated results reveal the competition between the two distinct pathways: OH-addition and direct H-abstraction. The former channels are found favorable at low-temperature and high-pressure range (e.g., T 
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On the potential energy surface constructed at the M06–2X/aug-cc-pVTZ level, the temperature- and pressure-dependent behaviors of the title reaction were characterized using the stochastic Rice–Ramsperger–Kassel–Marcus based Master Equation (RRKM-ME) rate model. The corrections of the hindered internal rotation and quantum tunneling treatments were included. The calculated results reveal the competition between the two distinct pathways: OH-addition and direct H-abstraction. The former channels are found favorable at low-temperature and high-pressure range (e.g., T &lt; 900 K and P = 760 Torr) where non-Arrhenius and positive pressure-dependent behaviors of the rate constants are noticeably observed, while the latter predominate at temperatures higher than 900 K at atmospheric pressure and no pressure dependence on the rate constant is found. The predicted global rate constants are in excellent agreement with laboratory values; thus, the derived kinetic parameters are recommended for modeling/simulation of N-heterocycle-related applications in atmospheric and even in combustion conditions. Besides, pyrrole should not be considered as a persistent organic pollutant owing to its short atmospheric lifetime (∼1 h) towards OH radicals. The secondary mechanisms of the subsequent reactions of two OH-pyrrole adducts (namely, I1 and I2) with two abundant species, O2/NO, which are relevant to the atmospheric degradation process, were also investigated. It is also revealed by TD-DFT calculations that two OH-pyrrole adducts (I1 &amp;I2), nine intermediates, Ii (i = 3–11) and four products (P1, P2, P3 and P6) can undergo photodissociation under the sunlight. [Display omitted] •Detailed kinetic mechanism of the pyrrole + OH reaction is first theoretically reported for 200 – 2000 K &amp; 1 – 7600 Torr.•Mechanism shift, together with kinetic behaviors, between OH-addition and H-abstraction channels depends on both T and P.•The calculated numbers are in good agreement with experimental data at different T&amp;P conditions.•Pyrrole is not a persistent organic pollutant due to its short life-time towards OH radicals.•Some adducts and products can photolyze under the sunlight.</description><identifier>ISSN: 0045-6535</identifier><identifier>EISSN: 1879-1298</identifier><identifier>DOI: 10.1016/j.chemosphere.2020.127850</identifier><identifier>PMID: 32818845</identifier><language>eng</language><publisher>England: Elsevier Ltd</publisher><subject>And atmospheric chemistry ; Atmosphere ; Hydroxyl Radical ; Kinetics ; Master equation ; OH radical ; Oxidation-Reduction ; POPs ; Pyrrole ; Pyrroles ; Rate constants</subject><ispartof>Chemosphere (Oxford), 2021-01, Vol.263, p.127850, Article 127850</ispartof><rights>2020 Elsevier Ltd</rights><rights>Copyright © 2020 Elsevier Ltd. 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On the potential energy surface constructed at the M06–2X/aug-cc-pVTZ level, the temperature- and pressure-dependent behaviors of the title reaction were characterized using the stochastic Rice–Ramsperger–Kassel–Marcus based Master Equation (RRKM-ME) rate model. The corrections of the hindered internal rotation and quantum tunneling treatments were included. The calculated results reveal the competition between the two distinct pathways: OH-addition and direct H-abstraction. The former channels are found favorable at low-temperature and high-pressure range (e.g., T &lt; 900 K and P = 760 Torr) where non-Arrhenius and positive pressure-dependent behaviors of the rate constants are noticeably observed, while the latter predominate at temperatures higher than 900 K at atmospheric pressure and no pressure dependence on the rate constant is found. The predicted global rate constants are in excellent agreement with laboratory values; thus, the derived kinetic parameters are recommended for modeling/simulation of N-heterocycle-related applications in atmospheric and even in combustion conditions. Besides, pyrrole should not be considered as a persistent organic pollutant owing to its short atmospheric lifetime (∼1 h) towards OH radicals. The secondary mechanisms of the subsequent reactions of two OH-pyrrole adducts (namely, I1 and I2) with two abundant species, O2/NO, which are relevant to the atmospheric degradation process, were also investigated. It is also revealed by TD-DFT calculations that two OH-pyrrole adducts (I1 &amp;I2), nine intermediates, Ii (i = 3–11) and four products (P1, P2, P3 and P6) can undergo photodissociation under the sunlight. [Display omitted] •Detailed kinetic mechanism of the pyrrole + OH reaction is first theoretically reported for 200 – 2000 K &amp; 1 – 7600 Torr.•Mechanism shift, together with kinetic behaviors, between OH-addition and H-abstraction channels depends on both T and P.•The calculated numbers are in good agreement with experimental data at different T&amp;P conditions.•Pyrrole is not a persistent organic pollutant due to its short life-time towards OH radicals.•Some adducts and products can photolyze under the sunlight.</description><subject>And atmospheric chemistry</subject><subject>Atmosphere</subject><subject>Hydroxyl Radical</subject><subject>Kinetics</subject><subject>Master equation</subject><subject>OH radical</subject><subject>Oxidation-Reduction</subject><subject>POPs</subject><subject>Pyrrole</subject><subject>Pyrroles</subject><subject>Rate constants</subject><issn>0045-6535</issn><issn>1879-1298</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2021</creationdate><recordtype>article</recordtype><recordid>eNqNkMFOwzAMhiMEYmPwCqg8QEeSJm1ynCZgSJN2gXOUJq6WsTZVUhB7ezI6EEdOluz_s-UPoTuC5wST8n43N1tofey3EGBOMU19WgmOz9CUiErmhEpxjqYYM56XvOATdBXjDuMEc3mJJgUVRAjGp2i9qDPXucH57M11MDiTtWC2unOxzXyTbVb591gPYDM9nI6mlP90ViesO6b6Qwh-D9footH7CDenOkOvjw8vy1W-3jw9Lxfr3BRVNeQCakxwbY0tK2YtBtsAFkUlbMM4rdI_jDeCaVILkNbQgmrblJLVklEomShmSI57TfAxBmhUH1yrw0ERrI6G1E79MaSOhtRoKLG3I9u_1y3YX_JHSQosxwCkDz4cBBWNg86AdQHMoKx3_zjzBSoLfmA</recordid><startdate>202101</startdate><enddate>202101</enddate><creator>Mai, Tam V.-T.</creator><creator>Nguyen, Hieu T.</creator><creator>Huynh, Lam K.</creator><general>Elsevier Ltd</general><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><orcidid>https://orcid.org/0000-0003-3036-2574</orcidid></search><sort><creationdate>202101</creationdate><title>Ab initio kinetic mechanism of OH-initiated atmospheric oxidation of pyrrole</title><author>Mai, Tam V.-T. ; Nguyen, Hieu T. ; Huynh, Lam K.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c377t-8eb010bdcd674dd0edfe08378df452720245f84a1b8e9dc232adf694b942e6483</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2021</creationdate><topic>And atmospheric chemistry</topic><topic>Atmosphere</topic><topic>Hydroxyl Radical</topic><topic>Kinetics</topic><topic>Master equation</topic><topic>OH radical</topic><topic>Oxidation-Reduction</topic><topic>POPs</topic><topic>Pyrrole</topic><topic>Pyrroles</topic><topic>Rate constants</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Mai, Tam V.-T.</creatorcontrib><creatorcontrib>Nguyen, Hieu T.</creatorcontrib><creatorcontrib>Huynh, Lam K.</creatorcontrib><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><jtitle>Chemosphere (Oxford)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Mai, Tam V.-T.</au><au>Nguyen, Hieu T.</au><au>Huynh, Lam K.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Ab initio kinetic mechanism of OH-initiated atmospheric oxidation of pyrrole</atitle><jtitle>Chemosphere (Oxford)</jtitle><addtitle>Chemosphere</addtitle><date>2021-01</date><risdate>2021</risdate><volume>263</volume><spage>127850</spage><pages>127850-</pages><artnum>127850</artnum><issn>0045-6535</issn><eissn>1879-1298</eissn><abstract>The comprehensive kinetic mechanism of the OH-initiated gas-phase oxidation of pyrrole is first theoretically reported in a broad range of conditions (T = 200–2000 K &amp;P = 1–7600 Torr). On the potential energy surface constructed at the M06–2X/aug-cc-pVTZ level, the temperature- and pressure-dependent behaviors of the title reaction were characterized using the stochastic Rice–Ramsperger–Kassel–Marcus based Master Equation (RRKM-ME) rate model. The corrections of the hindered internal rotation and quantum tunneling treatments were included. The calculated results reveal the competition between the two distinct pathways: OH-addition and direct H-abstraction. The former channels are found favorable at low-temperature and high-pressure range (e.g., T &lt; 900 K and P = 760 Torr) where non-Arrhenius and positive pressure-dependent behaviors of the rate constants are noticeably observed, while the latter predominate at temperatures higher than 900 K at atmospheric pressure and no pressure dependence on the rate constant is found. The predicted global rate constants are in excellent agreement with laboratory values; thus, the derived kinetic parameters are recommended for modeling/simulation of N-heterocycle-related applications in atmospheric and even in combustion conditions. Besides, pyrrole should not be considered as a persistent organic pollutant owing to its short atmospheric lifetime (∼1 h) towards OH radicals. The secondary mechanisms of the subsequent reactions of two OH-pyrrole adducts (namely, I1 and I2) with two abundant species, O2/NO, which are relevant to the atmospheric degradation process, were also investigated. It is also revealed by TD-DFT calculations that two OH-pyrrole adducts (I1 &amp;I2), nine intermediates, Ii (i = 3–11) and four products (P1, P2, P3 and P6) can undergo photodissociation under the sunlight. [Display omitted] •Detailed kinetic mechanism of the pyrrole + OH reaction is first theoretically reported for 200 – 2000 K &amp; 1 – 7600 Torr.•Mechanism shift, together with kinetic behaviors, between OH-addition and H-abstraction channels depends on both T and P.•The calculated numbers are in good agreement with experimental data at different T&amp;P conditions.•Pyrrole is not a persistent organic pollutant due to its short life-time towards OH radicals.•Some adducts and products can photolyze under the sunlight.</abstract><cop>England</cop><pub>Elsevier Ltd</pub><pmid>32818845</pmid><doi>10.1016/j.chemosphere.2020.127850</doi><orcidid>https://orcid.org/0000-0003-3036-2574</orcidid></addata></record>
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subjects And atmospheric chemistry
Atmosphere
Hydroxyl Radical
Kinetics
Master equation
OH radical
Oxidation-Reduction
POPs
Pyrrole
Pyrroles
Rate constants
title Ab initio kinetic mechanism of OH-initiated atmospheric oxidation of pyrrole
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