Basheer Aazaad, Angappan Mano Priya, Rubini Subramani
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The latter result in the formation of carbon dioxide (CO<sub>2</sub>), formic acid (HCOOH), which contributes to the formation of SOA and climate change. The reaction mechanism in this study was initiated through H-abstraction reaction, followed by dehydrogenation and decarboxylation reaction of both DCAs. The rate coefficients of OA, MA with OH, Cl and NO<sub>3</sub> radicals are determined theoretically using variational transition state theory (VTST) with Eckart tunnelling method in the temperature range of 278–1000 K. At 298 K, the rate coefficient of OA with OH, Cl and NO<sub>3</sub> are 2.48 × 10<sup>−15</sup>, 2.37 × 10<sup>−20</sup>, 6.16 × 10<sup>−23</sup> in cm<sup>3</sup> molecule<sup>−1</sup> s<sup>−1</sup>, whereas MA with OH, Cl and NO<sub>3</sub> are 9.76 × 10<sup>−14</sup>, 1.01 × 10<sup>−12</sup> and 5.89 × 10<sup>−18</sup> in cm<sup>3</sup> molecule<sup>−1</sup> s<sup>−1</sup>, respectively. Our present results shed light on the atmospheric implications of two DCAs and provide the significant insight for the atmospheric pathways.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":1.9000,"publicationDate":"2024-05-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Environmental implications of oxalic and malonic acids with tropospheric oxidants\",\"authors\":\"Basheer Aazaad, Angappan Mano Priya, Rubini Subramani\",\"doi\":\"10.1002/poc.4639\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Dicarboxylic acids (DCAs) are major players in the formation of secondary organic aerosols (SOAs) and climate change. DCAs have potential impact on human health and environmental issues ranging from local scale to global scale participate mainly in the cloud condensation. 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引用次数: 0
摘要
二羧酸(DCA)是二次有机气溶胶(SOA)形成和气候变化的主要参与者。二羧酸对人类健康和环境问题具有潜在影响,影响范围从局部到全球,主要参与云的凝结。在这方面,草酸(OA)和丙二酸(MA)是大气中最主要的 DCAs。利用 M06-2X、ωB97XD/cc-pVTZ 和 6-311++G(2df,2p)理论水平,研究了 OA 和 MA 与对流层中最活跃的氧化剂(即 OH、Cl 和 NO3 自由基)在大气中的完全降解机制。为了评估大气的影响,本研究深入探讨了 OA 和 MA 与上述自由基的归宿及其随后的二级反应。后者的结果是形成二氧化碳(CO2)和甲酸(HCOOH),从而导致 SOA 的形成和气候变化。本研究中的反应机制是通过 H-萃取反应启动,然后是两种 DCAs 的脱氢和脱羧反应。在 278-1000 K 的温度范围内,采用变异过渡态理论(VTST)和 Eckart 隧道法对 OA、MA 与 OH、Cl 和 NO3 自由基的速率系数进行了理论测定。在 298 K 时,OA 与 OH、Cl 和 NO3 的速率系数分别为 2.48 × 10-15、2.37 × 10-20、6.16 × 10-23 in cm3 molecule-1 s-1,而 MA 与 OH、Cl 和 NO3 的速率系数分别为 9.76 × 10-14、1.01 × 10-12 和 5.89 × 10-18 in cm3 molecule-1 s-1。我们目前的研究结果揭示了两种 DCA 对大气的影响,并为大气路径提供了重要启示。
Environmental implications of oxalic and malonic acids with tropospheric oxidants
Dicarboxylic acids (DCAs) are major players in the formation of secondary organic aerosols (SOAs) and climate change. DCAs have potential impact on human health and environmental issues ranging from local scale to global scale participate mainly in the cloud condensation. In this context, oxalic acid (OA) and malonic acid (MA) are the most dominant DCAs in the atmosphere. A full atmospheric degradation mechanism of OA and MA with the most reactive tropospheric oxidants, namely, OH, Cl and NO3 radicals, were studied using M06-2X, ωB97XD/cc-pVTZ and 6-311++G(2df,2p) level of theories. To evaluate the atmospheric influence, this study enables us to deep investigation of fate of OA and MA with respect to the mentioned radicals and their subsequent secondary reactions. The latter result in the formation of carbon dioxide (CO2), formic acid (HCOOH), which contributes to the formation of SOA and climate change. The reaction mechanism in this study was initiated through H-abstraction reaction, followed by dehydrogenation and decarboxylation reaction of both DCAs. The rate coefficients of OA, MA with OH, Cl and NO3 radicals are determined theoretically using variational transition state theory (VTST) with Eckart tunnelling method in the temperature range of 278–1000 K. At 298 K, the rate coefficient of OA with OH, Cl and NO3 are 2.48 × 10−15, 2.37 × 10−20, 6.16 × 10−23 in cm3 molecule−1 s−1, whereas MA with OH, Cl and NO3 are 9.76 × 10−14, 1.01 × 10−12 and 5.89 × 10−18 in cm3 molecule−1 s−1, respectively. Our present results shed light on the atmospheric implications of two DCAs and provide the significant insight for the atmospheric pathways.
期刊介绍:
The Journal of Physical Organic Chemistry is the foremost international journal devoted to the relationship between molecular structure and chemical reactivity in organic systems. It publishes Research Articles, Reviews and Mini Reviews based on research striving to understand the principles governing chemical structures in relation to activity and transformation with physical and mathematical rigor, using results derived from experimental and computational methods. Physical Organic Chemistry is a central and fundamental field with multiple applications in fields such as molecular recognition, supramolecular chemistry, catalysis, photochemistry, biological and material sciences, nanotechnology and surface science.