当前位置：
X-MOL 学术
›
J. Phys. Chem. A
›
论文详情
Our official English website, www.x-mol.net, welcomes your
feedback! (Note: you will need to create a separate account there.)
Cl Atoms and OH Radicals Initiated Kinetic and Mechanistic Study on the Degradation of Propyl Butanoate under Tropospheric Conditions.
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2019-12-12 , DOI: 10.1021/acs.jpca.9b09546 Parth Gupta 1 , Balla Rajakumar 1
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2019-12-12 , DOI: 10.1021/acs.jpca.9b09546 Parth Gupta 1 , Balla Rajakumar 1
Affiliation
|
The reactivity of various OVOCs (mainly esters) in the troposphere leads to the generation of various organics, which in turn leads to an increase in the cloud acidity of the Earth's atmosphere. Hence, it becomes necessary to understand the mechanistic aspects of the reaction of these molecules with dominant atmospheric agents. In this study, the tropospheric degradation of one such ester, propyl butanoate (PB; CH3CH2CH2COOCH2CH2CH3) was studied with OH radicals and Cl atoms at the CCSD(T)//M06-2x/6-311+G(2d,2p) and CCSD(T)//BHandHLYP/6-311+G(2d,2p) level of theories over the studied temperature range of 200-400 K. The Arrhenius expressions obtained using the CVT/SCT/ISPE method were calculated as kPB + Cl (200-400 K) = 1.3 × 10-14 T1.3 exp[1335/T] cm3 molecule-1 s-1 and kPB + OH (200-400 K) = 1.8 × 10-26 T4.6 exp[4469/T] cm3 molecule-1 s-1. The obtained kinetics was also well validated against the SAR (structure-activity relationship)-based rate coefficients. The most prominent H-abstraction reaction channels were investigated for the PB + OH/Cl reaction. The abstraction of H atoms attached to the carbon atom present in the β-position to the ester (-C(O)O-) functionality was found to go via the lowest energy activation barriers for the reaction of PB toward both OH radicals and Cl atoms. The product degradation channels were also elucidated in an O2/NOx-rich environment. Moreover, to gauge the impact of the emitted PB on the troposphere, atmospheric lifetimes, radiative efficiencies, global warming potentials, and photochemical ozone creation potentials were also calculated and are included in the manuscript.
中文翻译：
Cl原子和OH自由基引发的对流层条件下丁酸丙酯降解的动力学和机理研究。
对流层中各种OVOC（主要是酯）的反应性导致各种有机物的产生，进而导致地球大气层的云酸度增加。因此，有必要了解这些分子与主要大气因子反应的机理。在这项研究中，使用CCSD（T）// M06-2x / 6-311 + G（2d，2p）和OH自由基和Cl原子研究了一种这样的酯，对羟基苯甲酸丁酯（PB; CH3CH2CH2COOCH2CH2CH3）的对流层降解。在研究的200-400 K的温度范围内，CCSD（T）// BHandHLYP / 6-311 + G（2d，2p）的理论水平。使用CVT / SCT / ISPE方法获得的Arrhenius表达式计算为kPB + Cl （200-400 K）= 1.3×10-14 T1.3 exp [1335 / T] cm3分子-1 s-1和kPB + OH（200-400 K）= 1.8×10-26 T4.6 exp [4469 / T] cm3分子-1 s-1。相对于基于SAR（结构-活性关系）的速率系数，也很好地验证了获得的动力学。研究了PB + OH / Cl反应中最突出的H吸收反应通道。发现与存在于酯（-C（O）O-）的β-位上的碳原子相连的H原子的抽象经过最低的能量活化势垒，使PB既朝着OH自由基又朝着Cl反应原子。在富含O2 / NOx的环境中也阐明了产物降解的通道。此外，为评估排放的PB对对流层的影响，还计算了大气寿命，辐射效率，全球变暖潜势和光化学臭氧生成潜势，并将其包括在手稿中。
更新日期：2019-12-13
中文翻译：
Cl原子和OH自由基引发的对流层条件下丁酸丙酯降解的动力学和机理研究。
对流层中各种OVOC（主要是酯）的反应性导致各种有机物的产生，进而导致地球大气层的云酸度增加。因此，有必要了解这些分子与主要大气因子反应的机理。在这项研究中，使用CCSD（T）// M06-2x / 6-311 + G（2d，2p）和OH自由基和Cl原子研究了一种这样的酯，对羟基苯甲酸丁酯（PB; CH3CH2CH2COOCH2CH2CH3）的对流层降解。在研究的200-400 K的温度范围内，CCSD（T）// BHandHLYP / 6-311 + G（2d，2p）的理论水平。使用CVT / SCT / ISPE方法获得的Arrhenius表达式计算为kPB + Cl （200-400 K）= 1.3×10-14 T1.3 exp [1335 / T] cm3分子-1 s-1和kPB + OH（200-400 K）= 1.8×10-26 T4.6 exp [4469 / T] cm3分子-1 s-1。相对于基于SAR（结构-活性关系）的速率系数，也很好地验证了获得的动力学。研究了PB + OH / Cl反应中最突出的H吸收反应通道。发现与存在于酯（-C（O）O-）的β-位上的碳原子相连的H原子的抽象经过最低的能量活化势垒，使PB既朝着OH自由基又朝着Cl反应原子。在富含O2 / NOx的环境中也阐明了产物降解的通道。此外，为评估排放的PB对对流层的影响，还计算了大气寿命，辐射效率，全球变暖潜势和光化学臭氧生成潜势，并将其包括在手稿中。
京公网安备 11010802027423号