Eine Plattform für die Wissenschaft: Bauingenieurwesen, Architektur und Urbanistik
Eine Plattform für die Wissenschaft: Bauingenieurwesen, Architektur und Urbanistik
The new inspiration from the theoretical re-exploration of traditional autoxidation pathways leading to sulfate formation in the haze episode
https://orcid.org/0000-0003-2415-3872
Abstract The high concentration and fast accumulation of sulfate have been identified in most of the haze episodes’ events. It is well known that the autoxidation process is one of the most common and essential routes for sulfate formation. However, the detailed mechanism underlying sulfate formation, especially that from oxygen (O2) involved autoxidation process, has not been fully established since there is no direct experimental proof available till now. In this work, we thoroughly explored the possible sulfate formation pathways involving O2 through high-level quantum chemical calculation investigation. It is revealed that in the autoxidation process, the reaction of SO3 − with O2 will occur on the doublet potential energy surface to form SO5 −. We further proposed a pH dependent reaction mechanism in which SO5 − will react with different forms of SO2 (HOSO2 −, SO3 2−) through four different pathways to produce sulfate. More importantly, by calculating the branching ratios for different pathways, we found the most dominant path involving O2 in sulfate formation in almost all the atmospherically relevant pH during pollution period. In this path, SO5 − react with SO3 2− through two steps: a O atom transfer process and a subsequent single electron transfer (SET) process. Detailed calculation results emphasize the importance of autoxidation mechanism in explaining sulfate formation during pollution period, and therefore provide some important and detailed information for understanding the possible reason of haze episode.
Graphical abstract Display Omitted
Highlights We explored the unidentified sulfate formation mechanisms involving O2. As the important chain carrier, SO− 5 could be formed via the reaction of SO− 3 with 3O2. The chain reaction mechanisms of SO− 3 oxidized by O2 varies with atmospheric pH. O transfer and subsequent SET from SO− 5 + SO3 2− is a key route for sulfate formation.
The new inspiration from the theoretical re-exploration of traditional autoxidation pathways leading to sulfate formation in the haze episode
https://orcid.org/0000-0003-2415-3872
Abstract The high concentration and fast accumulation of sulfate have been identified in most of the haze episodes’ events. It is well known that the autoxidation process is one of the most common and essential routes for sulfate formation. However, the detailed mechanism underlying sulfate formation, especially that from oxygen (O2) involved autoxidation process, has not been fully established since there is no direct experimental proof available till now. In this work, we thoroughly explored the possible sulfate formation pathways involving O2 through high-level quantum chemical calculation investigation. It is revealed that in the autoxidation process, the reaction of SO3 − with O2 will occur on the doublet potential energy surface to form SO5 −. We further proposed a pH dependent reaction mechanism in which SO5 − will react with different forms of SO2 (HOSO2 −, SO3 2−) through four different pathways to produce sulfate. More importantly, by calculating the branching ratios for different pathways, we found the most dominant path involving O2 in sulfate formation in almost all the atmospherically relevant pH during pollution period. In this path, SO5 − react with SO3 2− through two steps: a O atom transfer process and a subsequent single electron transfer (SET) process. Detailed calculation results emphasize the importance of autoxidation mechanism in explaining sulfate formation during pollution period, and therefore provide some important and detailed information for understanding the possible reason of haze episode.
Graphical abstract Display Omitted
Highlights We explored the unidentified sulfate formation mechanisms involving O2. As the important chain carrier, SO− 5 could be formed via the reaction of SO− 3 with 3O2. The chain reaction mechanisms of SO− 3 oxidized by O2 varies with atmospheric pH. O transfer and subsequent SET from SO− 5 + SO3 2− is a key route for sulfate formation.
The new inspiration from the theoretical re-exploration of traditional autoxidation pathways leading to sulfate formation in the haze episode
https://orcid.org/0000-0003-2415-3872
Abstract The high concentration and fast accumulation of sulfate have been identified in most of the haze episodes’ events. It is well known that the autoxidation process is one of the most common and essential routes for sulfate formation. However, the detailed mechanism underlying sulfate formation, especially that from oxygen (O2) involved autoxidation process, has not been fully established since there is no direct experimental proof available till now. In this work, we thoroughly explored the possible sulfate formation pathways involving O2 through high-level quantum chemical calculation investigation. It is revealed that in the autoxidation process, the reaction of SO3 − with O2 will occur on the doublet potential energy surface to form SO5 −. We further proposed a pH dependent reaction mechanism in which SO5 − will react with different forms of SO2 (HOSO2 −, SO3 2−) through four different pathways to produce sulfate. More importantly, by calculating the branching ratios for different pathways, we found the most dominant path involving O2 in sulfate formation in almost all the atmospherically relevant pH during pollution period. In this path, SO5 − react with SO3 2− through two steps: a O atom transfer process and a subsequent single electron transfer (SET) process. Detailed calculation results emphasize the importance of autoxidation mechanism in explaining sulfate formation during pollution period, and therefore provide some important and detailed information for understanding the possible reason of haze episode.
Graphical abstract Display Omitted
Highlights We explored the unidentified sulfate formation mechanisms involving O2. As the important chain carrier, SO− 5 could be formed via the reaction of SO− 3 with 3O2. The chain reaction mechanisms of SO− 3 oxidized by O2 varies with atmospheric pH. O transfer and subsequent SET from SO− 5 + SO3 2− is a key route for sulfate formation.
The new inspiration from the theoretical re-exploration of traditional autoxidation pathways leading to sulfate formation in the haze episode
Liu, Jiarong (Autor:in) / Buren, Jirigala (Autor:in) / Ji, Lin (Autor:in) / Zhang, Shaowen (Autor:in) / Zhang, Xiuhui (Autor:in)
Atmospheric Environment ; 287
04.06.2022
Aufsatz (Zeitschrift)
Elektronische Ressource
Englisch
Analysis of a Summertime PM2.5 and Haze Episode in the Mid-Atlantic Region
| Taylor & Francis Verlag | 2003