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DOI | 10.3184/146867817X14954764850360 |
Halocarbenes may deplete atmospheric ozone | |
Mamantov, Andrew | |
发表日期 | 2017 |
ISSN | 1468-6783 |
卷号 | 42期号:4页码:307-333 |
英文摘要 | Photooxidation of tetrachloroethylene (PERC) and trichloroethylene (TCE) in simulated tropospheric smog chamber studies occurs with a time delay, accelerating simultaneous decreasing O-3/chlorinated ethylene (CE) concentrations along with increasing CCl2O, which is attributed to CCl2 in the case of PERC and CCl2 or CHCl for TCE. The carbenes, chlorinated acetyl chlorides and CCl2O products may result from the rearrangement of the oxidised and/or excited oxidised CE, e.g. an epoxide. Analyses indicate scavenging experiments have not proved the existence of Cl atoms as being responsible for chlorinated acetyl chloride formation. Halocarbenes may form complexes with O-3 which can undergo electron transfer (ET) and lead to dissociation of O-3 to O-2 and O and regeneration of carbene, resulting in a chain reaction. The direction of ET may be determined by the smallest differential HOMO-LUMO energy between the carbene and O-3 which results in greater transition state stabilisation. Similarities in the reactions of O-3 with carbenes and simple alkenes, nucleophilic carbenes with electron-poor alkenes and electrophilic carbene PhCCl with alkyl-substituted alkenes, i.e. (1) complex formation, (2) very low or negative activation energies and (3) the ability to undergo ET reactions with alkylalkenes are discussed. The possibility of the world-wide used perhalocarbons, e.g. perfluorinated carbons, hydroperhalocarbons, their halogenated replacements and starting materials degrading to halocarbenes which may degrade O-3, is analysed. |
英文关键词 | photooxidation;haloethylene;halocarbene;chain reaction;atmospheric ozone depletion;perhalocarbons;stratosphere |
语种 | 英语 |
WOS记录号 | WOS:000417536000001 |
来源期刊 | PROGRESS IN REACTION KINETICS AND MECHANISM |
来源机构 | 美国环保署 |
文献类型 | 期刊论文 |
条目标识符 | http://gcip.llas.ac.cn/handle/2XKMVOVA/62273 |
作者单位 | US EPA, Washington, DC 20460 USA |
推荐引用方式 GB/T 7714 | Mamantov, Andrew. Halocarbenes may deplete atmospheric ozone[J]. 美国环保署,2017,42(4):307-333. |
APA | Mamantov, Andrew.(2017).Halocarbenes may deplete atmospheric ozone.PROGRESS IN REACTION KINETICS AND MECHANISM,42(4),307-333. |
MLA | Mamantov, Andrew."Halocarbenes may deplete atmospheric ozone".PROGRESS IN REACTION KINETICS AND MECHANISM 42.4(2017):307-333. |
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