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三种氟氯化碳替代候选物：CHCF=CH、(CF)₂C=CH和(±)-CFCF=CHF的OH引发的对流层降解的产物分布及机制

Product distribution and mechanism of the OH initiated tropospheric degradation of three CFC replacement candidates: CHCF[double bond, length as m-dash]CH, (CF)C[double bond, length as m-dash]CH and (/)-CFCF[double bond, length as m-dash]CHF.

作者信息

Rivela Cynthia B, Tovar Carmen M, Gibilisco Rodrigo, Teruel Mariano A, Barnes Ian, Wiesen Peter, Blanco María B

机构信息

Instituto de Investigaciones en Fisicoquímica de Córdoba (I.N.F.I.Q.C.), CONICET, Dpto. de Fisicoquímica, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Ciudad Universitaria 5000 Córdoba Argentina

Physikalische Chemie/FBC, Bergische Universitaet Wuppertal Wuppertal Germany.

出版信息

RSC Adv. 2019 Feb 14;9(10):5592-5598. doi: 10.1039/c8ra09627a. eCollection 2019 Feb 11.

DOI:10.1039/c8ra09627a
PMID:35515909
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9060772/
Abstract

The OH radical initiated photodegradation of 2-fluoropropene (CHCF[double bond, length as m-dash]CH), 3,3,3-trifluoro-2-(tri-fluoromethyl)propene ((CF)C[double bond, length as m-dash]CH) and (/)-1,2,3,3,3-pentafluoropropene ((/)-CFCF[double bond, length as m-dash]CHF) has been investigated for the first time using a 1080 L quartz-glass environmental chamber at 298 ± 2 K and atmospheric pressure of synthetic air coupled with FTIR spectroscopy to monitor reactants and products. The major products observed in the OH reaction were CHC(O)F (98 ± 5)% together with HC(O)H (89 ± 7)% as a co-product, CFC(O)F (103 ± 8)% together with HC(O)F (96 ± 7)% as a co-product and CFC(O)CF (91 ± 8)% together with HC(O)H (98 ± 12)% as a co-product from the C-C bond cleavage channel of the intermediate hydroxyalkoxy radical, formed by addition of OH to the terminal carbon of the double bond which is designated C of 2-fluoropropene, (/)-1,2,3,3,3-pentafluoropropene and 3,3,3-trifluoro-2-(tri-fluoromethyl)propene, respectively. The present results are compared with previous studies for the reaction of OH with the separate isomers () and () of 1,2,3,3,3-pentafluoropropene. In addition, atmospheric implications of the reactions studied are discussed.

摘要

首次在298±2 K和合成空气大气压条件下，使用1080 L石英玻璃环境舱，并结合傅里叶变换红外光谱（FTIR）来监测反应物和产物，研究了羟基自由基引发的2-氟丙烯（CHCF=CH）、3,3,3-三氟-2-（三氟甲基）丙烯（(CF)C=CH）和（/）-1,2,3,3,3-五氟丙烯（（/）-CFCF=CHF）的光降解反应。在羟基自由基反应中观察到的主要产物是，CHC(O)F（98±5）%，副产物为HC(O)H（89±7）%；CFC(O)F（103±8）%，副产物为HC(O)F（96±7）%；以及CFC(O)CF（91±8）%，副产物为HC(O)H（98±12）%，这些产物分别来自中间体羟基烷氧基自由基的碳-碳键断裂通道，该中间体是通过羟基自由基加成到双键的末端碳原子上形成的，双键的末端碳原子分别指定为2-氟丙烯、（/）-1,2,3,3,3-五氟丙烯和3,3,3-三氟-2-（三氟甲基）丙烯的C。将目前的结果与先前关于羟基自由基与1,2,3,3,3-五氟丙烯的单独异构体（）和（）反应的研究进行了比较。此外，还讨论了所研究反应对大气的影响。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4b29/9060772/0130c6d96c33/c8ra09627a-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4b29/9060772/83c913d66fc6/c8ra09627a-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4b29/9060772/016fc8be2fed/c8ra09627a-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4b29/9060772/8eadc4606d75/c8ra09627a-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4b29/9060772/a2c4f5227346/c8ra09627a-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4b29/9060772/0130c6d96c33/c8ra09627a-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4b29/9060772/83c913d66fc6/c8ra09627a-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4b29/9060772/016fc8be2fed/c8ra09627a-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4b29/9060772/8eadc4606d75/c8ra09627a-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4b29/9060772/a2c4f5227346/c8ra09627a-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4b29/9060772/0130c6d96c33/c8ra09627a-f5.jpg

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