气相亚硝酸烷基二酯电子轰击电离解离机理研究

发布时间：2018-06-22 17:20

本文选题：亚硝酸烷基二酯 + 质谱　；参考：《物理化学学报》2017年08期

【摘要】：亚硝酸烷基二酯(R_2C(ONO)(CH_2)_nC(ONO)R_2)因其双官能团的特殊性而具有极高活性,在大气中极易产生烷氧自由基和氮氧化物,从而导致温室效应和光化学污染。因此研究亚硝酸烷基二酯的解离机理对理解其在大气中的光化学及热化学过程具有重要意义。本文采用气质联用(GC-MS)等方法研究了6种二酯(1,2-、1,3-亚硝酸丙二酯,1,2-、2,3-和1,4-亚硝酸丁二酯和1,5-亚硝酸戊二酯)在70 eV电子轰击下的解离过程,发现断裂碎片对二酯的结构具有特征性指示作用。我们发现除常见O NO键断裂产生的NO~+碎片离子峰外,同时也观测到因αC C键断裂产生的R_2C(ONO)~+碎片离子峰。通过对不同产物碎片所对应的解离路径的分析得出亚硝酸烷基二酯不同于其热解及光解的解离机理,即其直接发生O NO键或C C键的断裂。
[Abstract]:Because of the particularity of its bifunctional groups, the alkyl diesters R2C (CH2) (CH2) C (ONO) R2) are highly active, and they are easy to produce alkoxy radicals and nitrogen oxides in the atmosphere, resulting in Greenhouse Effect and photochemical pollution. Therefore, it is important to study the dissociation mechanism of alkyl nitrite in understanding its photochemical and thermochemical processes in the atmosphere. In this paper, the dissociation processes of six kinds of diesters (1 (1) 2 ~ (2) -N ~ (2 +), 1 (2)-(2)-(2) (2)-(2)-(2)-(2)-(2)-(2)-(2)-(2)-(2)-(2)-(2)-(2)-(2)-(2)-(2)-(2)-(2)-(2)-(2)- It is found that the fracture fragments have characteristic indicative effect on the structure of diesters. In addition to the no ~ fragment ion peaks produced by the common O _ (no) bond fracture, we also observed the R _ 2C (ONO) ~ fragment ion peak due to the 伪 C ~ (C) C bond rupture. By analyzing the dissociation paths corresponding to different product fragments, it is found that the dissociation mechanism of alkyl nitrite is different from that of pyrolysis and photolysis, that is, the breaking of O, O, O, O, O, O, O, O, O, O, O, O, or C, C bonds.
【作者单位】：北京师范大学化学系;
【基金】：国家自然科学基金(21373033和21173024)资助项目~~
【分类号】：O621.13;X51

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