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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Reactivity at Low Temperature of Carbon Suboxide (C_3O_2) with Amorphous Surface of HCl Hydrates Monitored by FTIR Spectroscopy
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Reactivity at Low Temperature of Carbon Suboxide (C_3O_2) with Amorphous Surface of HCl Hydrates Monitored by FTIR Spectroscopy

机译：FTIR光谱监测低温下二氧化碳（C_3O_2）与HCl水合物非晶态表面的反应性

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摘要

An experimental study, monitored by FTIR spectroscopy, of the spontaneous reaction of C_3O_2 with HCl on the acid hydrate surface has been performed at low temperature. The first appearing reaction product at 85 K was assigned to chloroformylketene while the second, appearing at 145 K, to malonyl dichloride by comparison with previously reported data in matrix isolation spectroscopy. C_3O_2 was deposited at 80 K over an amorphous surface of HCl hydrates mainly formed from ionic species (H_3O~+(H_2O)_(n - 1)Cl~-; n = 1-3, 4, 6), prepared by codeposition of a H_2O : HCl gaseous mixture at 80 K. The reactions were promoted by warming the substrate from 80 to 200 K. Experiments showed that monohydrate H_3O~+Cl~- was more reactive than higher hydrates by easier C_3O_2 protonation. Reactions are described by an ionic mechanism catalyzed by ice water and occurring on the surface. Spectral evidence of HCl amorphous hydrates, chloroformylketene, and malonyl dichloride are reported.
机译：通过FTIR光谱监测的实验研究是在低温下进行的C_3O_2与HCl在酸性水合物表面上的自发反应。与先前报道的基质分离光谱数据相比，第一个在85 K出现的反应产物被分配给氯甲酰乙烯酮，而第二个在145 K出现的反应产物被赋予了丙二酰二氯。 C_3O_2以80 K沉积在主要由离子物种（H_3O〜+（H_2O）_（n-1）Cl〜-; n = 1-3，4，6）形成的HCl水合物的非晶表面上，通过共沉积在80 K下生成H_2O：HCl气体混合物。通过将底物从80 K加热到200 K来促进反应。实验表明，一水合物H_3O〜+ Cl〜-的C_3O_2质子化作用比高水合物的反应活性高。反应是通过冰水催化并在表面发生的离子机理来描述的。据报道，有HCl无定形水合物，氯甲酰乙烯酮和丙二酰二氯的光谱证据。

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