Khodot Eugeny N, Lischiner Iosif I, Naudet Valerie, Frolov Vladimir, Kamnev Alexander A
N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 119991 Moscow, Russia.
Joint Institute of High Temperatures, Russian Academy of Sciences, 125412 Moscow, Russia.
Spectrochim Acta A Mol Biomol Spectrosc. 2024 Jan 5;304:123265. doi: 10.1016/j.saa.2023.123265. Epub 2023 Aug 15.
The possibility of the reaction of ethylene at cryogenic temperatures with dinitrogen tetroxide (NO), at least at -40 °C, has been demonstrated. An infrared (IR) spectroscopic analysis of the condensed reaction products was carried out, which showed the presence of substances containing organic nitro compounds and organic nitrates. The latter particularly means the possibility of the formation of explosive substances, as in the known explosive cryogenic reaction of NO with butadiene. The fundamental possibility of such a reaction is of importance for the organization of cryogenic production of gases from raw materials containing ethylene and nitrogen oxide impurities. The sensitivity of the experimental setup was demonstrated by using the example of the known reaction of NO with butadiene. The temperature and time characteristics of the latter reaction have been found. To determine the temperature range of possible reactions of ethylene with NO, thermograms of the process of heating the reactive mixture at a constant rate were analyzed. To ensure the sensitivity of the qualitative analysis of thermograms of the reaction of ethylene with NO in the linear heating mode, a quasi-differential method was proposed that uses the temperature of the cryo-thermostat coolant, which varies linearly with time, as the reference temperature. Some recently published theoretical results concerning the mechanisms of NO isomerization are discussed which may be useful for further studies in establishing the mechanisms and predicting the ratios of the products and their yields for the reaction of NO with olefins under particular experimental conditions.
已证明乙烯在低温下，至少在-40°C时与四氧化二氮（NO）发生反应的可能性。对冷凝反应产物进行了红外（IR）光谱分析，结果表明存在含有有机硝基化合物和有机硝酸盐的物质。后者尤其意味着存在形成爆炸性物质的可能性，就像NO与丁二烯的已知低温爆炸反应一样。这种反应的基本可能性对于从含有乙烯和氮氧化物杂质的原料中低温生产气体的工艺组织具有重要意义。通过以NO与丁二烯的已知反应为例，证明了实验装置的灵敏度。已确定了后者反应的温度和时间特性。为了确定乙烯与NO可能发生反应的温度范围，分析了以恒定速率加热反应混合物过程的热谱图。为了确保在直线加热模式下对乙烯与NO反应热谱图进行定性分析的灵敏度，提出了一种准微分方法，该方法使用随时间线性变化的低温恒温器冷却剂的温度作为参考温度。讨论了最近发表的一些关于NO异构化机理的理论结果，这些结果可能有助于进一步研究在特定实验条件下确定NO与烯烃反应的机理以及预测产物比例和产率。
