In this study, in situ infrared spectroscopy techniques and thermogravimetric analysis coupled with mass spectrometry (TGA-MS) are employed to characterize the reactivity of the ionic liquid, 1-butyl-3-methylimidazolium dicyanoborohydride (BMIM+DCBH-), in comparison to the well-characterized 1-butyl-3-methylimidazolium dicyanamide (BMIM+DCA-) ionic liquid. TGA measurements determined the enthalpy of vaporization (ΔHvap) to be 112.7 ± 12.3 kJ/mol at 298 K. A rapid scan Fourier transform infrared spectrometer was used to obtain vibrational information useful in tracking the appearance and disappearance of species in the hypergolic reactions of BMIM+DCBH- and BMIM+DCA- with white fuming nitric acid (WFNA) and in the thermal decomposition of these energetic ionic liquids. Attenuated total reflectance measurements recorded the infrared spectra of the reactant sample (BMIM+DCBH-) and the liquid reaction products after reacting with WFNA. Computational chemistry efforts, aided by the experimental results, were used to propose key reaction pathways leading to the hypergolic ignition of BMIM+DCBH- + WFNA. Experimental results indicate that the hypergolic reaction of BMIM+DCBH- with WFNA generates both common and unique intermediates as compared to previous BMIM+DCA- + WFNA investigations: nitrous oxide was generated during both hypergolic reactions indicating that it may play a crucial role in the hypergolic ignition process, NO2 was generated in significantly higher concentrations for BMIM+DCBH- than for BMIM+DCA-, CO2 was only generated for BMIM+DCA-, and HCN was only generated during thermal decomposition and hypergolic ignition of BMIM+DCBH-.

中文翻译：

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二氰基硼氢化物离子液体的热分解和高分子量反应。

在这项研究中，采用原位红外光谱技术和热重分析结合质谱法（TGA-MS）来表征离子液体1-丁基-3-甲基咪唑二氰基硼氢化物（BMIM + DCBH-）与表征良好的1-丁基-3-甲基咪唑双氰胺（BMIM + DCA-）离子液体。TGA测量确定在298 K下的汽化焓（ΔHvap）为112.7±12.3 kJ / mol。快速扫描傅立叶变换红外光谱仪用于获得振动信息，可用于跟踪BMIM的高声反应中物种的出现和消失。 + DCBH-和BMIM + DCA-与白色发烟硝酸（WFNA）以及这些高能离子液体的热分解。衰减的全反射率测量记录了与WFNA反应后反应物样品（BMIM + DCBH-）和液体反应产物的红外光谱。在实验结果的帮助下，计算化学工作被用于提出导致BMIM + DCBH- + WFNA超高分子量点燃的关键反应途径。实验结果表明，与以前的BMIM + DCA- + WFNA研究相比，BMIM + DCBH-与WFNA的高声反应可产生共同的和独特的中间体：在这两个高声反应过程中均产生一氧化二氮，表明其可能在在高声点火过程中，BMIM + DCBH-产生的NO2浓度明显高于BMIM + DCA-，仅BMIM + DCA-产生CO2，