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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Vapor Pressure of Hexamethylene Triperoxide Diamine (HMTD) Estimated Using Secondary Electrospray Ionization Mass Spectrometry
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Vapor Pressure of Hexamethylene Triperoxide Diamine (HMTD) Estimated Using Secondary Electrospray Ionization Mass Spectrometry

机译：二次电喷雾电离质谱法估算六亚甲基三氧化二胺（HMTD）的蒸气压

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摘要

A rapid method for vapor pressure measurement was developed and used to derive the vapor pressure curve of the thermally labile peroxide-based explosive hexamethylene triperoxide diamine (HMTD) over the temperature range from 28 to 80 degrees C. This method uses a controlled flow of vapor from a solid-phase HMTD source that is presented to an ambient-pressure-ionization mass spectrometer equipped with a secondary-electrospray-ionization (SESI) source. The subpart-per-trillion sensitivity of this system enables direct detection of HMTD vapor through an intact [M + H](+) ion in real time at temperatures near 20 degrees C. By calibrating this method using vapor sources of cocaine and heroin, which have known pressure-temperature (P-T) curves, the temperature dependence of HMTD vapor was determined, and a Clausius-Clapeyron plot of ln[P (Pa)] vs 1/[T (K)] yielded a straight line with the expression ln[P (Pa)] = {(-11091 +/- 356) x 1/[T (K)]} + 25 +/- 1 (error limits are the standard error of the regression analysis). From this equation, the sublimation enthalpy of HMTD was estimated to be 92 +/- 3 kJ/mol, which compares well with the theoretical estimate of 95 kJ/mol, and the vapor pressure at 20 degrees C was estimated to be similar to 60 parts per trillion by volume, which is within a factor of 2 of previous theoretical estimates. Thus, this method provides not only the first direct experimental determination of HMTD vapor pressure but also a rapid, near-real-time capability to quantitatively measure low-vapor-pressure compounds, which will be useful for aiding in the development of training aids for bomb-sniffing canines.
机译：开发了一种快速的蒸气压测量方法，并用于推导在温度范围为28至80摄氏度的热不稳定的过氧化物基爆炸性六亚甲基三氧化二胺（HMTD）的蒸气压曲线。该方法使用受控的蒸气流由固相HMTD源提供给配备了次级电喷雾电离（SESI）源的环境压力电离质谱仪。该系统的万亿分之几的灵敏度使得可以通过完整的[M + H]（+）离子在20摄氏度附近的温度下实时实时实时检测HMTD蒸汽。通过使用可卡因和海洛因的蒸汽源校准该方法，具有已知的压力-温度（PT）曲线，确定了HMTD蒸气的温度依赖性，并且ln [P（Pa）]对1 / [T（K）]的Clausius-Clapeyron图产生了一条直线，其表达式为ln [P（Pa）] = {（-11091 +/- 356）x 1 / [T（K）]} + 25 +/- 1（误差极限是回归分析的标准误差）。根据该方程式，HMTD的升华焓估计为92 +/- 3 kJ / mol，与理论估计值95 kJ / mol很好地比较，并且在20摄氏度时的蒸气压估计为60每万亿分之一体积，这是先前理论估计值的2倍之内。因此，该方法不仅提供了HMTD蒸气压的直接直接实验测定方法，而且还提供了快速，近实时的定量测量低蒸气压化合物的能力，这将有助于开发用于训练的辅助器械。炸弹嗅探犬。

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