Abstract The thermal decomposition of the chloride adduct of pentaerythritol tetranitrate (PETN) has been studied with a new cross-flow sample introduction, dual shutter, ion mobility spectrometer. Chloride anions, produced in… Click to show full abstract
Abstract The thermal decomposition of the chloride adduct of pentaerythritol tetranitrate (PETN) has been studied with a new cross-flow sample introduction, dual shutter, ion mobility spectrometer. Chloride anions, produced in an ion source, react with PETN introduced by a nebulizer into a flow of heated gas orthogonal to the drift gas flow. This cross-flow procedure allows PETN introduction from solution at drift gas temperatures where the PETN∙Cl¯ intensity is sufficiently intense and stable to allow characterization of its thermal decomposition kinetics. Dual shutter operation allows the selection of PETN∙Cl¯ for observation of its thermal decomposition in the electrostatic drift field. In this adduct, Cl¯ displaces NO3¯ in an SN2 reaction with an activation energy of 80 ± 7 kJ mol-1 over the temperature range 145 °C–165 °C. At temperatures above 165 °C, decomposition occurs before ion selection, resulting in the release of NO3¯ and PETN∙NO3¯ becomes the sole adduct ion. PETN∙NO3¯ decomposes over the temperature range 175 °C–200 °C with an activation energy of 92 ± 8 kJ mol-1. Density functional calculations are used to interpret the results.
               
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