Rajapakse Maneeshin Y, Stone John A, Eiceman Gary A
Department of Chemistry and Biochemistry, New Mexico State University , Las Cruces, New Mexico 88003, United States.
J Phys Chem A. 2014 Apr 17;118(15):2683-92. doi: 10.1021/jp412444b. Epub 2014 Apr 2.
A dual-shutter ion mobility spectrometer operating at atmospheric pressure and interfaced to a gas chromatograph for sample introduction has been used to study the reaction of Cl(-) with explosives. Of particular interest was an investigation of the formation of NO3(-) from the reaction of the Cl(-) with nitroglycerin (NG). The adduct NG·Cl(-) together with NO3(-) and NG·NO3(-) compose the mobility spectrum. Over the temperature range 111 to 122 °C, NG·NO3(-) is stable, but NG·Cl(-) decomposes to NO3(-) and 1,2-dinitro-3-chloropropane (DNClP). The activation energy and pre-exponential factor for this first order decomposition are 80 ± 3 kJ mol(-1) and 1.3 × 10(12) s(-1), respectively. Ab initio calculation shows that the reaction is a substitution reaction occurring over a two well potential energy profile with stable ion-molecule complexes NG·Cl(-) and DNClP·NO3(-).
一种在大气压下运行并与气相色谱仪相连用于进样的双快门离子迁移谱仪已被用于研究Cl(-)与炸药的反应。特别令人感兴趣的是对Cl(-)与硝化甘油（NG）反应生成NO3(-)的研究。加合物NG·Cl(-)与NO3(-)和NG·NO3(-)构成了迁移谱。在111至122°C的温度范围内，NG·NO3(-)是稳定的，但NG·Cl(-)分解为NO3(-)和1,2 - 二硝基 - 3 - 氯丙烷（DNClP）。该一级分解反应的活化能和指前因子分别为80±3 kJ mol(-1)和1.3×10(12) s(-1)。从头算计算表明，该反应是一个在具有稳定离子 - 分子络合物NG·Cl(-)和DNClP·NO3(-)的双阱势能面上发生的取代反应。
