کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
675434 | 1459618 | 2007 | 17 صفحه PDF | دانلود رایگان |
عنوان انگلیسی مقاله ISI
Liquid state thermochemical decomposition of neat 1,3,5,5-tetranitrohexahydropyrimidine (DNNC) and its DNNC-d2, DNNC-d4, DNNC-d6 structural isotopomers: Mechanistic entrance into the DNNC molecule
دانلود مقاله + سفارش ترجمه
دانلود مقاله ISI انگلیسی
رایگان برای ایرانیان
کلمات کلیدی
موضوعات مرتبط
مهندسی و علوم پایه
مهندسی شیمی
جریان سیال و فرایندهای انتقال
پیش نمایش صفحه اول مقاله
![عکس صفحه اول مقاله: Liquid state thermochemical decomposition of neat 1,3,5,5-tetranitrohexahydropyrimidine (DNNC) and its DNNC-d2, DNNC-d4, DNNC-d6 structural isotopomers: Mechanistic entrance into the DNNC molecule Liquid state thermochemical decomposition of neat 1,3,5,5-tetranitrohexahydropyrimidine (DNNC) and its DNNC-d2, DNNC-d4, DNNC-d6 structural isotopomers: Mechanistic entrance into the DNNC molecule](/preview/png/675434.png)
چکیده انگلیسی
Global kinetics for the liquid state thermochemical decomposition of neat 1,3,5,5-tetranitrohexahydropyrimidine (DNNC), perdeuterio-labeled DNNC-d6, and partially deuterium-labeled DNNC-d2 and DNNC-d4 isotopomers were obtained by isothermal differential scanning calorimetry (IDSC). Molecular kinetic deuterium isotope effect (KDIE) values obtained with DNNC and DNNC-d6 from 174 to 194 °C revealed that CH bond rupture regulates both an endothermic catalytic initiation and the exothermic propagation of the liquid thermochemical decomposition process. Using IDSC-based KDIE comparisons with the DNNC-d2, DNNC-d4, and DNNC-d6 isotopomers, a more detailed chemical structure/mechanistic relationship emerged by entering the interior of the DNNC molecule. Here structural kinetic KDIE results showed the rate-controlling CH bond rupture has its origin at the non-equivalent C-2 methylene group sandwiched between the two nitrated DNNC nitrogen ring atoms, versus at the chemically equivalent C-4 and C-6 methylene ring positions located elsewhere in the DNNC molecule. Elucidation of such mechanistic features should aid in the structural design of new high-energy compounds with improved thermochemical properties. A 170.0 kJ/mol activation energy appeared for the endothermic induction period, and a lower 104.2 kJ/mol activation energy was determined for the exothermic acceleratory portion of the DNNC decomposition process. The global liquid and solid state thermochemical decomposition processes for DNNC are compared.
ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Thermochimica Acta - Volume 464, Issues 1â2, 25 November 2007, Pages 42-58
Journal: Thermochimica Acta - Volume 464, Issues 1â2, 25 November 2007, Pages 42-58
نویسندگان
S.A. Shackelford, J.A. Menapace, J.F. Goldman,