无水NTO金属盐的合成、晶体结构、热形为和应用研究

3-nitro-1,2,4-triazol-5-one (NTO) is a compound with high energy, compaction and low sensitivity. Since 1980s, many laboratories and research institutes have studied its explosive properties and compact behavior, however, reports on the properties of NTO metal salts were little seen. After experimental selection, methanol, ethanol and dimethylformamide were considered as the solvent in the synthetic reaction of NTO metal salts. 10 NTO salts were prepared and characterized by elemental analysis and FT-IR analysis and one of the NTO cadmium salts was determined as [Cd(NTO)6](ClO4)2. The single crystal of 7 NTO salts (NTO sodium salt, NTO rubidium salt, NTO magnesium salt, NTO strontium salt, NTO cadmium salt, NTO yttrium salt and NTO dimethylamine salt) were cultured through slow evaporation. Their crystal structures were determined with a four-circle X-ray diffractometer. The thermal decomposition mechanism of the NTO metal salts were performed by DSC, TG-DTG and the non-isothermal kinetics of the thermal decomposition of NTO magnesium salt was studied. The thermodynamic properties of these NTO metal salts were studied by a microcalorimetry and the standard enthalpy of formation, lattice enthalpy and lattice energy have been determined. The unit-cell parameters of these NTO salts were listed below: NTO sodium salt: a=0.6303(1) nm, b=0.8285(1)nm, c=1.1574(2) nm, β=103.85(1)o, V=0.5868(2)nm3, Dc =1.925g/cm3, Z =4, μ=0.238 mm-1, F(000) =344;NTO rubidium salt: a=0.6330(1) nm, b=0.8241(2) nm, c=1.2964(3) nm,β=97.90(1)o, V=0.6699(2) nm3, Z=4, Dc=2.306g/cm3, μ=7.365mm-1, F(000)=448;.NTO magnesium salt: a=2.3101(3)nm, b=0.6472(1)nm, c=1.4118(3)nm, β=124.05(1)o, V =1.7489 (5)nm3, Dc =1.620g/cm3, Z =4,μ=0.191mm-1, F(000)=888;NTO strontium salt: a=1.1034(1) nm, b=2.2742(2) nm, c=0.63398(1) nm,β=101.798(13)o, V=1.5573(4)nm3, Z=2, Dc=1.936g/cm3, μ=3.545mm-1, F(000)=540; .NTO cadmium salt: a=2.1229(3)nm, b=0.6261(8)nm, c=2.1165(3)nm, β＝90.602(3)o, V=2.977(6)nm3, Z = 4, Dc = 2.055g/cm3, μ= 15.45cm-1, F(000) = 1824.NTO yttrium salt: a=0.6773(2)nm, b=2.0866(2)nm, c=0.6551(1)nm,β=102.98(2)o, V=0.9021(1) nm3, Z=4, Dc=1.970 g/cm3, μ=3.3487mm-1, F(000)=540;.NTO dimethylamine salt: a = 0.7116(1)nm, b=0.8735(2)nm, c=1.3160(3)nm,β= 101.12(2)o, V=0.8026(3) nm3, Dc=1.450 g/cm3, Z = 4, μ=0.123mm-1, F(000)=368..According to the crystal structures, the distinct data of the spatial arrangement of atoms or ions, the chemical coordination, the space structure, the bond lengths and the bond orders between atoms, offer us evidences on studying these materials and their regularity in atomic level, deepen our knowledge of the relationship of structure and properties. This study provides theoretical references on designing this kind of new needed material and clearly explaining the thermal decomposition behavior and thermodynamic properties of NTO metal salts. The thermal decomposition mechanism of NTO metal salts were cleared out the materials' thermal behavior and the ultimate decomposition products which provides accurate data for the application. Moreover, the determination of the non-isothermal kinetic equation of the thermal decomposition of NTO magnesium salt, the critical temperature of thermal explosion Tb＝243.1℃ and the entropy of activation = -66.74 Jmol-1K-1, enthalpy of activation = 119.2 kJmol-1 and free energy of activation = 152.44 kJmol-1 at Tpdo, provides us with basic data to use this kind of material in energetic catalyst.This project connects basic research with application, micro research and macro. The studies on the synthesis, crystal structure, thermal decomposition and thermodynamic properties of these NTO salts, construct a bridge between the properties of materials and the spatial arrangement, the coordination of the atoms, thermochemistry properties, which provides evidences and directions in application of this kind of materials.

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