Chemical Study Including The Synthesis Of High-nitrogen Organic Metal Complexes And Ionic Compounds, Structure, Thermodynamic Properties And Quantum

1,2,4-Triazole compounds are one of the important and high density energetic density materials. Because of its high energy associated with their five heterocyclic structure ring, it is very important to study the synthesis and the properties of 1,2,4-triazole compounds for futher theoretical research and practical application.Seven energetic ionic compounds and two metal complexes of 1,2,4-triazole compounds were synthesized in this paper, and the nine compounds were characterized by elemental analysis, IR and 1HNMR. The single crystals of seven compounds were obtained by slow solvent evaporation method at room temperature and their crystal structures were obtained by a four-circle X-ray diffractometer. The seven compounds are:4-Amino-1,2,4-triazole picrate(4ATz-PA),3-Amino-1,2,4-tria zole 3-Nitro-1,2,4-triazol-5-one salt(3ATz-NTO),Picrates of 3,5-Diamino-1,2,4-triazole(DAT·PA),Ethylenediamine salt 3-Nitro-1,2,4-triazole[3NTa-(CH2)2(NH2)2-H2O],Imidazole picrate(MZ-PA),Dimethylamine salt of 3,5-2-nitrobenzoic acid [DNBA-CH2(NH2)2] and Diacetatobis(4-Amino-1,2,4-triazole) Zinc [Zn(4ATz)2(CH3 COO)2].The geometries and frequencies of the compound 4ATz·PA,3ATz·NTO,DAT·PA,MZ-PA and DNBA·CH2(NH2)2 were fully optimized with Gaussian 03 package. Frontier orbital energy and natural atomic charges were provided. The calculated bond values of distances and bond angles were compared with the experimental ones and they were in accord with those of the theoretical values.The DSC, TG/DTG methods were used to study the thermal behaviors of the above nine compounds under a non-isothermal condition. The Kissinger method, Ozawa method, the general integral equation and differential equation method were used to determine the kinetic parameters and the thermal decomposition mechanism function of Cu(4ATz)2Cl2-H2O in the exothermic processes. The enthalpy of activation (△H≠), entropy of activation (△S≠), Gibbs free energy of activation (△G≠) and critical temperature of the thermal explosion (Tb) of the compound were obtained. The thermal stability of these compounds also were discussed.The specific heat capacity of the above seven compounds were determined with continuous Cp mode of Micro-DSC III micro-heat instrument. Enthalpy, entropy and Gibbs free energy of compounds between 283 K and 353 K, relative to the standard temperature 298.15 K, were calculated through thermodynamic equations. Furthermore, the specific heat capacity of the compound 3ATz-NTO,DAT·PA,MZ·PA and DNBA-CH2(NH2)2 were calculated by Gaussian 03 package and using the above determination result of specific heat capacity.