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Non-isothermal Decomposition Kinetics of a New High-energy Organic Potassium Salt: K(DNDZ)
Xu, Kangzhen,Zhao, Fengqi,Song, Jirong,Ren, Xiaolei,Gao, Hongxu,Xu, Siyu,Hu, Rongzu Korean Chemical Society 2009 Bulletin of the Korean Chemical Society Vol.30 No.10
A new high-energy organic potassium salt, 2-(dinitromethylene)-1,3-diazepentane potassium salt K(DNDZ), was synthesized by reacting of 2-(dinitromethylene)-1,3-diazepentane (DNDZ) and potassium hydroxide. The thermal behavior and non-isothermal decomposition kinetics of K(DNDZ) were studied with DSC, TG/DTG methods. The kinetic equation is $\frac{d{\alpha}}{dT}$ = $\frac{10^{13.92}}{\beta}$3(1 - $\alpha$[-ln(1 - $\alpha$)]$^{\frac{2}{3}}$ exp(-1.52 ${\times}\;10^5$ / RT). The critical temperature of thermal explosion of K(DNDZ) is $208.63\;{^{\circ}C}$. The specific heat capacity of K(DNDZ) was determined with a micro-DSC method, and the molar heat capacity is 224.63 J $mol^{-1}\;K^{-1}$ at 298.15 K. Adiabatic time-to-explosion of K(DNDZ) obtained is 157.96 s.
Syntheses and Thermal Behaviors of Rb(FOX-7)·H<sub>2</sub>O and Cs(FOX-7)·H<sub>2</sub>O
Luo, Jinan,Xu, Kangzhen,Wang, Min,Song, Jirong,Ren, Xiaolei,Chen, Yongshun,Zhao, Fengqi Korean Chemical Society 2010 Bulletin of the Korean Chemical Society Vol.31 No.10
Two new energetic organic alkali metal salts, 1,1-diamino-2,2-dinitroethylene rubidium salt [Rb(FOX-7)${\cdot}H_2O$] and 1,1-diamino-2,2-dinitroethylene cesium salt [Cs(FOX-7)${\cdot}H_2O$], were synthesized by reacting of 1,1-diamino-2,2-dinitroethylene (FOX-7) and rubidium chloride or cesium chloride in alkali methanol aqueous solution, respectively. The thermal behaviors of Rb(FOX-7)${\cdot}H_2O$ and Cs(FOX-7)${\cdot}H_2O$ were studied with DSC and TG methods. The critical temperatures of thermal explosion of the two compounds are 216.22 and $223.73^{\circ}C$, respectively. Specific heat capacities of the two compounds were determined with a micro-DSC method, and the molar heat capacities are 217.46 and $199.47\;J\;mol^{-1}\;K^{-1}$ at 298.15 K, respectively. The adiabatic times-to-explosion were also calculated to be a certain value of 5.81 - 6.36 s for Rb(FOX-7)${\cdot}H_2O$, and 9.92 - 10.54 s for Cs(FOX-7)${\cdot}H_2O$. After FOX-7 becoming alkali metal salts, thermal decomposition temperatures of the compounds heighten with the rise of element period, but thermal decomposition processes become intense.
Syntheses and Thermal Behaviors of Rb(FOX-7)·H2O and Cs(FOX-7)·H2O
Jinan Luo,Kangzhen Xu,Min Wang,Jirong Song,Xiaolei Ren,Yongshun Chen,Fengqi Zhao 대한화학회 2010 Bulletin of the Korean Chemical Society Vol.31 No.10
Two new energetic organic alkali metal salts, 1,1-diamino-2,2-dinitroethylene rubidium salt [Rb(FOX-7)·H2O] and 1,1-diamino-2,2-dinitroethylene cesium salt [Cs(FOX-7)·H2O], were synthesized by reacting of 1,1-diamino-2,2-dinitroethylene (FOX-7) and rubidium chloride or cesium chloride in alkali methanol aqueous solution, respectively. The thermal behaviors of Rb(FOX-7)·H2O and Cs(FOX-7)·H2O were studied with DSC and TG methods. The critical temperatures of thermal explosion of the two compounds are 216.22 and 223.73 oC, respectively. Specific heat capacities of the two compounds were determined with a micro-DSC method, and the molar heat capacities are 217.46 and 199.47 J mol‒1K‒1 at 298.15 K, respectively. The adiabatic times-to-explosion were also calculated to be a certain value of 5.81 - 6.36s for Rb(FOX-7)·H2O, and 9.92 - 10.54 s for Cs(FOX-7)·H2O. After FOX-7 becoming alkali metal salts, thermal decomposition temperatures of the compounds heighten with the rise of element period, but thermal decomposition processes become intense.
Cong Ma, Jie Huang,Jie Huang,Yi Tang Zhong,Kangzhen Xu,Jirong Song,Zhao Zhang 대한화학회 2013 Bulletin of the Korean Chemical Society Vol.34 No.7
Two new high-nitrogen energetic compounds ZTO·2H2O and ZTO(phen)·H2O have been synthesized (where ZTO = 4,4-azo-1,2,4-triazol-5-one and phen = 1,10-phenanthroline). The crystal structure, elemental analysis and IR spectroscopy are presented. Compound 1 ZTO·2H2O crystallizes in the orthorhombic crystal system with space group Pnna and compound 2 ZTO(phen)·H2O in the triclinic crystal system with space group P-1. In ZTO(phen)·H2O, there is intermolecular hydrogen bonds between the -NH group of ZTO molecule (as donor) and N atom of phen molecule (as acceptor). Thermal decomposition process is studied by applying the differential scanning calorimetry (DSC) and thermo thermogravimetric differential analysis (TG-DTG). The DSC curve shows that there is one exothermic peak in ZTO·2H2O and ZTO(phen)·H2O, respectively. The critical temperature of thermal explosion (Tb) for ZTO·2H2O and ZTO(phen)·H2O is 282.21 oC and 195.94 oC, respectively.
Ren, Yinghui,Li, Dan,Yi, Jianhua,Zhao, Fengqi,Ma, Haixia,Xu, Kangzhen,Song, Jirong Korean Chemical Society 2010 Bulletin of the Korean Chemical Society Vol.31 No.7
4-Amino-1,2,4-triazole copper complex (4-ATzCu) was synthesized, and its thermal behaviors, nonisothermal decomposition reaction kinetics were studied by DSC and TG-DTG techniques. The thermal decomposition reaction kinetic equation was obtained as: $d\alpha$ / dt =$10^{22.01}$ (1-$\alpha$)[-ln(1-$\alpha$)]$^{1/3}$ exp($-2.75\times10^4$ /T). The standard mole specific heat capacity of the complex was determined and the standard molar heat capacity is 305.66 $J{\cdot}mol^{-1}{\cdot}K^{-1}$ at 298.15 K. The entropy of activation $({\Delta}S^{\neq})$, enthalpy of activation $({\Delta}H^{\neq})$, and Gibbs free energy of activation $({\Delta}G^{\neq})$ are calculated as 171.88 $J{\cdot}mol^{-1}{\cdot}K^{-1}$ 225.81 $kJ{\cdot}mol^{-1}$ and 141.18 $kJ{\cdot}mol^{-1}$, and the adiabatic time-to-explosion of the complex was obtained as 389.20 s.
Yinghui Ren,Dan Li,Jianhua Yi,Fengqi Zhao,Haixia Ma,Kangzhen Xu,Jirong Song 대한화학회 2010 Bulletin of the Korean Chemical Society Vol.31 No.7
4-Amino-1,2,4-triazole copper complex (4-ATzCu) was synthesized, and its thermal behaviors, nonisothermal decomposition reaction kinetics were studied by DSC and TG-DTG techniques. The thermal decomposition reaction kinetic equation was obtained as: dα / dt =1022.01 (1−α )[−ln(1−α )]1/3 exp(−2.75×104 /T) . The standard mole specific heat capacity of the complex was determined and the standard molar heat capacity is 305.66 J·mol‒1·K‒1 at 298.15 K. The entropy of activation ( ΔS ≠ ), enthalpy of activation (ΔH ≠), and Gibbs free energy of activation ( ΔG≠) are calculated as 171.88 J·mol‒1·K‒1, 225.81 kJ·mol‒1 and 141.18 kJ·mol‒1, and the adiabatic time-to-explosion of the complex was obtained as 389.20 s.
Non-isothermal Decomposition Kinetics of a New High-energy Organic Potassium Salt: K(DNDZ)
Kangzhen Xu,Xiaolei Ren,Fengqi Zhao,Hongxu Gao,Siyu Xu,Rongzu Hu,Jirong Song 대한화학회 2009 Bulletin of the Korean Chemical Society Vol.30 No.10
A new high-energy organic potassium salt, 2-(dinitromethylene)-1,3-diazepentane potassium salt K(DNDZ), was synthesized by reacting of 2-(dinitromethylene)-1,3-diazepentane (DNDZ) and potassium hydroxide. The thermal behavior and non-isothermal decomposition kinetics of K(DNDZ) were studied with DSC, TG/DTG methods. The kinetic equation is d 1013.92 3(1 ) dT ααβ= −2[−ln(1 − α )]3 exp(−1.52 × 105 / RT). The critical temperature of thermal explosion of K(DNDZ) is 208.63 oC. The specific heat capacity of K(DNDZ) was determined with a micro-DSC method, and the molar heat capacity is 224.63 J mol‒1 K‒1 at 298.15 K. Adiabatic time-to-explosion of K(DNDZ) obtained is 157.96 s.
Ren, Xiaolei,Zuo, Xiangang,Xu, Kangzhen,Ren, Yinghui,Huang, Jie,Song, Jirong,Wang, Bozhou,Zhao, Fengqi Korean Chemical Society 2011 Bulletin of the Korean Chemical Society Vol.32 No.7
A novel energetic material, 1-amino-1-(2,4-dinitrophenylhydrazinyl)-2,2-dinitroethylene (APHDNE), was synthesized by the reaction of 1,1-diamino-2,2-dinitroethylene (FOX-7) and 2,4-dinitrophenylhydrazine in N-methyl pyrrolidone (NMP) at 110 $^{\circ}C$. The theoretical investigation on APHDNE was curried out by B3LYP/6-311+$G^*$ method. The IR frequencies analysis and NMR chemical shifts were performed and compared with the experimental results. The thermal behavior of APHDNE was studied by DSC and TG/DTG methods, and can be divided into two crystal phase transition processes and three exothermic decomposition processes. The enthalpy, apparent activation energy and pre-exponential factor of the first exothermic decomposition reaction were obtained as -525.3 kJ $mol^{-1}$, 276.85 kJ $mol^{-1}$ and $10^{26.22}s^{-1}$, respectively. The critical temperature of thermal explosion of APHDNE is 237.7 $^{\circ}C$. The specific heat capacity of APHDNE was determined with micro-DSC method and theoretical calculation method, and the molar heat capacity is 363.67 J $mol^{-1}K^{-1}$ at 298.15 K. The adiabatic time-to-explosion of APHDNE was also calculated to be a certain value between 253.2-309.4 s. APHDNE has higher thermal stability than FOX-7.
Xiaolei Ren,Xiangang Zuo,Kangzhen Xu,Yinghui Ren,Jie Huang,Jirong Song,Bozhou Wang,Fengqi Zhao 대한화학회 2011 Bulletin of the Korean Chemical Society Vol.32 No.7
A novel energetic material, 1-amino-1-(2,4-dinitrophenylhydrazinyl)-2,2-dinitroethylene (APHDNE), was synthesized by the reaction of 1,1-diamino-2,2-dinitroethylene (FOX-7) and 2,4-dinitrophenylhydrazine in Nmethyl pyrrolidone (NMP) at 110 ^oC. The theoretical investigation on APHDNE was curried out by B3LYP/6-311+G^* method. The IR frequencies analysis and NMR chemical shifts were performed and compared with the experimental results. The thermal behavior of APHDNE was studied by DSC and TG/DTG methods, and can be divided into two crystal phase transition processes and three exothermic decomposition processes. The enthalpy, apparent activation energy and pre-exponential factor of the first exothermic decomposition reaction were obtained as −525.3 kJ mol^−1, 276.85 kJ mol^−1 and 10^(26.22) s^−1, respectively. The critical temperature of thermal explosion of APHDNE is 237.7 ^oC. The specific heat capacity of APHDNE was determined with micro-DSC method and theoretical calculation method, and the molar heat capacity is 363.67 J mol^−1 K^−1 at 298.15 K. The adiabatic time-to-explosion of APHDNE was also calculated to be a certain value between 253.2-309.4 s. APHDNE has higher thermal stability than FOX-7.