The constant-volume combustion energy, △cU （DADE, s, 298.15 K）, the thermal behavior, and kinetics and mechanism of the exothermic decomposition reaction of 1,1-diamino-2,2-dinitroethylene （DADE） have been invest...The constant-volume combustion energy, △cU （DADE, s, 298.15 K）, the thermal behavior, and kinetics and mechanism of the exothermic decomposition reaction of 1,1-diamino-2,2-dinitroethylene （DADE） have been investigated by a precise rotating bomb calorimeter, TG-DTG, DSC, rapid-scan fourier transform infrared （RSFT-IR） spectroscopy and T-jump/FTIR, respectively. The value of △cHm （DADE, s, 298.15 K） was determined as （-8518.09±4.59） j·g^-1. Its standard enthalpy of combustion, △cU （DADE, s, 298.15 K）, and standard enthalpy of formation, △fHm （DADE, s, 298.15 K） were calculated to be （-1254.00±0.68） and （- 103.98±0.73） kJ·mol^-1, respectively The kinetic parameters （the apparent activation energy Ea and pre-exponential factor A） of the first exothermic decomposition reaction in a temperature-programmed mode obtained by Kissinger＇s method and Ozawa＇s method, were Ek=344.35 kJ·mol^-1, AR= 1034.50 S^-1 and Eo=335.32 kJ·mol^-1, respectively. The critical temperatures of thermal explosion of DADE were 206.98 and 207.08 ℃ by different methods. Information was obtained on its thermolysis detected by RSFT-IR and T-jump/FTIR.展开更多
The constant-volume combustion energy, cUD(GUDN, s, 298.15 K), enthalpy of solution in acetic ether, solmHQD and kinetic behavior of the exothermic decomposition reaction of the title compound (GUDN) are deter-mined b...The constant-volume combustion energy, cUD(GUDN, s, 298.15 K), enthalpy of solution in acetic ether, solmHQD and kinetic behavior of the exothermic decomposition reaction of the title compound (GUDN) are deter-mined by a precise rotating bomb calorimeter, a Calvet microcalorimeter and DSC, respectively. Its standard en-thalpy of combustion, cmHQD (GUDN, s, 298.15 K), standard enthalpy of formation, fHQDm (GUDN, s, 298.15 K) and kinetic parameters of the exothermic main decomposition reaction in a temperature-programmed mode [the apparent activation energy (aE) and pre-exponential factor (A)] are calculated. The values of cUD (GUDN, s, 298.15 K), cmHQD (GUDN, s, 298.15 K), fmHQD(GUDN, s, 298.15 K) and solmHQD of GUDN are (-7068.64±2.37) J·g-1, (-1467.66±0.50) kJ·mol-1, (-319.76±0.58) kJ·mol-1 and (165.737±0.013) kJ·mol-1, respectively. The kinetic model function in integral form and the value of aEand A of the exothermic main decomposition reaction of GUDN are 220.20 kJ·mol-1 and 1021.18 s-1, respectively. The critical temperature of thermal explosion of GUDN is 217.6 ℃展开更多
The reaction enthalpy of coordination reaction of lanthanum chloride with Glycine is determined by solution calorimetry in an isoperibel reaction calorimeter. The calormetric solvent is the solution of hydrochloric ac...The reaction enthalpy of coordination reaction of lanthanum chloride with Glycine is determined by solution calorimetry in an isoperibel reaction calorimeter. The calormetric solvent is the solution of hydrochloric acid (2 mol· L－ 1), a new thermochemical cycle is designed. According to the results, the following date: (298.2 K)=－ 4.310 kJ· mol－ 1 (La(Gly)3Cl3· 5H2O, s, 298.2 K)=－ 4222.93 kJ· mol－ 1 were obtained.展开更多
Two coordination compounds of rare earth perchlorates with alanine and imidazole, [RE(Ala)n(Im)(H2O)]- (ClO4)3(s) (RE=La, n=3; RE=Nd, n=2), have been prepared and characterized. The standard molar enthalpies of reacti...Two coordination compounds of rare earth perchlorates with alanine and imidazole, [RE(Ala)n(Im)(H2O)]- (ClO4)3(s) (RE=La, n=3; RE=Nd, n=2), have been prepared and characterized. The standard molar enthalpies of reaction for the following two reactions, LaCl37H2O(s)+3Ala(s)+Im(s)+3NaClO4(s)=[La(Ala)3(Im)(H2O)]- (ClO4)3(s)+3NaCl(s)+6H2O(l) (1) and NdCl36H2O(s)+2Ala(s)+Im(s)+3NaClO4(s)=[Nd(Ala)2(Im)(H2O)]- (ClO4)3(s)+3NaCl(s)+5H2O(l) (2), were determined by solution-reaction calorimetry, at T=298.15 K, as 36.168±0.642 kJmol-1 and 48.590±0.934 kJmol-1 respectively. From the results and other auxiliary quantities, the standard molar enthalpies of formation of [La(Ala)3(Im)(H2O)](ClO4)3(s) and [Nd(Ala)2(Im)(H2O)] (ClO4)3(s) were derived, fmHD!{[La(Ala)3(Im)(H2O)](ClO4)3, s}=(-2984.8±1.0) kJmol-1 and fmHD! {[Nd(Ala)2(Im)(H2O)]- (ClO4)3, s}=(-2387.8±0.8) kJmol-1 , respectively.展开更多
文摘The constant-volume combustion energy, △cU （DADE, s, 298.15 K）, the thermal behavior, and kinetics and mechanism of the exothermic decomposition reaction of 1,1-diamino-2,2-dinitroethylene （DADE） have been investigated by a precise rotating bomb calorimeter, TG-DTG, DSC, rapid-scan fourier transform infrared （RSFT-IR） spectroscopy and T-jump/FTIR, respectively. The value of △cHm （DADE, s, 298.15 K） was determined as （-8518.09±4.59） j·g^-1. Its standard enthalpy of combustion, △cU （DADE, s, 298.15 K）, and standard enthalpy of formation, △fHm （DADE, s, 298.15 K） were calculated to be （-1254.00±0.68） and （- 103.98±0.73） kJ·mol^-1, respectively The kinetic parameters （the apparent activation energy Ea and pre-exponential factor A） of the first exothermic decomposition reaction in a temperature-programmed mode obtained by Kissinger＇s method and Ozawa＇s method, were Ek=344.35 kJ·mol^-1, AR= 1034.50 S^-1 and Eo=335.32 kJ·mol^-1, respectively. The critical temperatures of thermal explosion of DADE were 206.98 and 207.08 ℃ by different methods. Information was obtained on its thermolysis detected by RSFT-IR and T-jump/FTIR.
基金Project supported by the Science and Technology Foundation of Shaanxi Key Laboratory of Physico-Inorganic Chemistry (No. 29-3 2001) the Science and Technology Foundation of the National Defence Key Laboratory of Propellant and Explosive Combustion of
文摘The constant-volume combustion energy, cUD(GUDN, s, 298.15 K), enthalpy of solution in acetic ether, solmHQD and kinetic behavior of the exothermic decomposition reaction of the title compound (GUDN) are deter-mined by a precise rotating bomb calorimeter, a Calvet microcalorimeter and DSC, respectively. Its standard en-thalpy of combustion, cmHQD (GUDN, s, 298.15 K), standard enthalpy of formation, fHQDm (GUDN, s, 298.15 K) and kinetic parameters of the exothermic main decomposition reaction in a temperature-programmed mode [the apparent activation energy (aE) and pre-exponential factor (A)] are calculated. The values of cUD (GUDN, s, 298.15 K), cmHQD (GUDN, s, 298.15 K), fmHQD(GUDN, s, 298.15 K) and solmHQD of GUDN are (-7068.64±2.37) J·g-1, (-1467.66±0.50) kJ·mol-1, (-319.76±0.58) kJ·mol-1 and (165.737±0.013) kJ·mol-1, respectively. The kinetic model function in integral form and the value of aEand A of the exothermic main decomposition reaction of GUDN are 220.20 kJ·mol-1 and 1021.18 s-1, respectively. The critical temperature of thermal explosion of GUDN is 217.6 ℃
文摘The reaction enthalpy of coordination reaction of lanthanum chloride with Glycine is determined by solution calorimetry in an isoperibel reaction calorimeter. The calormetric solvent is the solution of hydrochloric acid (2 mol· L－ 1), a new thermochemical cycle is designed. According to the results, the following date: (298.2 K)=－ 4.310 kJ· mol－ 1 (La(Gly)3Cl3· 5H2O, s, 298.2 K)=－ 4222.93 kJ· mol－ 1 were obtained.
基金Project supported by the Teaching and Research Award Program for Outstanding Young Professors in High Education Institute Ministry of Educa-tion China.
文摘Two coordination compounds of rare earth perchlorates with alanine and imidazole, [RE(Ala)n(Im)(H2O)]- (ClO4)3(s) (RE=La, n=3; RE=Nd, n=2), have been prepared and characterized. The standard molar enthalpies of reaction for the following two reactions, LaCl37H2O(s)+3Ala(s)+Im(s)+3NaClO4(s)=[La(Ala)3(Im)(H2O)]- (ClO4)3(s)+3NaCl(s)+6H2O(l) (1) and NdCl36H2O(s)+2Ala(s)+Im(s)+3NaClO4(s)=[Nd(Ala)2(Im)(H2O)]- (ClO4)3(s)+3NaCl(s)+5H2O(l) (2), were determined by solution-reaction calorimetry, at T=298.15 K, as 36.168±0.642 kJmol-1 and 48.590±0.934 kJmol-1 respectively. From the results and other auxiliary quantities, the standard molar enthalpies of formation of [La(Ala)3(Im)(H2O)](ClO4)3(s) and [Nd(Ala)2(Im)(H2O)] (ClO4)3(s) were derived, fmHD!{[La(Ala)3(Im)(H2O)](ClO4)3, s}=(-2984.8±1.0) kJmol-1 and fmHD! {[Nd(Ala)2(Im)(H2O)]- (ClO4)3, s}=(-2387.8±0.8) kJmol-1 , respectively.
