A relationship is established, using the least squares method, between the standard enthalpy of formation and the standard enthalpy of formation divided by the exothermic denitration decomposition peak absolute temper...A relationship is established, using the least squares method, between the standard enthalpy of formation and the standard enthalpy of formation divided by the exothermic denitration decomposition peak absolute temperature corresponding to β →0.展开更多
The standard formation enthalpy of the glycine complex with erbium chloride was determined by using an isoperibolic calorimeter with the hydrochloric acid solution(2 mol/L) as a calorimetric solvent according a propos...The standard formation enthalpy of the glycine complex with erbium chloride was determined by using an isoperibolic calorimeter with the hydrochloric acid solution(2 mol/L) as a calorimetric solvent according a proposed thermochemical cycle. The following values were obtained: Δ r H θ m(298.15 K)=-3.331 kJ/mol Δ f H θ m(Er(Gly) 3Cl 3·3H 2O,s,298.15 K)=-3 632.0展开更多
The dissolution enthalpies of the [Sm(NO 3) 3[KG-*3]·6H 2O(s)+4Ala(s)] and Sm(Ala) 4(NO 3) 3 and Sm(Ala) 4(NO 3) 3·H 2O(s) have been measured at 298.15 K using a homemade isoperibolic calorimeter with hydroc...The dissolution enthalpies of the [Sm(NO 3) 3[KG-*3]·6H 2O(s)+4Ala(s)] and Sm(Ala) 4(NO 3) 3 and Sm(Ala) 4(NO 3) 3·H 2O(s) have been measured at 298.15 K using a homemade isoperibolic calorimeter with hydrochloric acid solution(2 mol/L) as solvent. The standard molar enthalpy of the coodination reaction of alanine with samarium nitrate has been determined via a designed thermochemical cycle, and ΔHθ r,m= 21 393 kJ/mol was obtained. The standard molar enthalpy of formation of the complex Sm(Ala) 4-(NO 3) 3·H 2O has been calculated to be ΔHθ f,m[Sm(Ala) 4(NO 3) 3[KG-*2]·H 2O,s,298.15 K]= = -3 865.2 kJ/mol.展开更多
A ternary solid complex Lu(Et2dtc)3(phen) has been obtained from the reaction of hydrated lutetium chloride with sodium diethyldithiocarbamate (NaEt2dtc), and 1,10-phenanthroline (o-phen·H2O) in absolute ethanol....A ternary solid complex Lu(Et2dtc)3(phen) has been obtained from the reaction of hydrated lutetium chloride with sodium diethyldithiocarbamate (NaEt2dtc), and 1,10-phenanthroline (o-phen·H2O) in absolute ethanol. IR spectrum of the complex indicates that Lu3+ binds with sulfur atom in the Na(Et2dtc)3 and nitrogen atom in the o-phen. The enthalpy change of liquid-phase reaction of formation of the complex, △CHM- (l), was determined to be (-32.821 ± 0.147 ) kJ·mol-1 at 298.15 K by an RD-496 Ⅲ type heat conduction microcalormeter. The enthalpy change of the solid-phase reaction of formation of the complex, △CHM- (s), was calculated to be (104.160 ± 0.168) kJ · mol-1 on the basis of an appropriate thermochemistry cycle. The thermodynamics of liquid-phase reaction of formation of the complex was investigated by changing the temperature of liquid-phase reaction. Fundamental parameters, such as the activation enthalpy (△HM-), the activation entropy (?驻SM-), the activation free energy (△GM-), the apparent reaction rate constant (k), the apparent activation energy (E), the pre-exponential constant (A) and the reaction order (n), were obtained by combination the reaction thermodynamic and kinetic equations with the data of thermokinetic experiments. The molar heat capacity of the complex, cm, was determined to be (82.23 ± 1.47) J·mol-1·K-1 by the same microcalormeter. The constant-volume combustion energy of the complex, ΔcU, was determined as (-17 898.228 ± 8.59) kJ·mol-1 by an RBC-Ⅱtype rotating-bomb calorimeter at 298.15 K. Its standard enthalpy of combustion, △CHM-, and standard enthalpy of formation, △CHM-, were calculated to be (-17 917.43 ± 8.11) kJ·mol-1 and (-859.95 ±10.12) kJ·mol-1, respectively.展开更多
The solid-solid state coord ination reaction enthalpy of CaO w ith ascorb ic ac id has been determ ined by solution calorim e-try in an isoperibel reaction calorim eter at 298.2K.The calorim ietric solvent is 2mol/L H...The solid-solid state coord ination reaction enthalpy of CaO w ith ascorb ic ac id has been determ ined by solution calorim e-try in an isoperibel reaction calorim eter at 298.2K.The calorim ietric solvent is 2mol/L HC l.A thermochem ical cyc le has been de-signed,and the standard Enthalpy of form ation for Ca(C6H7O6)2.4H2O(s) has been calcu lated.The recomm ended values of standard enthalpy of form ationΔfHΘm[Ca(C6H7O6)2.4H2O,s] is-3941.5kJ.展开更多
文摘A relationship is established, using the least squares method, between the standard enthalpy of formation and the standard enthalpy of formation divided by the exothermic denitration decomposition peak absolute temperature corresponding to β →0.
文摘The standard formation enthalpy of the glycine complex with erbium chloride was determined by using an isoperibolic calorimeter with the hydrochloric acid solution(2 mol/L) as a calorimetric solvent according a proposed thermochemical cycle. The following values were obtained: Δ r H θ m(298.15 K)=-3.331 kJ/mol Δ f H θ m(Er(Gly) 3Cl 3·3H 2O,s,298.15 K)=-3 632.0
文摘The dissolution enthalpies of the [Sm(NO 3) 3[KG-*3]·6H 2O(s)+4Ala(s)] and Sm(Ala) 4(NO 3) 3 and Sm(Ala) 4(NO 3) 3·H 2O(s) have been measured at 298.15 K using a homemade isoperibolic calorimeter with hydrochloric acid solution(2 mol/L) as solvent. The standard molar enthalpy of the coodination reaction of alanine with samarium nitrate has been determined via a designed thermochemical cycle, and ΔHθ r,m= 21 393 kJ/mol was obtained. The standard molar enthalpy of formation of the complex Sm(Ala) 4-(NO 3) 3·H 2O has been calculated to be ΔHθ f,m[Sm(Ala) 4(NO 3) 3[KG-*2]·H 2O,s,298.15 K]= = -3 865.2 kJ/mol.
文摘A ternary solid complex Lu(Et2dtc)3(phen) has been obtained from the reaction of hydrated lutetium chloride with sodium diethyldithiocarbamate (NaEt2dtc), and 1,10-phenanthroline (o-phen·H2O) in absolute ethanol. IR spectrum of the complex indicates that Lu3+ binds with sulfur atom in the Na(Et2dtc)3 and nitrogen atom in the o-phen. The enthalpy change of liquid-phase reaction of formation of the complex, △CHM- (l), was determined to be (-32.821 ± 0.147 ) kJ·mol-1 at 298.15 K by an RD-496 Ⅲ type heat conduction microcalormeter. The enthalpy change of the solid-phase reaction of formation of the complex, △CHM- (s), was calculated to be (104.160 ± 0.168) kJ · mol-1 on the basis of an appropriate thermochemistry cycle. The thermodynamics of liquid-phase reaction of formation of the complex was investigated by changing the temperature of liquid-phase reaction. Fundamental parameters, such as the activation enthalpy (△HM-), the activation entropy (?驻SM-), the activation free energy (△GM-), the apparent reaction rate constant (k), the apparent activation energy (E), the pre-exponential constant (A) and the reaction order (n), were obtained by combination the reaction thermodynamic and kinetic equations with the data of thermokinetic experiments. The molar heat capacity of the complex, cm, was determined to be (82.23 ± 1.47) J·mol-1·K-1 by the same microcalormeter. The constant-volume combustion energy of the complex, ΔcU, was determined as (-17 898.228 ± 8.59) kJ·mol-1 by an RBC-Ⅱtype rotating-bomb calorimeter at 298.15 K. Its standard enthalpy of combustion, △CHM-, and standard enthalpy of formation, △CHM-, were calculated to be (-17 917.43 ± 8.11) kJ·mol-1 and (-859.95 ±10.12) kJ·mol-1, respectively.
文摘The solid-solid state coord ination reaction enthalpy of CaO w ith ascorb ic ac id has been determ ined by solution calorim e-try in an isoperibel reaction calorim eter at 298.2K.The calorim ietric solvent is 2mol/L HC l.A thermochem ical cyc le has been de-signed,and the standard Enthalpy of form ation for Ca(C6H7O6)2.4H2O(s) has been calcu lated.The recomm ended values of standard enthalpy of form ationΔfHΘm[Ca(C6H7O6)2.4H2O,s] is-3941.5kJ.
基金the National Natural Science Foundation of China(21273171,21127004,21173168)Scientific Research Program Funded by Shaanxi Provincial Education Department,China(11JK0578,11JS110)~~
文摘利用精密绝热热量仪测定了配合化合物Zn(Met)_3(NO_3)_2·H_2O(s)(Met=L-α-蛋氨酸)在78-371 K温区的摩尔热容.通过热容曲线解析,得到了该配合物的起始脱水温度为T_D=325.10 K.将该温区的摩尔热容实验值用最小二乘法拟合得到了摩尔热容(C_p)对约化温度(T)的多项式方程,由此计算得到了配合物的舒平热容值和热力学函数值.基于设计的热化学循环,选择100 mL 2 mol·L^(-1)HCl溶液为量热溶剂,利用等温环境溶解-反应热量计,得到了298.15 K配合物的标准摩尔生成焓Δ_f H_m^0[Zn(Met)_3(NO_3)_2·H_2O,s]=-(1472.65±0.76)J·mol^(-1).
基金supported by the National Natural Science Foundation of China (20373072)Construct Program of the Key Discipline in Hunan Province,China (Applied Chemistry)~~
