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
The partial and the integral enthalpies of mixing of liquid Al-Cr and Ni-Cr binary alloys have been determined by high temperature isoperibolic calorimetry at 1723±5 K and 1729±5 K, respectively. The results...The partial and the integral enthalpies of mixing of liquid Al-Cr and Ni-Cr binary alloys have been determined by high temperature isoperibolic calorimetry at 1723±5 K and 1729±5 K, respectively. The results were analytically described by the thermodynamically adapted power series (TAPS). The enthalpies of mixing values for both binary liquid melts are small and negative and in good agreement with the available literature data. Minima of the mixing enthalpies of liquid Al-Cr and Ni-Cr alloys are -7.0 kJ·mol-1 at 46 at. pct Cr and -3.0 kJ·mol-1 at 37 at. pct Cr, respectively.展开更多
A coordination compound of erbium perchlorate with L-α-glutamic acid, [Er2（Glu）2（H2O）6]（ClO4）4·6H2O（s）, was synthesized. By chemical analysis, elemental analysis, FTIR, TG/DTG, and comparison with releva...A coordination compound of erbium perchlorate with L-α-glutamic acid, [Er2（Glu）2（H2O）6]（ClO4）4·6H2O（s）, was synthesized. By chemical analysis, elemental analysis, FTIR, TG/DTG, and comparison with relevant literatures, its chemical composition and structure were established. The mechanism of thermal decomposition of the complex was deduced on the basis of the TG/DTG analysis. Low-temperature heat capacities were measured by a precision automated adiabatic calorimeter from 78 to 318 K. An endothermic peak in the heat capacity curve was observed over the temperature region of 290-318 K, which was ascribed to a solid-to-solid phase transition. The temperature Ttrans, the enthalpy △transHm and the entropy △transSm of the phase transition for the compound were determined to be： （308.73±0.45） K, （10.49±0.05） kJ·mol^-1 and （33.9±0.2） J·K^-1·mol^-1. Polynomial equation of heat capacities as a function of the temperature in the region of 78-290 K was fitted by the least square method. Standard molar enthalpies of dissolution of the mixture [2ErCl3·6H2O（s）＋2L-Glu（s）＋6NaClO4·H2O（s）] and the mixture {[Er2（Glu）2（H2O）6]（ClO4）4·6H2O（s）＋6NaCl（s）} in 100 mL of 2 mol·dm^-3 HClO4 as calorimetric solvent, and {2HClO4（1）} in the solution A＇ at T=298.15 K were measured to be, △dHm,1=（31.552±0.026） kJ·mol^-1, △dHm,2 = （41.302±0.034） kJ·mol^-1, and △dHm,3 = （ 14.986 ± 0.064） kJ·mol^-1, respectively. In accordance with Hess law, the standard molar enthalpy of formation of the complex was determined as △fHm-=-（7551.0±2.4） kJ·mol^-1 by using an isoperibol solution-reaction calorimeter and designing a thermochemical cycle.展开更多
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.
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).
文摘The partial and the integral enthalpies of mixing of liquid Al-Cr and Ni-Cr binary alloys have been determined by high temperature isoperibolic calorimetry at 1723±5 K and 1729±5 K, respectively. The results were analytically described by the thermodynamically adapted power series (TAPS). The enthalpies of mixing values for both binary liquid melts are small and negative and in good agreement with the available literature data. Minima of the mixing enthalpies of liquid Al-Cr and Ni-Cr alloys are -7.0 kJ·mol-1 at 46 at. pct Cr and -3.0 kJ·mol-1 at 37 at. pct Cr, respectively.
基金Project supported by the National Natural Science Foundation of China （No. 20673050）.
文摘A coordination compound of erbium perchlorate with L-α-glutamic acid, [Er2（Glu）2（H2O）6]（ClO4）4·6H2O（s）, was synthesized. By chemical analysis, elemental analysis, FTIR, TG/DTG, and comparison with relevant literatures, its chemical composition and structure were established. The mechanism of thermal decomposition of the complex was deduced on the basis of the TG/DTG analysis. Low-temperature heat capacities were measured by a precision automated adiabatic calorimeter from 78 to 318 K. An endothermic peak in the heat capacity curve was observed over the temperature region of 290-318 K, which was ascribed to a solid-to-solid phase transition. The temperature Ttrans, the enthalpy △transHm and the entropy △transSm of the phase transition for the compound were determined to be： （308.73±0.45） K, （10.49±0.05） kJ·mol^-1 and （33.9±0.2） J·K^-1·mol^-1. Polynomial equation of heat capacities as a function of the temperature in the region of 78-290 K was fitted by the least square method. Standard molar enthalpies of dissolution of the mixture [2ErCl3·6H2O（s）＋2L-Glu（s）＋6NaClO4·H2O（s）] and the mixture {[Er2（Glu）2（H2O）6]（ClO4）4·6H2O（s）＋6NaCl（s）} in 100 mL of 2 mol·dm^-3 HClO4 as calorimetric solvent, and {2HClO4（1）} in the solution A＇ at T=298.15 K were measured to be, △dHm,1=（31.552±0.026） kJ·mol^-1, △dHm,2 = （41.302±0.034） kJ·mol^-1, and △dHm,3 = （ 14.986 ± 0.064） kJ·mol^-1, respectively. In accordance with Hess law, the standard molar enthalpy of formation of the complex was determined as △fHm-=-（7551.0±2.4） kJ·mol^-1 by using an isoperibol solution-reaction calorimeter and designing a thermochemical cycle.
