Thermochemistry on the Complex of Erbium Perchlorate with L-α-Glutamic Acid [Er2(L-Glu)2(H2O)6](ClO4)4·6H2O(s)  

Thermochemistry on the Complex of Erbium Perchlorate with L-α-Glutamic Acid [Er2(L-Glu)2(H2O)6](ClO4)4·6H2O(s)

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作  者:邸友莹 张剑 谭志诚 

机构地区:[1]College of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng, Shandong 252059, China [2]Therrnochemistry Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023, China

出  处:《Chinese Journal of Chemistry》2007年第10期1423-1429,共7页中国化学(英文版)

基  金:Project supported by the National Natural Science Foundation of China (No. 20673050).

摘  要: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.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.

关 键 词:[Er2(Glu)2(H2O)6](ClO4)4·6H2O(s) adiabatic calorimetry heat capacity isoperibol solution-reaction calorimetry standard molar enthalpy of formation 

分 类 号:O614.344[理学—无机化学] O642[理学—化学]

 

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