物理化学学报 >> 2002, Vol. 18 >> Issue (10): 865-870.doi: 10.3866/PKU.WHXB20021001

研究论文    下一篇

水杨醛-1H-苯并三唑-1-乙酰腙与镧(Ⅲ)配合物的制备、表征及热化学

何水样;曹文凯;胡亭;赵建设;张维平;薛岗林;胡荣祖   

  1. 西北大学化学系,陕西省物理无机化学重点实验室,西安　710069
  • 收稿日期:2002-01-08 修回日期:2002-03-11 发布日期:2002-10-15
  • 通讯作者: 何水样 E-mail:xdhsy@263.net

Synthesis, Characterization and Thermochemical Properties of La(III) with Salicylaldehyde-1H- benzotriazol-1-aceylhydrazone

He Shui-Yang;Cao Wen-Kai;Hu Ting;Zhao Jian-She;Zhang Wei-Ping;Xue Gang-Lin;Hu Rong-Zu   

  1. Department of Chemistry, Northwest University, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, Xi'an　710069
  • Received:2002-01-08 Revised:2002-03-11 Published:2002-10-15
  • Contact: He Shui-Yang E-mail:xdhsy@263.net

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摘要： 在甲醇中,利用水杨醛-1H-苯并三唑-1-乙酰腙(C15H13N5O2,简称SBTH)与高氯酸镧反应,制得一新配合物,经元素分析、化学分析并结合热分析确定了其组成为La(C15H12N5O2)( C15H11N5O2)•2.5H2O.利用电导测定、红外光谱、1H NMR和TG-DTG等手段推测了配合物的结构.用微热量计测定了配合物在不同浓度(b)时的溶解焓,用计算机拟合求得该配合物的标准摩尔溶解焓(ΔsolHmΘ=－135.62 kJ•mol－1)及溶解焓(ΔsolH)的经验公式(ΔsolH=－135.62－11633b＋3761.5b1/2),并由此分别推导出配合物的相对表观摩尔焓(Li)、相对偏摩尔焓(Li)以及配合物稀释焓(ΔdilH1,2)的经验公式:Li=－11633b＋3761.5b1/2；Li=－23266b＋5642.2b1/2和ΔdilH1,2=－11633(b21/2－b11/2)＋3761.5(b2－b1).还研究了配合物的热分解过程,利用Kissinger公式计算了配合物主要分解阶段的表观活化能(Ea=470.24 kJ•mol－1).

关键词: 水杨醛-1H-苯并三唑-1-乙酰腙, 稀土, 溶解焓, 热分解, 活化能

Abstract: A new rare earth complex La(C15H12N5O2)( C15H11N5O2)•2.5H2O has been synthesized. Attempts have been made to ascertain its probable structure on the basis of elemental analyzes, molar conductivities, IR, 1H NMR and TG-DTG. It is suggested that the complex has a eight-coordinated configuration. The enthalpies of solution in DMF for the complex were measured by means of a micro calorimeter. The data of standard molar enthalpy of solution (ΔsolHmΘ=－135.62 kJ•mol－1) and the empirical formulae of enthalpy of solution (ΔsolH=－135.62－11633b＋3761.5b1/2) for the complex at different concentration b (mol•kg－1) were obtained. And relative apparent molar enthalpy (Li),relative partial molar enthalpy (Li)) and enthalpy of dilution (ΔdilH1,2) were drawn up respectively by the data of enthalpies of solution of the complex: Li=－11633b＋2761.5b1/2, Li=－23266b＋5642.2b1/2 and ΔdilH1,2=－11633(b21/2－b11/2)＋3761.5(b2－b1).The second-stage decomposition reaction for the complex was studied and the apparent activation energy was obtained by the Kissinger's formulae.

Key words: Salicylaldehyde-1H-benzotriazol-1-aceylhydrazone, Rare earth, 　Enthalpy of solution, Thermal decomposition, Activation energy