色谱

色谱

• 研究论文 • 上一篇    下一篇

高效液相色谱法测定金属配合物｛Fe［3-(2-吡啶基)-5,6-二苯基-1,2,4-三嗪］3｝2+两种几何异构体的动力学转变

朱维晃1,吴丰昌2,黄廷林1   

  1. 1.School of Environment and Municipal Engineering, Xi’an University of Architecture and Technology, Xi’an 710055, China; 2.State Key Laboratory of Environmental Geochemistry, Institute of Geochemistry, the Chinese Academy of Sciences, Guiyang 550002, China
  • 收稿日期:2008-10-27 修回日期:2008-10-27 出版日期:2008-10-27 发布日期:1983-09-25
  • 通讯作者: 吴丰昌
  • 基金资助:
    国家自然科学基金(Nos. 40525011, 40632011)、陕西省自然科学基金(No. 2007E241)和西安建筑科技大学校内人才基金(No. RC0613)项目.

Determination of kinetic transformation of two geometrical isomers of the ［Fe(PDT)3］2+ by high performance liquid chromatography

ZHU Weihuang1, WU Fengchang2, HUANG Tinglin1   

  1. 1.School of Environment and Municipal Engineering, Xi’an University of Architecture and Technology, Xi’an 710055, China; 2.State Key Laboratory of Environmental Geochemistry, Institute of Geochemistry, the Chinese Academy of Sciences, Guiyang 550002, China
  • Received:2008-10-27 Revised:2008-10-27 Online:2008-10-27 Published:1983-09-25
  • Contact: WU Fengchang2

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摘要： 通过高效液相色谱法研究了3-(2-吡啶基)-5,6-二苯基-1,2,4-三嗪(PDT)和Fe(Ⅱ)的配合物［Fe(PDT)3］2+的面式和经式两种几何异构体之间的动力学平衡过程。结果表明:不同温度(30,35,40,45 ℃)下,两种几何异构体含量(x)之间的相互转变均符合动力学一级反应,其xeln［(xe-x0)/(xe-x)］值和反应时间t(min)之间的关系分别为:xeln［(xe-x0)/(xe-x)］=0.082t+0.729 (r2=0.9911,T=45 ℃),xeln［(xe-x0)/(xe-x)］=0.049t+0.598 (r2=0.9987,T=40 ℃),xeln［(xe-x0)/(xe-x)］=0.022t+0.586 (r2=0.9987,T=35 ℃),xeln［(xe-x0)/(xe-x)］=0.012t+0.591(r2=0.9988,T=30 ℃)。两种异构体之间的动力学相互转变过程中的活化焓(ΔH)、活化熵(ΔS)和活化能(ΔEa)分别为:ΔH=103.84 kJ·mol-1,ΔS=271.93 J·mol-1·K-1,ΔEa=86.74 kJ·mol-1 (面式异构体向经式异构体转变);ΔH=106.47 kJ·mol-1,ΔS=257.65 J·mol-1·K-1,ΔEa=94.43 kJ·mol-1 (经式异构体向面式异构体转变)。

关键词: ｛Fe［3-(2-吡啶基)-5,6-二苯基-1,2,4-三嗪］3｝2+, 动力学转变 , 高效液相色谱法, 几何异构体, 金属配合物

Abstract: The kinetic transformation of the two isomers of the ［Fe(PDT)3］2+ (PDT: 3-(2-pyridyl)-5,6-diphenyl-1,2,4-triazine) was studied by high performance liquid chromatography. The transformation between two isomers was proved to be treated kinetically as the first-order reaction. At different reaction temperatures, the linear regression equations between xeln［(xe-x0)/(xe-x)］ and t(min) were as follows: xeln［(xe-x0)/(xe-x)］=0.082t+0.729 (r2=0.9911, T=45 ℃), xeln［(xe-x0)/(xe-x)］=0.049t+0.598 (r2=0.9987, T=40 ℃), xeln［(xe-x0)/(xe-x)］=0.022t+0.586 (r2=0.9987, T=35 ℃), xeln［(xe-x0)/(xe-x)］=0.012t+0.591(r2=0.9988, T=30 ℃). The activation enthalpy (ΔH), activation entropy (ΔS), and activation energy (ΔEa) characterizing the kinetic transformation were as follows: ΔH=103.84 kJ·mol-1, ΔS=271.93 J·mol-1·K-1, ΔEa=86.74 kJ·mol-1 (fac-isomer→mer-isomer); ΔH=106.47 kJ·mol-1, ΔS=257.65 J·mol-1·K-1, ΔEa=94.43 kJ·mol-1 (mer-isomer→fac-isomer).

Key words: ｛Fe［3-(2-pyridyl)-5,6-diphenyl-1,2,4-triazine］3｝2+, geometrical isomers, kinetic transformation , metal complex, high performance liquid chromatography (HPLC)