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,两种几何异构体含最(x)之间的相互转变均符合动力学一级反应,其xeln[(Xe-Xo)/(xe-x)]值和反应时间t(min)之间的关系分别为:xeln[(xe-xo)/(xe-x)]=0.082t+0.729(r2=0.9911,T=45℃),xeln[(xe-xo)/(Xe-x)]=0.049t+0.598(r2=0.9987,T=40℃),xeln[(xe-xo)/(xe-x)]=0.022t+0.586(r2=0.9987,T=35℃),xeln[(xe-xo)/(xe-x)]=0.012t+0.59I(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(△H+)、活化熵(△S+)和活化能(△Ea)分别为:△H+=103.84 kJ·mol-1,△S+=271.93 J·mol-1·K-1,△Ea=86.74 kJ·mol-1(面式异构体向经式异构体转变);△H+=106.47 kJ·mol-1,△S+=257.65J·mol-1·K-1,△Ea=94.43kJ·mol-1(经式异构体向面式异构体转变).
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