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用Union Giken RA-401停流分光光度计对丙酮溶剂中咪唑(Im)与对位取代四苯基卟啉铁(Ⅲ)(Fe(p-X)TPPCl X=Cl,H,CH_3,OCH_3)的轴向配位快速反应动力学进行了研究.提出了反应机理.以CA-033E微机对实验数据进行处理,得到似平衡步的平衡常数K和速控步的速率常数k,并算出了似平衡步的△H、△S以及速控步活化参数△日~≠、△S~≠.发现△H、△S、△H~≠、AS~≠、InK、Ink分别与Hammett取代常数σ呈直线关系;AH~≠和△S~≠存在等动力学关系.
The interaction between imidazole (Im) and para-substituted tetraphenylporphyrin iron (Ⅲ) (Fe (pX) TPPCl X = Cl, H, CH_3, OCH_3) in acetone solvent was monitored by Union Giken RA- The kinetics of coordination reaction was studied and the reaction mechanism was proposed.The experimental data were processed by CA-033E microcomputer to get the equilibrium constants K of the equilibrium steps and the rate constants k of the velocity control steps, and the equilibrium-like steps ΔH, △ S, and Acceleration step activation parameters ΔD, ΔS ~ ≠. It is found that ΔH, ΔS, ΔH ~ ≠, AS ~ ≠, InK, and Ink have a linear relationship with Hammett’s substitution constant σ ; AH ~ ≠ and △ S ~ ≠ existence of such dynamic relationship.