镉(Ⅱ)、汞(Ⅱ)离子催化四苯基卟啉锌(Ⅱ)的生成反应动力学研究  

THE KINETICS OF FORMATION REACTION OF TETRAPHENYLPORPHYRINATOZINC (Ⅱ) IN THE PRESENCE OF CADMIUM (Ⅱ) AND MERCURY (Ⅱ) ION

作　　者：陈正华[1] 朱志昂[1] 陈红卫[1] 张智慧[1] 阮文娟[1] 陈荣悌[1] 

机构地区：[1]南开大学化学系

出　　处：《无机化学学报》1998年第1期40-46,共7页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金;天津自然科学基金

摘　　要：在二甲基甲酰胺和水混合溶剂中及在大阳离子Ｍ（Ⅱ）（Ｍ（Ⅱ）＝Ｃｄ（Ⅱ）、Ｈｇ（Ⅱ））的催化下，用分光光度法研究了四苯基卟啉锌Ｚｎ（Ⅱ）ＴＰＰ的生成反应动力学，提出了反应机理：Ｍ（Ⅱ）＋Ｈ２ＴＰＰＫ２Ｍ（Ⅱ）＊Ｈ２ＴＰＰＭ（Ⅱ）＊Ｈ２ＴＰＰ＋Ｚｎ（Ⅱ）ｋ３→Ｚｎ（Ⅱ）ＴＰＰ＋Ｍ（Ⅱ）＋２Ｈ＋Ｚｎ（Ⅱ）＋Ｈ２ＴＰＰＫ１Ｚｎ（Ⅱ）＊Ｈ２ＴＰＰＺｎ（Ⅱ）＊Ｈ２ＴＰＰｋ１→Ｚｎ（Ⅱ）ＴＰＰ＋２Ｈ＋Ｚｎ（Ⅱ）＊Ｈ２ＴＰＰ＋Ｚｎ（Ⅱ）ｋ２→Ｚｎ（Ⅱ）ＴＰＰ＋Ｚｎ（Ⅱ）＋２Ｈ＋研究了温度对反应动力学参数的影响，求得各平衡步的ΔｒＨ０ｍ，ΔｒＳ０ｍ及其他基元反应的活化参数Δ≠Ｈｍ，Δ≠Ｓｍ。Kinetics of formation reaction of tetraphenylporphyrinatozinc (Ⅱ) in mixture of DMF and H_2O has been studied spectrophotometrically in the presence of large cation M(Ⅱ) (M(Ⅱ)=cadmium (Ⅱ) and mercury (Ⅱ) ion). The mechanisms of reaction were proposed.M(Ⅱ)+H2TPPM*H2TPP K2M*H2TPP+Zn(Ⅱ)Zn(Ⅱ)TPP+M(Ⅱ)+2H+k3Zn(Ⅱ)+H2TPPZn*H2TPPK1Zn*H2TPPZn(Ⅱ)TPP+2H+k1Zn*H2TPP+Zn(Ⅱ)Zn(Ⅱ)TPP+Zn(Ⅱ)+2H+k2The effect of temperature on the reaction has been investigated. The standard molar enthalpy change ΔrHm0 and standard molar entropy change ΔrS0m of preequilibrium step and the activation parameters Δ≠Hm, Δ≠Sm of elementary step have been calculated.

关 键 词：四苯基卟啉锌 生成反应动力学 镉 汞 催化 

分 类 号：O614.241[理学—无机化学]