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)+H2TPPM*H2TPP K2M*H2TPP+Zn(Ⅱ)Zn(Ⅱ)TPP+M(Ⅱ)+2H+k3Zn(Ⅱ)+H2TPPZn*H2TPPK1Zn*H2TPPZn(Ⅱ)TPP+2H+k1Zn*H2TPP+Zn(Ⅱ)Zn(Ⅱ)TPP+Zn(Ⅱ)+2H+k2The effect of temperature on the reaction has been investigated. The standard molar enthalpy change ΔrHm0 and standard molar entropy change ΔrS0m of preequilibrium step and the activation parameters Δ≠Hm, Δ≠Sm of elementary step have been calculated.
出处
《无机化学学报》
SCIE
CAS
CSCD
北大核心
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
关键词
四苯基卟啉锌
生成反应动力学
镉
汞
催化
tetraphenylporphyrin tetraphenylporphyrinatozinc (Ⅱ)kinetics of formation reaction mechanism of reactioncatalysis of Cd(Ⅱ) and Hg(Ⅱ) ion
