摘要
研究了在３５±０．１℃、离子强度０．５ｍｏｌ／Ｌ（ＫＣｌ）条件下，甲酸根、乙酸根、丙酸根和丁酸根分别催化Ｃｕ（Ⅱ）离子与四溴化间－四（Ｎ－乙酸甲酯基－３－吡啶基）卟啉（Ｈ２ＴＢ－Ｎ－ＡＣＭＳｐｙＰＢｒ４）的反应动力学及其机理，该类反应对卟啉和Ｃｕ（Ⅱ）离子均为一级反应，反应动力学方程为：ｄ［Ｃｕｐ４＋］／ｄｔ＝ｋ｛（１．０＋ｂ［Ａ－］）／（１．０＋Ｋ３，４·［Ｈ＋］２）｝［Ｃｕ２＋］［ｐ］Ｔ，在甲酸－甲酸根缓冲体系中，ｋ＝２．９８ｍｏｌ－１ｄｍ３·ｓｅｃ－１，ｂ＝１５４×１０２ｍｏｌ－２，ｄｍ６·ｓｅｃ－１，Ｋ３，４＝６．９２８×１０３；在乙酸－乙酸根缓冲体系中，ｋ＝３．４２ｍｏｌ－１·ｄｍ３·ｓｅｃ－１，ｂ＝２．２９×１０３ｍｏｌ－２·ｄｍ６·ｓｅｃ－１，Ｋ３，４＝６．９２８×１０３；在丙酸－丙酸根缓冲体系中，ｋ＝３．００ｍｏｌ－１·ｄｍ３·ｓｅｃ－１，ｂ＝５．９０×１０２ｍｏｌ－２·ｄｍ６·ｓｅｃ－１，Ｋ３，４＝７．００７×１０３；在丁酸－丁酸根缓冲体系中，ｋ＝３．１４ｍｏｌ－１·ｄｍ３·ｓｅｃ－１，ｂ＝３．７５×１０２ｍｏｌ－２·ｄｍ６·ｓｅｃ－１，Ｋ３，４＝６．９２１×１０３；讨论了有机酸根的碱性与?
Kinctics of the coordination reaction of tctrakis(N-carbomethoxymcthyl0-3-pyridyl)orphyrin with Cu(Ⅱ)ion have been studied in formatc.acetate,propionate and butyrate buffcr solution and in the rangeofpH 3-5 at 35.0±0.1℃ and an ionic strcngth of0。5mol/ L(KCl).The reaction is found to be first order for both Cu(Ⅱ)and porphyrin and tobe anion catalysis of organic acid.The effcct of concentration of catalyst and metal ion,andpH value of solution were discussed.The rate equation of the rcaction were expressed asd[CuP4+].dt=k{(1.0+b[A-1]/(1.0+b[A-])/1.0+K3,4[H+])}[Cu2+][P]T;where k=2.98mol-1.dm+3.scc-1,b=1.54×102mol-2dm6.sec-1,K3,4=6.928×102,for formate buffer system;k=3.42mol-1。dm sec-1 b= 229×102mol dm6 sec-1.K3,4= 5.409 ×103,for acetate system;k=300mol-1 dm3 sec-1,b=5.90×102mol-2 dm sec-1,K3,4=7.007×103,for propionatesystcm;k=3.14mol-1·dm3·sec-1,b=3.75 ×102mol-2·dm6·scc-1, K3,4= 6.921×103,forbutyrate system.The mechanism of the reaction were proposed.The deformation of the ring ofporphyrins is the general condition in the reaction.
出处
《无机化学学报》
CSCD
北大核心
1994年第3期227-233,共7页
Chinese Journal of Inorganic Chemistry
基金
国家自然科学基金
关键词
铜离子
卟啉
嵌入反应
反应动力学
chemical reaction kinetics incorporate reaction porphyrin copper(Ⅱ) ion
