4(2-吡啶偶氮)间苯二酚对钪(Ⅲ)与四-(4-三甲胺基苯基)卟啉显色反应催化机理的研究
STUDY OF THE CATALYTIC EFFECT OF 4-(PYRIDYLAZO)-RESORCINOL ON THE CHROMOGENIC REACTION OF SCANDIUM(Ⅲ) WITH T-(4-TMAP) P
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摘要: 在沸水加热的条件下,在pH 7.6的硼砂-盐酸缓冲介质中,单偶氮试剂PAR能加速Sc(Ⅲ)与四-(4-三甲胺基苯基)卟啉(TAPP)的反应,反应重现性好,配合物稳定,配合物组成为1∶2,配合物稳定常数为3.1×106,最大吸收波长位于421 nm,表观摩尔吸光系数为7.94×106L·mol-1·cm-1,Sc(Ⅲ)含量在0-0.04 μg/10 mL范围内服从比耳定律.将拟定的方法应用于钛白粉中钪的测定,并测得回收率在92.0%-97.5%之间,初步探讨了催化反应的可能机理,认为:① Sc(Ⅲ)与PAR先形成活性的中间络合物,改变了溶液条件使与卟啉的反应易于进行;② 带负电荷的PAR与带正电荷的卟啉之间形成缔合物使卟吩环变形,从而使与Sc(Ⅲ)的反应易于进行.Abstract: It was found that by the addition of a definite amount of 4-(pyridylazo)-resorcinol (PAR),the chromogenic reaction of Sc(Ⅲ) with T-(4-TMAP) P was catalyzed and gone to completion in a borate buffer medium of pH 7.6 and when heated in a boiling water bath.The absorption maximum of the complex was found at 421 nm.The apparent molar absorptivity (ε421) was found to be 7.94×106L·mol-1·cm-1,and the linearity range was in the range of 0 to 0.04 μg per 10 mL of solution.The composition ratio Sc∶T-(4-TMAP) P was found as 1 to 2.After completion of color reaction,no significant change in absorbance of the colored complex was observed in 3 h.The stability constant of the complex was determined and a value of 3.1×106(k) was obtained.In the analysis of a titania sample,recovery test for scandium was made by standard addition method,and results obtained were in the range from 92.0% to 97.5%.The mechanism of the catalytic effect of PAR was studied and conclusion was drawn priliminarily as follows: ① an active intermediate complex was formed between Sc(Ⅲ) and PAR,which made a change of the solution condition and made it easier to replace the proton from the porphrin ring;② an ion-association complex was formed between the negatively charged PAR and the positively charged T-(4-TMAP) P,leading to a distortion of the porphrin ring and making it easier to react with the active intermediate complex of scandium.