ゼフィラミンの存在におけるアルミニウムおよび銅のクロムアズロールS錯体の吸光光度法による検討

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The complex formation reactions of Chromazurol S (CAS, H4L) with aluminum or copper in the presence of zephiramine (ZCl) were studied by spectrophotometry. As the acid dissociations of CAS were effected by the concentration of zephiramine and the reactions between CAS and zephiramine were not stoichiometric, zephiramine was omitted from the chemical equations. An excessive CAS and aluminum formed a 1:2 acidic complex, Al(HLZ)-2, (the absorption maximum at 620nm) below pH 5.1 and a 1:3 complex, Al(LZ2)33- (the absorption maximum at 610nm) above pH 5.2 in the presence of zephiramine, whereas they formed AlL25- and AlL39- in the absence of zephiramine. Consequently, the 1:2 acidic complex of CAS with aluminum was possibly formed by an action of zephiramine. However, an excessive CAS with copper formed a 1:2 acidic complex, Cu (HLZ2)2, (the absorption maximum at 620nm), which has different structure from that of aluminum both in the presence and absence of zephiramine. The absorbance of the 1:2 acidic complexes of CAS such as Al (HLZ)-2 and Cu(HLZ2)2, was very much enhanced by an action of micelle of zephiramine having a positive charge. Thus their molar absorptivity was 1.08×105 and 1.40×105, respectively. Only the absorption spectrum of H2LZ2 which has unsymmetrical distribution of charge in CAS was shifted in the presence of zephiramine, hence we considered that the absorption of the 1:2 acidic complexes of CAS which have the same structure as H2LZ2 was also shifted largely by the micelle having a positive charge. Since the 1:2 acidic complexes showed the highest absorbances in the presence of zephiramine among that of CAS, they were applied to the determination of aluminum and copper. The calibration cruves obey Beer's law for 0.010.3ppm of aluminum in solutions containing 3.4×10-4M CAS and 2.72×10-3M zephiramine and at pH 4.55.1 and for 0.0250.6ppm of copper solutions containing 1.7×10-3M CAS and 4.35×10-3M zephiramine and at pH7 where the formation of the 1:2 acidic complex of the metal ion with CAS was concluded, respectively.
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ゼフィラミンの存在におけるアルミニウムおよび銅のクロムアズロールS錯体の吸光光度法による検討

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