Effects of two-phase reactions on composition and potential response of zirconium(IV)-tetraphenylporphyrin complexes as carrier for citrate-selective electrode

Analytical Chemistry
Hiroyuki HattoriAkio Yuchi

Abstract

The reactions between zirconium(IV)-tetraphenylporphyrin(tpp)-hydroxide complexes ([ZrIV2(OH)4(tpp)2] and [ZrIV(OH)2(tpp)]) in chlorobenzene and various acids (HX: HClO4, HCl, HNO3, CH3COOH) in water were studied. Three species [ZrIV2(OH)3(tpp)2],X, [ZrIV(OH)X(tpp)], and [ZrIVX2(tpp)] were identified, and their stability constants were determined. The extent of formation of each species depends on the coordination ability and lipophilicity of X-. The performance of these complexes was evaluated as a carrier of an anion-selective electrode. The cationic complex [ZrIV2(OH)3(tpp)2],X exhibited selectivity following the Hofmeister series to weakly coordinating anions, while showing a super-Nernstian response to strongly coordinating citrates. The latter suggests the cleavage of the dimeric structure. The dichloro complex [ZrIVCl2(tpp)] was prone to hydrolyze in contact with an aqueous solution and gave drifting potentials. The monochloro complex [ZrIV(OH)Cl(tpp)] was more stable and strongly responded to acetates, which may be ascribed to substitution of a weakly bound chloride. A slow hydrolysis giving [ZrIV(OH)2(tpp)], however, caused gradual deterioration of this strong response to acetates. Conditioning of the membrane in 1 M H...Continue Reading

Citations

Jan 15, 2014·Analytical Sciences : the International Journal of the Japan Society for Analytical Chemistry·Akio Yuchi
Dec 12, 2017·Analytical Sciences : the International Journal of the Japan Society for Analytical Chemistry·Takuya DoiAkio Yuchi
Oct 22, 2016·Chemistry : a European Journal·Oriana BreaJosé Elguero
May 23, 2015·Chemical Reviews·Nathalie BusschaertPhilip A Gale
Mar 8, 2017·Analytical Chemistry·Yuma YagiAkio Yuchi
Jul 13, 2006·The Journal of Physical Chemistry. a·Ying ZhangKe An Li
Jun 15, 2006·Analytical Chemistry·Eric Bakker, Yu Qin

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