Acidic Polyol-Boric Acid Complex Chemistry and Its Application to Boron Analysis

作者:Shao, Chaoying*; Miyazaki, Yoshinobu; Matsuoka, Shiro; Takehara, Ko; Fujimori, Takao; Yoshimura, Kazuhisa
来源:Bunseki Kagaku, 2012, 61(3): 177-184.
DOI:10.2116/bunsekikagaku.61.177

摘要

B-11 NMR measurements showed that boric acid reacts with the polyol compounds, chromotropic acid, Tiron and 2,3-dihydroxynaphthalene-6-sulfonate, to form complexes with 1 : 1 and 1 : 2 stoichiometries. The equilibria of the complexation depend on the pH in the solution. The 1 : 2 complex is formed in an acidic or a neutral solution, while the 1 : 1 complex occurs in a higher pH range. Kinetic studies revealed that the reaction of 1 : 1 complex formation is much faster than that of 1 : 2 complex formation. A proton catalyzes both the reactions of 1 : 2 complex formation and its decomposition. On the basis of equilibrium and kinetic information, a novel method of on-line absorptiometric determination for trace amounts of boron was developed using a chromotropic acid presorbed anion-exchange column. On-line reaction and separation were achieved by controlling the pH conditions in solutions to accelerate 1 : 2 complex formation in the concentration process at pH 3 and to stabilize the complex in the separation process at pH 8. The 1 : 2 complex was satisfactorily separated from excess free ligand and matrix components by changing the concentration of NaClO4 in the eluent; its peak height on a chromatogram monitored at 350 nm was used for boron determination. The sensitivity could be enhanced by increasing the sample amount introduced, and the detection limit (3 sigma) was 0.05 mu g dm(-3) of boron when 13.4 cm(3) of the sample was used. The method has been successfully applied to the determination of trace boron in river water, ion-exchanged water and steels. Based on the electrochemical activities of respective species in the boron-chromotropic acid and boron-Tiron systems, methods for monitoring the boron concentration in RO desalination processes were also proposed.

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