Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT) (방사성폐기물학회지)

Korean Radioactive Waste Society (한국방사성폐기물학회)
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Spectroscopic Studies on U(VI) Complex with 2,6-Dihydroxybenzoic acid as a Model Ligand of Humic Acid

분광학을 이용한 흄산의 모델 리간드인 2,6-Dihydroxybenzoic acid와 우라늄(VI)의 착물형성 반응에 관한 연구

  • Received : 2011.09.09
  • Accepted : 2011.12.27
  • Published : 2011.12.30
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Abstract

In this study the complex formation reactions between uranium(VI) and 2,6-dihydroxybenzoate (DHB) as a model ligand of humic acid were investigated by using UV-Vis spectrophotometry and time-resolved laser-induced fluorescence spectroscopy (TRLFS). The analysis of the spectrophotometric data, i.e., absorbance changes at the characteristic charge-transfer bands of the U(VI)-DHB complex, indicates that both 1:1 and 1:2 (U(VI):DHB) complexes occur as a result of dual equilibria and their distribution varies in a pH-dependent manner. The stepwise stability constants determined (log $K_1$ and log $K_2$) are $12.4{\pm}0.1$ and $11.4{\pm}0.1$. Further, the TRLFS study shows that DHB plays a role as a fluorescence quencher of U(VI) species. The presence of both a dynamic and static quenching process was identified for all U(VI) species examined, i.e., ${UO_2}^{2+}$, $(UO_2)_2{(OH)_2}^{2+}$, and $(UO_2)_3{(OH)_5}^+$. The fluorescence intensity and lifetimes of each species were measured from the time-resolved spectra at various ligand concentrations, and then analyzed based on Stern-Volmer equations. The static quenching constants (log $K_s$) obtained are $4.2{\pm}0.1$, $4.3{\pm}0.1$, and $4.34{\pm}0.08$ for ${UO_2}^{2+}$, $(UO_2)_2{(OH)_2}^{2+}$, and $(UO_2)_3{(OH)_5}^+$, respectively. The results of Stern-Volmer analysis suggest that both mono- and bi-dentate U(VI)-DHB complexes serve as groundstate complexes inducing static quenching.

UV-Vis 분광광도법과 시간분해 레이저 유도 형광분광법(TRLFS)을 이용하여 흄산의 모사 리간드로 사용한 2,6-Dihydroxybenzoate(DHB)와 U(VI)의 착물형성반응을 조사하였다. U(VI)-DHB 착물 고유의 전하이동 흡수 스펙트럼을 분석한 결과, 착물형성반응은 우라늄-리간드 비가 1:1 또는 1:2 착물을 형성하는 이중 평형반응이며, 산도에 따라 착물종의 분포가 변한다는 것을 밝혔다. 계산된 착물형성상수 (log $K_1$ and log $K_2$)는 $12.4{\pm}0.1$과 $11.4{\pm}0.1$이다. 이에 더하여, TRLFS 방법으로 조사한 결과, DHB는 U(VI) 화학종들의 형광 소광제(quencher)로서 역할을 한다는 것을 확인하였다. 특히, 확인된 U(VI) 화학종 모두(${UO_2}^{2+}$, $(UO_2)_2{(OH)_2}^{2+}$과 $(UO_2)_3(OH)_5{^+})$에서 정적 (static) 및 동적 (dynamic) 소광작용이 공존하는 것으로 관찰되었다. 시간분해 형광 스펙트럼으로부터 리간드 농도에 따른 U(VI) 화학종의 형광세기와 형광수명을 측정하였으며, Stern-Volmer 식을 이용하여 분석하였다. 결정된 정적소광계수(KS)는 ${UO_2}^{2+}$, $(UO_2)_2{(OH)_2}^{2+}$ 과 $(UO_2)_3(OH)_5+$에 대하여 각각 $4.2{\pm}0.1$, $4.3{\pm}0.1$ 과 $4.34{\pm}0.08$이다. Stern-Volmer 식을 이용한 분석 결과, 단일 또는 이중 배위자 구조(mono- and bi-dentate)의 U(VI)-DHB 착물이 모두 정적소광효과에 관여하는 바닥상태 착물임을 확인하였다.

Keywords

References

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