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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 31, Number 3
JKCSEZ 31(3)
June 20, 1987 

 
Title
Redox Reaction Mechanisms of Thorium (Ⅳ) Complexes with Crown Ethers in Dimethylsulfoxide

디메틸술폭시드용매중에서 Thorium (Ⅳ)-Crown Ether 착물의 산화-환원 반응메카니즘
Author
Hak-Jin Jung, Oh-Jin Jung, Hyouck-Choon Suh

정학진, 정오진, 서혁춘
Keywords
Abstract
DMSO와 H2O용매 중에서 결합구조가 밝혀진 동공의 크기를 달리한 토륨(Ⅳ) 착물들의 전기전도도를 측정하여 해리현상과 전해질의 행동을 알아 보고 DMSO용매중에서 polarography와 cyclic voltammography적 거동을 조사하여 합성착물의 산화환원반응 메카니즘, 가역성을 알아 보고 환원과정에 관여하는 전자수 및 착물의 확산계수를 계산하였다. 그 결과 반양성자성 용매에서 모든 착물들은 1:1전해질로, 물에서는 1:4전해질로 각각 행동하고, DMSO용매중에서 각 착물의 환원반응은 1전자 1단계의 환원반응으로 가역적이며 확산계수는 착물종에 따라 5.831 × 10-6∼6.900 × 10-6이었다. 그리고 모든 착물의 물분자는 -1.8V(대조전극, SCE)이상에서 분해를 일으켜 수소기체를 발생한다.

The electrical conductances for the thorium (Ⅳ) complexes with crown ethers have been measured in DMSO, and water solvents, and the oxidation-reduction reaction mechanisms, electron number and diffusion coefficients in the reversible reduction process have been examined by polarography and cyclic voltammography. The dissociation mole ratio of Th4+ and nitrate ion are 1:1 and in aprotic solvent, and 1:4 in protic solvent like as water. The limiting molar conductances of all complexes in aprotic solvent have been found to be in the range of 92.2∼159 ohm-1cm2mol-1. In aprotic solvent, DMSO, the reduction of each complex is reversible by one electron reduction of one step, and the range of diffusion coefficients is observed to be 5.83 × 10-6∼6.90 × 10-6. The complexes which have reduction step were hydrolyzed above at 1.8volt with reference saturated calomel electrode, generating the hydrogen gas. The reaction mechanisms of thorium (Ⅳ)-crown ether complexes appear as follows. Thm(Ⅳ)Ln(H2O)x(NO3)4y DMSO= Thm(Ⅳ)Ln(H2O)x(NO3)4y-1+ + NO3- Thm(Ⅳ)Ln(H2O)x(NO3)y-1 + e-↔E1/2 = -1.44∼1.49V [Thm(Ⅲ)Ln(H2O)x](NO3)y-1 [Thm(Ⅲ)Ln(H2O)x](NO3)y-1 ↔ Thm(Ⅲ)Ln(OH)x(NO3)y-x-1 + xNO3- + H+ xH+ e-↔E = - 1.8V (x/2)H2

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