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아세토니트릴에서 구리와 카드뮴의 2,2'-Bipyridine과 Ethylenediamine 착물에 대한 폴라로그래프적 연구
박두원,이흥락,배준웅,Park, Du Won,Lee Heung Lark,Bae Zun Ung 대한화학회 1974 대한화학회지 Vol.18 No.3
Polarographic behaviors of copper and cadmium complexes with 2,2'-bipyridine and ethylenediamine in acetonitrile have been investigated by the DC and AC polarography. The reduction processes are estimated as follows; $Cu(II)-bipy. \;complex\;{\longrightarrow^{e^-}_{E_{1/2}\risingdotseq+0.1V}}\;Cu(I)-bipy.\;complex\;{\longrightarrow^{e^-}_{E_{1/2}=-0.43V}}\;Cu(Hg)$$Cu(II)-en.\;complex\;{\longrightarrow^{e^-}}\;Cu(I)-en.\;complex\;{times}\;{\longrightarrow^{e^-}_{E_{1/2}=-0.56V}}\;Cu(Hg)$$Cu(II)-bipy. \;complex\;{\longrightarrow^{e^-}_{E_{1/2}=-0.57V}}\;Cu(I)-bipy.\;complex\;{\longrightarrow^{2e^-}_{E_{1/2}=-0.97V}}\;Cd(I)-bipy\;complex$$Cu(II)-en.\;complex\;{\longrightarrow^{e^-}_{E_{1/2}=+0.05V}\;Cu(I)-en.\;complex{\longrightarrow^{e^-}_{E_{1/2}=-0.92V}}\;Cu(Hg)$ The limiting currents of all steps are controlled by diffusion. The number of ligand and the dissociation constant for Cu(Ⅰ)-bipy. complex were found to be n = 2 and $K_d=(1.5{\pm}0.1){\times}10^{-7}$, respectively. 물 아닌 용매 아세토니트릴에서 구리와 카드뮴의 2,2´-비피리딘(bipy.)과 에틸렌디아민(en.) 착물의 성질의 직류와 교류폴라로그래프로 조사한 결과 각 착물의 전극과정은 아래와 같이 생각된다. $Cu(II)-bipy. \;complex\;{\longrightarrow^{e^-}_{E_{1/2}\risingdotseq+0.1V}}\;Cu(I)-bipy.\;complex\;{\longrightarrow^{e^-}_{E_{1/2}=-0.43V}}\;Cu(Hg)$$Cu(II)-en.\;complex\;{\longrightarrow^{e^-}}\;Cu(I)-en.\;complex\;{times}\;{\longrightarrow^{e^-}_{E_{1/2}=-0.56V}}\;Cu(Hg)$$Cu(II)-bipy. \;complex\;{\longrightarrow^{e^-}_{E_{1/2}=-0.57V}}\;Cu(I)-bipy.\;complex\;{\longrightarrow^{2e^-}_{E_{1/2}=-0.97V}}\;Cd(I)-bipy\;complex$$Cu(II)-en.\;complex\;{\longrightarrow^{e^-}_{E_{1/2}=+0.05V}\;Cu(I)-en.\;complex{\longrightarrow^{e^-}_{E_{1/2}=-0.92V}}\;Cu(Hg)$이상의 모든 파는 학산에만 의존한다. 또 Cu(Ⅰ)-bipy. 착물의 리간드의 수는 2이며, 착물해리상수 $K_d=(1.5{\pm}0.1){\times}10^{-7}$이었다.