• Journal of the Korean Chemical Society
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• v.35 no.6
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• pp.707-712
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• 1991

N'-phenyl-N-(2-chloroethyl)-N-aminourea has been prepared from N'-phenyl-N-(2-chloroethyl)-N-nitrosourea by means of the electrochemical reduction with the mercury pool electrolytic cell. In order to find out the optimum condition of the reaction, the voltammetric behaviors for N'-aryl-N-(2-chloroethyl)-N-nitrosourea derivatives have been investigated by the cyclic voltammetry and polarography. The peak potentials was shifted to the negative direction as the pH value of the solution decrease. The substituent effects of phenyl ring on the peak potential were not observed in this case. (5:3) EtOH/4 N-HCl mixed solution was employed for the electrolysis. The applied potential was -0.7 V vs. Ag/AgCl/4 N-HCl electrode. The number of electrons participated to the reduction process was 4, respectively. The product was identified by FT-IR, NMR, mass and/or elemental analysis data.

• Journal of the Korean Chemical Society
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• v.33 no.5
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• pp.496-503
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• 1989

The chemical behavior of trivalent lanthanide (Pr(III) and Yb(III)) and 2, 2, 6, 6-tetramethyl-3, 5-heptanedione(dipivaloylmethane) complexes was investigated by the use of direct current, differential pulse polarography and cyclic voltammetry. In this study, it was founded that the reduction of trivalent lanthanide complexes was observed by one electron transfer process at Epc = -0. 13 V and -0.80 V of Pr(III), and -0.02 V of Yb(III) vs. Ag-AgCl electrode. Also, it was founded that the treatment of DP and CV to the case of a first-order chemical equilibrium reaction preceding a reversible and irreversible one electron transfer reaction, (a >0. 5) the socalled ErCr electrode process. The equilibrium constant (lnK) obtained, of various solvents, these constant were founded to be increases with decreasing dielectric constant of the solvents. Plots of lnK for these reaction against ln(l/D) for the solvents was fairly straight lines, and the behavior of the heavier lanthanides was decreased equilibrium constant with increasing atomic number.

• Journal of the Korean Chemical Society
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• v.38 no.2
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• pp.136-145
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• 1994

Polymeric complexes such as M(Ⅱ)(PVPS)(SND), M(Ⅱ)(PVPS)(SOPD) have been prepared with monomeric complexes, M(Ⅱ)(SND) and M(Ⅱ)(SOPD)[M: Co(Ⅱ), Ni(Ⅱ), and Cu(Ⅱ)] and polymer PVPS. These complexes have been indentified by elemental analysis, spectroscopy, and T.G.A. From the results, it was found that M(Ⅱ)(PVPS)(SND), M(Ⅱ)(PVPS)(SOPD) complexes were penta-coordinated configuration. Electrochemical properties of these complexes studied by cyclic voltammetry and differential pulse polarography in 0.1 M TEAP-DMF solution at glassy carbon electrode. Co(Ⅱ)(PVPS)(SND) and Co(Ⅱ)(PVPS)(SOPD) showed irreversible two step reduction, such as Co(Ⅲ)/Co(Ⅱ) and Co(Ⅱ)/Co(Ⅰ), and Ni(Ⅱ)(PVPS)(SND), Ni(Ⅱ)(PVPS)(SOPD), Cu(Ⅱ)(PVPS)(SND), and Cu(Ⅱ)(PVPS)(SOPD) complexes showed irreversible one step reduction, such as Ni(Ⅱ)/Ni(Ⅰ) and Cu(Ⅱ)/Cu(Ⅰ), respectively.

• Journal of the Korean Chemical Society
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• v.35 no.4
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• pp.405-409
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• 1991

The electrochemical behaviors of copper-1-(2-thiazolylazo)-2-naphthol [Cu(II)-TAN] complex in acetonitrile (AN) solution have been investigated by the use of polarography, controlled potential coulometry and UV-Vis spectroscopy. Cu(II)-TAN complex exhibit three reduction waves at -0.91 V, -1.34 V and -1.65 V vs. S.C.E. in acetonitrile solution containing 5.0 ${\times}\;10^{-3}$M tetraethylammonium perchlorate. Every reduction wave is diffusion controlled. The first reduction wave is considerably reversible and this process is attributed to the formation of anion radical. The second reduction process to the dianion is followed by a chemical reaction producing a complex of hydrazo complex. The third reduction process produce Cu(Hg) amalgam and amine compound.

• Journal of the Korean Chemical Society
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• v.6 no.1
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• pp.10-13
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• 1962

Titanium in solution of EDTA (Ethylenediaminetetraacetic acid) yield well-defined, reversible polarographic waves. In this report, a polarographic method for rapid determination of titanium in the Korean ilmenite was proposed, This polarographic method is based on the measurement of polarogram in the supporting electrolyte of EDTA. As the pH is increased the wave become more irreversible the diffusion current are diminished, and the half wave potential become more negative. In spite of the complication arising from numerous titanium species, in 0.2 M of EDTA, pH 6.3, the titanium waves are reproducible and analytically useful. In this medium titanium ion give well-defined reduction wave, and the half wave potential were -0.61V vs S.C.E. at pH 6.3. At the same time, the wave had a linear relationship between the concentration of titanium ion and the wave height. The Korean ilmenites were analyzed by this method and satisfactory results were obtained.

• Journal of the Korean Chemical Society
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• v.33 no.2
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• pp.215-224
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• 1989

Electrochemical reductions of $trans-[Co(en)_2X_2](ClO_4)_n$ (where X is cyanide, nitrite, ammonia, and isothiocyanate) were investigated by cyclic voltammetry and polarography at mercury and glassy carbon electrode. $trans-[Co(en)_2(CN)_2]ClO_4$ was reduced to Co(II) complex followed by adsorption to the mercury electrode. Cyanide ion was not released from the reduced Co(II) complex but the cyanide and (en) were released after the reduction to metallic cobalt. The other complexes except $trans-[Co(en)_2(CN)_2]ClO_4$ were reduced to cobalt(II) complexes followed by release of monodendate ligand, and (en) was released at the reduction step to metallic cobalt. $trans-[Co(en)_2(NO_2)_2]ClO_4$ was reduced to cobalt(Ⅱ) complex, and $NO_2^-$ ion was released followed by electroreduction through ECE mechanism at pH 2. On glassy carbon electrode, all complexes of Co(III) were reduced to Co(II) complexes with irreversible one-electron diffusion controlled reaction in which (en) was not released at this step. Increasing absorption wave number of complexes caused to negative shift of peak potential.

• Analytical Science and Technology
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• v.7 no.3
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• pp.361-369
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• 1994

Voltammetric behavior of some light lanthanide ions($La^{3+}$, $Pr^{3+}$, $Nd^{3+}$, $Sm^{3+}$ and $Eu^{3+}$) in acetonitrile(AN) and dimethylformamide(DMF) has been investigated by direct current, differential pulse polarography and cyclic voltammetry. The reduction of $La^{3+}$, $Pr^{3+}$ and $Nd^{3+}$ in 0.1M TEAP proceeded directly to the metallic state through three-electron charge transfer of irreversible process where as $Sm^{3+}$ and $Eu^{3+}$ proceeded by charge transfer of two steps. As the results of the cyclic voltammetric investigation, the first step reduction of $Sm^{3+}$ and $Eu^{3+}$ were a quasireversible reaction, the second step reductions were an irreversible reaction. The cathodic peak currents of the differential pulse polarogram showed adsorptive properties at lower sweep rates and high concentrations of these metal ions. The peak potenital was shifted to a negative petential and the peak current decreased with the increase of percentage of water in AN. On the other hand, the peak potential was shifted to a positive potential and the peak current decreased with an increased percentage of water in DMF.

• Journal of the Korean Chemical Society
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• v.18 no.3
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• pp.202-209
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• 1974

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.

• Journal of the Korean Chemical Society
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• v.30 no.1
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• pp.51-56
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• 1986

Polarographic behavior of cadmium(II) and copper (II) complexes of 1,5-diphenylcarbohydrazide in dimethylsulfoxide have been investigated by the DC polarography. The reduction processes are estimated as follows; Cd(II)${\cdot}$DPH Complex$\frac{e^-}{(E_{\frac{1}{2}}=-0.12V)}$${\to}$Cd(I)${\cdot}$DPH Complex. Cd(I)${\cdot}$DPH Complex$\frac{e^-}{(E_{\frac{1}{2}}=-0.74V)}$${\to}$Cd(Hg) + nDPH. Cu(II)${\cdot}$DPH Complex$\frac{e^-}{(E_{\frac{1}{2}}=-0.44V)}$${\to}$Cu(I)${\cdot}$DPH Complex. Cu(I)${\cdot}$DPH Complex$\frac{e^-}{(E_{\frac{1}{2}}=-0.84V)}$${\to}$Cu(Hg) + nDPH. The limiting currents of all reduction wave are irreversible. The number of ligand and the dissociation constant for Cu(I)${\cdot}$1.5-diphenylcarbohydrazide complex were found to be 2 and 5.12 ${\times}10^{-8}$, respectively. All reduction waves of complexes are irreversible. Based on the experimental results, the polarographic reductions of complexes in dimethylsulfoxide solution occurred in two one-electron steps.

• Journal of the Korean Chemical Society
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• v.34 no.6
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• pp.561-568
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• 1990

Voltammetric behavior of some light lanthanide ions (La$^{3+}$, Pr$^{3+}$, Nd$^{3+}$, Sm$^{3+}$, and Eu$^{3+}$) in various supporting electrolytes has been investigated by several electrochemical techniques. The peak potentials and the peak currents, their dependency on the concentration, temperature and pH effects, the reversibility of the electrode reactions are described. The reduction of La$^{3+}$, Pr$^{3+}$ and Nd$^{3+}$ in 0.1 M lithium chloride proceeds by a three-electron change directly to the metallic state (Ln$^{3+}$ ＋ 3e- → Ln$^0$) and charge transfer is totally irreversible. However, the reduction of Sm$^{3+}$ in 0.1 M tetramethylammonium iodide and Eu$^{3+}$ in 0.1 M lithium chloride proceeds in two stages (Ln$^{3+}$ ＋ e- → Ln$^{2+}$ and Ln$^{2+}$ ＋ 2e- → Ln$^0$). At pH values lower than ca.4 the hydrated lanthanide species (Ln(OH)$^{2+}$) reduced before the lanthanide ions (Ln$^{3+}$) due to the catalytic effect of hydrogen ions, and peak current increase with in the order Eu$^{3+}$ < Sm$^{3+}$ < Nd$^{3+}$ < Pr$^{3+}$ < La$^{3+}$ in differential pulse polarography. Some representative plots of $i_{pc}V^{-1/2} (proportional to current function) vs. V show considerable influence of hydrogen ion/lanthanide ion concentration in cyclic voltammetry. It is shown that a reaction of lanthanide ions with proton and/or water and catalytic reaction is enhanced at lower pH and at decreased lanthanide ion concentration.