• Journal of the Korean Electrochemical Society
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• v.15 no.4
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• pp.256-263
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• 2012

This study was performed to investigate the separation of cesium cations by using an electrochemical ion exchanger of nickel hexacyanoferrate($KNiFe(CN)_6$) film electrode. Potential, current, and charge passing through the cyclic voltammograms were measured in singular and binary solutions of 1.0M $NaNO_3$ and 1.0M $CsNO_3$. Before and after each experiment, the structural morphology and atomic composition of $KNiFe(CN)_6$ were analyzed by SEM and EDS, respectively. The ion selectivity of $KNiFe(CN)_6$ was also observed by the voltammograms and atomic compositions measured in the solution alternated between sodium and cesium. As the result of this study, it was found that the electrically switched $KNiFe(CN)_6$ ion exchanger had the significant advantage of 40 times or longer durability than conventional organic or inorganic ion exchanger. It was also shown that the $KNiFe(CN)_6$ ion exchanger had high selectivity for cesium over sodium.

• Journal of the Korean Chemical Society
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• v.31 no.4
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• pp.334-343
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• 1987

The Chemical reactions between $NiL_m{^{2+}}\{$Ni(rac-1[14]7-diene)^{2+},\;Ni(meso-1[14]7-diene)^{2+},\;Ni(1[14]4-diene)^{2+},\;{\alpha}-Ni(rac-[14]-decane)^{2+},\;{\beta}-Ni(rac-[14]-decane)^{2+},\;and\;Ni(meso-[14]-decane)^{2+}$}\and\ CN^-$ ion were studied by the spectrophotometric method. The equilibrium constants (K_1$) for the 1:1 complex ion, $[NiL_m(CN)]^+\;with\;NiL_m{^{2+}}\;and\;CN^-$ ion were determined in the range of 3 to $25^{\circ}C$. The $K_1\;for\;Ni(rac-1[14]7-diene)^{2+},\;Ni(meso-1[14]7-diene)^{2+},\;Ni(1[14]4-diene)^{2+},\;{\alpha}-Ni(rac-[14]-decane)^{2+},\;{beta}-Ni(rac-[14]-decane)^{2+},\;and\;Ni(meso-[14]-decane)^{2+}\;at\;15^{\circ}C$ was 4.7, 5.3, 6.2, 7.5, 9.4, and 9.8, respectively. The values of $K_1$ decreased with increasing temperature. From the temperature effect on equilibrium constant ($K_1$), thermodynamic parameters $({\Delta}H^{\circ},\;{\Delta}S^{\circ},\;{\Delta}G^{\circ})$ for reaction were evaluated and the reaction of $NiL_m{^{2+}}\;and\;CN^-$ ion was exothermic. $NiL_m{^{2+}\;reacts\;with\;CN^-$ ion to give $Ni(CN)_4{^{2-}}$ ion and macrocyclic ligand $(L_m)$. The kinetics of formation of the $Ni(CN)_4{^{2-}}$ ion of varying the $[CN^-],\;[HCN],\;and\;[OH^-]$ have been investigated at 3∼$25^{\circ}C\;and\;0.5M\;NaClO_4$. Maintaining a constant $[CN^-],\;k_{obs}/[CN^-]^2$ increases linearly with increasing [HCN]. In the presence of large quantities of $[OH^-],\;k_{obs}/[CN^-]^2$ also increases linearly with $[OH^-]$. From the temperature effect on kinetic constant (k_{obs})$, parameter of activation $({\Delta}H^{\neq},\;{\Delta}S^{\neq})$ of reaction of $NiL_m{^{2+}}\;with\;CN^-$ ion were determined. For the $Ni(rac-1[14]7-diene)^{2+},\;Ni(meso-1[14]7-diene)^{2+},\;{\alpha}-Ni(rac-[14]-decane)^{2+},\;{\beta}-Ni(rac-[14]-decane)^{2+},\;and\;Ni(meso-[14]-decane)^{2+}\;series\;{\Delta}H^{\neq}$ gradually decrease as the d-d transition energy, $ν(cm^{-1})$ decrease. And the reaction of the five $NiL_m{^{2+}}\;with\;CN^-$ ion take place by way of equal paths.

• Journal of Surface Science and Engineering
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• v.29 no.5
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• pp.556-562
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• 1996

Carbon nitride (CN) films were synthesized on silicon substrates by a combined ion-beam and laser-ablation method under various conditions; ion-beam energy and ion-beam current were varied. Raman spectroscopy and spectroscopic ellipsometry (SE) were employed to characterize respectively the structural and the optical properties of the CN films. Raman spectra show that all the CN films are amorphous independent of the ion-beam current and the ion-beam energy. Refractive indices, extinction coefficients and optical band gaps which were determined from the measured SE spectra exhibit a significant dependence on the synthesis conditions. Especially, the decrease of the refractive indices and the shrinkage of the optical band gap is noticeable as the ion-beam current and/or the ion-beam energy increase.

• Journal of the Korean Chemical Society
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• v.29 no.1
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• pp.38-44
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• 1985

Photoreaction path for the monocyanochromium (Ⅲ) ion was inferred from the experimentally observed product ratio and theoretical analysis. The angular overlap model was used to analyze the d-orbital of various intermediates along a selected reaction coordinate and to determine quartet state energy level. A loss of equatorial ammine leads to pentacoordinated square pyramid with CN- ligand in an equatorial position. The SP(CNeq) intermediate undergoes a rearrangement by the N-Cr-CN bending. This process leads to a trigonal bipyramidal intermediate in which the CN- ligand is located in equatorial position. The subsequent association with a solvent molecule should probably proceed by lateral attack an one edge of the equatorial triangle. The assumption adopted above was consistent with experimental results.

• Analytical Science and Technology
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• v.25 no.3
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• pp.159-163
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• 2012

A spectrofluorimetric method has been developed for the determination of free $CN^-$ in real samples with fluorescent safranine-O. When safranine-O interacts electrostatistically with $CN^-$, the fluorescent intensity of safranine-O is decreased. Several experimental conditions such as pH of the sample solution and the amount of safranine-O were optimized. $Ag^+$ interfered higher than any other ions. Interference of $Ag^+$ could be disregarded because $Ag^+$ was scarcely contained or mostly complexed with $CN^-$ in selected real samples. With this proposed method, the linear range of $CN^-$ was from 5.0 to 110 ng/mL and the detection limit of $CN^-$ was 2.9 ng/mL. For validating this technique, real samples (Cu, Ag, Au electroplating wastewater, and untreated wastewater in university and in sewage treatment plant) were used. Recovery yields of 91.5%~106.0% were obtained. Based on experimental results, it is proposed that this technique can be applied to the practical determination of free $CN^-$.

• Journal of the Korean Electrochemical Society
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• v.23 no.1
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• pp.11-17
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• 2020

The Prussian blue analogues of Fe₂(CN)₆ and Na_xFe₂(CN)₆ are prepared by precipitation method and evaluated the electrochemical characteristics as positive electrode materials for lithium-ion batteries (LIBs) because of their low cost. Fe₂(CN)₆ shows a low reversible capacity of 34.6 mAh g^-1, whereas sodium-containing Na_xFe₂(CN)₆ exhibits a reversible capacity of 107.5 mAh g^-1 when the discharge process proceeds first. When charging is first carried out to remove sodium in the structure, the reversible capacity of 114.1 mAh g^-1 is achieved and the cycle performance is further improved. In addition, Na_x-Fe₂(CN)₆ is synthesized at 0℃, room temperature (RT), and 60℃, respectively. Regardless of the synthesis temperature, Na_xFe₂(CN)₆ shows similar initial reversible capacity, but the crystallite size is formed smaller and improved cycle performance when synthetic temperature is lower. The sample synthesized at 0℃ shows a reversible capacity of 86.4 mAh g^-1 at the 120^th cycle and maintains 76.8% of the initial capacity.

• Journal of the Korean Chemical Society
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• v.47 no.6
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• pp.547-552
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• 2003

Separation and determinations of Co(II) and Ni(II) ions as their 4-(2-pyridylazo)resorcinol(PAR) chelates by reversed-phase capillary high-performance liquid chromatography(RP-CpHPLC) were performed. Among many capillary columns, Vydac C4 column was selected and acetonitrile solution was used as mobile phase. The effect of pH and MeCN concentration(%) on the retention factor, k and peak intensity was examined and discussed. As a results, it was found that 22.5% MeCN and pH 5.60 was adequate as mobile phase for the separation of the two metal ions and determination of Co(II) ion, but the mobile phase condition for Ni(II) ion determination was 22.5% MeCN of pH 7.20. Detection limit(D.L., S/N=3) of Co(II) and Ni(II) ions were $2.0{\times}10{-7}$ M(14.9 ppb) and $1.0{\times}10{-6}$ M(59.2 ppb), respectively.

• Bulletin of the Korean Chemical Society
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• v.24 no.12
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• pp.1781-1784
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• 2003

Determination of Co(II) ion as a 4-(2-thiazolylazo)resorcinol(TAR) or 5-methyl-4-(2-thiazolylazo)resorcinol(5MTAR) chelate was accomplished by reversed-phase capillary high-performance liquid chromatography (RP-Capillary-HPLC) using a Vydac $C_4$ column and MeCN-water mixture as mobile phase. The effect of change in pH and MeCN percentage of the mobile phase on the retention factor, k and peak intensity were evaluated. It was found that 30% MeCN (v/v) of pH 5.60 or 7.20 was adequate as mobile phase when TAR or 5MTAR is used. Detection limit (D.L., S/N=3) in each case was $2.0\;{\times}\;10^{-7}$M (11.8 ppb) and $3.0\;{\times}\;10^{-7}$ M (17.7 ppb). The Co(II) ion in mineral and waste water was determined with the optimum column and mobile phase.

• Journal of the Korean Chemical Society
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• v.36 no.3
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• pp.405-411
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• 1992

The substitution reaction and structrue of products obtained from the reaction of Equatorial-Skew-[Co(TRDTRA)($OH_2$)] (TRDTRA = trimethylenediaminetriacetate) with $CN^-, NO^{-}_{2}$ and $NCS^-$ ions have been investigated by means of electronic absorption spectroscopy and theoretical calculation based on the Yamatera's theory. According to kinetic data, the substitution reaction order for the complexes such as $CN^-, NO^{-}_{2}$ and $NCS^-$ was the first order, respectively, and overall reaction order was second order. It has been determined that the structure of products having $CN^{-} and NO^{-}_{2}$ ions was Polar-Chair type complexes which were accompanying with isomerization and having $NCS^-$ ion was Equatorial-Skew type complex which was not accompanying with isomerization.

• Journal of the Korean Chemical Society
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• v.9 no.2
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• pp.67-70
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• 1965

Polarographic studies of reduction of Ni(Ⅱ)-CN complex on Hg-electrode have indicated that $Ni(CN)_4^{2-}$ is reduced by two paths, via one electron process Ni(CN)42- + e [1]↔[2] Ni(CN)43- =(eq) Ni(CN)2- + 2CN- and via two electron process Ni(CN)42- + 2e [3]→ 1/2[Ni(CN)33-]2 + CN- of which reduction [1] must be faster than reduction [3]. At very dilute cyanide concentration (0.004 to 0.01 M) cathodic wave is practically responsible for reaction [1] and two cyanide ions appear to contribute to the reaction. As increasing cyanide ion concentration the rate of oxidation reaction [2] catalysed by Hg increases and reaction [1] and [2] approach to equilibrium. Therefore, reaction [3] represents the cathodic wave at high concentration of cyanide (above 0.2 M). This mechanism can also explain the fact that limiting current at $[CN^-]$ = 8 M is approximately twice of that at 0.004 M CN.