• Journal of the Korean Chemical Society
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• v.34 no.5
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• pp.460-464
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• 1990

Proton behavior was investgated for the redox reaction of trans-[$Co(en)_2(NO_2)Cl]^+$ with aqueous Fe(II) in acidic solution by UV/vis-spectrophotometric method. The reaction order of proton is first one and the rate constant(k$_H^+$) is 6.7 ${\times}\;10^{-1}L^2/mol^2{\cdot}min$. The values of $E_a$, ${\{Delta}H^{\neq}$, ${\{Delta}S^{\neq}$ are 14.5 Kcal/mol, 13.8 Kcal/mol and -18.3e.u., respectively. As the result of analysis of kinetic data, it has been found that this reaction proceeds through inner-sphere mechanism.

• Analytical Science and Technology
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• v.10 no.6
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• pp.427-432
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• 1997

A selective method for the determination of iron(III) ion with a sodium dodecyl sulfate(SDS) modified glassy carbon electrode was proposed. It was based on the electrostatic attraction and complexation of the SDS modifier, $(DS^-)_n-Fe^{3+}$. The determination of iron(III) ion was performed by a differential pulse voltammetry(DPV), and the reduction peak potential of $(DS^-)_n-Fe^{3+}$ was +0.466(${\pm}0.002$)V vs. Ag/AgCl. For the determination of iron(III) ion, a linear calibration curve was obtained within the iron(III) ion concentration range of $0.50{\times}10^{-5}{\sim}10{\times}10^{-5}mol/L$, and the detection limit was $0.14{\times}10^{-5}mol/L$. $Cu^{2+}$, $Ni^{2+}$, $Co^{2+}$, $Pb^{2+}$, $Zn^{2+}$, and $Mn^{2+}$ showed little or no effect on the determination of iron(III) ion, respectively. But, ion such as each $CN^- $ and $SCN^-$ interfered seriously.

• Journal of the Korean Chemical Society
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• v.26 no.5
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• pp.304-309
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• 1982

The fluorescence yields of chl-a and-b complexes bound to silicon dimer, tetramer and hexamer containing pyridine group in diethyl ether solvent, were shown the transition of excited energy through silicon polymer chain, and the maximum energy quenching were appeared at 1 : 1 ratio of chl-a and pyridine group in silicon polymer but the chl-b complexes were shown the maximum energy of fluorescene emission at the same ratio.

• Journal of the Korean Chemical Society
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• v.32 no.4
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• pp.318-322
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• 1988

We studied the aquation reaction of s-cis-$[Co(eee)Cl_2]^+$ and s-cis-$[Co(eee)Br_2]^+$ complex ions under the various temperatures and pressures. In these complexes eee is $NH_2-CH_2CH_2-S-CH_2CH_2-NH_2$. The rate law of the aquation reactions of these two complexes obeys $Rate = k_{obsd}$[CO(III)], where rate constants of s-cis-$Co(eee)Cl_2]^+$ and s-cis-$[Co(eee)Br_2]^+$ respectively are $0.687{\times}10^{-4}$ $sec^{-1}$ and $4.10{\times}10^{-4}$ $sec^{-1}$ in condition of 0.1M $HClO_4\;and\;40^{\circ}C$. In the same condition, the activation entropies of s-cis-[Co(eee)$Cl_2$]+ and s-cis-(Co(eee)Br_2$]+ complexes respectively are -15.5 eu and -7.54eu, and the activation volumes are $-4.6cm^3mole^{-1}$ and $-4.2cm^3mole^{-1}$. From these data, we could infer the mechanism of the aquation reaction as the interchange dissociation (Id) mechanism.

• Journal of the Korean Chemical Society
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• v.33 no.3
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• pp.273-280
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• 1989

The spectra of the $Co^{II}CyDTA$(CyDTA: cyclohexyldiaminetetraacetic acid) complex have been measured in aqueous solution of pH = 6-13.2. The red shift of the spectrum in the more basic solution was ascribed to the transformation of $CoCyDTA^{2-}$ into $CoCyDTA(OH)^{3-}$. The equilibrium constant, $K_{OH} = [CoCyDTA(OH)^{3-}]/[CoCyDTA^{2-}][OH^-]$ was $75M^{-1}$ at $40^{\circ}C$. The electron transfer reactions of $CoCyDTA^{2-}$ and $CoCyDTA(OH)^{3-}$ with $Fe(CN)_6^{3-}$ have been studied using spectrophotometric technique in the range of pH applied to the determination of equilibrium constant. The pseudo first-order rate constants observed ($k_{obs}$) were not changed upto pH = 10.8, but increased with increasing pH in the range of pH = $10.8{\sim}13.0$. The rate law reduced in the range of pH = 6-13 was $k_{obs} = (k_3[CoCyDTA^{2-}] + k_4[CoCyDTA(OH)^{3-}])/(1+K_1[CoCyDTA^{2-}])$. The rate constants of the reactions (3a) and (3b), $k_3$ and $k_4$ respectively have been determined to be 0.529 and $4.500M^{-1}sec^{-1}$ at $40^{\circ}C$. The activation entropies (147{\pm}1.1JK^{-1} mol^{-1}$ at pH = 10.8) and activation volumes $(6.25cm^3mol^{-1}, pH = 10.8)$ increased with increasing pH, while the activation enthalpy (12.44 ${\pm}$ 0.20 kcal/mole) was independent of pH. Using the pH effect on the rate constants, the activation entropies and the activation volumes, the mechanism of the electron transfer reaction for $Co^{II}-Fe^{III}$ system was discussed.

• Economic and Environmental Geology
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• v.56 no.6
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• pp.847-870
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• 2023

The safe disposal of high-level radioactive waste requires accurate predictions of the long-term geochemical behavior of radionuclides. To achieve this, the present study was conducted to model geochemical behaviors of uranium (U), plutonium (Pu), and palladium (Pd) under different hydrogeochemical conditions that represent deep groundwater in Korea. Geochemical modeling was performed for five types of South Korean deep groundwater environment: high-TDS saline groundwater (G1), low-pH CO₂-rich groundwater (G2), high-pH alkaline groundwater (G3), sulfate-rich groundwater (G4), and dilute (fresh) groundwater (G5). Under the pH and Eh (redox potential) ranges of 3 to 12 and ±0.2 V, respectively, the solubility and speciation of U, Pu, and Pd in deep groundwater were predicted. The result reveals that U(IV) exhibits high solubility within the neutral to alkaline pH range, even in reducing environment with Eh down to -0.2 V. Such high solubility of U is primarily attributed to the formation of Ca-U-CO₃ complexes, which is important in both G2 located along fault zones and G3 occurring in granitic bedrocks. On the other hand, the solubility of Pu is found to be highly dependent on pH, with the lowest solubility in neutral to alkaline conditions. The predominant species are Pu(IV) and Pu(III) and their removal is predicted to occur by sorption. Considering the migration by colloids, however, the role of colloid formation and migration are expected to promote the Pu mobility, especially in deep groundwater of G3 and G5 which have low ionic strengths. Palladium (Pd) exhibits the low solubility due to the precipitation as sulfides in reducing conditions. In oxidizing condition, anionic complexes such as Pd(OH)₃^-, PdCl₃(OH)₂^-, PdCl₄^2-, and Pd(CO₃)₂^2- would be removed by sorption onto metal (hydro)oxides. This study will improve the understanding of the fate and transport of radionuclides in deep groundwater conditions of South Korea and therefore contributes to develop strategies for safe high-level radioactive waste disposal.

• Journal of the Korean Chemical Society
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• v.38 no.10
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• pp.719-725
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• 1994

Kinetic studies were carried out for substitution reaction of $cis-[Co(NH_3)_4Cl(OH_2)]^{2+}(\mu$ = 0.75) with GlyOR (R = $C_2H_5$, $CH_3$, H) in pH 5 buffer solution at $20^{\circ}C$ by UV/Vis-spectrophotometry. We obtained cis-[Co$(NH_3)_4$Cl(glyOR)]$^{2+}$ as product. The reaction turns out to be first order for Co(III) and GlyOR, respectively. The rate constants are obtained as 9.21, 11.66 and 15.33 l${\cdot}\;mol^{-1}{\cdot}sec^{-1}$ for GlyOEt, GlyOMt and GlyOH, respectively. The activation parameters $E_a,\;{\Delta}H^{\neq}\;and\;{\Delta}S^{\neq}$ for GlyOEt were obtained as 65.77, 63.35 kJ/mol and -53.51(e.u.), respectively and were obtained as 70.91, 68.50 kJ/mol and -38.42(e.u.) for GlyOMt. In case of GlyOH, respectable values of 79.72, 77.30 kJ/mol and -26.59(e.u.) were obtained. On the basis of kinetic data and the observed activation parameters, we propose that the proper mechanism involves $S_N$2 step.

• Journal of Soil and Groundwater Environment
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• v.14 no.4
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• pp.23-32
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• 2009

The sorption of europium (Eu (III)) onto kaolinite and the influence of humic acids over a range of pH 3 ~ 11 has been studied by batch adsorption experiment (V/m = 250 : 1 mL/g, $C_{Eu(III)}\;=\;1\;{\times}\;10^{-5}\;mol/L$, $C_{HA}\;=\;5{\sim}50\;mg/L$, $P_{CO2}=10^{-3.5}\;atm$). The concentrations of HA and Eu(III) in aqueous phase were measured by UV absorbance at 254nm (e.g., $UV_{254}$) and ICP-MS after microwave digestion for HA removals, respectively. Results showed that the HA sorption onto kaolinite was decreased with increasing pH and their sorption isotherms fit well with the Langmuir adsorption model (except pH 3). Maximum amount ($q_{max}$) for the HA sorption at pH 4 to 11 was ranged from 4.73 to 0.47 mg/g. Europium adsorption onto the kaolinite in the absence of HA was typical, showing an increases with pH and a distinct adsorption edge at pH 3 to 5. However in the presence of HA, Eu adsorption to kaolinite was significantly affected. HA was shown to enhance Eu adsorption in the acidic pH range (pH 3 ~ 4) due to the formation of additional binding sites for Eu coming from HA adsorbed onto kaolinite surface, but reduce Eu adsorption in the intermediate and high pH above 6 due to the formation of aqueous Eu-HA complexes. The results on the ternary interaction of kaolinte-Eu-HA are compared with those on the binary system of kaolinite-HA and kaolinite-Eu and adsorption mechanism with pH was discussed.

• Journal of the Korean Chemical Society
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• v.41 no.9
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• pp.465-470
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• 1997

A chiral pentadentate ligand, 1,9-bis(S)-prolyl-1,9-dioxo-2,5,8-triaza-nonane, (S,S-prochen) which shows the stereospecific reaction was synthesized from the reaction of S-proline and diethylenetriamine (dien). The red-violet $[Co(SS-prodien)H_2O]ClO_4$ was prepared by the oxidation of the aqueous solution dissolving $CoCl_2{\cdot}6H_2O$ and S,S-prodien. Elemental analysis, electronic absorption spectroscopy, and $^{13}C-NMR$ spectroscopy suggest that the geometrical structure of the Co(III) complex to be an ${\alpha}{\beta}$ (ffm) form, where the dien moiety of the ligand chelates the metal center to comprise a facial isomer, and an aqua ligand coordinates a cis site to the secondary nitrogens of the dien. Based upon the CD spectroscopic analysis, it seems that the absolute configuration of the ${\alpha}{\beta}$(ffm)-$[Co(SS-prodien)H_2O]ClO_4$ has the ${\Lambda}$-form.

• Journal of Korean Society of Environmental Engineers
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• v.30 no.3
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• pp.345-351
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• 2008

Fe-impregnated activated carbon(Fe-AC) was prepared by Fe(III) loading on activated carbon(AC) in various preparation pH. In order to evaluate the stability of Fe-AC, dissolution of iron from Fe-AC in acidic conditions was measured. In addition, batch experiments were conducted to monitor the removal efficiency of copper by Fe-AC. Results of stability test for Fe-AC showed that the amount of extracted iron increased with contact time but decreased with increasing solution pH. The dissolved amount of iron gradually increased at solution pH 2 and finally 13% of the total iron loaded on activated carbon was extracted after 12 hr. However dissolution of iron was negligible over solution pH 3. Removal of Cu(II) by Fe-AC was greatly affected by solution pH and was decreased as solution pH increased as well as initial Cu(II) concentration decreased. Surface complexation modeling was performed by considering inner-sphere complexation reaction and using the diffuse layer model with MINTEQA2 program.