• Journal of the Korean Chemical Society
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• v.28 no.2
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• pp.130-134
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• 1984

The polarographic behavior of benzeneazoresorcinol (BAR) in acetonitrile as an aprotic solvent has been investigated by direct current polarography and controlled-potential coulometry. The reduction of BAR in $1.0{\times}10^{-2}$M tetraethylammonium perchrolate solution proceeds along four one-electron steps to give the corresponding amine compounds. Each reduction wave was considerably diffusion-controlled and not completely reversible.

• Journal of the Korean Chemical Society
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• v.27 no.1
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• pp.24-30
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• 1983

The polarographic behavior of 1-(2-pyridylazo)-2-naphthol (PAN) in acetonitrile as an aprotic solvent has been investigated. The reduction of PAN in $10^{-2}$ molarity of tetraethyl-ammonium perchlorate acetonitrile solution proceeds along two one-electron steps to give the corresponding hydrazo compound. Every reduction wave was diffusion controlled and considerably reversible. The reduction mechanism of PAN in acetonitrile is estimated as follows;

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.8 no.1
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• pp.19-32
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• 2010

Electrolytic reduction technology is essential for the purpose of adopting pyroprocessing into spent oxide fuel as an alternative option in a back-end fuel cycle. Spent fuel consists of various metal oxides, and each metal oxide releases an oxygen element depending on its chemical characteristic during the electrolytic reduction process. In the present work, an electrolytic reduction behavior was estimated for voloxidized spent fuel based on the assumption that each metal-oxygen system is independent and behaves as an ideal solid solution. The electrolytic reduction was considered as a combination of a Li recovery and chemical reactions between the metal oxides such as uranium oxide and the produced Li metal. The calculated result revealed that most of the metal oxides were reduced by the process. It was evaluated that a reduced fraction of lanthanide oxides increased with a decreasing $Li_2O$ concentration. However, most of the lanthanides were expected to be stable in their oxide forms. In addition, a semi-empirical model for describing $U_3O_8$ electrolytic reduction behavior was proposed by considering Li diffusion and a chemical reaction between $U_3O_8$ and Li. Experimental data was used to determine model parameters and, then, the model was applied to calculate the reduction yield with time and to estimate the required time for a 99.9% reduction.

• Proceedings of the Korean Powder Metallurgy Institute Conference
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• 2001.04a
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• pp.33-33
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• 2001

• Proceedings of the Korean Ceranic Society Conference
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• 2000.10a
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• pp.83.2-83
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• 2000

• Proceedings of the Korean Ceranic Society Conference
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• 2002.10a
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• pp.41.2-41
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• 2002

• Resources Recycling
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• v.31 no.1
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• pp.29-36
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• 2022

The hydrogen reduction behavior of molybdenum oxides was studied using a horizontal-tube reactor. Reduction was carried out in two stages: MoO₃ → MoO₂ and MoO₂ → Mo. In the first stage, a mixed gas composed of 30 vol% H₂ and 70 vol% Ar was selected for the MoO₃ reduction because of its highly exothermic reaction. The temperature ranged from 550 to 600 ℃, and the residence time ranged from 30 to 150 min. In the second step, pure H₂ gas was used for the MoO₂ reduction, and the temperature and residence time ranges were 700-750 ℃ and 30-150 min, respectively. The hydrogen reduction behavior of molybdenum oxides was found to be somewhat different between the two stages. For the first stage, a temperature dependence of the reaction rate was observed, and the best curve fittings were obtained with a surface reaction control mechanism, despite the presence of intermediate oxides under the conditions of this study. Based on this mechanism, the activation energy and pre-exponential were calculated as 85.0 kJ/mol and 9.18 × 10⁷, respectively. In addition, the pore size within a particle increases with the temperature and residence time. In the second stage, a temperature dependence of the reaction rate was also observed; however, the surface reaction control mechanism fit only the early part, which can be ascribed to the degradation of the oxide crystals by a volume change as the MoO₂ → Mo phase transformation proceeded in the later part.

• Journal of the Korean Chemical Society
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• v.35 no.4
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• pp.374-378
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• 1991

The electrochemical reduction behavior of Bilirubin (BR) in phosphate buffer (pH 7.8) solution was studied by DC polarography, differential pulse polarography, cyclic voltammetry and controlled potential coulometry. In DC polarogram, two reduction waves of BR were found. The half wave potentials of two reduction waves were -1.32 and -1.51 volts vs. Ag/AaCl respectively. The current type of 1st reduction wave was diffusion-controlled and the 2$^{nd}$ reduction wave was diffusion current containing a little kinetic current. The electrochemical reduction process of BR at each reduction step was all irreversible. The prewave appeared at lower concentration than 3.4 ${\times}$ 10$^{-4}$M, this prewave was identified as adsorption prewave. And the number of electron transfered in reduction steps, n$_{app}$ was two for the 1st reduction step and one for the 2$^{nd}$ reduction step.

• Proceedings of the Korean Radioactive Waste Society Conference
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• 2009.06a
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• pp.291-291
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• 2009

한국원자력연구원의 파이로 실험 시설인 ACPF (ACP Facility)에는 공학규모 전해환원 반응기가 설치되어 공정 대용량화를 위한 연구가 수행되고 있다 본 연구에서는 전해환원 공정의 Scale-up을 위해 기존 반응기를 개선하여 전해환원 실험을 수행한 결과를 담고 있다. 장치의 대형화 빛 원격운전성 향상을 위해 기존의 전해환원 반응기의 상부 플랜지는 보다 간단하게 정리되었으며 염 이송에 의한 고온 조건 노출 시간을 줄임과 동시에 염 재사용을 목적으로 상부 플랜지는 이중으로 설계되었다. 따라서, 반응 종료후 전극이 설치된 상부 플랜지를 들어 올림으로서 반응기를 불활성 분위기로 유지하는 동시에 전해환원 금속전환체를 회수 할 수 있도록 반응기가 제작되었다. 또한, 새로운 반응기는 용융염 내의 강제 유동을 위해 아르곤 버블링이 가능하도록 설계 제작되었다. 새로 제작 설치된 전해환원 반응기를 사용하여 산화물 분말을 혼합하여 준비한 모의 사용후핵연료를 사용하여 전해환원 실험을 수행하였다. 그 결과, 산화물이 충진된 음극의 전영역에서 고루 96% 이상의 높은 금속전환율을 얻었으며 시간에 따라 선택된 FP들의 용융염 내 거동을 측정하였다. 실리더 형태의 음극에서 Cs, Sr 등의 원소들이 용융염으로 시간에 따라 용출되는 것을 확인하였으며 동시에 반응기 재질인 Fe 등도 일부 용융염에서 검출되었다. 아르곤 버블링에 의한 강제 유동은 전압 및 전류 거동에는 큰 영향을 미치지 못하였으나 염의 휘발량을 증가시켜 영조성올 변화시키는 것으로 측정되었다. ACPF의 전해환원 실험결과를 바탕으로 반응기를 상부 기체상과 하부 액체상으로 나누어 전산모사를 수행하였다 상부 기체상은 유입되는 아르곤 기체와 발생되는 산소기체의 흐름을 모사하는 결과를 얻었으며 온도 및 산소의 분압을 계산하였다. 하부 액체상에서는 전기장을 모사하여 전류 밀도 등을 3차원으로 모사하였다.

• Journal of the Korean Chemical Society
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• v.37 no.5
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• pp.483-490
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• 1993

Voltammetric behavior of heavy lanthanide ions has been investigated by the DC, DPP and CV in acetonitrile solution. The reduction of $Gd^{3+}, Tb^{3+}, Dy^{3+}, Ho^{3+}, Er^{3+}, Tm^{3+} 및 Lu^{3+} proceed by three-electron change to the metallic state with totally irreversibility in 0.1M tetraethylammonium perchlorate. However, the reduction of Yb(Ⅲ) proceeds in two steps $(Yb^{3+} ＋ e^- \Leftrightarrow Yb^{2+} and Yb^{2+} ＋ 2e^- → Yb^0)$. The first reduction of Yb(Ⅲ) showed quasi reversible behavior, but the second reduction was irreversible in cyclic voltammetry. The cathodic peak current showed adsorptive properties in high concentration with lower sweep rate. The electroreduction of heavy lanthanides in water-acetonitrile mixture has been studied. In water-acetonitrile mixture, the negative shift of the peak potential and the decrease peak current were observed increasing water concentration. Also the Yb(Ⅲ) reduction to Yb(Ⅲ) has been deviated from quasi-reversible character with increase water amount. These results drive from the high solvation abilities of water which has high donor number.