• Nuclear Engineering and Technology
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• v.51 no.4
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• pp.1163-1168
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• 2019

Hydrodynamic properties have been investigated for promising extraction systems: $0.05mol\;L^{-1}$ solutions of di(N-ethyl-4-ethylanilide) of 2,2'-bipyridine-6,6'-dicarboxylic acid, di(N-ethyl-4-fluoroanilide) of 2,6-pyridinedicarboxylic acid and di(N-ethyl-4-hexylanilide) of 2,2'-bipyridine-6,6'-dicarboxylic acid in meta-nitrobenzotrifluoride (F-3) or trifluoromethylphenyl sulfone (FS-13) diluents. To evaluate the perspectives for their use as extraction mixtures at the final stage of the nuclear fuel cycle, the change in density, viscosity, surface tension, and phase separation rate under irradiation with accelerated electrons was studied. The concentrations of extractants in the irradiated mixtures have been determined and the radiation-chemical yields have been calculated. Irradiation significantly decreases the phase separation rate at the stages of extraction and back extraction for all the studied systems. The viscosity of the DYP-7 solution in FS-13 increase above the values suitable for its use in extraction processes.

• Journal of the Korean Electrochemical Society
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• v.10 no.3
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• pp.219-228
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• 2007

The phase-shift method and correlation constants, i.e., the electrochemical impedance spectroscopy (EIS) techniques for studying linear relationships between the behaviors (${\varphi}\;vs.\;E$) of the phase shift ($0^{\circ}{\leq}-{\varphi}{\leq}90^{\circ}$) for the optimum intermediate frequency and those (${\theta}\;vs.\;E$) of the fractional surface coverage ($1{\geq}{\theta}{\geq}0$), have been proposed and verified to determine the Langmuir, Frumkin, and Temkin adsorption isotherms (${\theta}\;vs.\;E$) of H for the cathodic $H_2$ evolution reaction (HER) at noble and transition-metal/aqueous solution interfaces. At the Pt/0.1 MKOH aqueous solution interface, the Langmuir, Frumkin, and Temkin adsorption isotherms (${\theta}\;vs.\;E$), equilibrium constants ($K=5.6{\times}10^{-10}\;mol^{-1}\;at\;0{\leq}{\theta}<0.81$, $K=5.6{\times}10^{-9}{\exp}(-4.6{\theta})\;mol^{-1}\;at\;0.2<{\theta}<0.8$, and $K=5.6{\times}10^{-10}{\exp}(-12{\theta})\;mol^{-1}\;at\;0.919<{\theta}{\leq}1$, interaction parameters (g = 4.6 for the Temkin and g = 12 for the Frumkin adsorption isotherm), rates of change of the standard free energy ($r=11.4\;kJ\;mol^{-1}$ for g=4.6 and $r=29.8\;kJ\;mol^{-1}$ for g=12), and standard free energies (${\Delta}G_{ads}^0=52.8\;kJ\;mol^{-1}\;at\;0{\leq}{\theta}<0.81,\;49.4<{\Delta}G_{\theta}^0<56.2\;kJ\;mol^{-1}\;at\;0.2<{\theta}<0.8$ and $80.1<{\Delta}_{\theta}^0{\leq}82.5\;kJ\;mol^{-1}\;at\;0.919<{\theta}{\leq}1$) of OH for the anodic $O_2$ evolution reaction (OER) are also determined using the phase-shift method and correlation constants. The adsorption of OH transits from the Langmuir to the Frumkin adsorption isotherm (${\theta}\;vs.E$), and vice versa, depending on the electrode potential (E) or the fractional surface coverage (${\theta}$). At the intermediate values of ${\theta}$, i.e., $0.2<{\theta}<0.8$, the Temkin adsorption isotherm (${\theta}\;vs.\;E$) correlating with the Langmuir or the Frumkin adsorption isotherm (${\theta}\;vs.\;E$), and vice versa, is readily determined using the correlation constants. The phase-shift method and correlation constants are accurate and reliable techniques to determine the adsorption isotherms and related electrode kinetic and thermodynamic parameters. They are useful and effective ways to study the adsorptions of intermediates (H, OH) for the sequential reactions (HER, OER) at the interfaces.

• Nuclear Engineering and Technology
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• v.52 no.9
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• pp.2034-2040
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• 2020

The gas evolution from mixtures consisting of 0.2 M solution of N,N,N',N'-tetra-n-octyldiglycolamide (TODGA) in n-alcohol (n-decanol or n-nonanol) with Isopar-M diluent was investigated during thermal oxidation. The effect of ionizing radiation on their thermal stability has been studied. It has been determined that the volume of gaseous thermolysis products increases by 260% in the case of n-nonanol and 80% in the case of n-decanol compared to non-irradiated solutions. It has been shown that the gas evolution rate and gas volume increase when the irradiated mixture saturated with nitric acid is heated. However, there are no prerequisites for the development of autocatalytic oxidation.

• Nuclear Engineering and Technology
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• v.51 no.7
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• pp.1799-1804
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• 2019

The concept of a new method, the CARBEX (CARBonate EXtraction) process, was proposed for reprocessing of spent uranium oxide fuel. The proposed process is based on use of water solutions of $Na_2CO_3$ or $(NH_4)_2CO_3$ and solvent extraction (SE) by the quaternary ammonium compounds for selective recovery and purification of U from the fission products (FPs). Applying of SE allows to reach high degree of purification of U from FPs. Carrying out the processes in poorly aggressive alkaline carbonate media leads to increasing safety of SNF's reprocessing and better selectivity of separation of lanthanides and actinides. Moreover carbonate reprocessing media allows to carry out a recycling and regeneration of reagents. We have been done laboratory scale experiments on the extraction components of simulated voloxidated spent fuel in the solutions of NaOH or $Na_2CO_3-H_2O_2$ and recovery of U from carbonate solutions by SE method using carbonate of methyltrioctylammonium in toluene. It was shown that the purification factors of U from impurities of simulated FPs reached values $10^3-10^5$. The received results support our opinion that CARBEX after the further development can become more safe, simple and profitable method of spent fuel reprocessing.

• Journal of the Korean Chemical Society
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• v.55 no.2
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• pp.268-278
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• 2011

Corrosion of aluminum in 0.1 M HCl solution in the absence and presence of ${\beta}$-blocker inhibitors (atenolol, propranolol, timolol and nadolol) was investigated using weight loss, potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques. The inhibition efficiency increased with inhibitor concentration and decreased with rise of temperature. Potentiodynamic polarization curves revealed that they acted as cathodic inhibitors. Some thermodynamic parameters were calculated and discussed. All inhibitors were adsorbed on Al surface obeying Frumkin isotherm. All EIS tests exhibited one capacitive loop which indicates that the corrosion reaction is controlled by charge transfer process. The inhibition efficiencies of all test methods were in good agreement.

• Journal of the Korean Electrochemical Society
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• v.9 no.1
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• pp.19-28
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• 2006

The phase-shift method for determining the Langmuir, Frumkin, and Temkin adsorption isotherms ($\theta_H\;vs.\;E$) of H for the cathodic $H_2$ evolution reaction (HER) at a Pt/0.1 M KOH solution interface has been proposed and verified using cyclic voltammetric, differential pulse voltammetric, and electrochemical impedance techniques. At the Pt/0.1 M KOH solution interface, the Langmuir and Temkin adsorption isotherms ($\theta_H\;vs.\;E$), the equilibrium constants ($K_H=2.9X10^{-4}mol^{-1}$ for the Langmuir and $K_H=2.9X10^{-3}\exp(-4.6\theta_H)mol^{-1}$ for the Temkin adsorption isotherm), the interaction parameters (g=0 far the Langmuir and g=4.6 for the Temkin adsorption isotherm), the rate of change of the standard free energy of $\theta_H\;with\;\theta_H$ (r=11.4 kJ $mol^{-1}$ for g=4.6), and the standard free energies (${\Delta}G_{ads}^{\circ}=20.2kJ\;mol^{-1}$ for $k_H=2.9\times10^{-4}mol^{-1}$, i.e., the Langmuir adsorption isotherm, and $16.7<{\Delta}G_\theta^{\circ}<23.6kJ\;mol^{-1}$ for $K_H=2.9\times10^{-3}\exp(-4.6\theta_H)mol^{-1}$ and $0.2<\theta_H<0.8$, i.e., the Temkin adsorption isotherm) of H for the cathodic HER are determined using the phase-shift method. At intermediate values of $\theta_H$, i.e., $0.2<\theta_H<0.8$, the Temkin adsorption isotherm ($\theta_H\;vs.\;E$) corresponding to the Langmuir adsorption isotherm ($\theta_H\;vs.\;E$), and vice versa, is readily determined using the constant conversion factors. The phase-shift method and constant conversion factors are useful and effective for determining the Langmuir, Frumkin, and Temkin adsorption isotherms of intermediates for sequential reactions and related electrode kinetic and thermodynamic data at electrode catalyst interfaces.

• Journal of the Korean Electrochemical Society
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• v.10 no.2
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• pp.132-140
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• 2007

The phase-shift method and correlation constants for studying a linear relationship between the behavior ($-{\varphi}\;vs.\;E$) of the phase shift ($0^{\circ}{\leq}-{\varphi}{\leq}90^{\circ}$) for the optimum intermediate frequency and that (${\theta}\;vs.\;E$) of the fractional surface coverage ($1{\geq}\theta{\geq}0$) have been proposed and verified to determine the Langmuir, Frumkin, and Temkin adsorption isotherms (${\theta}\;vs.\;E$) at noble metal/aqueous electrolyte interfaces. At an Ir/0.1 M KOH aqueous electrolyte interface, the Langmuir and Temkin adsorption isotherms (${\theta}\;vs.\;E$), equilibrium constants ($K=3.3{\times}10^{-4}\;mol^{-1}$ for the Langmuir and $K=3.3{\times}10^{-3}{\exp}(-4.6{\theta})\;mol^{-1}$ for the Temkin adsorption isotherm), interaction parameter (g = 4.6 for the Temkin adsorption isotherm), and standard free energies (${\Delta}G_{ads}^0=19.9kJ\;mol^{-1}\;for\;K=3.3{\times}10^{-4}\;mol^{-1}$ and $16.5<{\Delta}G_{\theta}^0<23.3\;kJ\;mol^{-1}\;for\;K=3.3{\times}10^{-3}{\exp}(-4.6{\theta})\;mol^{-1}\;and\;0.2<\theta<0.8$) of H for the cathodic $H_2$ evolution reaction are determined using the phase-shift method and correlation constants. The inhomogeneous and lateral interaction effects on the adsorption of H are negligible. At the intermediate values of ${\theta},\;i.e,\;0.2<{\theta}<0.8$, the Temkin adsorption isotherm (${\theta}\;vs.\;E$) correlating with the Langmuir or the Frumkin adsorption isotherm (${\theta}\;vs.\;E$), and vice versa, is readily determined using the correlation constants. The phase-shift method and correlation constants are accurate and reliable techniques to determine the adsorption isotherms (${\theta}\;vs.\;E$) and related electrode kinetic and thermodynamic parameters(K, g, ${\Delta}G_{ads}^0, {\Delta}G_{\theta}^0$).

• Bulletin of the Korean Chemical Society
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• v.21 no.11
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• pp.1085-1089
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• 2000

The effect of 2-hydroxyacetophenone-aroyl hydrazone derivatives on the inhibition of copper corrosion in 3N nitric acid solution at 303 K was investigated by galvanostatic polarization and thermometric techniques. A significant decrease in the cor rosion rate of copper was observed in the presence of the investigated compounds. The corrosion rate was found to depend on the nature and concentrations of the inhibitors. The degree of surface coverage of the adsorbed inhibitors is determined from polarization measurements, and it was found that the results obey the Frumkin adsorption isotherm. The inhibitors acted as mixed-type inhibitors, but the cathode is more polarized. The relative inhibitive efficiency of these compounds has been explained on the basis of structure dependent electron donor properties of the inhibitors and the nature of the metal-inhibitor interaction at the surface. Also, some thermodynamic data for the adsorption process ( ΔGa* and f ) are calculated and discussed.

• Journal of the Korean Electrochemical Society
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• v.2 no.2
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• pp.70-74
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• 1999

The electrode kinetic parameters at the Pd/0.5 M LiOH electrolyte interface have been qualitatively studied using the phase-shift method. The phase shift $(\phi)$ depends on both the cathode potential (E>0) and frequency (f), and $\theta$ is inversely proportional to the fractional surface coverage $\theta$. At an intermediate frequency (10 Hz), the phase-shift profile $(\phi\;vs.\;E)$ can be related to the fractional surface coverage $(\theta\;vs.\;E)$. The phase-shift method can be used to estimate or plot the Frumkin adsorption isotherm. The rate (r) of change of the free energy of adsorption with $({\theta})$ is 22.3 kJ/mol. The equilibrium constant (K) for adsorption and the standard free energy $({\Delta}G_{\theta})$ of the adsorbed hydrogen atom $(H_{ads})$ are $3.7\times10^{-3}{\Delta}G_{\theta}>-8.4kJ/mol$, respectively. For 1$0.38>\theta>0$, the energy liberation or the exothermic reaction for hydrogen adsorption at the Pd cathode can be occurred. The electrode kinetic parameters $(r,\;K,\;{\Delta}G_{\theta}$ depend on the fractional surface coverage $({\theta})$ or the phase shift $(\phi)$.

• Nuclear Engineering and Technology
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• v.52 no.1
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• pp.109-114
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• 2020

This work presents the results of laboratory scale tests of the CARBOFLUOREX (CARBOnate FLUORide EXtraction) process - a novel technology for the recovery of U and Pu from the solid fluorides residue (fluorination ash) of Fluoride Volatility Method (FVM) reprocessing of spent nuclear fuel (SNF). To study the oxidative leaching of U from the fluorination ash (FA) by Na₂CO₃ or Na₂CO₃-H₂O₂ solutions followed by solvent extraction by methyltrioctylammonium carbonate in toluene and purification of U from the fission products (FPs) impurities we used a surrogate of FA consisting of UF₄ or UO₂F₂, and FPs fluorides with stable isotopes of Ce, Zr, Sr, Ba, Cs, Fe, Cr, Ni, La, Nd, Pr, Sm. Purification factors of U from impurities at the solvent extraction refining stage reached the values of 10⁴-10⁵, and up to 10⁶ upon the completion of the processing cycle. Obtained results showed a high efficiency of the CARBOFLUOREX process for recovery and separating of U from FPs contained in FA, which allows completing of the FVM cycle with recovery of U and Pu from hardly processed FA.