• Journal of the Korean Electrochemical Society
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• v.7 no.4
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• pp.194-200
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• 2004

The constant correlation factors between the Temkin and the Langmuir or the Frumkin adsorption isotherms of over-potentially deposited hydrogen (OPD H) for the cathodic H2 evolution reaction (HER) at poly-Pt and Re/0.5M $H_2SO_4$ and poly-Ni/0.05 M KOH aqueous electrolyte interfaces have been experimentally and consistently found using the phase-shift method. At intermediate values of the fractional surface coverage $(\theta),\;i.e.,\;02<{\theta}<0.8$, the Langmuir and Temkin adsorption isotherms of OPD H for the cathodic HER are correlated to each other even though the adsorption conditions or processes are different from each other. At the same range of $\theta$, correspondingly, the Frumkin and Temkin adsorption isotherms of OPD H for the cathodic HER are correlated to each other. The equilibrium constants $(K_o)$ for the Temkin adsorption isotherms $({\theta}\;vs.\; E)$ are consistently ca. 10 times greater than those (K, Ko) for the corresponding Langmuir or Frumkin adsorption isotherms ($({\theta}\;vs.\; E)$. The interaction parameters (g) for the Temkin adsorption isotherms $({\theta}\;vs.\; E)$ are consistently ra. 4.6 greater than those (g) for the corresponding Langmuir or Frumkin adsorption isotherms $({\theta}\;vs.\; E)$. These numbers (10 times and 4.6) can be taken as constant correlation factors between the corresponding adsolftion isotherms (Temkin, Langmuir, Frumkin) at the interfaces. The Temkin adsorption isotherm corresponding to the Langmuir or the Frumkin adsorption isotherm, and vice versa, can be effectively verified or confirmed using the constant correlation factors. Both the phase-shift methodand constant correlation factors are useful and effective for determining or confirming the suitable adsorption isotherms (Temkin, Langmuir, Frumkin) of intermediates for sequential reactions in electrochemical systems.

• Nuclear Engineering and Technology
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• v.50 no.8
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• pp.1421-1425
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• 2018

The dynamics of gas release at thermal oxidation of extraction systems on the basis of diamides of dicarbonic acids in fluorinated sulphones with 14 mol/L $HNO_3$ was investigated. The effect of preirradiation of the mixtures with accelerated electrons on the kinetics of their thermolysis was determined. The mixtures were heated in an autoclave at temperatures of 170 and $200^{\circ}C$ and irradiated using an electron accelerator to absorbed doses of 0.1, 0.5, and 1.0 MGy. It has been shown that no conditions for autocatalytic oxidation at thermolysis of extraction mixtures irradiated up to a dose of 1 MGy were developed.

• Journal of the Korean Electrochemical Society
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• v.16 no.4
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• pp.211-216
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• 2013

At Pt(111), Pt(100), Pt, and Rh interfaces, the Frumkin adsorption isotherm of underpotentially deposited hydrogen (UPD H) and related electrode kinetic data are determined using the standard Gibbs energy of adsorption. The Temkin adsorption isotherm of UPD H correlating with the Frumkin adsorption isotherm of UPD H is readily determined using the correlation constants between the Temkin and Frumkin or Langmuir adsorption isotherms. At the Pt(111), Pt(100), Pt, and Rh interfaces, the lateral repulsive interaction between the UPD H species is interpreted using the interaction parameter for the Frumkin adsorption isotherm. The lateral repulsive interaction between the UPD H species at the Pt(111), Pt(100), Pt, and Rh interfaces is significantly different from the lateral attractive interaction between the overpotentially deposited hydrogen (OPD H) species at Pt, Ir, and Pt-Ir alloy interfaces.

• Nuclear Engineering and Technology
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• v.54 no.9
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• pp.3580-3585
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• 2022

The thermal stability of carbohydrazide, hydrazine nitrate, acetohydroxamic acid in nitric acid solutions has been studied at atmospheric pressure and above atmospheric pressure. The volumes of gaseous products of thermolysis and the maximum rate of gas evolution have been determined at atmospheric pressure. It has been shown that, despite the high rate of gas evolution and large volumes of evolved gases, the conditions for the development of autocatalytic oxidation are not created. Exothermic processes are observed in a closed vessel in the temperature range of 50-250 ℃. With an increase in the concentration of nitric acid, the temperatures of the onset of exothermic effects for all mixtures decrease, and the values of the total thermal effects of reactions increase, to the greatest extent for solutions with carbohydrazide.

• Korean Chemical Engineering Research
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• v.54 no.6
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• pp.734-745
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• 2016

This review article described the electrochemical Frumkin, Langmuir, and Temkin adsorption isotherms of over-potentially deposited hydrogen (OPD H) and deuterium (OPD D) for the cathodic $H_2$ and $D_2$ evolution reactions (HER, DER) at Pt, Ir, Pt-Ir alloy, Pd, Au, and Re/normal ($H_2O$) and heavy water ($D_2O$) solution interfaces. The Frumkin, Langmuir, and Temkin adsorption isotherms of intermediates (OPD H, OPD D, etc.) for sequential reactions (HER, DER, etc.) at electrode/solution interfaces are determined using the phase-shift method and correlation constants, which have been suggested and developed by Chun et al. The basic procedure of the phase-shift method, the Frumkin, Langmuir, and Temkin adsorption isotherms of OPD H and OPD D and related electrode kinetic and thermodynamic parameters, i.e., the fractional surface coverage ($0{\leq}{\theta}{\leq}1$) vs. potential (E) behavior (${\theta}$ vs. E), equilibrium constant (K), interaction parameter (g), standard Gibbs energy (${\Delta}G_{\theta}{^{\circ}}$) of adsorption, and rate (r) of change of ${\Delta}G_{\theta}{^{\circ}}$ with ${\theta}$ ($0{\leq}{\theta}{\leq}1$), at the interfaces are briefly interpreted and summarized. The phase-shift method and correlation constants are useful and effective techniques to determine the Frumkin, Langmuir, and Temkin adsorption isotherms and related electrode kinetic and thermodynamic parameters (${\theta}$ vs. E, K, g, ${\Delta}G_{\theta}{^{\circ}}$, r) at electrode/solution interfaces.

• Journal of the Korean Electrochemical Society
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• v.4 no.4
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• pp.146-151
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• 2001

The Frumkin adsorption isotherm of the over-potentially deposited hydrogen (OPD H) for the cathodic $H_2$ evolution reaction (HER) at the poly-Ni|0.05M KOH aqueous electrolyte interface has been studied using the phase-shift method. The behavior of the phase shift $(0^{\circ}\leq{\phi}\leq90^{\circ})$ for the optimum intermediate frequency corresponds well to that of the fractional surface coverage $(1\geq{\theta}\geq0)$ at the interface. The phase-shift method, i.e., the Phase-shift profile $(-{\phi}\;vs.\;E)$ for the optimum intermediate frequency, can be used as a new method to estimate the Frumkin adsorption isotherm $(\theta\;vs.\;E)$ of the OPD H for the cathodic HER at the interface. At the poly-Ni|0.05M KOH aqueous electrolyte interface, the rate (r) of change of the standard free energy of the OPD H with $\theta$, the interaction parameter (g) for the Frumkin adsorption isotherm, the equilibrium constant (K) for the OPD H with $\theta$, and the standard free energy $({\Delta}G_{\theta})$ of the OPD H with ${\theta}$ are $24.8kJ mol^{-1},\;10,\;5.9\times10^{-6}{\leq}K{\leq}0.13,\;and\;5.1\leq{\Delta}G_{\theta}\leq29.8kJ\;mol^{-1}$. The electrode kinetic parameters $(r,\;g,\;K,\;{\Delta}G_{\theta})$ depend strongly on ${\theta} (0{\leq}{\theta}{\leq}1)$.

• Journal of the Korean Electrochemical Society
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• v.15 no.1
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• pp.54-66
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• 2012

The phase-shift method and correlation constants, which are unique electrochemical impedance spectroscopy techniques for studying the linear relationship between the phase shift ($90^{\circ}{\geq}-{\varphi}{\geq}0^{\circ}$) vs. potential (E) behavior for the optimum intermediate frequency ($f_o$) and the fractional surface coverage ($0{\leq}{\theta}{\leq}1$) vs. E behavior, are proposed and verified to determine the Frumkin, Langmuir, and Temkin adsorption isotherms and the related electrode kinetic and thermodynamic parameters. At Ni/0.5 M $H_2SO_4$ and 0.1M LiOH aqueous solution interfaces, the Frumkin and Temkin adsorption isotherms (${\theta}$ vs. E) of H for the cathodic hydrogen ($H_2$) evolution, interaction parameters (g), equilibrium constants (K), standard Gibbs energies (${\Delta}G^0_{\theta}$) of H adsorption, and rates of change (r) of ${\Delta}G^0_{\theta}$ with ${\theta}$ have been determined using the phase-shift method and correlation constants. A lateral repulsive interaction (g>0) between the adsorbed H species appears. The value of K in the alkaline aqueous solution is much greater than that in the acidic aqueous solution.

• Nuclear Engineering and Technology
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• v.55 no.2
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• pp.391-407
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• 2023

This article provides a survey of wet (aqueous) methods for recovery, separation, and purification of uranium from fission products in carbonate solutions during the reprocessing of spent nuclear fuel and methods for removal of radionuclides from alkaline radioactive waste. The main methods such as selective direct precipitation, ion exchange, and solvent extraction are considered. These methods were compared and evaluated for reprocessing of spent nuclear fuel in carbonate media according to novel alternative non-acidic methods and for treatment processes of alkaline radioactive waste.

• Nuclear Engineering and Technology
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• v.55 no.10
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• pp.3808-3814
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• 2023

The thermal stability of nitric acid solutions after contact with non-irradiated and irradiated tributyl phosphate (TBP) and its solution in Isopar-M has been studied. It has been established that exothermic processes occur during heating due to the interaction of soluble radiolysis products and the decomposition of the extractant with nitric acid. Such processes can occur at temperatures below 100 ℃, but unlike a thermal explosion that occurs in seconds, they are longer in time and are accompanied by weak heat evolution. Their intensity depends on the composition of the extractant, the concentration of HNO₃, and the volume ratio of the organic and aqueous phases. The presence of extractant degradation products in raffinates does not pose a risk of a rapid evolution of gaseous products during evaporation, however, the presence of reducing agents can significantly increase the intensity of the exothermic decomposition of raffinates.

• Journal of the Korean Electrochemical Society
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• v.12 no.1
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• pp.26-33
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• 2009

The phase-shift method and correlation constants, i.e., the unique electrochemical impedance spectroscopy (EIS) techniques for studying the linear relationship between the behavior ($-{\varphi}$ vs. E) of the phase shift ($90^{\circ}{\geq}-{\varphi}{\geq}0^{\circ}$) for the optimum intermediate frequency and that ($\theta$ vs. E) of the fractional surface coverage ($0{\leq}{\theta}{\leq}1$), have been proposed and verified to determine the Langmuir, Frumkin, and Temkin adsorption isotherms of H and related electrode kinetic and thermodynamic parameters at noble metal (alloy)/aqueous solution interfaces. At a Zr/0.2 M ${H_2}{SO_4}$ aqueous solution interface, the Frumkin and Temkin adsorption isotherms ($\theta$ vs. E), equilibrium constants (K = $1.401{\times}10^{-17}\exp(-3.5{\theta})mol^{-1}$ for the Frumkin and K = $1.401{\times}10^{-16}\exp(8.1{\theta})mol^{-1}$ for the Temkin adsorption isotherm), interaction parameters (g = 3.5 for the Frumkin and g = 8.1 for the Temkin adsorption isotherm), rates of change of the standard free energy (r = $8.7\;kJ\;mol^{-1}$ for g = 3.5 and r = $20\;kJ\;mol^{-1}$ for g = 8.1) of H with $\theta$, and standard free energies ($96.13{\leq}{\Delta}G^0_{\theta}{\leq}104.8\;kJ\;mol^{-1}$ for K = $1.401{\times}10^{-17}\exp(-3.5{\theta})mol^{-1}$ and $0{\leq}{\theta}{\leq}1$ and ($94.44<{\Delta}G^0_{\theta}<106.5\;kJ\;mol^{-1}$ for K = $1.401{\times}10^{-16}\exp(-8.1{\theta})mol^{-1}$ and $0.2<{\theta}<0.8$) of H are determined using the phase-shift method and correlation constants. At 0.2 < $\theta$ < 0.8, the Temkin adsorption isotherm correlating with the Frumkin adsorption isotherm, and vice versa, is readily determined using the correlation constants. The phase-shift method and correlation constants are probably the most accurate, useful, and effective ways to determine the adsorption isotherms of H and related electrode kinetic and thermodynamic parameters at highly corrosion-resistant metal/aqueous solution interfaces.