Molten Salt Reactor (MSR) is one of the 4th generation nuclear power systems which is its verified technology in physically and chemically. Among the various salts used for MSR system, the eutectic composition of NaCl-MgCl2 system maintains the liquid state at around 450°C, in the same time, it has high solubility for nuclear fuel chlorides. This characteristic has high advantage for lowering the operating temperature for the MSR, which could reduce the problem of hightemperature corrosion by salt for structural materials significantly. In particular, since MgCl2 has the similar standard reduction potential with nuclear fuel, is used as a surrogate for, many basic researches have been conducted for verifying characteristic of MgCl2. It is well-known that main short-advantage of MgCl2 is hygroscopic properties. MgCl2 changes to MgCl2-xH2O state easily by absorbing moisture in air condition. The hydrated MgCl2 is producing MgOHCl by thermally decomposing at high temperature, the formed MgOHCl corrodes structural materials, even small amount of MgOHCl gives significant damage. Therefore, the purification of MgCl2 has been required for long-term operation of MSR using MgCl2 as a base salt. In this study, the purification of eutectic composition salt for NaCl-MgCl2 has been mainly performed by considering its thermodynamic properties and electrochemical characteristic, and the experimental results have been discussed.

Decontamination is one of the important processes for dismantling nuclear power plants. The purpose of decontamination is to reduce the radiation levels of contaminated nuclear facilities, ensuring the safety of workers involved in decommissioning and minimizing the amount of radioactive waste. In this study, we investigate the reaction mechanisms and their thermodynamic energies of the HyBRID (Hydrazine-Based Reductive participated metal Ion Decontamination) process for decontamination of the primary coolant system of a nuclear power plant. We computed the thermodynamic properties of HyBRID dissolution mechanisms in which corrosion metal oxides accumulated in the primary coolant systems along with radionuclides are dissolved by HyBRID decontamination agents (H2SO4/N2H4/CuSO4). The HyBRID reaction mechanism has been studied using a commercial database (HSC Chemistry®), but Cu ions have been used instead of Cu-hydrazine complexes when calculating reactions due to the absence of thermodynamic properties for Cu-hydrazine complexes. To address this limitation, we supplemented the quantum calculations with Cu-hydrazine complexes using the density functional calculations. It is intended to simulate a more practical reactions by calculating the reactions considering Cu-hydrazine complexes, and to improve understanding of the HyBRID dissolution reactions by qualitatively and quantitatively comparing the reactions without considering the complex formation.

The permanent disposal of discharged spent nuclear fuel (SNF) and contaminated radioactive waste generated from the subsequent chemical treatments of SNF has become a serious pending issue in many countries that operate the nuclear power plants. Among the diverse engineering solutions proposed for the disposal of high-level radioactive waste (HLW), deep geological disposal (DGD) has been considered as the most proven and safe option to prevent any significant release of radionuclides into the biosphere and to predictably ensure the long-term performance of disposal system. The DGD system consists of multiple structural components; the bentonite clay-based buffer and tunnel backfills are designed to perform the primary hydrogeochemical functions of 1) inhibiting the ingress of groundwater and reactive substances that could compromise the integrity of canister and 2) retarding the migration of released radionuclides into biosphere by providing the sufficient chemisorption sites. Montmorillonite, which is a 2:1 phyllosilicate mineral belonging to smectite group, constitutes the majority of bentonite, and it mainly predominate the swelling and chemisorption capacities of the clay material. Thus, it is essentially required to thoroughly understand the chemical interactions of major radionuclides and other important substances with montmorillonite in advance to accurately evaluate the long-term retention performance of engineered barriers and to reduce the uncertainties in the safety assessment of a deep geological repository (DGR) ultimately. Thus far, sorption of dissolved species onto mineral adsorbents has been generally described and quantified using the simple sorption-desorption distribution coefficient (Kd) concept; since any specific reaction mechanisms are not considered and reflected in the Kd concept, an empirical Kd value is intrinsically dependent on the aqueous conditions under which it was measured. In this framework, substantial scientific efforts have been made to develop a robust basis for geochemically parametrizing the sorption phenomena more reliably, and the application of thermodynamic sorption modeling (TSM), which is based on the chemical principle of mass action laws, has been studied with the aim of improving overall confidence in the description of radionuclide migration under a wide range of aquatic conditions. The disposal performance demonstration R&D division of KAERI introduced a new reference Ca-bentonite clay called Bentonil-WRK (Clariant Korea) for HLW disposal research in 2021 as the domestic Ca-bentonite sources have being depleted. We successfully separated and purified Ca-montmorillonite from the Bentonil-WRK clay, and its geochemical characteristics were meticulously studied by means of XRD, BET, CEC, FT-IR analyses and controlled acid-base titration. In this work, chemical sorption behaviors of aqueous iodide and benzoate, which are a major fission product in HLW and a model ligand of complex natural organic matters present in the deep geological environment, onto the purified Camontmorillonite were assessed under ambient conditions of S/L = 5 g/L, I = 0.01 M CaCl2, pH = 4- 9, pCO2 = 10-3.4 atm, and T = 25°C. Further, their unique adsorption envelopes and corresponding thermodynamic reaction constants refined from the diffuse double layer model (DDLM)-based inverse modeling of experimental sorption data were discussed.

This study presents the synthesis, characterization, and utilization of marine macroalgae-derived bio-carbon catalysts (BC and KOH-AC) for the efficient conversion of waste cooking oil (WCO) into biodiesel. The biochar (BC) was produced through slow pyrolysis of macroalgal biomass, which was subsequently activated with potassium hydroxide (KOH) to produce a KOH-modified activated carbon (KOH-AC) catalyst. Advanced characterization techniques, including SEM, EDX, XRD, FTIR, and TGA, were used to examine the physicochemical characteristics of the catalysts. The synthesized catalysts were utilized to produce biodiesel from WCO, and the results revealed that the highest biodiesel yields, 98.96%, and 47.54%, were obtained using KOH-AC and BC catalysts, respectively, under optimal reaction conditions of 66 °C temperature, 12.3 M/O molar ratio, 130 min time, and 3.08 wt.% catalyst loading via RSM optimization. The kinetic and thermodynamic parameters, such as k, Ea, ΔH, ΔS, and ΔG, were determined to be 0.0346 min− 1, 43.31 kJ mol− 1, 38.98 kJ mol− 1, − 158.38 J K− 1 mol− 1, and 92.58 kJ mol− 1, respectively. The KOH-AC catalyst was recycled up to five times, with a significant biodiesel yield of 80.37%. The fuel properties of the biodiesel met ASTM (D6751) specifications, ensuring that it has excellent fuel characteristics and can be used as an alternative fuel.

This study examined the efficacy of various chlorinating agents in partitioning light water reactor spent fuel, with the aim of optimizing the chlorination process. Through thermodynamic equilibrium calculations, we assessed the outcomes of employing MgCl2, NH4Cl, and Cl2 as chlorinating agents. A comparison was drawn between using a single agent and a sequential approach involving all three agents (MgCl2, NH4Cl, and Cl2). Following heat treatment, the utilization of MgCl2 as the sole chlorinating agent resulted in a moderate separation. Specifically, this method yielded a solid separation with 96.9% mass retention, 31.7% radioactivity, and 44.2% decay heat, relative to the initial spent fuel. In contrast, the sequential application of the chlorinating agents following heat treatment led to a final solid separation characterized by 93.1% mass retention, 5.1% radioactivity, and 15.4% decay heat, relative to the original spent fuel. The findings underscore the potential effectiveness of a sequential chlorination strategy for partitioning spent fuel. This approach holds promise as a standalone technique or as a complementary process alongside other partitioning processes such as pyroprocessing. Overall, our findings contribute to the advancement of spent fuel management strategies.

The safe disposal of high-level radioactive waste (HLW), including the discharged spent nuclear fuel (SNF) and contaminated by-products produced from relevant chemical treatments, has become a serious pending problem for numerous countries that operate the nuclear power plants. The deep geological disposal (DGD) has thus far been considered the most proven and viable solution for isolation of the HLW and preventing any significant release of radionuclides into the biosphere. The DGD system consists of the multiple engineered and natural barrier components. Among them, the montmorillonite-based buffer and tunnel backfills are designed to perform the two major geochemical functions: 1) preventing the ingress of groundwater and any chemicals that compromise the safety of waste canister and 2) retarding the migration of released radionuclides by providing sufficient chemisorption sites. Therefore, it is essential to investigate the sorption mechanism of radionuclides onto montmorillonite and develop a thermodynamic reaction model in advance in order to accurately predict the long-term performance of engineered barriers and to reduce the uncertainties in the safety assessment of a deep geological repository (DGR) ultimately; thus far, sorption of chemical species onto mineral adsorbents has been widely described based on the concept of sorption-desorption distribution coefficient (Kd), the value of which is intrinsically conditional, and active scientific efforts have been made to develop robust thermodynamic sorption models which offer the potential to improve confidence in demonstration of radionuclide migration under a wide range of geochemical conditions. The natural montmorillonites are generally classified into Na-type or Ca-type according to its exchangeable cation, and the Ca-montmorillonite containing clays are being considered as candidate materials for the engineered barriers of DGR in several countries; they generally have advantages of higher thermal conductivity and lower price than the Na-montmorillonite based clays, but their sorption capacities are still comparable. In this framework, we aimed to investigate the chemical interactions of Ca-montmorillonite with selenite [Se(IV)], which is a major oxyanionic species in terms of HLW disposal, and develop a reliable thermodynamic sorption model (TSM). The present work summarizes the characterization of Ca-montmorillonite separated from the newly adopted reference bentonite (Bentonil-WRK) by means of XRD, BET, FTIR, CEC measurement, and acid-base titration. Further, its sorption behaviors with aqueous selenite species under aqueous conditions of S/L = 5 g/L, I = 0.01-0.1 m CaCl2, pH = 4.5-8.5, pCO2 = 10-3.5 atm, and T = 25°C were examined, and the resulting thermodynamic data are discussed as well.

For the safety assessment of the high-level radioactive waste (HLRW) disposal, the thermodynamic data such as solubility products, formation constants of complexes, redox equilibrium constants of radionuclides, and their reaction enthalpy and entropy are required. In order to recommend and summarize the reliable data, thermodynamic databases (TDB) have been persistently developed through the OECD-NEA TDB projects and an updated TDB of actinides has been recently published in 2020. To date, reliable data for Pu reactions are scarce due to the possibility of coexistence of four different oxidation states, Pu(III-VI) by redox equilibria in solutions. To determine the thermodynamic data for the reaction of each Pu oxidation state, it is necessary to precisely control the oxidation state and quantitatively analyze all reactants, products and bi-products by using highly sensitive speciation techniques. Since 2004, the nuclear chemistry research team in KAERI has been focused on developing techniques for the sensitive chemical speciation by using laser-based spectroscopy and determining thermodynamic data of actinides such as U, Pu, Am. In this paper, chemical speciation and thermodynamic studies on Pu in KAERI are reviewed. A combination of a commercial spectrophotometer and a capillary cell was adopted for a sensitive chemical speciation of Pu(III-VI) in solutions. A sensitive detection of trace amount of Pu colloids was carried out with the laser-induced breakdown detection (LIBD) system. Pu(VI) complexation with hydroxide or carbonate ions were investigated under strong oxidation conditions controlled with hypochlorite (NaOCl). The solubility product of Pu(OH)3(am) and formation constant of Pu(III)-OH speices were determined by a combination of wet-chemistry experiments and several analysis methods of spectrophotometry, LIBD, radiometry under a strong reducing condition controlled by electrochemistry. More recently, we reported the reaction enthalpy and entropy data for the formation of Pu(OH)2+ and the dissolution of Pu(OH)3(am). A preliminary data for reaction between Pu(III) and organic matter will be presented.

Abstract In the present study, the effect of nickel nitrate addition as a catalytic precursor for the in situ formation of Ni nanoparticles during the heating process has been investigated on the modification of microstructure and graphitization of amorphous carbon resulting from pyrolysis of phenolic resin. For this purpose, the prepared resin samples were cured in carbon substrate with and without additives at temperatures of 800, 1000, and 1250 °C. XRD, FESEM, and TEM studies were performed to investigate the phase and microstructural changes in the samples during the heating process. In addition to phase and microstructural studies, thermodynamic calculations of the reactions performed for the in situ formation of nickel nanoparticles and their effective factors during the curing process were performed. The results indicated that nickel nitrate is transformed to nickel nanoparticles of different sizes during the reduction process in a reduced atmosphere. The in situ formation of nickel nanoparticles and its catalytic effect led to the graphitization of carbon resulting from the pyrolysis of phenolic resin at a temperature of 800 °C and above. By increasing temperature, the morphology of the formed graphite changed and hollow carbon nanotubes, carbon cells, and onion skin carbon were formed in the microstructure. It was also observed that by increasing the temperature and the amount of additive, carbon nanotubes and their size are increased. A noteworthy point from thermodynamic calculations during the formation of nickel nanoparticles was that the nickel nanoparticles themselves acted as accelerators of nickel oxide reduction reactions and the formation of nickel nanoparticles. This increases the amount of amorphous carbon graphitization resulting from the pyrolysis of phenolic resin which leads to the formation of more carbon nanotubes at higher temperatures.

A deep geological disposal system, which consists of the engineered and natural barrier components, is the most proven and widely adopted concept for a permanent disposal of the high level radioactive waste (HLW) thus far. The clay-based engineered barrier is designed to not only absorb mechanical stress caused by the geological activities, but also prevent inflow of groundwater to canister and outflow of radionuclides by providing abundant sorption sites. The principal mineralogical constituent of the clay material is montmorillonite, which is a 2:1 phyllosilicate having two tetrahedral sheets of SiO2 sandwiching an octahedral sheet of Al2O3. The stacking of SiO2 and Al2O3 sheets form the layered structures, and ion-exchange and water uptake reactions occur in the interlayer space. In order to reliably assess the radionuclide retention capacity of engineered barrier under wide geochemical conditions relevant to the geological disposal environments, sorption mechanisms between montmorillonite and radionuclides should be explicitly investigated in advance. Thus far, sorption behavior of mineral adsorbents with radionuclides has been quantified by the sorption-desorption distribution coefficient (Kd), which is simply defined as the ratio of radionuclide concentration in the solid phase to that in the equilibrium solution; the Kd value is conditional, and there have been scientific efforts to develop geochemically robust bases for parameterizing the sorption phenomena more reliably. In this framework, application of thermodynamic sorption model (TSM), which is theoretically based on the concept of widely accepted equilibrium models for aquatic chemistry, offers the potential to improve confidence in demonstration of radionuclide sorption reactions on the mineral adsorbents. Specifically, it is generally regarded in the TSM that coordination of radionuclides on montmorillonite takes place at the surficial aluminol and silanol groups while their ion-exchange reactions occur in the interlayer space also. The effects of electrical charge on the surface reactions are additionally corrected in accordance with the numerous theories of electrochemical interface. The present work provides an overview of the current status of application of TSM for quantifying sorption behaviors of radionuclides on montmorillonite and experimental results for physical separation and characterization of Ca-montmorillonite from the newly adopted reference bentonite (Bentonil- WRK) by means of XRD, BET, FTIR, CEC measurement, and acid-base titration. The determined mineralogical and chemical properties of the montmorillonite obtained will be used as input parameters for further sorption studies of radionuclides with the Bentonil-WRK montmorillonite.

Strontium is known as a salt-soluble element during the electrolytic oxide reduction (EOR) process. The chemical behavior of SrO during EOR was investigated via thermodynamic calculations to provide quantitative data on the chemical status of Sr. To achieve this, thermodynamic calculations were conducted using HSC chemistry software for various EOR conditions. It was revealed that SrO reacts with LiCl salt to produce SrCl2, even in the presence of Li2O, and that the ratio of SrCl2 depends on the initial concentration of Li2O dissolved in LiCl. It was found that SrO reacts with Li to produce Sr during EOR and that the reduced Sr reacts with LiCl salt to produce SrCl2. As a result, the proportions of metallic forms were lower in Sr than in La and Nd under various EOR conditions. The thermodynamic calculations indicated that the three chemical forms of SrO, SrCl2, and Sr co-exist in the EOR system under an equilibrium with Li, Li2O, and LiCl.

양이온성 계면활성제 (DTAB, TTAB 및 CTAB)에 의한 아닐린의 가용화현상을 연구하기 위하여 UV-Vis법을 이용하여 가용화상수(Ks)와 열역학 함수들을 계산하고 비교하였다. 그리고 이온염과 유기물의 첨가가 가용화상수에 어떠한 영향을 미치는지를 조사하였다. 또한 온도변화에 따른 Ks값의 변화를 계면활성제 종류별로 비교하고 분석하였으며, 가용화상수로부터 구한 여러 열역학적 함수를 비교하고 검토함으로써 아닐린의 가용화현상을 미시적으로 분석하고 해석하고자 하였다. 그 결과 양이온성 계면활성제에 의한 아닐린의 가용화현상에 대한 Gibbs 자유에너지와 엔탈피 변화 값은 모두 음의 값을 그리고 엔트로피 변화값은 모두 양의 값을 나타내었다. 가용화상수 값은 온도가 증가함에 따라 감소하고 계면활성제의 탄소사슬의 길이가 증가할수록 증가하였다. 이온염의 농도가 증가함에 따라 가용화에 대한 Gibbs 자유에너지값은 증가하다가 감소하는 경향을 보였다. 그리고 n-부탄올의 농도가 증가함에 따라 Gibbs 자유에너지는 계속 증가하는 경향을 보였다.

사고저항성 핵연료의 일환으로 UO2 입자가 세라믹 셀 벽으로 둘러싸인 미세구조를 갖는 세라믹 미소셀 UO2 소결체를 개발 중이다. 이는 핵분열생성물들을 UO2 펠렛 내에 포집하여 펠렛 외부로의 방출을 저감함으로써 봉내압 상승을 완화하고 응력부식균열 발생률을 낮춘다. 생성량이나 방사능 측면에서 위험한 핵분열생성물 중 하나로 여겨지는 세슘은 세라믹 미소셀 소결체 내에서 셀 물질과 화학반응 하여 포집될 수 있다. 따라서, 세슘 포집능은 해당 화학반응의 열역학적, 속도론적 특성에 의해 결정된다. 역으로, 미소셀 소결체의 조성설계 시 해당 반응에 대한 열역학적 예측이 필수적이다. 본 연구는 세라믹 현재 개발 중인 여러 미소셀 조성(Si-Ti-O, Si-Cr-O, Si-Al-O)에 대해 세슘의 포집능을 평가하는 열역학적 계산을 다룬다. 계 산에 앞서 먼저 HSC Chemistry를 이용해 세슘과 셀 물질의 물리/화학적 상태를 정의한 후, LWR 정상운전 모사환경에서 계 산된 세슘포텐셜(ΔGCs)과 산소포텐셜(ΔG02)에 근거하여 세슘포집 반응성을 평가하였다. 계산 결과에 근거하면, 세슘 포집 반응은 상기 모든 조성에서 자발적일 것으로 예상되며 이로써 조성설계의 근거를 제시함과 동시에 세슘의 포집능을 평가하는 효과적인 방법을 제공한다.