• Journal of the Korean Applied Science and Technology
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• v.7 no.1
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• pp.93-105
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• 1990

Semicarbazone formation of nine monosubstituted benzaldehydes was studied kinetically in 20% methanol buffer solution at 15, 25, 35, and $45^{circ}C$. The rate of p-nitrobenzaldehyde semicarbazone formation is 2.7 times as fast as that of benzaldehyde, while p-hvdroxybenzaldehyde is 3.6 times as slow as that of benzaldehyde. Activation energies for p-chlorobenzaldehyde, benzaldehyde, p-methylbenzaldehyde, p-methoxybenzaldshyde, p-hydroxybenzaldehyde, and p-dimethylaminobenzaldehyde semicarbazone formation are calculated as 5.80, 6.19, 6.57, 7.06, 8.03, and 6.46 kcal/mol respectively. It is concluded from the effect of ionic strength that the reaction is affected by not ions but neutral molecules involving hydrogen bonding between oxygen atom of carbonyl group and hydrogen atom of acid-catalyst, and concerted attack of the necleophilic reagent, free base on carbonyl compound. Also, the effect of solvent composition is small in 20% and 50% methanol (and ethanol) aqueous solutions. The ${\rho}-{\sigma}$ plots for the rates of semicarbazone formation at pH 7.1 show a linear ${\rho}-{\sigma}$ relationship (${\rho}=0.14l$, in contrast to that at pH 2.75 and pH 5.4 corresponding to ${\rho}-{\sigma}$ correlations reparted by Jencks. The rate of semicarbazone formation at pH 5.4 show a relationship which is convex upward, resulting in a break in the curve but at pH 2.75, slight difference from a linear relationship. As a result of studying citric acid catalysis, second-order rate constants increase linearly with citric acid concentration and show a 2 times increase as the catalyst concentration is varied from 0.025 to 0.1 mol/1 at pH 2,9, but slight increase at pH 5.3. The rate-determining step is addition below pH 5 but is dehydration between pH 5 and 7. Conclusively, the rate-determining step of the reaction changes from dehydration to addition in respect to hydrogen ion activity near pH 5. The ortho: para rate ratio of the hydroxybenzaldehydes for semicarbazone formation is about 17 at $15^{\circ}C$. It is concluded that the results constitute strong evidence in favor of greater stabilization of p- than o-hydroxybenzaldehyde by substituent which donate electrons by resonance and is due to hydrogen bonding between the carbon-bound hydrogen of the-CHO group and the oxygen atom of the substituent.

• Bulletin of the Korean Chemical Society
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• v.33 no.1
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• pp.48-54
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• 2012

The $[Fe_4S_4]^{2+}$ clusters with 2-, 3-, and 4-pyridinemethanethiolate (S2-Pic, S3-Pic, and S4-Pic, respectively) terminal ligands have been synthesized from the ligand substitution reaction of the $(^nBu_4N)_2[Fe_4S_4Cl_4]$ (I) cluster. The new $(^nBu_4N)_2[Fe_4S_4(SR)_4]$ (R = 2-Pic; II, 3-Pic; III, 4-Pic; IV) clusters were characterized by FTIR and UV-Vis spectroscopy. Cluster II was crystallized in the monoclinic space group C2/c with a = 24.530 (5) $\AA$, b = 24.636(4) $\AA$, c = 21.762(4) $\AA$, ${\beta}=103.253(3)^{\circ}$, and Z = 8. The X-ray structure of II showed two unique 2:2 site-differentiated $[Fe_4S_4]^{2+}$ clusters due to the bidentate-mode coordination by 2-pyridinemethanethiolate ligands. Cluster III was crystallized in the same monoclinic space group C2/c with a = 26.0740(18) $\AA$, b = 23.3195(16) $\AA$, c = 22.3720(15) $\AA$, ${\beta}=100.467(2)^{\circ}$, and Z = 8. The 3-pyridinemethanethiolate ligand of III was coordinated to the $[Fe_4S_4]^{2+}$ core as a terminal mode. Cluster IV with 4-pyridinemethanethiolate ligands was found to have a similar structure to the cluster III. Fully reversible $[Fe_4S_4]^{2+}/[Fe_4S_4]^+$ redox waves were observed from all three clusters by cyclic voltammetry measurement. The electrochemical potentials for the $[Fe_4S_4]^{2+}/[Fe_4S_4]^+$ transition decreased in the order of II, III and IV, and the reduction potential changes by the ligands were explained based on the structural differences among the complexes. The complex III was reacted with sulfonium salt of $[PhMeSCH_2-p-C_6H_4CN](BF_4)$ in MeCN to test possible radical-involving reaction as a functional model of the [$Fe_4S_4$]-SAM (S-adenosylmethionine) cofactor. However, the isolated reaction products of 3-pyridinemethanethiolate-p-cyanobenzylsulfide and thioanisole suggested that the reaction followed an ionic mechanism and the products formed from the terminal ligand attack to the sulfonium.

• Economic and Environmental Geology
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• v.12 no.1
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• pp.41-49
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• 1979

A literature review is made on the physical and chemical characteristics of clay minerals in acidic solutions from the mineralogical and hydrometallurgical viewpoints. Some of the important characteristics of clays are their ability to cation exchange, swelling, and incongruent dissolution in acidic solutions. Various clay minerals can take up metallic ions from solution via cation exchange mechanism. Generally, cation exchange capacity increases in the following order : kaolinite, halloysite, illite, vermiculite, and montmorillonite. In acidic solutions, the cation uptake such as copper by clay minerals is strongly inhibited by hydrogen and aluminum ions and thus is not economically significant factor for recovery of metals such as uranium and copper. In acidic solutions, the cation uptake is substial. Swelling is minimal at lower pH, possibly due to lattice collapse. Swelling may be controllable with montmorillonite type clays by exchanging interlayer sodium with lithium and/or hydroxylated aluminum species. The effect of add on clay minerals are : 1. Division of aggregates into smaller plates with increase in surface area and porosity. 2. Clay-acid reactions occur in the following order: (i) $H^+$ replacement of interlayer cations, (ii) removal of octahedral cations, such as Al, Fe, and Mg, and (iii) removal of tetrahedral Al ions. Acid attack initiates, around the edges of the clay particles and continued inward, leaving hydrated silica gel residue around the edges. 3. Reaction rates of (ii) and (iii) are pseudo-1st order and proportional to acid concentration. Rate doubles for every temperature increment of $10^{\circ}C$. Implications in in-situ leaching of copper or uranium with acid are : 1. Over the life span of the operation for a year or more, clays attacked by acid will leave silica gel. If such gel covers the surface of valuable mineral surfaces being leached, recovery could be substantially delayed. 2. For a copper deposit containing 0.5% each of clay minerals and recoverable copper, the added cost due to clay-acid reaction is about 1.5c/lb of copper (or 0.93 lbs of $H_2SO_4/1b$ of copper). This acid consumption by clay may be a factor for economic evaluation of in-situ leaching of an oxide copper deposit.

• Journal of the Korean Chemical Society
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• v.38 no.10
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• pp.753-762
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• 1994

Dephosphorylation of diphenyl- or isopropylphenyl-4-nitrophenylphosphinate (DPNPIN or IPNPIN) mediated by $OH^-$ or o-iodosobenzoate ion ($IB^-$) are relatively slow in aqueous solution. The reactions in CTAX micellar solutions are, however, very accelerated, because CTAX micelles can accommodate both reactants in their Stern layer in which they can easily react, while hydrophilic $OH^-$(or $IB^-$) and hydrophobic phosphinates are not mixed in water. Even though the concentrations (> $10^{-3}$ M) of $OH^-$(or $IB^-$) in CTAX solutions are much larger amounts than those ($6{\times}10^{-6}$ M) of phosphinates, the rate constants of the dephosphorylations are largely influenced by change of the concentration of the ions, which means that the reactions are not followed by the pseudo first order kinetics. In comparison to effect of the counter ions of CTAX in the reactions, CTACl is more effective on the dephosphorylation of DPNPIN (or IPNPIN) than CTABr due to easier expelling of $Cl^-$ ion by $OH^-$(or $IB^-$) ion from the micelle, because of easier solvation $Cl^-$ ion by water molecules. The reactivity of IPNPIN with $OH^-$(or $IB^-$) is lower than that of DPNPIN. The reason seems that the 'bulky' isopropyl group of IPNPIN hinders the attack of the nucleophiles. The mechanism of reaction of IPNPIN with IB- ion concluded as 'nucleophilic' instead of 'general basic' by a trapping experiment and a measured kinetic isotope effect.

• Korean Journal of Heritage: History & Science
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• v.53 no.4
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• pp.188-197
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• 2020

Termites play an important role as decomposers of the forest ecosystem, while simultaneously causing enormous damage to wooden structures. Currently, two species of subterranean termites have been reported in Korea, and termite damage to historical wooden buildings is occurring nationwide due to climate change, forest fertility, and the locational characteristics of historical wooden buildings. Subterranean termites make their nests underground or inside timber. Termites move underground and access wooden structures through the lower parts of the buildings, adjacent to the ground. Once termites attack the wooden structures, it not only spoils the authenticity of cultural heritage structure, but also hampers structural stability due to the decrease in the strength of the material. Therefore, it is important to prevent termite damage before it occurs. Chemical treatments are mainly used in Korea to control and prevent the damage. In foreign countries, physical barriers are also used to prevent entry to wooden buildings, along with chemical treatments. Physical barriers involve installing nets or particles that termites cannot pass through in the lower part of the building, around the pipes, and between the edges of the building or exterior walls and interior materials. Advantages of a physical barrier are that it is an eco-friendly method, maintains long-term effect after installation, and does not require the use of chemical treatments. Prior to applying physical barriers, studies into the characteristics of termite species must be undertaken. In this study, we evaluated the minimum passage size that each caste of Reticulitermes speratus kyushuensis can move through. We found that workers, soldiers, and secondary reproductive termites were able to pass through diameters of 0.7mm, 0.9mm, and 1.1mm respectively. Head height of termites was an important factor in determining the minimum passing size. Results from the current study will be used as a basis to design the mesh size for physical barriers to prevent damage by termites in historical wooden buildings in Korea.

• Journal of the Korea Concrete Institute
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• v.26 no.1
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• pp.71-78
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• 2014

The long term integrity of concrete cask is very important for spent nuclear fuel dry storage system. However, there are serious concerns about early deterioration of concrete cask from creaking and corrosion of reinforcing steel by chloride ion because the cask is usually located in seaside, expecially by combined deterioration such as chloride ion and heat, carbonation. This study is to investigate the relation between temperature and chloride ion diffusion of concrete. Immersion tests using 3.5% NaCl solution that were controlled in four level of temperature, i.e. 20, 40, 65, and $90^{\circ}C$, were conducted for four months. The chloride ion diffusion coefficient of concrete was predicted based on the results of profiles of Cl- ion concentration with the depth direction of concrete specimens using the method of potentiometric titration by $AgNO_3$. Test results indicate that the diffusion coefficient of chloride ion increases remarkably with increasing temperature, and there was a linear relation between the natural logarithm values of the diffusion coefficients and the reciprocal of the temperature from the Arrhenius plots. Activation energy of concrete in this study was about 46.6 (W/C = 40%), 41.7 (W/C = 50%), 30.7 (W/C = 60%) kJ/mol under a temperature of up to $90^{\circ}C$, and concrete with lower water-cement ratio has a tendency towards having higher temperature dependency.

• Journal of the Korea Concrete Institute
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• v.15 no.1
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• pp.25-34
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• 2003

The degradation of reinforced concrete (RC) structures due to physical and chemical attacks has been a major issue in construction engineering. Deterioration of RC structures by chloride attack followed by reinforcement corrosion is one of the serious problems. An objective of this study is to develop a form of mathematical model of chloride ingress into concrete. In order to overcome some limits of the previous approaches, a chloride ingress model, consisting of chloride solution intrusion through the capillary pore and chloride ion diffusion through the pore water, was proposed. Moreover, the variability of chloride ion diffusivity due to the degree of hydration of cement, relative humidity in pore, exposure condition, and variation of chloride binding, was considered in the model. In order to verify the proposed model, the results predicted by the proposed model were compared with analysis results of Life-365, a computer program for predicting the service life of reinforced concrete structures exposed to chlorides. In conclusion, the proposed model would be promising to predict the chloride ion profile and to estimate the service life of RC structures.

• Journal of the Korea Institute of Information Security & Cryptology
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• v.30 no.4
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• pp.745-756
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• 2020

An ICS(industrial control system) is a complex system that safely and efficiently monitors and controls industrial processes such as electric power, water treatment, transportation, automation plants and chemical plants. Because successful cyber attacks targeting ICS can lead to casualties or serious economic losses, it becomes a prime target of hacker groups sponsored by national state. Cyber campaigns such as Stuxnet, Industroyer and TRITON are real examples of successful ICS attacks, and were developed based on the deep knowledge of the target ICS. Therefore, for incident investigation of ICSs, inspectors also need knowledge of control processes and accident investigation techniques specialized for ICSs. Because there is no applicable technology, it is especially necessary to develop techniques and tools for embedded controllers located at cyber and physical boundaries. As the first step in this research, we reviewed logging capability of 4 PLC(Programmable Logic Controller)s widely used in an ICS area, and checked whether selected PLCs generate logs that can be used for digital investigation in the proposed cyber attack scenario.

• Economic and Environmental Geology
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• v.29 no.2
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• pp.215-225
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• 1996

All the radionuclides in high-level nuclear waste will decay to harmless levels eventually but for some radionuclides decay is so slow that their radiation remains dangerous for times on the order of tens or hundreds of thousands of years. At the present time, the most favorite disposal plan for high-level radioactive waste is a mined geological disposal in which canister enclosing stable solid form of radioactive waste is placed in mined cavities locating hundred meters below the surface. The chief hazard in such disposal is dissolution of radionuclides from the waste in the groundwater that will eventually carry the dissolved radionuclides to surface environments. The hazard from possible escape of the radionuclides through groundwater can be delayed by engineered and geologic barriers. The engineered barriers can become useless by unexpected geologic catastrophe such as volcanism, earthquake, and tectonic movement and by fraudulent work such as careless construction, improperly welded canisters within the first few decades or centuries. As a result, dangerously radioactive waste which is still intensively radioactive is directly exposed to attack by moving groundwater. All the more, it is almost impossible to control repositories for times more than 10,000 years. Therefore, naturally controlled geologic, barriers whose properties will not be changed within 10,000 years are important to guarantee the safety of repositories of high-level radioactive waste. In Sweden and France, the suitability of granite for the mined geological disposal of high-level waste has been studied intensively. According to the research in Sweden and France, granites has the following physio-chemical characteristics which can delay the transportation of radionuclide by groundwater. First, the permeabilities of granites decreases as the depth increases and is $10^{-8}{\sim}10^{-12}m/s$ at depth below 300 m. Second, groundwater at depth below 300 m has pH=7-9 and reducing condition (Eh=-0.1~0.4). This geochemical condition is desirable to prevent both canister and solid waste from corrosion. Third most radionuclides are not transported by low solubilities and some radionuclide with high solubility such as Cs and Sr are retarded by absorption of geologic media through which ground water flows. Therefore, if high-level waste is disposed at depth below 300 m in the granite body which has a low permeability and is geologically stable more than 10,000 years, the safety of repositories from the hazard due to radionuclide escape can guaranteed for more than 10,000 years.

• Journal of Korean Ophthalmic Optics Society
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• v.19 no.3
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• pp.403-406
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• 2014

Purpose: In this study, we studied ocular disease by age in Ulsan. Methods: We checked medical record of 300 patients who visited eye clinic in Ulsan. Results: The main ocular disease on the age of 10 was keratitis, that of 20 was dry eye syndrome & keratitis, that of 30 was chalazion & conjunctivitis, that of 40~50 was conjunctivitis, that of 60 was conjunctivitis & cataract. Conclusions: The main cause of ocular disease of 10~20's are unsuitable wear of contact lenses & long-time use of smart phone as well as computer. That of 30~50's are allergic conjunctivitis and chemical material reaction as well as other several factors. Especially, attack rate of conjunctivitis of 30~50's is higher than city because of industrial area (Ulsan). The main cause of ocular disease in 50~60's is a kind of senility. Therefore, based on the results of this study, it could be used the basic data of education on ocular disease prevention in Ulsan.