• 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.

• Molecules and Cells
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• v.38 no.5
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• pp.409-415
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• 2015

Low-barrier hydrogen bonds (LBHBs) have been proposed to have important influences on the enormous reaction rate increases achieved by many enzymes. ${\Delta}^5$-3-ketosteroi isomerase (KSI) catalyzes the allylic isomerization of ${\Delta}^5$-3-ketosteroid to its conjugated ${\Delta}^4$-isomers at a rate that approache the diffusion limit. Tyr14, a catalytic residue of KSI, has been hypothesized to form an LBHB with the oxyanion of a dienolate steroid intermediate generated during the catalysis. The unusual chemical shift of a proton at 16.8 ppm in the nuclear magnetic resonance spectrum has been attributed to an LBHB between Tyr14 $O{\eta}$ and C3-O of equilenin an intermediate analogue, in the active site of D38N KSI. This shift in the spectrum was not observed in Y30F/Y55F/D38N and Y30F/Y55F/Y115F/D38N mutant KSIs when each mutant was complexed with equilenin, suggesting that Tyr14 could not form LBHB with the intermediate analogue in these mutant KSIs. The crystal structure of Y30F/Y55F/Y115F/D38N-equilenin complex revealed that the distance between Tyr14 $O{\eta}$ and C3-O of the bound steroi was within a direct hydrogen bond. The conversion of LBHB to an ordinary hydrogen bond in the mutant KSI reduced the binding affinity for the steroid inhibitors by a factor of 8.1-11. In addition, the absence of LBHB reduced the catalytic activity by only a factor of 1.7-2. These results suggest that the amount of stabilization energy of the reaction intermediate provided by LBHB is small compared with that provided by an ordinary hydrogen bond in KSI.

• Clean Technology
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• v.27 no.1
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• pp.69-78
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• 2021

Vegetable oils, such as palm oil and cashew nut shell liquid (CNSL), are used as major raw materials for bio-diesel in transportation and bio-heavy oil in power generation in South Korea. However, due to the high unsaturation degree caused by hydrocarbon double bonds and a high content of oxygen originating from the presence of carboxylic acid, the range of applications as fuel oil is limited. In this study, hydrotreating to saturate unsaturated hydrocarbons and remove oxygen in mixed bio-oil containing 1/1 v/v% palm oil and CNSL on monometallic catalysts (Ni and Cu) and bimetallic catalysts (Ni-Zn, Ni-Fe, Ni-Cu Ni-Co, Ni-Pd, and Ni-Pt) was perform under mild conditions (T = 250 ~ 400 ℃, P = 5 ~ 80 bar and LHSV = 1 h-1). The addition of noble metals and transition metals to Ni showed synergistic effects to improve both hydrogenation (HYD) and hydrodeoxygenation (HDO) activities. The most promising catalyst was Ni-Cu/��-Al2O3, and in the wide range of the Ni/Cu atomic ratio of 9/1~1/4, the conversion for HYD and HDO reactions of the catalysts were 90-93% and 95-99%, respectively. The tendency to exhibit almost constant reaction activity in these catalysts of different Ni/Cu atomic ratios implies a typical structure-insensitive reaction. The refined bio-oil produced by hydrotreating (HDY and HDO) had significantly lower iodine value, acid value, and kinetic viscosity than the raw bio-oil and the higher heating value (HHV) was increased by about 10%.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.10 no.1
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• pp.45-53
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• 2012

The metal chloride wastes from a pyrochemical process to recover uranium and transuranic elements has been considered as a problematic waste difficult to apply to a conventional solidification method due to the high volatility and low compatibility with silicate glass. In this study, a dechlorination approach to treat LiCl-KCl waste for final disposal was adapted. In this study, a $SiO_2-Al_2O_3-P_2O_5$ (SAP) inorganic composite as a dechlorination agent was prepared by a conventional sol-gel process. By using a series of SAPs, the dechlorination behavior and consolidation of reaction products were investigated. Different from LiCl waste, the dechlorination reaction occurred mainly at two temperature ranges. The thermogravimetric test indicated that the first reaction range was about $400^{\circ}C$ for LiCl and the second was about $700^{\circ}C$ for KCl. The SAP 1071 (Si/Al/P=1/0.75/1 in molar) was found to be the most favorable SAP as a dechlorination agent under given conditions. The consolidation test revealed that the bulk shape and the densification of consolidated forms depended on the SAP/Salt ratios. The leaching test by PCT-A method was performed to evaluate the durability of consolidated forms. This study provided the basic information on the dechlorination approach. Based on the experimental results, the dechlorination method using a $SiO_2-Al_2O_3-P_2O_5$ (SAP) could be considered as one of alternatives for the immobilization of waste salt.

• Journal of Korean Society of Environmental Engineers
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• v.29 no.8
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• pp.895-903
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• 2007

As for the increasing demanding on the development of direct-ecological landfill monitoring methods, it is needed for critically defining the condition of landfills and their influence on the environment, quantifying the amount of enzymes and bacteria mainly concerned with biochemical reaction in the landfills. This study was thus conducted to understand the fates of contaminants in association with groundwater quality parameters. For the study, groundwater was seasonally sampled from four closed unsanitary landfills(i.e. Cheonan(C), Wonju(W), Nonsan(N), Pyeongtaek(P) sites) in which microbial diversity was simultaneously obtained by 16S rDNA methods. Subsequently, a number of primer sets were prepared for quantifying the specific gene of representative bacteria and the gene of encoding enzymes dominantly found in the landfills. The relationship between water quality parameters and gene quantification were compared based on correlation factors. Correlation between DSR(Sulfate reduction bacteria) gene and BOD(Biochemical Oxygen Demand) was greater than 0.8 while NSR(Nitrification bacteria-Nitrospira sp.) gene and nitrate were related more than 0.9. A stabilization indicator(BOD/COD) and MTOT(Methane Oxidation bacteria), MCR(Methyl coenzyme M reductase), Dde(Dechloromonas denitrificans) genes were correlated over 0.8, but ferric iron and Fli(Ferribacterium limineticm) gene were at the lowest of 0.7. For MTOT, it was at the highest related at 100% over BOD/COD. In addition, anaerobic genes(i.e., nirS-Nitrite reductase, MCR. Dde, DSR) and DO were also related more than 0.8, which showing anaerobic reactions generally dependant upon DO. As demonstrated in the study, molecular biological investigation and water quality parameters are highly co-linked, so that quantitative real-time PCR could be cooperatively used for assessing landfill stabilization in association with the conventional monitoring parameters.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.5 no.3
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• pp.171-177
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• 2007

This study suggested a new method to stabilize molten salt wastes generated from the pyre-process for the spent fuel treatment. Using conventional sol-gel process, $SiO_2-Al_2O_3-P_2O_5$ (SAP) inorganic material that is reactive to metal chlorides were prepared. In this paper, the reactivity of SAP with the metal chlorides at $650{\sim}850$, the thermal stability of reaction products and their leach-resistance under the PCT-A test method were investigated. Alkali metal chlorides were converted into metal aluminosilicate($LixAlxSi1-_xO_{2-x}$) and metal phosphate($Li_3PO_4\;and\;Cs_2AlP_3O_{10}$) While alkali earth and rare earth chlorides were changed into only metal phosphates ($Sr_5(PO_4)_3Cl\;and\;CePO_4$). The conversion rate was about $96{\sim}99%$ at a salt waste/SAP weight ratio of 0.5 and a weight loss up to $1100^{\circ}C$ measured by thermogravimetric analysis were below 1wt%. The leach rates of Cs and Sr under the PCT-A test condition were about $10^{-2}g/m^2\;day\;and\;10^{-4}g/m^2\;day$. From these results, it could be concluded that SAP can be considered as an effective stabilizer for metal chlorides and the method using SAP will give a chance to reduce the volume of salt wasteform for the final disposal through further researches.

• The Korean Journal of Food And Nutrition
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• v.17 no.3
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• pp.294-301
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• 2004

Effects of superoxide dismutase(SOD), catalase(CAT), and such other proteins as bovine serum albumin(BSA), ovalbumin, lysozyme, and v-globulin on the autoxidation rates of L-ascorbic acid(AsA) in the absence of heavy metal ions and in the presence of Fe(III) or Cu(II) ions in water were examined. AsA was dissolved in a ultra-refined water at a concentration of 50 ${\mu}$M and 5 ${\mu}$M Fe(III) or 0.1 ${\mu}$M Cu(II) were added, and a oxygen gas was bubbled through the solution at a flow rate of 200 ml/min at 35$^{\circ}C$. The amount of remaining AsA in the reaction mixture was determined by using a UV spectrophotometer(at 265 nm). It was found that the Cu(II) at a concentration of 0.1 ${\mu}$M had a more accelerated for the autoxidation of AsA than Fe(III) at 5 ${\mu}$M. Moreover, it was confirmed that the ratio of remaining AsA was significantly larger in the presence of SOD, CAT, BSA, ovalbumin, lysozyme, and v-globulin than in the absence of proteins. The stabilization of AsA by various proteins were confirmed during the autoxidation of AsA in the presence of Fe(III) or Cu(II) in water. It was suggested that the non-enzymatic effects of SOD, CAT and some other proteins might be involves in the stabilization of AsA.

• Journal of Soil and Groundwater Environment
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• v.14 no.6
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• pp.78-86
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• 2009

Applicability of CaO and steel slag as stabilizers in the treatment of field and paddy soils near Pungjeong mine contaminated with arsenic and cationic heavy metals was investigated from batch and column experiments. Immobilization of heavy metals was evaluated by TCLP dissolution test. Immobility of heavy metal ions was less than 15% when steel slag alone was used. This result suggests that $Fe_2O_3$ and $SiO_2$, known as the major component of steel slag, have little effect for the immobilization of heavy metal ions due to acidity of TCLP solution. Immobilization of cationic heavy metals was little affected by the ratio of CaO and steel slag while arsenic removal was increased as the ratio of steel slag to CaO increased. In the column test, concentrations of both arsenic and cationic heavy metals in effluents were below the water discharge guideline over the entire reaction period. This result can be explained by the immobilization of cationic heavy metals from the increased pH in soil solution as well as by the formation of insoluble $Ca_3(AsO_4)_2$. From this work, it is possible to suggest that arsenic and cationic heavy metals can be concurrently stabilized by application of both CaO and steel slag.

• Economic and Environmental Geology
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• v.43 no.1
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• pp.13-20
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• 2010

Acid mine drainage (AMD) from abandoned mine sites typically has low pH and contains high level of various heavy metals, aggravating ground- and surface water qualities and neighboring environments. This study investigated removal of heavy metals in a biological treatment system, mainly focusing on the removal by adsorption on a substrate material. Bench-scale batch experiments were performed with a mushroom compost to evaluate the adsorption characteristics of heavy metals leached out from a mine tailing sample and the role of SRB in the overall removal process. In addition, adsorption experiments were perform using an artificial AMD sample containing $Cd^{2+}$, $Cu^{2+}$, $Pb^{2+}$ and $Zn^{2+}$ to assess adsorption capacity of the mushroom compost. The results indicated Mn leached out from mine tailing was not subject to microbial stabilization or adsorption onto mushroom compost while microbially mediated stabilization played an important role in the removal of Zn. Fe leaching significantly increased in the presence of microbes as compared to autoclaved samples, and this was attributed to dissolution of Fe minerals in the mine tailing in a response to the depletion of $Fe^{3+}$ by iron reduction bacteria. Measurement of oxidation reduction potential (ORP) and pH indicated the reactive mixture maintained reducing condition and moderate pH during the reaction. The results of the adsorption experiments involving artificial AMD sample indicated adsorption removal efficiency was greater than 90% at pH 6 condition, but it decreased at pH 3 condition.

• Bulletin of the Korean Chemical Society
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• v.27 no.9
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• pp.1310-1314
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• 2006

Sulfur-substituted $LiMn_{0.9}Cr_{0.1}O_{2-x}S_x$ $(0\;\leq\;x\;\leq\;0.1)$ layered oxides have been prepared by solid state reaction under inert atmosphere. From powder X-ray diffraction analyses, all the present lithium manganates were found to be crystallized with monoclinic-layered structure. Electrochemical measurements clearly demonstrated that, in comparison with the pristine $LiMn_{0.9}Cr_{0.1}O_2$, the sulfur-substituted derivatives exhibit smaller discharge capacities for the entire cycle range but the recovery of discharge capacity after the initial several cycles becomes faster upon sulfur substitution. The effect of the sulfur substitution on the chemical bonding nature of $LiMn_{0.9}Cr_{0.1}O_{2-x}S_x$has been investigated using X-ray absorption spectroscopic (XAS) analyses at Mn and Cr K-edges. According to Mn K-edge XAS results, the trivalent oxidation state of manganese ion remains unchanged before and after the substitution whereas the local structure around manganese ions becomes more distorted with increasing the substitution rate of sulfur. On the other hand, the replacement of oxygen with sulfur has negligible influence on the local atomic arrangement around chromium ions, which is surely due to the high octahedral stabilization energy of $Cr^{+III} $ ions. Based on the present experimental findings, we have suggested that the decrease of discharge capacity upon sulfur substitution is ascribable to the enhanced structural distortion of $MnO_6$ octahedra and/or to the formation of covalent Li-S bonds, and the accompanying improvement of cyclability would be related to the depression of Mn migration and/or to the pillaring effect of larger sulfur anion.