• The Journal of the Convergence on Culture Technology
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• 제8권6호
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• pp.927-933
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• 2022

We synthesized (C₁₀H₈N₂H)₂Cr₂O₇, The structure of the product was characterized with FT-IR(infrared) and elemental analysis. The oxidation of benzyl alcohol by (C₁₀H₈N₂H)₂Cr₂O₇ in organic solvents showed that the reactivity increased with the increase of the dielectric constant. The oxidation of alcohols was examined by (C₁₀H₈N₂H)₂Cr₂O₇ in DMF, acetone. As a resuit, (C₁₀H₈N₂H)₂Cr₂O₇ was found as efficicent oxidizing agent that converted benzyl alcohol, allyl alcohol, primary alcohol and secondary alcohols to the corresponding aldehydes or ketones(65%~95%). The selective oxidation of alcohols was also examined by (C₁₀H₈N₂H)₂Cr₂O₇ in DMF, acetone. (C₁₀H₈N₂H)₂Cr₂O₇ was selective oxidizing agent(15%~95%) of benzyl alcohol, allyl alcohol and primary alcohol in the presence of secondary ones. In the presence of DMF solvent with acidic catalyst such as H₂SO₄. (C₁₀H₈N₂H)₂Cr₂O₇ oxidized benzyl alcohol(H) and its derivatives. The Hammett reaction constant(ρ) was -0.69(308K). The observed experimental data were used to rationalize the hydride ion transfer in the rate determining step.

• Bulletin of the Korean Chemical Society
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• 제29권4호
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• pp.772-776
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• 2008

Second-order rate constants ($k_N$) have been measured spectrophotometrically for reactions of 3,4-dintrophenyl 2-furoate (2) with a series of secondary alicyclic amines in 80 mol % $H_2O$/20 mol % dimethyl sulfoxide (DMSO) at 25.0 ${^{\circ}C}$. The Bronsted-type plot exhibits a downward curvature for the aminolysis of 2, which is similar to that reported for the corresponding reactions of 2,4-dintrophenyl 2-furoate (1). Substrate 2 is less reactive than 1 toward all the amines studied but the reactivity difference becomes smaller as the amine basicity increases. Dissection of the second-order rate constants into the microscopic rate constants has revealed that the reaction of 2 results in a smaller $k_2/k_{-1}$ ratio but slightly larger $k_1$ value than that of 1. Steric hindrance has been suggested to be responsible for the smaller $k_1$ value found for the reactions of 1, since the ortho-substituent of 1 would inhibit the attack of amines (i.e., the $k_1$ process).

• Journal of Korean Society of Environmental Engineers
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• 제38권11호
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• pp.603-610
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• 2016

This work studies the synthesis of birnessite (${\delta}-MnO_2$), a catalyst of oxidative-coupling reactions, from the powder of spent alkaline manganese batteries (SABP, <8 mesh) and evaluate its reactivity for 1-naphthol (1-NP) removals. Manganese oxides using commercial reagents ($MnSO_4$, $MnCl_2$) and the acid birnessite (A-Bir) by McKenzie method were also synthesized, and their crystallinity and reactivity for 1-NP were compared with one another. 96% Mn and 98% Zn were extracted from SABP by acid leaching at the condition of solid/liquid (S/L) ratio 1:10 in $1.0M\;H_2SO_4+10.5%\;H_2O_2$ at $60^{\circ}C$. From the acid leaching solution, 69% (at pH 8) and 94.3% (pH>13) of Mn were separated by hydroxide precipitation. Optimal OH/Mn mixing ratio (mol/mol) for the manganese oxide (MO) synthesis by alkaline (NaOH) hydrothermal techniques was 6.0. Under this condition, the best 1-NP removal efficiency was observed and XRD analysis confirmed that the MOs are corresponding to birnessite. Kinetic constants (k, at pH 6) for the 1-NP removals of the birnessites obtained from Mn recovered at pH 8 (${Mn^{2+}}_{(aq)}$) and pH>13 ($Mn(OH)_{2(s)}$) are 0.112 and $0.106min^{-1}$, respectively, which are similar to that from $MnSO_4$ reagent ($0.117min^{-1}$). The results indicated that the birnessite prepared from the SABP as a raw material could be used as an oxidative-coupling catalyst for removals of trace phenolic compounds in soil and water, and propose the recycle scheme of SAB for the birnessite synthesis.

• Korean Journal of Materials Research
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• 제31권6호
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• pp.313-319
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• 2021

Understanding of effects of changes in the particle size of the matrix material on the mullite whisker growth during the production of porous mullite is crucial for better design of new porous ceramics materials in different applications. Commercially, raw materials such as Al₂O₃/SiO₂ and Al(OH)₃/SiO₂ are used as starting materials, while AlF₃ is added to fabricate porous mullite through reaction sintering process. When Al₂O₃ is used as a starting material, a porous microstructure can be identified, but a more developed needle shaped microstructure is identified in the specimen using Al(OH)₃, which has excellent reactivity. The specimen using Al₂O₃/SiO₂ composite powder does not undergo mulliteization even at 1,400 ℃, but the specimen using the Al(OH)₃/SiO₂ composite powder had already formed complete mullite whiskers from the particle size specimen milled for 3 h at 1,100 ℃. As a result, the change in sintering temperature does not significantly affect formation of microstructures. As the particle size of the matrix materials, Al₂O₃ and Al(OH)₃, decreases, the porosity tends to decrease. In the case of the Al(OH)₃/SiO₂ composite powder, the highest porosity obtained is 75 % when the particle size passes through a milling time of 3 h. The smaller the particle size of Al(OH)₃ is and the more the long/short ratio of the mullite whisker phase decreases, the higher the density becomes.

• Journal of Hydrogen and New Energy
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• 제32권3호
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• pp.156-162
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• 2021

Mg hydride has a relatively high hydrogen storage amount of 7.6wt%, and inexpensive due to abundant resources, but has high reaction temperature and long reaction time because of treble oxidation reactivity and upper activation energy. Their range of applications could be further extended if their hydrogenation kinetics and degradation behavior could be improved. Therefore, the effect of CaO has improved the hydrogenation kinetics and slowed down the degradation. This study focused on investigating whether to improve the hydrogenation kinetics by synthesizing Mg₂NiH_x-5wt% CaO composites. The Mg₂NiH_x-5wt% CaO composites have been synthesized by hydrogen induced mechanical alloying. The synthesized composites were characterized by performing X-ray diffraction, Scanning Electron Microscopy, Brunauer-Emmett-Teller, Thermogravimetric, and Sivert's type automatic pressure-composition-temperature analysis. Hydriding kinetics were performed using an automatic PCT measurement system and evaluated over the temperature range of 423 K, 523 K, and 623 K. As a result of calculating the hydrogen adsorption amount through the hydrogenation kinetics curve, it was calculated as about 0.42wt%, 0.91wt%, and 1.15wt%, the highest at 623 K and the lowest at 423 K.

• Journal of Soil and Groundwater Environment
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• 제19권1호
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• pp.46-53
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• 2014

The purpose of this study is to promote utilization of paper mill sludge as an adsorbent for stabilizing heavy metals in contaminated water by measuring the adsorption capacity of paper mill sludge for cadmium and arsenic. To measure adsorption capacity of paper mill sludge, sorption isotherm experiments were analyzed by Langmuir and Freundlich isotherm models. Also, two methods of chemical modifications were applied to improve the adsorption capacities of paper-mill-sludge: the first method used sodium hydroxide (NaOH), called PMS-1, and the second method used the NaOH and tartaric acid ($C_4H_6O_6$) together, called PMS-2. For Cd adsorption, PMS-1 presented the increase of reactivity while PMS-2 presented the decline of reactivity compared to that of untreated paper-mill-sludge. In case of As adsorption, both PMS-1 and PMS-2 showed the decrease of adsorption capacities. This is because zeta-potential of paper mill sludge was changed to more negative values during chemical modification process due to the hydroxyl group in NaOH and the carboxyl group in $C_4H_6O_6$, respectively. Therefore, we may conclude that the chemical treatment process increases adsorption capacity of paper mill sludge for cation heavy metals such as Cd but not for As.

• Korean Chemical Engineering Research
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• 제45권6호
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• pp.566-572
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• 2007

Two hybrid catalysts for the direct synthesis of DME were prepared and the catalytic activity of these catalysts were investigated. The hybrid catalyst for the direct synthesis of DME was composed as the catalytic active components of methanol synthesis and dehydration. The methanol synthesis catalyst was formed from the precursor contained Cu and Zn, the methanol dehydration catalyst was used ${\gamma}-Al_2O_3$. As PM-CZ+D and CP-CZA/D, Two hybrid catalysts were prepared by physical mixing method (PM-CZ+D) and precipitation method (CP-CZA/D), respectively. PM-CZ+D was prepared by physically mixing methanol synthesis catalyst and methanol dehydration catalyst, CP-CZA/D was prepared by depositing Cu-Zn or Cu-Zn-Al components on ${\gamma}-Al_2O_3$. The crystallinity and the surface morphology of synthesized catalyst were analyzed by X-ray diffraction (XRD) and scanning electron microscope (SEM) to investigate the physical property of prepared catalyst. And BET surface area by $N_2$ adsorption and the surface area of Cu by $N_2O$ chemisorption were investigated about the hybrid catalysts. In addition, catalytic activity of these hybrid catalysts was examined with varying reaction conditions. At that time, the reaction temperature of $250{\sim}290^{\circ}C$, the reaction pressure of 50~70 atm, the $[H_2]/[CO]$ mole ratio of 0.5~2.0 and the space velocity of $1,500{\sim}6,000h^{-1}$ were investigated the catalytic activity. From these results, it was confirmed that the reactivity of CP-CZA/D was higher than that of PM-CZ+D. When the conditions of reaction temperature, pressure, $[H_2]/[CO]$ ratio and space velocity were $260^{\circ}C$, 50 atm and 1.0, $3,000h^{-1}$ respectively, CO conversion using CP-CZA/D hybrid catalyst was 72% and the CO conversion of CP-CZA/D was more than 20% compared with the CO conversion of PM-CZ+D. It was known that Cu surface area of CP-CZA/D hybrid catalyst was higher than that of hybrid PM-CZ+D catalyst using $N_2O$ chemisorption. It was assumed that the catalytic activity was improved because Cu particle of hybrid catalyst prepared by precipitation method was well dispersed.

• Journal of the Korean Chemical Society
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• 제34권2호
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• pp.165-170
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• 1990

The reactivity and structural change of optical active $[Co(edta)]^- and [Co(Hedta)Cl]^- complexes has been investigated in the presence of several catalyst (H^+, OH^-, and Cd^{2+}). When Δ-[Co(edta)]- complex was reacted with H^+ or OH^- as the catalyst, G-ring opening of ligand in the complex was accompanied, and then, optically active, [Co(Hedta)OH_2], and racemic mixture, [Co(edta)OH]_2- were produced. When (-)546-[Co(Hedta)Cl]- complex was reacted with Cd^{2+}$ as the catalyst, the Ring-close was accompanied, and Δ-[Co(edta)]- complex was produced, which the absolute configuration was retained.

• Bulletin of the Korean Chemical Society
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• 제33권10호
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• pp.3253-3257
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• 2012

Second-order rate constants for the reactions of phenyl Y-substituted-phenyl carbonates 5a-g with Z-substituted-phenoxides ($k_{Z-PhO^-}$) have been measured spectrophotometrically in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. 4-Nitrophenyl phenyl carbonate (5e) is up to 235 times more reactive than 4-nitrophenyl benzoate (4e). The Br$\o$nsted-type plot for the reactions of 5e with Z-substituted-phenoxides is linear with ${\beta}_{nuc}=0.54$, which is typical for reactions reported previously to proceed through a concerted mechanism. Hammett plots correlated with ${\sigma}^o$ and ${\sigma}^-$ constants for the reactions of 5a-f with 4-chlorophenoxide exhibit highly scattered points. In contrast, the Yukawa-Tsuno plot results in an excellent linear correlation with ${\rho}_Y=1.51$ and r = 0.52, indicating that the leaving-group departure occurs at the rate-determining step (RDS). A stepwise mechanism, in which leaving-group departure occurs at RDS, has been excluded since the incoming 4-$ClPhO^-$ is more basic and a poorer nucleofuge than the leaving Y-substituted-phenoxides. Thus, the reaction has been concluded to proceed through a concerted mechanism. Our study has shown that the modification of the nonleaving group from benzoyl to phenyloxycarbonyl causes a change in the reaction mechanism (i.e., from a stepwise mechanism to a concerted pathway) as well as an increase in the reactivity.

• Bulletin of the Korean Chemical Society
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• 제32권1호
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• pp.179-182
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• 2011

Second-order rate constants ($k_{OH^-}$) have been measured spectrophotometrically for reactions of Y-substituted phenyl phenyl thionocarbonates (4a-i) with $OH^-$ in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The $k_{OH^-}$ values for the reactions of 4a-i have been compared with those reported previously for the corresponding reactions of Y-substituted phenyl phenyl carbonates (3a-i) to investigate the effect of changing the electrophilic center from C=O to C=S on reactivity and mechanism. Thionocarbonates 4a-i are less reactive than the corresponding carbonates 3a-i although 4a-i are expected to be more reactive than 3a-i. The Bronsted-type plot for reactions of 4a-i is linear with $\beta_{lg}$ = -0.33, a typical $\beta_{lg}$ value for reactions reported to proceed through a stepwise mechanism with formation of an intermediate being the rate-determining step (RDS). Furthermore, the Hammett plot correlated with $\sigma^o$ constants results in much better linearity than that correlated with $\sigma^-$ constants, indicating that expulsion of the leaving group is not advanced in the RDS. Thus, alkaline hydrolysis of 4a-i has been concluded to proceed through a stepwise mechanism with formation of an intermediate being RDS, which is in contrast to the forced concerted mechanism reported for the corresponding reactions of 3a-i. Enhanced stability of the intermediate upon modification of the electrophilic center from C=O to C=S has been concluded to be responsible for the contrasting mechanisms.