• Korean Chemical Engineering Research
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• v.51 no.6
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• pp.661-665
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• 2013

Effect of organic acid on the preparation of indium-oxalate salt from indium scraps generated from ITO glass manufacturing process was studied. Effects of parameters, such as type and concentration of organic acids, pH of reactant, temperature, reaction time on indium-oxalate salt preparation were examined. The impurity removal efficiency was similar for both oxalic acid and citric acid, but citric acid did not make organic acid salt with indium. The optimum conditions were 1.5 M oxalic acid, pH 7, $80^{\circ}C$, and 6 hours. On the other hand, the recoveries increased with pH, but the purity decreased. The indium-oxalate salt purity prepared by two cycles was 99.995% (4N5). The indium-oxalate salt could be converted to indium oxide and indium metal by substitution reaction and calcination.

• Bulletin of the Korean Chemical Society
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• v.35 no.1
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• pp.177-181
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• 2014

Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for the reactions of Y-substituted-phenyl benzoates (5a-j) with potassium ethoxide (EtOK) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plots of $k_{obsd}$ vs. [EtOK] curve upward regardless of the electronic nature of the substituent Y in the leaving group. Dissection of $k_{obsd}$ into the second-order rate constants for the reactions with the dissociated $EtO^-$ and ion-paired EtOK (i.e., $k_{EtO^-}$ and $k_{EtOK}$, respectively) has revealed that the ion-paired EtOK is more reactive than the dissociated $EtO^-$. The Br${\phi}$nsted-type plots for the reactions with the dissociated $EtO^-$ and ion-paired EtOK exhibit highly scattered points with ${\beta}_{lg}$ = -$0.5{\pm}0.1$. The Hammett plots correlated with ${\sigma}^o$ constants result in excellent linear correlations, indicating that no negative charge develops on the O atom of the leaving Y-substituted-phenoxide ion in transition state. Thus, it has been concluded that the reactions with the dissociated $EtO^-$ and ion-paired EtOK proceed through a stepwise mechanism, in which departure of the leaving group occurs after the RDS, and that $K^+$ ion catalyzes the reactions by increasing the electrophilicity of the reaction center through a four-membered cyclic TS structure.

• Bulletin of the Korean Chemical Society
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• v.34 no.10
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• pp.2983-2988
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• 2013

Second-order rate constants ($k_N$) have been measured spectrophotometrically for the reactions of 4-chloro-2-nitrophenyl X-substituted-benzoates (1a-1h) with a series of cyclic secondary amines in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The Hammett plot for the reactions of 1a-1h with piperidine consists of two intersecting straight lines, while the Yukawa-Tsuno plot exhibits an excellent linear correlation with ${\rho}_X $ = 1.25 and r = 0.58, indicating that the nonlinear Hammett plot is not due to a change in the rate-determining step (RDS) but is caused by ground-state stabilization through resonance interactions for substrates possessing an electron-withdrawing group in the benzoyl moiety. The Br${\o}$nsted-type plot for the reactions of 4-chloro-2-nitrophenyl benzoate (1d) with a series of cyclic secondary amines curves downward with ${\beta}_2$ = 0.85, ${\beta}_1$ = 0.24, and $pK_a{^o}$ = 10.5, implying that a change in RDS occurs from the $k_2$ step to the $k_1$ process as the $pK_a$ of the conjugate acid of the amine exceeds 10.5. Dissection of $k_N$ into the microscopic rate constants $k_1$ and $k_2/k_{-1}$ ratio associated with the reaction of 1d reveals that $k_2$ is dependent on the amine basicity, which is contrary to generally held views.

• Journal of the Korean Wood Science and Technology
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• v.27 no.3
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• pp.63-72
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• 1999

For the purpose of improving the wet strength properties of paper, cellulosic fibers were modified by the processes of carbarmoylethylation and N-chlorocarbamoylethylation. Carbamoylethylated cellulose was prepared by the reaction of acrylamide with cellulosic fibers under the alkali catalyst, and N-chlorocarbamoylethylated cellulose was prepared by the addition of sodium hypochlorite into the carbamoylethylated cellulose. In carbamoylethylation reaction, the conditions of NaOH concentration, temperature and acrylamide addition rate were considered to be important factors. An initial reactivity and degree of substitution(DS) in carbamoylethylation of cellulosic fibers were effective according to increasing the addition rates of alkali, acrylamide and the temperature condition of $40^{\circ}C$. The effective wet strength properties by N-chlorocarbamoylethylation of cellulosic fibers were indicated under the conditions of DS 0.06. The wet strength of sheet was improved to 85% at the 100% basis of dry strength. From the photograph of scanning electron microscopy, fiber cuttings on the edge of sheet sample used in tensile strength testing were found in the N-chlorocarbamoylethylated sheet, due to the improvement of fiber bonding strength. The hypochlorite treatment was effective in the recycling of N-chlorocarbamoylethylated sheet, and was reduced the wet strength of sheet to be able to reslush.

• Journal of the Korean Ceramic Society
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• v.38 no.12
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• pp.1093-1096
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• 2001

The Solid solution of A $l_2$ $O_3$ into ZnO can be defined by the substitution reaction of Al$\^$3+/ ions into the Zn$\^$2+/ sites of ZnO crystal lattice, the tetrahedral interstices composed of four neighbor oxygen ions in the wurtzite structure. Since the reaction either creates new zinc vacancies or consumes the oxygen vacancies, it should be in equilibrium with ZnO nonstoichiometry and disorder reactions. The relationships make oxygen partial pressure P$\sub$o2/ control the concentrations of the vacancies and consequently limit the Al solubility in ZnO, [Al$\sub$zn/]$\sub$max/. This paper firstly reports with a refined model for defect quilibria in ZnO that the solubility decrease with the increase of P$\sub$o2/, [Al$\sub$zn/]$\sub$max/ P$\sub$o2/$\^$-1/4/.

• Journal of the Korean Chemical Society
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• v.37 no.6
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• pp.577-584
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• 1993

The reaction rates of para-substituted benzoyl chlorides with substituted pyridines have been measured employing the conductometry method in acetonitrile, and pseudo-first order and second order rate constants are determined at various pressures and temperatures. The activation parameters (${\Delta}V^\neq, {\Delta}{\beta}^{\neq}, {\Delta}H^{\neq}, {\Delta}S^{\neq} {\Delta}G^{\neq}$) and the Hammett ρ-values are determined from the values of rate constants. The values of △${\Delta}V^\neq, {\Delta}{\beta}^{\neq}and {\Delta}S^{\neq}$ are all negative. The Hammett ρ-values are negative for the nucleophile (ρ$_X$), and positive for the substrate (ρ$_Y$) over the pressure range studied. The results of kinetic studies for pressure and substituent show that these reactions proceed in typical S$_N$2 reaction mechanism and in bond formation favored with elevating pressure.

• Journal of the Korea Institute of Building Construction
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• v.10 no.2
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• pp.59-66
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• 2010

The purpose of this study is to determine the possibilities of blending carbon black, which is known for its permeability as well as its strong heat and fire resistance, into concrete, in a manner that reinforces its strengths mentioned above. Experiments show that in non-solidified, fresh-mixed concrete, the addition of carbon black effectively reduced slump level and air content due to its absorptiveness and minute particle size. It also showed good results in terms of coagulation time, penetration resistance and bleeding level. In solid concrete, it showed better strength than plain concrete. Due to the pozzolanic reaction, its strength became more pronounced over time. At approximately 850 degrees Celsius, the heat and fire resistance level increased in parallel to the level of chemical substitution (by carbon black). Drying shrinkage level appeared to be optimal, and environmental assessment test results related to CO, CO2 and formaldehyde also scored better than plain concrete. In summary, with the appropriate use of AE water-reducing agents, carbon black can prove to be a strong candidate as an ingredient for industry-grade concrete.

• Tribology and Lubricants
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• v.30 no.6
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• pp.323-329
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• 2014

The friction-reducing properties of lubricants containing ionic liquids based on ammonium dithiocarbamate are studied. The ionic liquids are produced through the following two steps: the synthesis of sodium alkyl dithiocarbamates via the substitution reaction of dialkylamine and carbon disulfide and their subsequent conversion into ammonium dithiocarbamate-based ionic liquids through an ion-exchange reaction with a quaternary alkyl ammonium halide salt. The structures of the ionic liquids are characterized by NMR spectroscopy and Fourier transform infrared spectroscopy. The isolated yields of the ionic liquids, which are viscous and pale yellow, are approximately 92%. The Brookfield viscosities and pour points of the ionic liquids are determined. Further, their wear resistances are measured through the four-ball wear test and the Schwingung Reibung Ver-schleiss (oscillation, friction, wear) test. The wear scar diameter of the lubricants containing 1 wt of the quaternary alkyl ammonium dithiocarbamate-based ionic liquids (0.475-0.631 mm) is significantly lower than that of the base oil (0.825 mm), proving that the ammonium dithiocarbamate-based ionic liquids have good friction-reducing characteristics. However, these friction-reducing characteristics fade significantly after long-term storage, owing to the degradation of the ionic liquids.

• Korean Chemical Engineering Research
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• v.57 no.3
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• pp.425-431
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• 2019

As rechargeable metal-air batteries will be ideal energy storage devices in the future, an active cathode electrocatalyst is required with bi-functionality on both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) during discharge and charge, respectively. Here, a class of perovskite cathode catalyst with a micro-tubular structure has been developed by controlling bi-functionality from different Ru and Ni dopant ratios. A micro-tubular structure is achieved by the activated carbon fiber (ACF) templating method, which provides uniform size and shape. At the perovskite formula of $LaCrO_3$, the dual dopant system is successfully synthesized with a perfect incorporation into the single perovskite structure. The chemical oxidation states for each Ni and Ru also confirm the partial substitution to B-site of Cr without any changes in the major perovskite structure. From the electrochemical measurements, the micro-tubular feature reveals much more efficient catalytic activity on ORR and OER, comparing to the grain catalyst with same perovskite composition. By changing the Ru and Ni ratio, the $LaCr_{0.8}Ru_{0.1}Ni_{0.1}O_3$ micro-tubular catalyst exhibits great bi-functionality, especially on ORR, with low metal loading, which is comparable to the commercial catalyst of Pt and Ir. This advanced catalytic property on the micro-tubular structure and Ru/Ni synergy effect at the perovskite material may provide a new direction for the next-generation cathode catalyst in metal-air battery system.

• Journal of the Korean Chemical Society
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• v.46 no.3
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• pp.187-193
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• 2002

The reaction rates of substituted 6-chloroquinoline with p-substituted benzoyichorides $p-CH_3,$ p-H, $p-NO_2$ have been measured by conductometry in acetonitrile, and the constants are determined at various temperatures (10, 15, 20, $25^{\circ}C$) and pressures (1, 200, 500, 1000 bar). From the values of rate constants, the activation parameters (Ea, ${\Delta}V^{\neq}$, ${\Delta}H^{\neq}$, ${\Delta}S^{\neq}$, ${\Delta}G^{\neq}$) and the pressure dependence of Hammett p values were determined. The rate constants increased with increasing temperatures and pressures, and are further increased to introduction to the electron donor substiuents in substrate $(p-NO_2)$ with 6-chloroqinoline. When the activation volume and the activation entropy are all negative And the Hammett p values are positive for the substrate over the pressure and temperature range studied. The results of kinetic studies for pressure and substituent show that thease reactions proceed in typical $S_N2$ reaction mechanism and "associative $S_N2$" in bond formation favored with increasing pressures.