• Bulletin of the Korean Chemical Society
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• v.17 no.2
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• pp.158-162
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• 1996

The steady-state emission and fluorescence lifetimes of 1,3-dipyrenylpropane were measured in silicate sol-gel and xerogel matrices. In sol solution, the fluorescence emission spectra of monomer and excimer resemble those in hydrocarbon solvents. In gel and xerogel condition, however, the fluorescence spectra exhibit significant change, largely confirming the intramolecular motions in gel pores are influenced by microviscosity. The rate constants for intramolecular excimer formation were obtained from the measured fluorescence lifetimes and the rate processes for excimer forming in silicate sol-gel are described by a simple kinetic scheme.

• Analytical Science and Technology
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• v.13 no.4
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• pp.466-473
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• 2000

The complex formation constants (${\beta}_{MLn}$) of potassium and various sodium-selective neutral carriers in solvent polymeric membranes have been determined using solvent polymeric membrane-based optodes and ion-selective electrodes (ISEs). Two different types of PVC-based membranes containing the H^+selective chromoionophore (ETH 5294) with and without a sodium ionophore (4-tert-bntylcalix[4]arenetetraacetic acid tetraethyl ester, ETH 2120, bis[(12-crown-4)methyl] dodecylmethylmalonate or monensin methyl ester) were prepared and their optical responses to either the changes in alkali metal cation (e.g., sodium and potassium) concentrations at a fixed pH (0.05 M Tris-HCl, pH 7.2) or varying pH at a fixed alkali metal cation concentration (0.1 M) were measured. The same type of membranes were also mounted in conventional electrode body and their potentiometric responses to varying pH at a fixed alkali metal cation concentration (0.1 M) were measured. The complex formation constants of the ligand could be calculated from the calibration plots of the relative absorbance vs. the activity ratios of cation and proton ($a_{M^+}/a_{H^+}$) and of the emf vs. pH. It was confirmed that the ratio values of the complex formation constants for the primary and interfering ions are closely related to the experimental selectivity coefficients of ISEs.

• Bulletin of the Korean Chemical Society
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• v.21 no.4
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• pp.393-400
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• 2000

2,2￠-Dihydroxyazobenzene (DHAB) was attached to poly(ethylenimine) (PEI) to obtain DHAB-PEI. Spectral titration revealed that uranyl, Fe(III), Cu(II), and Zn(II) ion form 1 : 1-type complexes with DHAB attached to PEI. Formation constants for the metal complexes formed by the DHAB moieties of DHAB-PEI were mea-sured by using various competing ligands. The results indicated thatthe concentrations of uranyl, Fe(III), and Cu(II) ions can be reduced to 10 -16 -10 -23 M at p 8 with DHAB-PEI when the concentration of the DHAB moiety is 1 residue M. By using cyanuric chloride as the coupling reagent, DHAB-PEI was immobilized on Sephadex G-25 resin to obtain DHAB-PEI-Seph. Binding of uranyl,Fe(III), Cu(II), and Zn(II) ion by DHAB-PEI-Seph was characterized by using competing ligands. A new method has been developed for characteriza-tion of metal sequestering ability of a chelating resin. Formation constants and metal-binding capacity of two sets of binding sites on the resin were estimated for each metal ion. DHAB-PI-Seph was applied to recovery of metals such as uranium,Fe, Cu, Zn, Pb, V, Mn, and W from seawater. The uranium recovery from seawaterby DHAB-PEI-Seph does not meet the criterion for economical feasibility partlydue to interference by Fe and Zn ions. The seawater used in the experiment was contaminated by Fe and Zn and, therefore, the efficiency of uranium extractionfrom seawater with DHAB-PEI-Seph could be improved if the experiment is carried out in a cleaner sea.

• Bulletin of the Korean Chemical Society
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• v.32 no.1
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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.

• Journal of the Korean Chemical Society
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• v.39 no.6
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• pp.440-445
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• 1995

The chemical compositions and stability constants, thermodynamic parameters for the neodymium(Ⅲ) complexes of substituted benzo-1,4,7,10,13-pentaoxacyclopentadecane(B15C5) have been determined by spectrophotometry and conductometry in methanol solution at various temperatures. As substituents, CH3, Br, CHO, NO2, and 3,4-(NO2)2 were used. In methanol solution the ratios of neodymium(Ⅲ) to the ligands in the complexes are 1 : 1. The stability constants were increased in order of B15C5-3,4-(NO2)2 < B15C5-NO2 < B15C5-CHO < B15C5-Br < B15C5 < B15C5-CH3. This observation can be explained in terms of the substituent effect. The order of stability constants was dimethylsulfoxide < acetone < acetonitrile in solution and the magnitudes were found to be inversely proportional to the solvents donicities. These results could be understood in terms of solvent basicity, ligand basicity, solvation of the cation, and entropy changes of complex formation.

• Journal of Environmental Science International
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• v.13 no.7
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• pp.667-674
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• 2004

The objective of this study was to investigate the effects of pH and temperature on the formation of bromate, which is ozonation by-products, during ozonation. In this experiment, the operating parameters including pH 3 ～ 10 and temperature 15 ～ $30^{\circ}C$ were studied. Through the study for the bromate formation, reaction rate constant, and ozonation effect index on pH and temperature, the results obtained are as follows. At the same initial pH condition, the increase of pH shown similar trends even if the reaction variables such as temperature and reaction time of ozonation were exchanged. As pH and temperature were increasing, the bromate concentration was increased but bromine(HOBr+OBr) was decreased with increasing pH from 3 to 10. The activation energy(J/mol) for bromate formation decreased with increasing pH. The rate constants of bromate formation for the reaction of ozone and bromide, and ozone dosage coefficient$(K_{0})$ increased with temperature and pH. Ozonation effect index(OI) decreased with increasing temperature and pH.

• Proceedings of the Korean Society For Composite Materials Conference
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• 2002.05a
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• pp.188-191
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• 2002

3-D orthogonal woven carbon/Al composites were fabricated using a pressure infiltration casting method. Especially, to minimize geometrical deformation of fiber pattern and $Al_4C_3$ formation, the process parameters of the minimum pressurizing force, melting temperature, delay and holding time of molten aluminum pressurizing was optimized through the PC-controlled monitoring system. Resonant ultrasound spectroscopy (RUS) was utilized to measure the effective elastic constants of 3-D orthogonal woven carbon/Al composites. The CTE measurement was conducted using strain gages in a heating oven.

• Journal of the Korean Chemical Society
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• v.35 no.2
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• pp.142-150
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• 1991

The complexation of hydrazide schiff base ligands such as N,N'-oxalylbis(salicylaldehyde hydrazone), N,N'-malonylbis(salicylaldehyde hydrazone), and N,N'-succinylbis(salicylaldehyde hydrazone) with Cd(II) ion was studied by polarographic method in DMSO solution. The order of stability constants was OBSH < MBSH < SBSH, and these ligands formed stable complexes with Cd(II) ion. The stability constants of complexation were measured at various temperatures. As the results, ${\Delta}$H and ${\Delta}$S of the complexation were distributed on the complex stabilities.

• Journal of the Korean Chemical Society
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• v.35 no.2
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• pp.135-141
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• 1991

The complexation of N,N'-oxalylbis(salicylaldehyde hydrazone) (OBSH) with Zn (II), Cd (II), and Pb(II) ions was studied by polarographic method in DMSO solution. The order of stability constants was Cd(II) < Zn(II) < pb(II), and all heavy metal ions formed stable complex with OBSH ligand. The stability constants of complexation were measured at various temperatures. As the results, enthalpy and entropy changes of the complexation were distributed on the complex stabilities.

• Bulletin of the Korean Chemical Society
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• v.11 no.2
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• pp.99-105
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• 1990

The Gutmann acceptor number(AN), solvatochromic parameters $({\alpha},{\beta}\;and\;{\pi}^{\ast})$ and hydrogen bonding equilibrium constants (KHB) were determined for three binary systems of methanol with 1,2-dimethoxyethane(DME), 1,2-dichloroethane(DCE) and pyridine (PYD). The solvolysis rate constants of t-butyl chloride, bromide and iodide were also determined in the three binary systems. Solvent properties and solvolysis rates have been discussed in the light of various solvent parameters. Solvolysis of t-butyl halides are most conveniently explained by the two-stage mechanism involving ion-pair intermediate with the ion-pair formation for chloride and ion pair dissociation for iodide as rate limiting.