• Applied Chemistry for Engineering
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• v.25 no.6
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• pp.648-653
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• 2014

Cr(VI)-heterocyclic complex (2,4'-bipyridinium chlorochromate) was synthesized by the reaction between heterocyclic compound(2,4'-bipyridine) and chromium trioxide, and characterized by IR and ICP analysis. The oxidation of benzyl alcohol using 2,4'-bipyridinium chlorochromate in various solvents showed that the reactivity increased with the increase of the dielectric constant (${\varepsilon}$), in the order : N,N-dimet-hylformamide (DMF) > acetone > chloroform > cyclohexene. In the presence of DMF solvent with acidic catalyst such as hydrochloric acid (HCl solution), 2,4'-bipyridinium chlorochromate oxidized benzyl alcohol (H) and its derivatives (p-$CH_3$, m-Br, m-$NO_2$). Electron-donating substituents accelerated the reaction rate, whereas electron acceptor groups retarded the reaction rate. The Hammett reaction constant (${\rho}$) was -0.67 (303 K). The observed experimental data have been rationalize the proton transfer occurred followed the formation of a chromate ester in the rate-determining step.

• Journal of the Korean Chemical Society
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• v.32 no.6
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• pp.528-535
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• 1988

The rates of oxygen ring formation of $[Mo_2O_3(Ox)_2(OxH)_2(NCS)_2]$ have been investigated spectrophotometric method in binary aqueous mixtures. Temperature was $20^{\circ}C$ to $40^{\circ}C$ and pressure was varied up to 1500 bar. The observed rate constants are increased by hydrogen ion and decreased by thiocyanate. The more increasing of co-solvents dielectric constant, the more stable intermediate is formed. The observed rate constant is given by, $k_{obs}^{-1} = k^{-1} (1 + K^{-1}[H_2O]^{-1}) All activation parameters are positive values. The oxygen ring formation of [Mo_2O_3(Ox)_2(OxH)_2(NCS)_2]$ is believed to be a interchange-dissociative mechanism..

• Journal of the Korean Chemical Society
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• v.38 no.6
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• pp.442-448
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• 1994

The rate constants of the nucleophilic reaction of ${\alpha}$-(n-butyl)-N-phenylnitrone and its derivatives have been determined by ultraviolet spectrophotometry at $25^{\circ}C$ and a rate equation which can be applied over a wide pH range was obtained. Final product of the addition reaction was $\alpha$-phenylthiobutylidene-aniline. Base on the rate equation, genernal base effect, substituent effect and final product, plausible mechanism of addition reaction have been proposed. Below pH 3.0 the reaction was inititated by the addition of thiophenol, and in the range of pH 3.0∼10.0, proceeded by the competitive addition of thiophenol and thiophenoxide anion. Above the pH 10.0, the reaction proceeded through the addition of a thiophenoxide anion.

• Polymer(Korea)
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• v.35 no.1
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• pp.60-65
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• 2011

In order to maximize the performance of polymer nano-composites, it is essential to understand an effect of a dispersion state on material properties as well as to achieve highly dispersed composites. In this work, a simple quantitative approach to evaluate the degree of dispersion was suggested for carbon nanotube (CNT) embedded polymer nano-composites. Through UV-visible spectroscopy analysis, the transmittance of nano-composites was measured at various dispersion states and it was found that the transmittance reduced as the dispersion state of CNT improved. Based on the results, an effective concentration factor for quantitative evaluation of dispersion state was introduced into the Beer-Lambert transmittance law. The proposed method and parameter to evaluate the degree of dispersion were verified by analyzing the transmittances at different dispersion states of CNT, concentrations of CNT and sample thicknesses.

• Journal of the Korean Chemical Society
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• v.54 no.4
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• pp.374-379
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• 2010

The interaction of dichlorophenol isomers with the micellar system of TTAB (tetradecyltrimethylammonium bromide) was studied by the UV/Vis spectrophotometric method. The solubilization constants ($K_s$) of dichlorophenol isomers into the micellar system have been measured with the change of temperature and the various thermodynamic parameters have been calculated and analyzed from these changes. The results show that the values of ${\Delta}G^{\circ}_s$ and ${\Delta}H^{\circ}_s$ are all negative within the measured temperature range. The effects of additives (n-butanol and NaCl) on the solubilization of dichlorophenol isomers have been also measured. There was a great change on the values of $K_s$ and CMC simultaneously with these additives. From these changes we can postulate the solubilization sites of each isomers in the micellar system of TTAB.

• Journal of the Korean Chemical Society
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• v.30 no.1
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• pp.3-8
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• 1986

The investigation of the effect of solvent structure on the first-order solvolysis of cis-$[Co(en)_2ClNO_2]^+$ion has been extended to water + co-solvent mixtures where the co-solvents are glycerol, ethylene glycol, isopropyl alcohol and t-butyl alcohol. Rates of solvolysis have been evaluated by spectrophotometric method at temperature 25∼30$^{\circ}$C. The polarity of solvent has influence on the variation of rate constant. The non-linear plot of the rate constant in log scale versus $\frac{D-1}{2D+1}$ implies that change in solvent structure with composition plays an important role in determining the variation of rate constant. The linearity of the plot of the rate constant in log scale versus the Grundwald-Winstein Y factor confirms that the solvolysis is an Id-type process with considerable extension of the metal chloride bond in the transition state. In the Kivinen equation the slope of the plot of log k versus $log(H_2O)$ suggests that the solvolysis is also an Id-type process. The application of free energy cycle shows that the effect of solvent structure is greater in the transition state than in the initial state.

• Journal of the Korean Chemical Society
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• v.27 no.5
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• pp.311-319
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• 1983

The dissociation constants of anilinium ion, o-toluidinium ion, phenol and o-chlorophenol were measured spectroscopically in aqueous solution over the temperature range of 10∼40$^{\circ}C$ and at the pressures up to 2,000 bars. The effects of temperature and pressure on the dissociation of the phenols are the same as those of the ordinary weak acids. Meanwhile the dissociation constants of anilinium ions are increased with temperature raising and decreased with pressure elevation. The effects of pressure on the constants can be explained by taking account of change of charge during dissociation reaction; there are increase in charge in the dissociation of phenols but anilinium ions are not. Several thermodynamic properties, ${\Delta}H^{circ}$,${\Delta}G^{circ}$, ${\Delta}S^{circ}$,${\Delta}V^{circ}$ and ${\beta}$ are calculated from those constants, and the dissociation reactions are discussed by them.

• Journal of the Korean Chemical Society
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• v.36 no.4
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• pp.584-588
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• 1992

The rate constants of hydrolysis of ${\alpha}$-(n-butyl)-N-phenylnitrone and its derivatives have been determined by UV spectrophotometry at 25$^{\circ}C$ and a rate equation which can be applied over a wide pH range was obtained. On the basis of rate equations derived and judging from the hydrolysis products obtained and from general base and substituent effects, plausible mechanisms of hydrolysis in various pH range have been proposed. Below pH 4.5, the hydrolysis was initiated by the protonation and followed by the addition of water to ${\alpha}$-carbon. Above pH 10.0, the hydrolysis was proceeded by the addition of hydroxide ion to ${\alpha}$-carbon. In the range of pH4.5∼10.0, the addition of water to nitrone is rate controlling step.

• Journal of the Korean Chemical Society
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• v.31 no.1
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• pp.37-44
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• 1987

The rates of solvolysis of $cis-[Co(en)_2Cl_2]^+$ complex have been investigated using spectrophotometric method at various pressures up to 1500 bar in several binary-aqueous mixtures(water-methyl alcohol, water-acetone, water-isopropyl alcohol and water-ethylene glycol). The activation volumes obtained from the pressure effect on rate constants were 1.13∼4.44 cm3mole-1 for methyl alcohol, 1.13∼3.59$cm^3mole^{-1}$ for acetone, 0.82∼3.44$cm^3mole^{-1}$ for isopropyl alcohol and 1.13∼2.68cm3mole-1 for ethylene glycol. In case of water-methyl alcohol, in addition to, the rates of solvolysis of this complex were determined in the presence of Fe(Ⅱ) ion and the activation volumes were -0.56∼1.59cm3mole$^{-1}$. The rates of solvolysis of this complex were analyzed by comparing with the results obtained from activation volumes and free energy cycle.

• Journal of the Korean Chemical Society
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• v.30 no.6
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• pp.526-531
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• 1986

The stability constants of 1,15-diaza-3,4:12,13-dibenzo-5,8,11-trioxacycloheptadecane (NenOdien H$_4$, L) with transition metal ions such as $Co^{2+},\;Ni^{2+},\;Cu^{2+},\;and\;Zn^{2+}$ have been determined by potentiometry in 95% methanol solution at 25$^{\circ}$C. The complex formation of the NenOdien $_4$ with the transition metal ions depends on the basicity of the donor atoms. The order of complex stability was Co(II) < Ni(II) < Cu(II) > Zn(II). The geometries of the complexes in solid state were discussed by visible-near infrared and infrared spectrophotometry, elemental analysis and electro-conductivity. The results suggest that the geometries of the solid complexes are octahedral for $[CoL_2(OH_2)Cl]Cl{\cdot}2H_2O$, $[NiL_2(OH_2)Cl]Cl{\cdot}2H_2O$, and $[ZnLCl_2]{\cdot}\frac{1}{2}H_2O$ and square pyramidal for [CuLCl]Cl, respectively.