• Journal of the Korean Chemical Society
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• v.22 no.6
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• pp.423-430
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• 1978

The initiation mechanism of trioxane polymerization catalyzed by Ti$Cl_4$ in nitrobenzene was investigated. The kinetic studies revealed that the rate of polymerization was drastically decreased by the addition of a minute amount of water or methanol. A third substance as cocatalyst was not required for the polymerization. Measurements of dielectric constants gave no evidence for the zwitterionic mechanism of the polymerization. The electric conductivity measurements of polymerization system and the initiator solution showed that the initiation was started by Ti$Cl_3^+$ cation, formed by a disproportionation of the initiator in nitrobenzene.

• Journal of the Korean Chemical Society
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• v.17 no.2
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• pp.85-94
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• 1973

The stability constants of the charge-transfer complexes formed between three derivatives of nitrobenzene, i.e., 1,3,5-trinitrobenzene, m-dinitrobenzene, nitrobenzene and eleven organic molecules such as $\alpha-picoline$, pyridine, dimethylsulfoxide, N, N'-dimethylacetamide, tetrahydrofurane, 1, 4-dioxane, diethyl ether, acetonitrile, propylene oxide, epichlorohydrine, and methyl acetate, have been determined by ultraviolet absorption spectroscopy in carbon tetrachloride solution at 25.0$^{\circ}C$. The parameters of the electrostatic effect ($E_D$) and covalent effect ($C_D$) for the eleven organic compounds have been calculated from the modified equation of the double-scale enthalpy,$logK = E_AC_A+E_DC_D$ and also the shift of C=O vibrational frequency in infrared spectra for N,N'-dimethylacetamide have been measured from the solutions of above organic compounds. The empirical equation, ${\Delta}{\nu}_{C=O} = 37.4-5.47E_D+12.1C_D$, related to the parameters and the frequency shift has been derived. It seems that the stabilities of the complexes principally depend on the covalent effect. Especially it is found that $\pi$ orbitals in molecules, in addition to the parameters, play the important role in forming the charge-transfer complexes.

• Journal of the Korean Chemical Society
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• v.21 no.6
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• pp.404-412
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• 1977

Electrochemical reduction of nitrobenzene (${\phi}NO_2$) and its derivatives on Pb electrode was studied by means of galvanostatic measurements and coulometric electrolysis in ethanol-water solvent. In acidic solutions phenylhydroxyl amine and aniline ethanol-water solvent. In acidic solutions phenylhydroxyl amine and aniline were produced while nitrosobenzene and coupled products such as azo-and hydrazobenzene were produced in basic solutions. Nitrosobenzene (${\phi}NO$) was not found to be an intermediate in the reduction reactions of ${\phi}NO_2$ in acidic solutions. No direct coupling between ${\phi}NO\;and\;{\phi}NHOH$ was observed to occur in the electrolyte solutions used. Mechanisms of the production of phenylhydroxylamine and nitrosobenzene are deduced from Tafel slope, pH dependence and reaction order with respect to nitrobenzene. Mechanism for the reduction of substituted nitrobenzenes seems to be identical to that of nitrobenzene.

• Journal of Soil and Groundwater Environment
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• v.6 no.1
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• pp.3-12
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• 2001

During ozonation process, the hydroxyl radical generation rates were measured under different experimental conditions (ozone feed rate, nitrobenzene concentration, hydroxyl radical scavenger, pH, HO$_2$O$_2$/O$_3$ etc.) Nitrobenzene could be decomposed by hydroxyl radical rather than ozone only and nitrobenzene decomposition rate was expressed with functions of ozone and nitrobenzene concentration. The rate was decreased as the hydroxyl radical scavenger concentration was increased, and all results were followed pseudo first-order reaction. Using a competitive method, hydroxyl radical generation rate was measured with probe compound and scavenger. It was proportional to ozone concentration, and 0.24mo1 of hydroxyl radical was produced with 1mol of ozone. Under different pH conditions, hydroxyl radical generation rates were measured (pH 10.2 (0.91Ms$^{-1}$ ) > pH 7.3 (0.72Ms$^{-1}$ ) > pH 5.6 (0.67Ms$^{-1}$ ) > pH 3.4 (0.63Ms$^{-1}$ )) showing higher generation rate at high pH values. Addition of hydrogen peroxide promoted the generation rate of hydroxyl radical. Considering the results of pH experiments and addition of hydrogen peroxide experiments, the hydroxyl radical generation rate was 1.6 times higher in hydrogen peroxide solution than in high pH solution, indicating addition of hydrogen peroxide is better promoter to produce the hydroxyl radical in ozonation. These results could be applied to AOPs to remediate the contaminated wastewater and groundwater.

• Journal of the Korean Chemical Society
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• v.35 no.4
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• pp.301-307
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• 1991

The solubilities of the n-propyl iodide in nitrobenzene and m-xylene have been measured at 8$^{\circ}$, 15$^{\circ}$ and 25$^{\circ}C$ in the presence and the absence of gallium iodide. When gallium iodide does not exist in the system, the solubility of n-propyl iodide in m-xylene is greater than in nitrobenzene, indicating a stronger interaction of n-propyl iodide with m-xylene than that with nitrobenzene. It could be thought that n-propyl iodide forms unstable complex with gallium iodide in the presence of gaillium iodide in the system. This complex has been assumed in various ways and evaluated, that instability constant (K value) is relatively certain under the assumption of 1:1 complex, n-C$_3H_7I{\cdot}GaI_3$. Therefore, the complex would form the following equilibrium in the solution: n-C$_3H_7{\cdot}GaI _3{\rightleftharpoons}n-C_3H_7I+1/2Ga_2I_6$ the instability of the complex of n-propyl iodide with gallium iodide is compared with similar complexes of gallium iodide with methyl iodide. The changes of enthalpy, free energy and entropy for the dissociation of the complex are also calculated.

• Journal of the Korean Chemical Society
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• v.20 no.6
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• pp.479-485
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• 1976

The rate of the bromine-exchange reaction between gallium bromide and n-butyl bromide in 1,2,4-trichlorobenzene and in nitrobenzene was measured at 19, 25 and 40$^{\circ}C$., using n-butyl bromide labelled with Br-82. The results indicated that the exchange reaction was second order with respect to gallium bromide and first order with respect to n-butyl bromide. The third-order rate constant determined at $19^{\circ}C.$ is 1.15{\times}10^{-4} l^2{\cdot}mole^{-2}{\cdot}sec^{-1}$ in 1,2,4-trichlorobenzene and $4.21{\times}10^{-4} l^2·$$mole^{-2}{\cdot}sec^{-1}$ in nitrobenzene. The activation energy, the enthalpy of activation and the entropy of activation for the exchange reaction were also determined.

• Applied Chemistry for Engineering
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• v.3 no.2
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• pp.288-295
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• 1992

The reduction of nitrobenzene by triirondodecacarbonyl over phase transfer catalysts was investigated. The phase transfer catalysts showed a good yield of aniline at room temperature. Benzyltriethylammonium chloride, tricaprylmethyl ammonium chloride, 18-crown-6 and polyethyleneglycol-400 were good phase transfer catalysts in this reaction. The effect of reaction temperature, concentration of sodium hydroxide and organic solvents on the reaction rate and yield of aniline were studied in this work.

• Journal of the Korean Chemical Society
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• v.14 no.1
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• pp.85-89
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• 1970

The rate of the bromine-exchange reaction between gallium bromide and isopropyl bromide in nitrobenzene was measured at 19$^{\circ},\;25^{\circ}$ and 40$^{\circ}C$., using isopropyl bromide labelled with Br-82. The results indicated that the exchange reaction was second order with respect to gallium bromide and first order with respect to isopropyl bromide. The third-order rate constant determined at 19$^{\circ}C$. was 3.2 ${\times}10^{-2}l^2{\cdot}mole^{-2}sec^{-1}$. The activation energy, the enthalpy of activation and the entropy of activation for the exchange reaction were also determined.

• Journal of the Korean Chemical Society
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• v.32 no.6
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• pp.513-519
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• 1988

The effect of pressure and temperature on the stabilities of hexamethylbenzene-1,3,5-trinitrobenzene charge transfer complex in carbon tetrachloride has been investigated by spectrophotometric measurements. The absorption spectra of charge transfer complexes were measured at 25, 40, $50^{\circ}C$ under 1, 200, 500, 1000, 1400 bar in this experiments. The equilibrium constants of the complex were increased with pressure and decreased with temperature rising. The absorption coefficients were increased with pressure and temperature. Change of volume, enthalpy, free energy and entropy for the formation of complexes were calculated from the equilibrium constants. The red-shift observed at a higher pressure, the blue-shift at a higher temperature and the relation between pressure and oscillator strength were discussed by means of thermodynamic fuctions.

• The Safety technology
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• no.100
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• pp.68-71
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• 2006