• Journal of the Korean Chemical Society
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• v.41 no.9
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• pp.443-448
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• 1997

Kinetics for the solvolyses of acyl chlorides and alkyl chlorides in hydroxylic solvent mixtures have been measured by conductometric method at various temperatures and pressures. The activation parameters (${\Delta}V^{\neq},\; {\Delta}H^{\neq},\; {\Delta}S^{\neq}$) were estimated from the rate constants. The reactivities of these reactions were also estimated from the correlation of the activation volumes with the activation entropies.

• Journal of the Korean Chemical Society
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• v.34 no.2
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• pp.184-188
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• 1990

Rates for reactions of substituted phenacyl bromides with imidazole and those of substituted imidazoles with phenacyl bromide were measured by an electric conductivity method. The rates were accelerated by electron-withdrawing substituents of phenacyl bromide and these reactions obeyed well both the linear free energy relationship and the isokinetic relationship. The relation between pKa's of substituted imidazoles and reaction constants fit the Bronsted rule. However, the case of 2-methylimidazole deviated far from this rule exerting steric hindrance. The reaction proceeded much faster in acetonitrile than in methanol and the observed ratio, k2 (acetonitrile)/k2 (methanol), was considerably larger than the value calculated from the Kirkwood equation.

• Journal of the Korean Chemical Society
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• v.38 no.11
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• pp.792-799
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• 1994

The spectral changes of 3,3'-diethyl oxacarbocyanine(DOC) in the aqueous solution and in the presence of polyacrylic acid(PAA) were studied by means of absorption and fluorescence spectroscopy. The spectral change of DOC in the aqueous solution with concentration changes is attributed to the formation of dimer. In the presence of PAA, the characteristic changes of metachromatic band with changes of P/D (the ratio between available binding site and the dye concentration) are found and the discussions are made in terms of stacking theory. A kinetic study of the interaction between DOC and PAA was also investigated by the absorption and fluorescence stopped-flow spectroscopy. The observed relaxation effect in PAA-DOC system can be described quantitatively by assuming two relaxation processes occur.

• Journal of the Korean Chemical Society
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• v.32 no.3
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• pp.227-232
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• 1988

A kinetic study was made to determine the mechanism of the aquation of $cis-[Co(en)_2(NH_3)Cl]^{2+}\;in\;Hg^{2+}$ aqueous solution. The progress of reaction was followed UV/vis-spectrophotometrically by a measurement of the absorbance at a specific wave length (530nm) of $cis-[Co(en)_2(NH_3)Cl]^{2+}$ as a function of time. The experimental results have shown that the reaction rate is dependent upon the concentration of $Hg^{2+}$ that act as a catalyst. And it was found that the overall reaction proceed with second order, first order with respect to Co(III) complex and $Hg^{2+}$. Activation parameters, ${\Delta}H^{\neq}\;and\;{\Delta}S^{\neq}$, were obtained as 12.9 kcal/mol and -19.3 e.u., respectively. We have proposed a plausible reaction mechanism which is consistent with the observed rate equation.

• Korean Chemical Engineering Research
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• v.46 no.3
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• pp.535-539
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• 2008

Conversion to oil, yield of styrene and formation of side products such as ${\alpha}-methyl$ styrene, ethyl benzene, benzene, toluene, dimer and trimer were affected by residue formed during thermal degradation. Also, control of reaction temperature had a difficulty at the first stage. Thus, new reaction system using wetted-wall type reactor was proposed and examined on various parameters such as reaction temperature, feeding rate and removal velocity of formed vapor. Optimun condition was obtained from continuous thermal degradation using wetted-wall type reactor and reaction kinetic study was carried out at new type reactor.

• Journal of the Korean Chemical Society
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• v.44 no.5
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• pp.429-434
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• 2000

The rate constants for the hydrolysis of styryldiphossphine oxide(SDPO) were deter-mined by ultraviolet visible spectrophotometric method and rate equation which can be applied over wide pH ranges was obtained. On the basis of pH-rate profile, hydrolysis product analysis, general base catalysis and substituent effect, a plausible hydrolysis mechanism is proposed : Below pH 4.5, the hydrolysis reaction is pro-ceeded by the attack of water to carbocation after protonaticentration of hydroxide ion.

• KSBB Journal
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• v.6 no.1
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• pp.99-103
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• 1991

The optimum conditions and rates of absorption of isobutylene in aqueous para-toluene sulfonic acid(PTSA) were studied experimentally in a stirred reactor. The effects of acid concentration(30-70 wt%), acid loading (0.3-5), mixing intensity(400-1000 rpm), and temperature ($20-80^{\circ}C$) on the absorption conditions were examined. The absorption rate of isobutylene was first order in isobutylene and variable order in PTSA concentrations. The apparent energy of activation was found to be 13 Kcal/mole.

• Resources Recycling
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• v.17 no.6
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• pp.34-42
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• 2008

The properties of sodium silicate solution were surveyed by using the yellow silicomolybdic method, and the formation of silica sol from sodium silicate solution and the growth of silica sol were investigated in this study. The $SiO_2$ content of 2 wt% in sodium silicate solution was proper to oxidize sodium silicate with sulfuric acid. After the removal of sodium ions in sodium silicate solution, the pH of silicate solution had to be controlled above 9 for the stabilization of silicate solution. The condensation between silicic acid species and silica nuclei surfaces has been studied at $20{\sim}80^{\circ}C$ and pH 10 in silicate solutions with silica nuclei. The reaction falls into two kinetics regimes, limited at high silicic acid species concentration by polymerization, but at lower concentration by a process whereby deposited silicic acid species condenses further to silica. The overall condensation is first-order in silicic acid species concentration, proceeded toward to pseudo equilibrium concentration, $C_x$, rather than the solubility of amorphous silica. The heat of solution of amorphous silica was 3.34 kcal/mol and exhibits an Arrhenius temperature dependence with an apparent activation energy of 3.16 kcal/mol in the range of $20{\sim}80^{\circ}C$.

• Applied Chemistry for Engineering
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• v.3 no.4
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• pp.649-656
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• 1992

The synthesis of epichlorohydrin was carried out by the epoxidation of allyl chloride with tert-butyl hydroperoxide(TBHP) over silica supported molybdenum catalyst. Kinetic study was performed at $60-80^{\circ}C$ and 10 atm with the molar ratio of TBHP/Allyl chloride between 0.01 and 0.1 in a batch reactor. The epoxidation of allyl chloride was inhibited by tert-butyl alcohol and kinetic data could be represented by Michaelis-Meten type rate equation. The reaction mechanism could be explained by the combination of reversible adsorption of TBHP and tert-butyl alcohol accompanied by reaction of allyl chloride with TBHP adsorbed on $Mo/SiO_2$ catalyst.

• Journal of the Korean Chemical Society
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• v.30 no.5
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• pp.475-482
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• 1986

Rates and equilibriurn of complex formation between $Ni^{2+}$ and D-penicillamine have been investigated in aqueous solutions. Kinetic study on the complex formation were performed in the pH range of 8∼9 by the use of pressure-jump technique. D-Penicillamine coordinates to the nickel(II) ion utilizing sulfur and nitrogen as donor atoms in the high pH condition (pH 9.2). However, in the pH range of 8.25∼9.07, the stepwise stability constant becomes drastically reduced and the undissociated mercapto group does not participate in bonding. The rate-determining step of the complexation reaction is found to be the release of a water molecule from the inner-coordination sphere of $Ni^{2+}$ ion.