• Journal of the Korean Chemical Society
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• v.23 no.1
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• pp.37-41
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• 1979

The kinetics of the reaction of benzyl m-nitrobenzenesulfonate with m-and p-substituted N,N-dimethylanilines in acetone have been investigated by an electric conductivity method. The effects of substituents on the reactivity of N,N-dimethylaniline and the existence of linear free energy relationship were discussed. The rate constants k were in the range 2.55∼487 $10^{-4}l{\cdot}mol^{-l}{\cdot}sec^{-1} (35^{\circ}C)$ and increased with the electron donating ability of substituents. In the present reaction, the Hammett plot was correlated with ${\sigma}$ substituent constant, especially using the new ${\sigma}$ value of 0.35 in p-MeO and it's ${\rho}$ value was found to be -1.37. r value for the reaction was very large than the value obtained in the reaction of benzyl bromide. $Br{\"{o}}nsted$ linear relationship was shown between rate constant and basicites except for p-MeO resulted from solvent effect. From the Bronsted plot, this reaction was suggested that the cleavage of the C${\cdot}{\cdot}{\cdot}$O bond in the $S_N2$ transition state proceed the bond formation.

• Journal of the Korean Chemical Society
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• v.19 no.2
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• pp.123-129
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• 1975

The rate constants of the hydrolysis of phenylvinylsulfone were determined by ultraviolet spectrophotometry at various pH and a rate equation which can be applied over wide pH range was obtained. The reaction mechanism of hydrolysis of phenylvinylsulfone and especially the catalytic contribution of hydroxide ion which did not study carefully before in acidic media, can be fully explained by the rate equation obtained. The rate equation reveals that: below pH 7, the reaction is initiated by the addition of water molecule to phenylvinylsulfone. At above pH 9, the overall rate constant is only dependent upon the concentration of hydroxide ion.

• Bulletin of the Korean Chemical Society
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• v.30 no.9
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• pp.2051-2056
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• 2009

The rate constants of alkaline fading of malachite green ($MG^+$) was measured in the presence of nonionic (TX-100), cationic (DTAB) and anionic (SDS) surfactants. This reaction was studied under pseudo-first-order conditions at 283∼303 K. The rate of fading reaction showed noticeable dependence on the electrical charge of the used surfactants. It was observed that the reaction rate constants were increased in the presence of TX-100 and DTAB and decreased in the presence of SDS. According to Hughs-Ingold rules for nucleophilic substitution reactions, the electric charge of MG/surfactant compound along with decrease in dielectric constant of $MG^+$ micro-environment in this compound varies the rate of fading reaction. Binding constants of surfactant molecules to $MG^+$ were calculated using cooperativity, pseudo-phase ion exchange and classical models and the related thermodynamic parameters were obtained by classical model. The results show that the binding of $MG^+$ to TX-100 is exothermic and binding of $MG^+$ to DTAB and SDS in some concentration ranges of the used surfactants is endothermic and in the other ones is exothermic.

• Environmental Analysis Health and Toxicology
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• v.16 no.3
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• pp.139-142
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• 2001

Acetanilide is a High Production Volume Chemical, which is produced about 2,300 tons/year in Korea as of 1998 survey. Most is used as an intermediate for synthesis of pharmaceuticals and dyes, and the chemical is one of seven chemicals of which human and environmental risk are being assessed by National Institute of Environmental Research under the frame of OECD SIDS program. The Atmospheric Oxidation Program for Microsoft Windows (AOPWIN) is used to estimates the rate constant for the atmospheric, gas－phase reaction between photochemically produced hydroxyl radicals and organic chemicals. It is also used to estimates the rate constant for the gas－phase reaction between ozone and olefinic/acetylenic compounds. The rate constants estimated by the program are then used to calculate atmospheric half－lives for organic compounds based upon average atmospheric concentrations of hydroxyl radicals and ozone. AOPWIN requires only a chemical structure to make these predictions. Structures are entered into AOPWIN by SMILES (Simplified Molecular Input Line Entry System) notations. In this study, one of environmental fate/distribution of the chemical elements, photodegradation of acetanilide was estimated using AOPWIN model based on SMILES notation and chemical name data.

• Journal of Pharmaceutical Investigation
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• v.35 no.5
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• pp.333-336
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• 2005

The objective of this study was to investigate the stability of tetracycline HCl on encapsulation into and inside reverse micelles. To do so, tetracycline HCl was first mixed with cetyltrimethylammonium bromide, water and ethyl formate to make reverse micelles. The degradation kinetics of tetracycline HCl inside the reverse micelles was then assessed by scrutinizing its stability data. Under our experimental conditions, the reverse micelles formed spontaneously in absence of any mixing devices. During the preparation of the reverse micelles, however, considerable portions of tetracycline HCl underwent a chemical reaction (e.g., epimerization). For instance, $51.4{\pm}0.6%$ of an initial concentration of tetracycline HCl was transformed into a degradation product. Once dissolved inside the reverse micelles, the degradation of tetracycline HCl followed an exponential decay pattern. The plot of log{the degradation rate of tetracycline HCl} versus log{tetracycline HCl concentration} made it possible to determine the order of degradation reaction and rate constant. It was proven that the degradation of tetracycline HCl inside the reverse micelles followed a first order kinetics with a rate constant of 0.0027 $hour^{-1}$. Meriting further investigation might be formulation studies to stabilize tetracycline HCl on encapsulation into and inside the reverse micelles.

• Journal of the Korean Chemical Society
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• v.27 no.1
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• pp.1-8
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• 1983

Solvent effects on nucleophilic substitution reaction of naphthalene sulfonyl chlorides with pyridine in protic and aprotic solvent have been studied by means of conductometry. Results showed that the rate constants increased with dielectric constants for protic solvents, while they decreased with dielectric constants for aprotic solvents, except for acetonitrile which has a higher dielectric constant but had also greater rate constant. The rate constants were shown to be more susceptible to polarity-polarizability parameter, , than to hydrogen bond donor acidity parameter, ${\alpha}$, indicating that the pulling effect of hydrogen bonding solvent.

• Journal of the Mineralogical Society of Korea
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• v.9 no.1
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• pp.1-6
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• 1996

Woolastonite from Susan occurs as intercalations in limestone beds of Lower Paleozoic Joseon Supergroup. It is a thermal metamorphic product of impure limestone. Electron microprobe analysis shows that it is considerably pure wollastonite. It has triclinic cell with a=7.932$\AA$, b=7.328$\AA$, c=7.069$\AA$, $\alpha$=89.995$^{\circ}$, $\beta$=$95.255^{\circ}$, and $ \Upsilon=103.367^{\circ}$.Dissolution behaviors of wollastonite have been studied conducting three different dissolution experiments; two different reactions with HC1 (one batch and one re-initialization experiment) and one traction with distilled water. In the batch type powder wollastonite-HCl reaction, pH of solution rapidly increases in the early stage and then its rate of increase slows down to reach plateau resulting in parabolic relationship with time. It is represented by the early rapid rise and fall in pH giving a sharp pH-edge and succeeding slow rise in the re-initialization experiment. The early rapid rise in pH is due to the rapid sorption of H- in solution to oxygens on the reactive surface of wollastonite and the fall in pH means that all reactive surface sites are occupied by H- ions and no more H- adsorption occurs. The slow rise in pH following the pH- edge is due to the dissolution of wollastonite as evidenced by the correlation of pH variation and cation concentration. Dissolution of powder wollastonite in HCl shows linear trend with time. Si is dissolved predominantly over Ca at a constant rate. Ca is dissolved predominantly in the very early stage. Dissolution rate of coarse-grained wollastonite fragments in distilled water is parabolic with times howing a rapid reaction in the early stage and a slow reaction in the advanced stage. The Ca/Si ratio in solution is high in the case of coarse-grained wollastonite fragment as compared with powder wollastonite. The coarse-grained wollastonite fragment-water (acid) reaction resulted in the solution with an elevated constant pH value (alkaline) giving an important significance on the environmental view point.

• Bulletin of the Korean Chemical Society
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• v.24 no.3
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• pp.318-324
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• 2003

A time-resolved probe beam deflection (PBD) technique was employed to study the energy relaxation dynamics of photofragments produced by photodissociation of $CH_3I$ at 266 nm. Under 500 torr argon environment, experimental PBD transients revealed two energy relaxation processes; a fast relaxation process occurring within an acoustic transit time (less than 0.2 ㎲ in this study) and a slow relaxation process with the relaxation time in several tens of ㎲. The fast energy relaxation of which signal intensity depended linearly on the excitation laser power was assigned to translational-to-translational energy transfer from the photofragments to the medium. As for the slow process, the signal intensity depended on square of the excitation laser power, and the relaxation time decreased as the photofragment concentration increased. Based on experimental findings and reaction rate constants reported previously, the slow process was assigned to methyl radical recombination reaction. In order to determine the rate constant for methyl radical recombination reaction, a theoretical equation of the PBD transient for a radical recombination reaction was derived and used to fit the experimental results. By comparing the experimental PBD curves with the calculated ones, the rate constant for methyl recombination is determined to be $3.3({\pm}1.0)\;{\times}\;10^6\;s^{-1}torr^{-1}$ at 295 ± 2 K in 500 torr Ar.

• Polymer(Korea)
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• v.29 no.1
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• pp.59-63
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• 2005

Kinetic study of a reaction between poly(caprolactone diol) and aliphatic isocyanate was investigated by FTIR spectroscopy. The reaction rate was obtained from analyzing the absorbance change of NCO peak (2265 $cm^{-1}$) in series IR spectra. In the results, the overall reaction between PCL and isocyanate conformed to the simple second-order law, and the rate constant increases with increasing reaction temperature. The activation energies obtained from the evaluation of kinetic data were 25.4∼30.9 kJ/mol for hexamethylene diisocyanate and 16.8∼22.1 kJ/mol for cyclohexylmethane diisocyanate, respectively.

• Journal of Environmental Impact Assessment
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• v.14 no.1
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• pp.17-24
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• 2005

This study was performed to evaluate the adsorption rate of phosphate corrosion inhibitor and reaction rate constant in drinking water distribution systems. The optimum concentration of corrosion inhibitor would vary depending on the quality of water, pipe materials, and condition of metal surfaces. The current adsorption study indicated that the residual phosphate concentration of the corrosion inhibitor decreased with the time as it adsorbed on the surface of pipe material. As time went by, the residual phosphate concentration became constant. It means that the formation of the corrosion protection film on metal surfaces is completed.