• Journal of the Korean Chemical Society
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• v.20 no.1
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• pp.15-18
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• 1976

The preferred conformation of benzenesulfenyl chloride was determined by EHMO calculation. It was found that the stability was dictated by the n-${\pi}$ conjugation of S atom with the benzene ring. The ethanolysis reaction of benzenesulfenyl chlorides has been studied. The rate constants obtained have been discussed in terms of substituent effects and d-orbital participation of sulfur atom. From a non-linear Hammett plot, bipyramid type of intermediate has been suggested.

• Journal of the Korean Chemical Society
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• v.26 no.5
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• pp.274-281
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• 1982

Ultraviolet spectrophotometric investigation have been carried out on the systems of pentamethylbenzene and hexamethylbenzene with iodine and iodine monochloride in carbon tetrachloride. The results reveal the formation of the one to one molecular complexes. The equilibrium constants were obtained in consideration of that absorption maxima due to the formation of the charge transfer complexes shift to blue with the increasing temperature. Thermodynamic parameters for the formation of the charge transfer complexes were calculated from these values. These results indicate that the complex formed between polymethylbenzene and iodine monochloride is more stable than that in the case of iodine. This may be a measure of their relative acidities toward polymethylbenzene, which is explained in terms of the relative electronegativities of halogen atoms. These results combined with previous studies of this series indicated that ${\lambda}_{max}$ shift to red with the increasing number of methyl groups on benezene ring and that the relative stabilities of these complexes increase in the order, Benzene < Toluene < Xylene < Durene < Mesitylene < Pentamethylbenzene < Hexamethylbenzene. The reason for the order found is thus additionally discussed.

• Korean Journal of Ecology and Environment
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• v.36 no.3 s.104
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• pp.295-303
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• 2003

Sorption kinetics of hydrophobic organic compounds (chlorobenzene and phenanthrene) in natural wetland soils was investigated using laboratory batch adsorbers. One -site mass transfer model (OSMTM) and two compartment first-order kinetic model (TCFOKM) were used to analyze sorption kinetics. Analysis of OSMTM reveals that apparent sorption equilibria were obtained within 10 to 75 hours for chlorobenzene and 2 hours for phenanthrene, respectively. For chlorobenzene, the sorption equilibrium time for surface soil was longer than that of deeper soil presumably due to physico-chemical differences between the soils. For phenanthrene, however, no difference in sorption equilibrium time was observed between the soils. As expected from the number of model parameters involved, the three-parameter TCFOKM was better than the two-parameter OSMTM in describing sorption kinetics, The fraction of fast sorption ($f_1$) and the first-order sorption rate constants for fast ($k_1$)and slow ($k_2$) compartments were determined by fitting experimental data to the TCFOKM. The results of TCFOKM analysis indicate that the sorption rate constant in the fast compartment($k_1$) was much greater than that of slow fraction($k_2$) . The fraction of the fast sorption ($f_1$) and the sorption rate constant in the fast compartment($k_1$) were increasing in the order of increasing $k_{ow}$, phenanthrene > chlorobenzene. The first-order sorption rate constants in the fast ($k_1$) and slow ($k_2$) compartments were found to vary from $10^{-0.1}\;to\;-10^{1.0}$ and from $10^{-4}\;to-10^{-2}$, respectively.

• Economic and Environmental Geology
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• v.35 no.2
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• pp.149-154
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• 2002

Column tests were carried out to examine the effect of surfactant solution conditions on surfactant-enhanced remediation of contaminated soil. The selected conditions of the surfactant solution were concentration and pH. 1,2,4-trichlo-robenzene (TCB) was chosen as the model hydrophobic organic substances. Sodium diphenyl oxide disulfonate (DOSL) and octylphenoxypoly ethoxyethanol (OPEE) surfactants were selected for this study. Two Iowa soils, Fruitfield sand and Webster clay loam, were leached with surfactant solution. The test results revealed that an optimum condition was achieved for 4 %(v/v) of concentration and 10 of pH, respectively. The maximum recoveries of added TCB (93-98%) were obtained when optimal conditions of each surfactant solution parameter were simultaneously met. The optimum conditions of these parameters may be useful for surfactant-assisted remediation in soil contaminated by TCB.

• Journal of the Korean Chemical Society
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• v.21 no.2
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• pp.83-88
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• 1977

Kinetic studies on the rates of reactions of 2, 4-dinitrochlorobenzene with p-toluidine, aniline and p-chloroaniline in $CH_3CH-CH_3OH$ binary solvent mixtures have been carried out. The experimental results have been explained in terms of the specific solvation by alcoholic hydrogen. It has been shown that the bond breaking step is rate determining in the solvent system studied and the energy barrier is getting low as the solvent changes from acetonitrile to methanol.

• Korean Journal of Environmental Biology
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• v.17 no.2
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• pp.129-138
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• 1999

Chlorinated aromatic compounds are one of the largest groups of environmental pollutants as a result of world-wide distribution by using them as herbicides, insecticides, fungicides, solvents, hydraulic and heat transfer fluids, plasticizers, and intermediates for chemical synthesis. Because of their toxicity, persistence, and bioaccumulation, the compounds contaminated ubiquitously in the biosphere has attracted public concerns in terms of serious influences to wild lives and a human being, such as carcinogenicity, mutagenicity, and disturbance in endocrine systems. The biological recalcitrance of the compounds is caused by the number, type, and position of the chlorine substituents as well as by their aromatic structures. In general, the carbon-halogen bonds increase the recalcitrance by increasing electronegativity of the substituent, so that the dechlorination of the compounds is focused as an important mechanism for biodegradation of chlorinated aromatics, along with the cleavage of aromatic rings. The removal of the chlorine substituents has been known as a key step for degradation of chlorinated aromatic compounds under aerobic condition. This can occur as an initial step via oxygenolytic, reductive, and hydrolytic mechanisms. The studies on the biochemistry and genetics about microbial dechlorination give us the potential informations for microbial degradation of xenobiotics contaminated in natural microcosms. Such investigations might provide biotechnological approaches to solve the environmental contamination, such as designing effective bioremediation systems using genetically engineered microorganisms.

• Nuclear Engineering and Technology
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• v.5 no.4
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• pp.321-333
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• 1973

The rates and activation parameters for the halide exchange reactions of substituted benzenesulfonylbromides (R-C$_{6}$H$_4$SO$_2$Br, R=p-MeO, p-$CH_3$, p-H, p-NO$_2$) in dry acetone at two temperatures were determined. It was found that the nucleophilicity order of Cl->I-$\geq$Br- for strong electron withdrawing-, and mild electron donating group, and of I-$\geq$Cl->Br- for strong electron donating group, Hammett plots showed slightly convoked characteristics which is similar to the plots of substituted benzenesulfonylchlorides, but contrary to the concaved nature for the halide exchange reactions of substituted benzyl chlorides. The rate of halogen exchange between benzenesulfonylbromide and lithium bromide decreased in the order of solvent : ($CH_3$)$_2$CO>$CH_3$CN》MeOH. The rates and activation parameters were also compared with those already known in the substituted benzenesulfonylchlorides. Theses were explained in terms of the structural properties of the transition state, and discussed the reaction mechanisms.s.

• Journal of the Korean Chemical Society
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• v.34 no.1
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• pp.19-28
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• 1990

The rate of chlorine-exchange reaction of antimony trichloride with benzyl, $\alpha$-phenyl ethyl and diphenyl methyl chlorides in nitrobenzene have been determined. The results indicate that the chlorine-exchange reaction follows second-order kinetics with respect to antimony trichloride and first-order kinetics with respect to organic chlorides. Rate = $k_3[SbCl_3]^2$ [Org-Cl] The rate constants of chlorine-exchange of antimony trichloride with organic chloride increase in the following order of the organic chlorides. Benzyl chloride < $\alpha$-phenyl ethyl chloride < diphenyl methyl chloride The mechanism of the chlorine-exchange reactions has been proposed.

• 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 environmental and Sanitary engineering
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• v.17 no.1
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• pp.63-68
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• 2002

Amount of styrene and divinylbenzene(DVB) was adjusted under injection of nitrogen, copolymer having crosslink of 1%, 2% and 5% was synthesized and zinc chloride was added to it. Put into benzene, swell it, add potassium iodide and 1-aza-15-crown-5 of 21.93g in toluene solution and functional resin which can adsorb heavy metal ions by stir reflex at $55^{\circ}C$ for 30 hours was synthesized. The content of divinylbenzene of this resin was increased as crosslink increase, macroporous gets smaller and the content of chlorine was reduced, which affects macrocyclic ligand in the process of substitution and content of nitrogen was also reduced. And the form of functional synthetic resin was distorted by substitution reaction of hydrogen and chlorine atoms.