• 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.

• Analytical Science and Technology
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• v.12 no.6
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• pp.540-549
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• 1999

The combustion temperature was controlled between $880^{\circ}C$ to $1070^{\circ}C$ to find the relation the combustion temperature and emission amount of PCDDs/PCDFs in the Municipal solid waste incinerator. The emission amount of PCDDs/PCDFs decreased when the temperature increased in the rear of the boiler. The PCDDs/PCDFs concentration were detected $7.82ng-TEQ/Nm^3$ at $880^{\circ}C$, $6.97ng-TEQ/Nm^3$ at $970^{\circ}C$ and $6.13ng-TEQ/Nm^3$ at $1070^{\circ}C$. Also, The chlorophenols, chlorobenzenes, and PCB concentration decreased by increasing the temperature from $880^{\circ}C$ to at $1070^{\circ}C$, and the isomer of the prescsors had a tendency to emit the higbly cbiorinated compounds.

• Journal of the Korean Chemical Society
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• v.18 no.1
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• pp.8-11
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• 1974

The solvolysis of p-substituted benzenesulfonyl chlorides $(substituents:p-H, p-Br, p-NO_2, p-OCH_3)$ in acetonitrile-water mixtures below 50 % of water content has been studied kinetically. Results show that Hammett plots give concaved curves but the mechanism is predominantly $S_N2$ and water acts both as nucleophile and general-base.

• Analytical Science and Technology
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• v.12 no.1
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• pp.68-74
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• 1999

The Concentrations of PCDDs/PCDFs and their precusors(chlorophenols, chlorobenzenes, PCB) were analyzed from the dioxin control device such as EP and SCR to know the emission patterns of these compounds and find the dioxin index compounds. The dioxin concentration increased 7 times in outlet part than inlet part of EP and the concentration of CBs, CPs and PCBs also were increased through this control device. These phenomia may be related to the operating temperature of Electroprecipitator(EP), which the operating temperature is near the $300^{\circ}C$, the method of the decreasing the operating temperature need to consider to prevent the formation of these compounds. In the selected catalytic reactor with wet scrubber(SCR+WS), these compounds were removed after passing the device over 90% for CPs, 30~40% for CBs and 60% for PCBs. But, the systematic study have to perform to reduce the formation of PCDDs/PCDFs and precusors.

• Journal of the Korean Chemical Society
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• v.17 no.3
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• pp.154-162
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• 1973

The rates and activation parameters for the halide $(Cl^{-}, Br^{-}, I^{-})$TeX> exchange reactions of substituted benzenesulfonyl-chloride, $XC_6H_4SO_2Cl$(X:p-MeO, H, p-Cl, p-Br, p-NO$_2l$) in dry acetone at two temperatures have been determined. It was found that the ion-pair of metal halide,$M^{+}X^{-}$, have negligible reactivity compared to free halide ions. It was also found that the nucleophilic order is $Cl^{-}>Br^{-}>I^{-}$for electron-donating substituent, and $Cl^{-}>I^{-}>Br^{-}$ for electron-withdrawing substituents. These results and convex nature of the Hammett plot are interpreted in the light of simple $S_N2$mechanism with the bond breaking becoming important for compounds with the electron withdra-wing substituents.

• Journal of the Korean Chemical Society
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• v.25 no.1
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• pp.7-12
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• 1981

Solvolysis of $p-CH_3, p-H, p-Cl and p-NO_2$-benzenesulfonyl chlorides have heen studied in MeOH-MeCN mixtures. A nonlinear Hammett plot with a ratio order of p-NO_2 > p-CH_3 > p-H > p-Cl was obtained; the reaction was thought to proceed by an S_N1-S_N2 borderline mechanism. In all cases the reactivity was a maximum at 90∼95%(v) methanol, whereas methanol monomer selectivity defined as fi = \frac{k1}{ki}i (k1; observed pseudo-first order rate constant: ki; hypothetical rate constant for MeOH solution having the same polymer structure as in the pure MeOH) was a maximum at 80% methanol with a decreasing order of fi as p-NO_2 > p-Cl > p-H > p-CH_3.$ This was interpreted as the decrease in tightness of transition state; the larger the fi, the tighter is the MeOH attached to the substrate, and hence the more susceptible the substrate becomes to the approaching monomer methanol.

• Journal of the Korean Chemical Society
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• v.20 no.5
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• pp.380-390
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• 1976

The trends of forming a charge transfer complex have been studied for electron donors such as anisole, 4-chloroanisole, 2,4-dichloroanisole, 2-fluoro-4-chloroanisole, 2-bromo-4-chloroanisole, 2-iodo-4-chloroanisole, 2-fluoro-4,6-dichloroanisole, 2,4,6-trichloroanisole, 2-bromo-4,6-dichloroanisole, 2-iodo-4,6-dichloroanisole, and 2-iodo-4,5,6-trichloroanisole, and electron acceptors such as iodine and iodine monochloride in the carbon tetrachloride or the hexane solvent system. It was found that the formation of a charge transfer complex was influenced by the Van der Waals Radii of the 2-halogen atoms on the benzene ring and further the overall steric moiety of the molecule of the electron donor. These trends were also experienced in a system of chloroform and one of the prementioned electron donor by means of a nuclear magnetic resonance spectrometry. The spectrophotometrical data on the formation of the charge transfer complex were presented and the results were discussed with views of the steric structure of the 2-halogen atom on the benzene ring.

• Journal of the Korean Chemical Society
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• v.29 no.6
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• pp.565-574
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• 1985

The rates of reaction between 4-substituted-2,6-dinitrochlorobenzenes with para-substituted anilines in methanol-acetonitrile mixtures were measured by conductometry. It was observed that the rate constant increases in the order of X = 4-$NO_2 {\gg}4-CN {\gg}4- CF_3$, where X is a substituent in the substrate. The rate constant also increases in the order of Y = p-O$CH_3{\gg}p- CH_3{\gg}H {\gg}p-Cl{\gg}m- NO_2$, where Y is a substituent in the aniline ring. Kinetic studies in the methanol-acetonitrile solvent system with various nucleophiles showed that the N-C bond forming step is making a great contribution to the overall second order rate constant. The electrophilic catalysis by methanol probably consists of the hydrogen bonding between alcoholic hydrogen and leaving chloride in the transition state. The nucleophilic catalysis by methanol may be ascribed to the formation of hydrogen bonds between alcoholic oxygen and hydrogens of amines in the transition state. All these experimental facts are supporting the operation of $S_N$Ar machanism with the second step being the rate determining. This mechanism can be successfully fitted to the PES model.

• 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.17 no.3
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• pp.163-168
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• 1973

Kinetic studies of p-substituted benzenesulfonyl chlorides have been carried out in 10~50 wt. % water-acetone mixtures. Results show that $S_N2$