• Journal of the Korean Chemical Society
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• v.29 no.6
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• pp.575-581
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• 1985

Ultraviolet spectrophotometric investigations have been carried out on the systems of benzene, naphthalene and phenanthrene with iodine 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 increasing temperature. Thermodynamic parameters for the formation of the charge transfer complexes were calculated from these values. These results indicate that the stabilities of the complexes formed between polynuclear aromatics and iodine increase with the number of aromatic rings. This may be a measure of the relative basicities of polynuclear aromatics toward iodine, which is explained in terms of the resonance of the interaction between aromatics and iodine. The results in this study were, additionally, compared with those of the polymethylbenzene series to be discussed the reason for them.

• Journal of the Korean Chemical Society
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• v.36 no.6
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• pp.933-940
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• 1992

Calix[6]arene react with formaldehyde and secondary amines to yields water soluble Mannich bases which can be converted to the corresponding quaternary salts. Treatment of the quaternary salts with a nucleophile such as cyano, ethoxy, and hydride yields p-substituted calix[6]arenes. Calix[8]arene too react with formaldehyde and diallyl amine to yield a water soluble Mannich base. The transport of neutral arenes through an aqueous phase along a concentration gradient mediated by those of water soluble calixarenes as molecular carrier was studied in a U-type cell. Naphthalene, anthracene, pyrene, and fluoranthene are tested as a neutral solid guest compounds for the transport experiment.

• Journal of the Korean Chemical Society
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• v.25 no.6
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• pp.351-360
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• 1981

Ultraviolet spectrophotometric investigations have been carried out on the system of durene with iodine, bromine, iodine monochloride and iodine monobromide in carbon tetrachloride. The results reveal the formation of the charge transfer complexes of the type, $C_6H_2(CH_3)_4{\cdot}X_2$ or $C_6H_2(CH_3)_4{\cdot}IX$(X denotes halogen atoms). The equilibrium constant were obtained in consideration of that absorption maxima due to the formation of the charge transfer complexes shift to blue with the increasing temperatures. The thermodynamic parameters, ${\Delta}H,\;{\Delta}G\;and\;{\Delta}S$ for the formation of the charge transfer complexes were calculated from these values. These results indicate that the relative stabilities of the durene complexes at each temperature decrease in the order, $ICl>IBr>I_2>Br_2$. This order may be a measure of their relative acidities toward durene, which is explained in terms of the relative polarizabilities of halogen molecules and the relative electronegativities of halogen atoms. These results combined with previous study of this series indicated that the relative stabilities of the polymethylbenzene complexes with iodine increase in the order; Benzene

• Journal of the Korean Chemical Society
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• v.25 no.2
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• pp.75-84
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• 1981

Ultraviolet spectrophotometric investigations have been carried out on the systems of mesitylene with iodine, bromine, iodine monochloride and iodine monobromide in carbon tetrachloride. The results reveal the formation of the charge transfer complexes of the type, $C_6H_3(CH_3)_3{\cdot}X_2$ or $C_6H_3(CH_3)_3{\cdot}IX$ (X denotes halogen atoms). 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 temperatures. Thermodynamic parameters, ${\Delta}H$, ${\Delta}G$ and ${\Delta}S$ for the formation of the charge transfer complexes were calculated from these values. These results indicate that the relative stabilities of the mesitylene complexes at each temperature decrease in the order, ICl > IBr > $I_2$ > $Br_2$. This order may be a measure of their relative acidities toward mesitylene, which is explaned in terms of the relative polarizabilities of halogen molecules and the relative electronegativities of halogen atoms. These results combined with previous study of this series indicated that the relative stabilities of the polymethylbenzene complexes with iodine increase in the order Benzene < Toluene < Xylene < Mesitylene Thus, analysis of these findings is discussed.

• Journal of the Korean Chemical Society
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• v.11 no.3
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• pp.100-104
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• 1967

The systems of aromatic amines such as aniline, N,N-dimethylaniline and N,N-diethylaniline with iodine or iodine monochloride in carbon tetrachloride have been examined spectrophotometrically. The results indicate the formation of one to one molecular complexes. The equilibrium constants obtained at room temperature for formation of the complexes are as follows: $C_6H_5NH_2{\cdot}I_2\;2.05$, $C_6H_5N(CH_3)_2{\cdot}I_2\;15.2$, $C_6H_5N(C_2H_5)_2{\cdot}I_2\;35.5$, $C_6H_5NH_2{\cdot}ICl\;18.5$, $C_6H_5N(CH_3)_2{\cdot}ICl\;25.6$, and $C_6H_5N(C_2H_5)_2\;42.0$ l $mole^{-1}$.

• Applied Chemistry for Engineering
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• v.7 no.5
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• pp.954-962
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• 1996

Four kind of polysilanes which had side chains of methyl, phenyl, and mixed structures, were synthesized and modified by doping with iodine. The structural, thermal, and electric characteristics of obtained polymers were systematically observed with iodine, The structural, thermal, and electric characteristics of obtained polymers were systematically observed with FT-IR, UV/VIS, TGA/DTG, DSC, and measurement of electric conductivity. From FT-IR spectra, it was confirmed that the synthesized polysilanes had side chains of methyl, phenyl, and mixed structures. The thermal stabilities of the polymers were found to increase with phenyl substituents. The polysilanes with phenyl side groups showed ${\sigma}-{\sigma}*$ transition absorption at wavelengths longer than 350 nm. The bathochromic shift of polysilanes with phenyl substituents relates probably to the narrowed band gap caused by delocalization of ${\pi}$-electron. The polymers doped with iodine showed multi-step pyrolysis behavior and higher residue compared with that of the undoped polymers. The electric conductivities of the undoped and doped polysilanes were $10^{-5}S/cm$ and $10^{-4}S/cm$, respectively.

• Journal of the Korean Chemical Society
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• v.39 no.5
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• pp.350-355
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• 1995

UV spectrophotometric investigation has been carried out on the system of charge-transfer (CT) complex with iodine and tetramethyltin in carbon tetrachloride solvent. The transient CT absorption spectrum can be observed in ${\lambda}_{max}=270nm$ and the subsequent disappearance of CT absorption spectrum was accompained by the cleavage of tetramethyltin with iodine (iododestannylation). From there, the rate constants for the iododestannylation were determined at 10, 20 and $35^{\circ}C$ up to 1200 bar and the reaction rates were increased with increasing temperature and pressure. From these rate constants, the values of the activation parameters (${\Delta}V^{\neq},\;{\Delta}{\beta}^{\neq},\;{\Delta}H^{\neq}\;and\;{\Delta}S^{\neq}$) were obtained and from these values discussed in terms of solvent structure variation of transition state and mechanism. From these results, it was found that the reaction is followed with $S_F2$ mechanism and weakened $S_F2$ mechanism nature by increasing pressure.

• Journal of the Korean Chemical Society
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• v.25 no.1
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• pp.1-6
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• 1981

Ultraviolet spectrophotometric investigations were carried out on the systems of o-, m-and p-xylene with iodine in carbon tetrachloride. The results reveal the formation of one to one molecular complexes of the type, $C_6H_4(CH_3)_2{\cdot}I_2. $The equilibrium constants of complexes were obtained in consideration of that absorption maxima has the blue shift with the increasing temperatures according to the formation of the charge transfer complexes. The thermodynamic parameters, $ {\Delta}$H, $ {\Delta}$G and $ {\Delta}$S for the formation of the charge transfer complexes were calculated from these values. These results combined with previous study of this series indicated that the relative stabilities of the polymethylbenzene complexes with iodine increase in the order, Benzene < Toluene < o-Xylene < p-Xylene These results are supposed to be the influence resulted from increase of electron density by the positive inductive effect and the steric hindrance effect.

• Journal of the Korean Chemical Society
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• v.37 no.3
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• pp.287-293
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• 1993

Ultraviolet spectrophotometric investigation has been carried out on the system of charge-transfer(CT) complex with iodine and tetramethyltin in n-hexane and acetone. From these results, the transient CT absorption spectrum can be observed and the subsequent disappearance of CT absorption spectrum is accompained by the cleavage of tetramethyltin with iodine (iododestannylation). Therefore, the rate constants for the iododestannylation were determined at 10, 25 and 35$^{\circ}C$ up to 1600 bar and the rates of reaction were increased with increasing temperature and pressure. From these rate constants, the values of the activation parameters (${\Delta}V^{\neq}$, ${\Delta}{\beta}^{\neq}$, ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$) were obtained and discussed in terms of solvent structure variation of transition state and mechanism from these values. It could postulated that the reaction is followed with S$_F$2 mechanism and weakened S$_F$2 mechanism nature by increasing pressure.

• Journal of the Korean Chemical Society
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• v.37 no.6
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• pp.555-561
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• 1993

Ultraviolet spectrophotometric investigation has been carried out on the system of iododestannylation iodine and tetramethyltin in methanol. The transient CT absorption spectrum can be observed and the subsequent disappearance of CT absorption spectrum was accompained by the cleavage of tetramethyltin with iodine. From there, the rate constants for the iododestannylation were determined at 10, 25 and 35$^{\circ}C$ up to 1600 bar and the reaction rates were increased with increasing temperature and pressure. From these rate constants, the values of the activation parameters (${\Delta}V^\neq,\;{\Delta}{\beta}^{\neq},\;{\Delta}H^{\neq},\;{\Delta}S^{\neq}\;and\;{\Delta}G^{\neq}$) were obtained. The activation volumes and activation compressibility coefficients were both negativity. The activation enthalpies were positive and activation entropies had large negative values. From these values discussed in terms of solvent structure variation of transition state and mechanism. From these results, it was found that the reaction is followed with $S_E2$ mechaenism and weakened $S_E2$ mechanism nature by increasing pressure.