• Bulletin of the Korean Chemical Society
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• v.26 no.8
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• pp.1246-1250
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• 2005

We have evaluated the hydroxyl group-solvent specific interactions by using a Lichrosorb RP18 stationary phase and by measuring the retention data of carefully selected solutes in 50/50, 60/40, 70/30, 80/20, and 90/10(v/v%) methanol/water eluents at 25, 30, 35, 40, 45, and 50 ${^{\circ}C}$. The selected solutes are 3 positional isomers of phenylpropanol, that is, 1-phenyl-1-propanol, 1-phenyl-2-propanol, and 3-phenyl-1-propanol. There exist clear discrepancies in ${\Delta}H^o$ (solute transfer enthalpy from the mobile to the stationary phase) and $T{\Delta}S^o$ (solute transfer entropy) among positional isomers. The difference in ${\Delta}H^o$ and $T{\Delta}S^o$ between secondary alcohols (1-phenyl-1-propanol and 1-phenyl-2-propanol)is negligible compared to the difference between the primary alcohol (1-phenyl-3-propanol) and secondary alcohols. The $T{\Delta}S^o$ values of 3-phenyl-1-propanol are close to those of butylbenzene while the $T{\Delta}S^o$ values of secondary alcohols are close to those of propylbenzene. The difference in ${\Delta}{\Delta}H^o$ (specific solute-mobile phase interaction enthalpy) between the primary alcohol and the secondary alcohol decreases with increase of methanol content in the mobile phase. A unique observation is an extremum for 1-phenyl-3-propanol in the plot of $T{\Delta}{\Delta}S^o$ vs. methanol volume %. The positive sign of $T{\Delta}{\Delta}S^o$ of 3-phenyl-1-propanol implies that the entropy of 3-phenyl-1-propanol is greater than that of the hypothetical alkylbenzene (the same size and shape as phenylpropanol) in the mobile phase.

• Bulletin of the Korean Chemical Society
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• v.16 no.7
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• pp.574-577
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• 1995

Solvatochromic effect and hydrogen bonding interaction of NPNOH, NPNO- and NPNOR were investigated. Electronic transition energies of the dyes were plotted against empirical solvent polarity parameters, Taft's π* and Reichardt's ET(30). Good correlations were observed when the excitation energies were plotted against the energy calculated by multiple linear regression method which was developed by Taft. There is an intrinsic difference between betaine for ET(30) polarity scale and the azoderivative, which is derived from the specific hydrogen bond incurred with probe molecules and solvents. The hydrogen bonding plays a very important role for stabilization of an excited state molecule by solvents especially when a solute possesses a negative charge as with NPNO-.

• Korean Journal of Fisheries and Aquatic Sciences
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• v.16 no.3
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• pp.239-245
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• 1983

Electrochemical adsorption always was accompanied with solvent displacement and relative size factor(x) of adsorbate and solvent and hydrogen coverage(${\theta}$) on the lead anodic film electrode formed in phosphoric acid in NaCl solution and the sea water at $15{\sim}35^{\circ}C$ were studied by means of constant current-potential method and potentiodynamic cathodic polarization method. In this experiment, various constants and thermodynamic quantities calculated from the hydrogen coverage were also described to explain the reactivities of di-iso-butylnitrosoamine(DBNA) and proton ($H^+$) according to the changes of interactions between solute and solvent in the bulk phase and interphase. It was investigated that the average values of relative size factor and the coverage of hydrogen atoms studied with the electrode of lead anodic film formed in phosphoric acid solution in 60mM DBNA+0.5M NaCl and in 60mM DBNA+$6\%0$ sea water were about 11.0 and 0.2 respectively. Hydrogen evolution was electrochemical mechanism because of substitutional adsorption of aromatic substance with their delocalization of electrons, but in the case of non-charge transfer adsorption of aliphatic substance(DBNA) interacting relatively little with the electrode, it was combination mechanism.

• Journal of the Korean Chemical Society
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• v.26 no.2
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• pp.107-113
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• 1982

Addition of dimedone to thioxanthylium ion generated from the oxidation of thioxanthene by thianthrene cation radical perchlorate in acetonitrile gave 9-(4,4-dimethylcyclohexane-2,6-dionyl)thioxanthylium perchlorate (2), whereas from the reverse addition between two reactants was obtained initially 9-(4,4-dimethylcyclohexane-2,6-dionyl)thioxanthene (1), which then underwent further reaction to give 2. The compound 2 was readily deprotonated in aq acetone to give 9-(4,4-dimethylcyclohexane-2,6-dionylidene)thioxanthene (3). However, 3 turned out to be in equilibrium with 2 in which three isosbestic points at 219, 289, and 348 nm were recorded in aq acetonitrile. The intensity and the position of the maximum absorption of 3 near 380 nm vary depending on the solvents which has been explained in terms of the solvent-solute interactions.

• Journal of the Korean Chemical Society
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• v.33 no.2
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• pp.149-155
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• 1989

1H-nmr chemical shifts and lineshapes of amino-protons of thioacetamide in n-alcohols were determined. The chemical shifts are discussed by the Reichardt's solvent polarity parameter, $E_T(30)$. The following relationship between ${delta}_{obs}\;and\;E_T(30)$ was obtained, ${\delta}_{obs}=a{\cdot}E_T(30)＋b{\cdot}(E_T(30))_2$ where a is a characteristic constant for the protons of thioacetamide in n-alcohol solutions and b is a constant for the solute(TA)-solvent (n-alcohols) interactions. The barrier of the hindered rotation about the N-C(S) bond in TA was obtained by analysis of the lineshape of the amino-protons in TA. The behavior of the hindered rotation as well as chemical shifts of the amino-protons in TA has been found to be closely related to the $E_T(30)$ of n-alcohols.

• Journal of Integrative Natural Science
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• v.14 no.3
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• pp.99-106
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• 2021

A mixture of alcohol and water is commonly used as antifreeze, liquor, and the fundamental solvents for the manufacture of cosmetics, pharmaceuticals, and inks in our daily life. Since various properties of alcohol water mixtures such as density, boiling or melting point, viscosity, and dielectric constant are determined by their mixing ratio, it is very important to know the mixing ratio to predict their properties. One of simple method to find the mixing ratio is measuring the density of the mixtures. However, it is not easy to predict the mixing ratio from the density of the mixtures because the relationship between mixing ratio and density has not been established well. The relationship is dependent on the relative sizes of solute and solvent molecules, and their interactions. Recently, an empirical model to predict the density of glycerol water mixture from their mixing ratio has been introduced. The suggested model is simple but quite accurate for glycerol water mixture. In this article, we investigated the applicability of this model to different alcohol water mixtures. Densities for six different alcohol water mixtures containing various alcohols (e.g., ethylene glycol, 1,3-propane diol, propylene glycol, methanol, ethanol, and 1-propanol) were simulated and compared to experimentally measured ones to investigate the applicability of the model proposed for glycerol water mixtures to other alcohol water mixtures. The model predicted the actual density of all alcohol water mixtures tested in this article with high accuracy at various ratios. This model can probably be used to predict the mixing ratio of other alcohol water mixtures from their densities beyond 6 alcohols tested in this article from their densities.

• Journal of the Korean Chemical Society
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• v.37 no.1
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• pp.22-35
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• 1993

The transport phenomena of the free amino acids through poly(hydroxyethyl methacrylate)[P(HEMA)] have been investigated with and without various kinds of surfactants solution and in the mixed surfactants solution. Glutamine has the highest diffusivity among 4 amino acids at 1CMC of cetyldimethylethylammonium bromide(CTABr) surfactant. Glutamic acid is not affected by the concentration of CTABr. Methionine and Lysine shows slight decreased diffusivity at 0.5 CMC, but increase its diffusivity at 1CMC and 2CMC due to the structure change of membrane and the viscosity change of surfactant solution. Glutamic acid has the highest diffusivity among four amino acids at sodium dodecyl sulfate(SDS) and Triton X-100 surfactant. In mixed surfactant solution, each amino acids shows high diffusivity through 45% water content membrane at the 0.5 mole fraction of SDS in the SDS/TX-100 surfactant mixtures. It has been found that not only the property of membrane but also the effects of solute-solvent interactions and solvent effect are very important as the permeation of amino acids occurs through P(HEMA) membrane. The diffusivities of free amino acids through membrane depend upon their molecular shape, size and charge.

• Journal of the Korean Chemical Society
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• v.36 no.1
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• pp.87-94
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• 1992

The elution behavior of polystyrenes(PS), polymethylmethacrylates (PMMA), polybutadienes(PB), PS-PMMA(SM) block copolymers and PS-PB star shaped copolymers on the cross-linked polystyrene gels was studied. An interpretation was proposed for the plots of log hydrodynamic volume versus retention volume of solutes in the mobile phases such as tetrahydrofuran, toluene, chloroform, methylene chloride and tetrahydrofuran-cyclohexane mixture. In order to predict the retention of solutes from their physical properties, multiple stepwise regression analysis was applied to obtain the correlation. The distribution coefficients($K_p$) of solute-gel interactions in GPC for homopolymers and PS copolymers were also obtained in terms of network-limited separation mechanism. In the cases of PS and PB, $K_p$ values approach unity, while $K_p$ values for PMMA decrease as MW increase in the good solvent, but in poor solvent, $K_p$ values increase as MW increase. $K_p$ values of PS copolymers are dependent on their MW and composition, therefore, morohology of SM block copolymer is predicted to be random phase. A single universal plot of log[η]M vs. $(V_r-V_o)/K_p$