• Journal of the Korean Chemical Society
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• v.39 no.11
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• pp.837-841
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• 1995

Thermodynamic parameters for the hydrogen bonding between thiopropionamide(TPA) and proton donors such as triethylphosphine oxide(TEPO), triphenylphosphine oxide(TPPO), trimethylphosphate(TMP), and tributyl phosphate(TBP) in dilute carbon tetrachloride solution have been measured by near-IR spectroscopy. The νa + amide Ⅱ combination band of TPA has been resolved into two Lorentzian-Gaussian product components which have been identified with monomeric TPA and 1 : 1 hydrogen bonded complex. The equilibrium constants and thermodynamic parameters for the formation of 1 : 1 hydrogen bonded complex have been obtained by the analysis of concentration and temperature dependent spectra. The standard enthalpies for the 1 : 1 hydrogen bonded complex formation of TPA with TEPO, TPPO, TMP, and TBP in CCl4 have been found to be - 21.4, - 16.8, - 12.8, and - 12.9 kJ/mol, respectively. The results are explained by the inductive and steric effects of substituents.

• Bulletin of the Korean Chemical Society
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• v.26 no.11
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• pp.1761-1766
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• 2005

Solvolysis rates of isopropenyl chloroformate (3) in water, $D_2O$, $CH_3OD$ and in aqueous methanol, ethanol, 2,2,2-trifluoroethanol (TFE), acetone, 1,4-dioxane as well as TFE-ethanol at 10 ${^{\circ}C}$ are reported. Additional kinetic data for pure water, pure ethanol and 80%(w/w) 2,2,2-trifuoroethanol (T)-water (W) at various temperatures are also reported. These rates show the phenomena of maximum rates in specific solvents (30% (v/v) methanol-water and 20% (v/v) ethanol-water) and, variations in relative rates are small in aqueous alcohols. The kinetic data are analyzed in terms of GW correlations, steric effect, kinetic solvent isotope effects (KSIE), and a third order model based on general base catalysis (GBC). Solvolyses based on predominately stoichiometric solvation effect relative to medium solvation are proceeding in 3 and the results are remarkably similar to those for p-nitrobenzoyl chloride (4) in mechanism and reactivity.

• Bulletin of the Korean Chemical Society
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• v.31 no.9
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• pp.2553-2556
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• 2010

On the basis of a simple modified Poisson-Boltzmann (SMPB) theory, taking into account the finite ionic size, the analytic expression for the effect of ionic size on the diffuse layer potential drop at negative charge densities has been given for the simple 1:1 electrolyte. It is shown that the potential drop across the diffuse layer depends on the size of the ions in the electrolyte. For a given electrolyte concentration and electrode charge density, the diffuse layer potential drop in a small ion system is smaller than that in a large ion system. It is also displayed that the diffuse layer potential drop is always less than the value of the Gouy-Chapman (GC) theory, and the deviation increases as the electrode charge density increases for a given electrolyte concentration. These theoretical results are consistent with the results of the Monte-Carlo simulation [Fawcett and Smagala, Electrochimica Acta 53, 5136 (2008)], which indicates the importance of including steric effects in modeling diffuse layer properties.

• Proceedings of the Materials Research Society of Korea Conference
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• 2010.05a
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• pp.23.2-23.2
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• 2010

Researches on the drying of particle/polymer suspensions receive attentions in technical applications such as manufacturing display and batteries. In this study, the effect of polymers on drying behavior of silica/poly(vinyl alcohol) suspension was investigated in terms of suspension stability and stress development during drying. The effect of polymer adsorption was studied by changing pH. More strongly flocculated suspension with lower pH became more dispersed and close-packed film after drying. Evaluation of potential energy allows us to suggest that the adsorbed polymers which bridge the particles introduce steric repulsion and lead flocculated suspension to dispersed film. When the effect of adsorption kinetics was studied by changing the mixing time, the adsorption amount, characteristic stress and dried film density showed a similar behavior in the form of with a single characteristic time. It implies that the drying process can be determined by simple characteristic equation with a single time constant.

• Journal of Environmental Science International
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• v.19 no.5
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• pp.565-575
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• 2010

This study is mainly focused on micellar effect of cetylpyridinium chloride(CPyCl) solution including alkylbenzimidazole(R-BI) on dephosphorylation of diphenyl-4-nitrophenylphosphinate(DPNPIN) in carbonate buffer(pH 10.7). The reactions of DPNPIN with R-BI$^{\ominus}$ are strongly catalyzed by the micelles of CPyCl. Dephosphorylation of DPNPIN is accelerated by BI$^{\ominus}$ ion in $10^{-2}M$ carbonate buffer(pH 10.7) of $4{\times}10^{-3}M$ CPyCl solution up to 100 times as compared with the reaction in carbonate buffer by no BI solution of $4{\times}10^{-3}M$ CPyCl. The value of pseudo first order rate constant($k^m_{BI}$) of the reaction in CPyCl solution reached a maximum rate constant increasing micelle concentration. Such rate maxima are typical of micellar catalyzed bimolecular reactions. The reaction mediated by R-BI$^{\ominus}$ in micellar solutions are obviously slower than those by BI$^{\ominus}$, and the reaction rate were decreased with increase of lengths of alkyl groups. It seems due to steric effect of alkyl groups of R-BI$^{\ominus}$ in Stern layer of micellar solution. The surfactant reagent, cetylpyridinium chloride(CPyCl), strongly catalyzes the reaction of diphenyl-4-nitrophenylphosphinate(DPNPIN) with alkylbenzimidazole (R-BI) and its anion(R-BI$^{\ominus}$) in carbonate buffer(pH 10.7). For example, $4{\times}10^{-3}M$ CPyCl in $1{\times}10^{-4}M$ BI solution increase the rate constant ($k_{\Psi}=1.0{\times}10^{-2}sec^{-1}$) of the dephosphorylation by a factor ca.14, when compared with reaction ($k_{\Psi}=7.3{\times}10^{-4}sec^{-1}$) in $1{\times}10^{-4}M$ BI solution(without CPyCl). And no CPyCl solution, in $1{\times}10^{-4}M$ BI solution increase the rate constant ($k_{\Psi}=7.3{\times}10^{-4}sec^{-1}$) of the dephosphorylation by a factor ca.36, when compared with reaction ($k_{\Psi}=2.0{\times}10^{-5}sec^{-1}$) in water solution(without BI). This predicts that the reactivities of R-BI$^{\ominus}$ in the micellar pseudophase are much smaller than that of BI$^{\ominus}$. Due to the hydrophobicity and steric effect of alkyl group substituents, these groups would penetrate into the core of the micelle for stabilization by van der Waals interaction with long alkyl groups of CPyCl.

• Journal of Photoscience
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• v.3 no.1
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• pp.43-47
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• 1996

The 77 K emission and excitation, and room-temperature UV-visible spectra of $\Lambda$-fac[Cr(L-ala)$_3$] (ala = alanine anion) have been measured. The ten electronic transitions due to spinallowed and spin-forbidden are assigned. With the observed electronic transition energies, ligand field optimizations have been performed to determine the bonding properties of L-alanine anion toward chromium(III). The angular overlap model (AOM) parameters obtained indicate that it is electron-donating ligand which has values of e$_{\sigma}O$, e$_{\pi}O$, and e$_{\sigma}N$ slightly lower than those of glycine anion (gly). It seem that the decrease of the ligand field properties is due to steric effect of extra methyl group and inductive effect of adjacent carbonyl group.

• Journal of Powder Materials
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• v.5 no.2
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• pp.133-138
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• 1998

The effect of $\beta$-$Si_3N_4$ seeding on microstructural development of silicon nitride based materials has been investigated. In particular, to observe more distinctly the abnormal grain growth in pressureless sintering, fine $\alpha$-$Si_3N_4$(mean particle size: 0.26 ${\mu}m$) powder classified by sedimentation method was used. It was possible to prepare silicon nitride with abnormally grown grains under low nitrogen pressure of 1 atm thanks to the heterogeneous nucleation on $Si_3N_4$ seed particles. The size and morphology of silicon nitride grains were strongly influenced by the presence of $\beta$-$Si_3N_4$ seed and overall chemical composition. For specimens with initially low $\beta$-content, the large grains grew without a significant impingement by other large grains. On the contrary, for specimens with initially high $\beta$-content, steric hindrance was effective. The resulting microstructure was less inhomogeneous and characterized by unimodal grain size distribution.

• Journal of the Korean Ceramic Society
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• v.33 no.2
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• pp.214-222
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• 1996

The effect of physicochemical properties of organic solvent and dispersant among organic solvent dispersant binder and plasticizer which are used as processing additives in MLCC fabrication process on the dispersion of BaTiO3 was studied. The steric and electrostatic stabilization mechanisms in dispersion of BaTiO3 in organic media were evaluated respectively. The sttability of BaTiO3 achieved bysteric stabilization was dependent on the fraction of surface coverage of dispersant adsorption on BaTiO3. The electrostatic repulsive forces of BaTiO3 particles dispersed in orgainc media was found to be appreciabley great and dependent mainly on the kinds of organic solvent used. The mechanism affecting the stability of BaTiO3 was studied by the method of rheologi-cal behaviors of BaTiO3 suspension.

• Journal of the Korean Chemical Society
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• v.43 no.3
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• pp.251-256
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• 1999

Viscosities of toluene were experimentally determined by the falling-ball method at several temperatures and pressures to investigate the pressure and temperature dependence of the viscosity of toluene. With the shear stress of the viscous flow of toluene, the shear free energy, the shear entropy, and the shear enthalpy were defined to discuss the variations of the shear thermodynamic properties with pressure. The effect of temperature and pressure on the shear thermodynamic properties obtained experimentally can be explained by means of the molecular thermal agitation due to temperature incleasing and the steric effect of the closed molecules of to Iuene due to pressure elevation.

• Journal of the Korean Chemical Society
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• v.13 no.1
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• pp.75-82
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• 1969

4-Ethyltropolone has been prepared in three steps from cyclopentadiene by a dichloroketene process, and at the same time, a comparison has also been made with the case of tropolone synthesis. In the addition reaction of dichloroketene to cyclopentadiene as well as to ethylcyclopentadiene, and also in the separation of cycloadducts from reaction mixture, the best results were given by prevention of the reactants from dimerization. Under these condition, the yields of cycloadducts were around 70% for both. Tropolone and 4-ethyltropolone were obtained in the yield of 51% and 32%, respectively, by hydrolysis of cycloadducts with potassium acetate in aqueous acetic acid. These results revealed that the steric effect of ethylgroup was more sensitive to the hydrolysis than to the cycloaddition reaction. A comparison of UV, IR and NMR spectroscopic results of 4-ethyltropolone with those of tropolone was also made together with a brief discussion of the tropolone ring system and ethylgroup effect.