• 한국산업융합학회 논문집
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• 제14권1호
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• pp.9-14
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• 2011

The excess molar enthalpies $H_m^E$ at T=298.15 K and p=101.3 kPa of ternary system {1,2-dichloropropane (1,2-DCP) + 1,3-dioxolane+ 1,4-dioxane} were predicted by using the binary contribution model of $Radojkovi{\check{c}}$ with correlated sub-binary Redlich-Kister parameters. Excess partial molar enthalpies ${\bar{H}}_i^E$ were also calculated for the binary systems {1,2-dichloropropane + 1,3-dioxolane}, {1,2-dichloropropane + 1,4-dioxane} and {1,3-dioxolane + 1,4-dioxane} using adjustable parameters of Redlich-Kister equation. By extrapolation of excess partial molar enthalpies to infinite dilution, limiting excess partial molar enthalpies ${\bar{H}}_i^{E,{\infty}}$ of each component were also obtained. The ternary excess molar enthalpies excess partial molar enthalpies of these sub-binary systems have been calculated by using our previously reported results.

• 대한화학회지
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• 제56권1호
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• pp.20-27
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• 2012

Complex permittivity spectra of Allyl Chloride (AC), 2-Butanone (2-BU) and their binary mixtures over the entire range of concentration were obtained using the Time Domain Reflectometry (TDR) technique in microwave frequency range at various temperatures. Static dielectric constant and relaxation time are obtained from complex permittivity spectra. Density ($\rho$) and refractive index ($n_D$) are also measured. These parameters are used to determine excess dielectric constant, excess inverse relaxation time, excess molar volume, excess molar refraction, polarity, Bruggeman factor and thermodynamic parameters viz. enthalpy of activation and entropy of activation. The values of static dielectric constant and relaxation time increases while density and refractive index decreases with the percentage of 2-Butanone in Allyl Chloride increases. Excess parameters were fitted to a Redlich-Kister equation.

• Bulletin of the Korean Chemical Society
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• 제16권5호
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• pp.432-436
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• 1995

The solubility of caffeine in compressed carbon dioxide has been measured to determine its fugacity coefficient between 330 and 410 K up to 500 bar. The result allows the calculation of the thermodynamic excess functions such as the molar excess enthalpy, the molar excess free energy, and the molar excess entropy. The pressure variations of the molar excess functions of caffeine in the caffeine-CO2 mixture were discussed and also compared them with those in the caffeine-NH3 mixture.

• 한국산업융합학회 논문집
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• 제4권2호
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• pp.193-198
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• 2001

2성분계 혼합물(1,2-dichloropropane + 2-methoxyethanol)에 대해 과잉몰 부피(excess molar volumes) $V^E$ 및 과잉 몰엔탈피(excess molar enthalpies) $H^E$를 298.15K에서 측정하였다. 혼합물의 밀도측정은 digital vibrating tube densimeter를 이용하였고, 과잉 몰엔탈피는 isothermal flow microcalorimeter를 이용하였다. 측정한 과잉 몰부피는 전 조성 영역에서 양의 편차를 나타내었으며, 과잉 몰엔탈피는 S 자형용 보였다. 또한 얻어진 data는 Nelder- Mead의 simplex method를 이용하여 Redlich-Kister 다항식에 접합 (fitting)하였다.

• 한국응용과학기술학회지
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• 제17권2호
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• pp.132-138
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• 2000

Excess enthalpies ($H^{E}$) were measured by isothermal flow calorimetry for the nonionic amphiphile 2-butoxyethanol/water mixtures at 10 different temperatures (48.5 to $70^{\circ}C$) around and above the lower consolute solution temperature, $T_{lc}$. $H^{E}$ exhibits U-shape for the binary mixtures, and is large and negative which reflects substantial interaction between two chemical species. When the commonly used, semi-empirical Redlich-Kister (RK) polynomials were fitted to the measured $H^{E}$, plots of $H^{E}$ vs. weight fraction provided more accurate fitting with fewer parameters than conventionally drawn $H^{E}$ vs. mole fraction plots. This was due to the enhanced symmetry of $H^{E}$ vs. weight fraction plots. Using the fitted Redlich-Kister polynomials and the Gibbs-Helmholtz relation, temperature dependence of the activity coefficients were found and compared to the values determined from vapor-liquid equilibria. The activity coefficients were in the range of one to three, indicating that the binary system deviates from ideality but not substantially. They slightly depended on temperature and the temperature effect was equivalent to 10 % change in the activity coefficients.

• Metals and materials international
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• 제24권6호
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• pp.1386-1393
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• 2018

The solubility of $TiO_2$ in $NaF-CaF_2-BaF_2$ ternary eutectic melts was investigated at the temperature range of $1025-1150^{\circ}C$. The least-squares equation was obtained from the relationship between the reciprocal temperature and the natural logarithm of the titanium concentration in the melts saturated with $TiO_2$. The corresponding partial molar enthalpy of dissolution of $TiO_2$ was found to be 188 kJ/mol. The titanium saturation concentration was 3.73 wt% at $1100^{\circ}C$. From the titanium concentration change with the added amount of $TiO_2$ at different holding time after a final stirring, it was found that not only complete dissolution of $TiO_2$ but also enough sedimentation of excessive $TiO_2$ should be guaranteed to obtain more reliable solubility data. The holding time of 10 h was found to be enough for the excessive $TiO_2$ particles to settle down in our experimental conditions. It is noteworthy that in case of adding $TiO_2$ in excess of its solubility, the $Ba_{1.12}(Ti_8O_{16})$ phase was observed at the lower and bottom of the solidified salt ingots.

• Bulletin of the Korean Chemical Society
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• 제2권3호
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• pp.90-96
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• 1981

The significant structure theory of liquids has been successfully applied to the sodium ammonia solution. In applying the theory to sodium ammonia solution, we assumed there were four species in solution, i.e., sodium cation, solvated electron, triple ion, and free electron and equilibria existed between them. Based on these assumptions, we set up the model explaining the anomalous properties of sodium ammonia solution. The partition function for sodium ammonia solution is composed of the partition functions for the above four species and also for the Debye-Huckel excess free energy term. Agreements between calculated and experimental values of the thermodynamic quantities, such as molar volume, vapor pressure, partial molar enthalpy and entropy, and chemical potential as well as viscosity are quite satisfactory.

• Bulletin of the Korean Chemical Society
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• 제11권4호
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• pp.309-313
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• 1990

The rates of solvolysis of trans-$[Co(N-eten)_2Cl_2)$+ (N-eten; N-ethylethylenediamine) have been investigated using spectrophotometric method in binary aqueous mixtures containing methyl alcohol, isopropyl alcohol, t-butyl alcohol, ethylene glycol and glycerol. The values of ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$ obtained from temperature effect on the rate constants were $80{\sim}84 kJmol^{-1}$ and $- 28{\sim} - 45 JK^{-1}mol^{-1}.$ Extrema found in the variation of the enthalpy and entropy of activation with solvent composition correlated very well with extrema in the variation of the physical properties of mixture which relate to sharp change in the solvent structure. The reaction mechanism was discussed in terms of correlation diagrams involving the exess molar Gibbs function of mixing for the binary mixtures. The behavior of this cobalt(Ⅲ) complex was compared with that of t-butyl chloride. The application of free energy cycle to the process initial state to transition state in water and in the mixture showed that the solvation of transition state had dominant effect on the rates in the mixtures. It was found that $S_N1$ character was increased with increasing the content of co-solvent in the mixture.