• Title/Summary/Keyword: Solid-Liquid Equilibria

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Solid-liquid phase equilibria on the GdBa2Cu3O7-δ stability phase diagram in low oxygen pressures (1 - 100 mTorr)

  • Lee, J.W.;Lee, J.H.;Moon, S.H.;Yoo, S.I.
    • Progress in Superconductivity and Cryogenics
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    • v.14 no.4
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    • pp.28-31
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    • 2012
  • We report the solid-liquid phase equilibria on the $GdBa_2Cu_3O_{7-{\delta}}$ (GdBCO) stability phase diagram in low oxygen pressures ($PO_2$) ranging from 1 to 100 mTorr. On the basis of the GdBCO stability phase diagram experimentally determined in low oxygen pressures, the isothermal sections of three different phase fields on log $PO_2$ vs. 1/T diagram were schematically constructed within the $Gd_2O_3-Ba_2CuO_y-Cu_2O$ ternary system, and the solid-liquid phase equilibria in each phase field were described. The invariant points on the phase boundaries include the following three reactions; a pseudobinary peritectic reaction of $GdBCO{\leftrightarrow}Gd_2O_3$ + liquid ($L_1$), a ternary peritectic reaction of $GdBCO{\leftrightarrow}Gd_2O_3+GdBa_6Cu_3O_y$ + liquid ($L_2$), and a monotectic reaction of $L_1{\leftrightarrow}GdBa_6Cu_3O_y+L_2$. A conspicuous feature of the solid-liquid phase equilibria in low $PO_2$ regime (1 - 100 mTorr) is that the GdBCO phase is decomposed into $Gd_2O_3+L_1$ or $Gd_2O_3+GdBa_6Cu_3O_y+L_2$ rather than $Gd_2BaCuO_5+L$ well-known in high $PO_2$ like air.

Experimental Study of the Phase Equilibria for $CO_2$ in Liquified Natural Gas Components at 77-219K

  • Yun, Sang-Kook
    • International Journal of Air-Conditioning and Refrigeration
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    • v.11 no.2
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    • pp.61-66
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    • 2003
  • In order to prevent roll-over and a rapid boil-off of LNG in tanks, the phase equilibria of carbon dioxide in liquefied natural gas components as binary mixtures at cryogenic temperatures have been experimentally measured using Fourier transform infrared spectroscopy in conjunction with a specially designed variable pressure/temperature cryostat cell (pathlength 2 mm; pressures up to 30 bar). Solid carbon dioxide has been found to be comparatively soluble in liquid nitrogen (3.25$\times$${10}^{-6}$ mole fraction), liquid methane (1.04$\times$${10}^{-4}$ mole fraction), liquid ethane (3.1$\times$${10}^{-2}$ mole fraction) and liquid propane (6.11$\times$${10}^{-2}$ mole fraction) at their normal boiling temperatures. The solubilities of carbon dioxide in various cryogens, which increased with increasing temperature, are much lower than those obtained by others using gas chromatography. The differences are attributed to infrared spectroscopy selectively measuring dissolved solute in situ whereas gas chromatography measures microscopic particulate solid in addition to dissolved solute.

A Study on the Solid-liquid Equilibria for Benzene+aniline, Benzene+nitrobenzene, p-xylene+cyclohexane (Benzene+aniline, benzene+nitrobenzene, p-xylene+cyclohexane계의 고액평형에 관한 연구)

  • Park, So-Jin;Paik, Seung-Kwan
    • Applied Chemistry for Engineering
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    • v.9 no.6
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    • pp.864-869
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    • 1998
  • In this work, the solid-liquid equilibria (SLE) of some aromatic organic mixtures including benzene, widely used as an industrial solvent, were measured by static method using our own made experimental apparatus. The accuracy and reproducibility of apparatus were tested by comparing experimental results with literature values for 1-dodecanol+cyclohxane and benzene + p-xylene systems. The SLE for new binary systems of benzene+aniline, benzene+nitrobenzene, p-xylene+cyclohexane were measured afterwards and compared with the calculated values by modified UNIFAC(Dortmund) equation.

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Approximate Nonrandom Two-Fluid Lattice-Hole Theory. Thermodynamic Properties of Real Mixtures

  • 유기풍;신훈용;이철수
    • Bulletin of the Korean Chemical Society
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    • v.18 no.8
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    • pp.841-850
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    • 1997
  • A simple molecular theory of mixtures is formulated based on the nonrandom two-fluid lattice-hole theory of fluids. The model is applicable to mixtures over a density range from zero to liquid density. Pure fluids can be completely characterized with only two molecular parameters and an additional binary interaction energy is required for a binary mixture. The thermodynamic properties of ternary and higher order mixtures are completely defined in terms of the pure fluid parameters and the binary interaction energies. The Quantitative prediction of vapor-liquid, and solid-vapor equilibria of various mixtures are demonstrated. The model is useful, in particular, for mixtures whose molecules differ greatly in size. For real mixtures, satisfactory agreements are resulted from experiment. Also, the equation of state (EOS) is characterized well, even the liquid-liquid equilibria behaviors of organic mixtures and polymer solutions with a temperature-dependent binary interaction energy parameter.

Studies of Solid-Liquid Phase Equilibria for Mixtures of N-vinyl-2-pyrrolidone+2-pyrrolidone and Growth Rate of N-vinyl-2-pyrrolidone Crystal Using Melt Crystallization (N-vinyl-2-pyrrolidone과 2-pyrrolidone 혼합물의 고-액 상평형 및 용융결정화를 이용한 N-vinyl-2-pyrrolidone의 결정성장속도 연구)

  • Kim, Sun Hyung;Seo, Myoung Do;Tak, Moon Seon;Kim, Woo Sik;Yang, Dae Ryuk;Kang, Jeong Won
    • Korean Chemical Engineering Research
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    • v.51 no.5
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    • pp.587-590
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    • 2013
  • Solid-liquid equilibria for mixtures composed of n-vinyl-2-pyrrolidone (NVP) and 2-pyrrolidone were measured as a basic study for the melt crystallization process to remove 2-pyrrolidone as impurity included in NVP. A differential scanning calorimeter (DSC) and a crystallizer were used and the experimental results obtained from two methods were similar. The mixture showed a eutectic system which has a single composition at the minimum melting temperature. Calculation results from simple thermodynamic equations were found in general agreements with present data. To determine the growth rate of NVP crystal which is important for the design of crystallization process, thicknesses of the crystal were measured with the time using a layer melt crystallizer. The growth rates increased as cooling temperatures decreased. Heat transfer coefficient correlated from present data was found to successfully describe the crystal growth behavior.

Solid-Liquid Equilibria and Excess Molar Volumes, Refractive Indices and Deviation in Viscosity for Binary Systems of C3-C6 Carboxylic Acids (Carboxylic acid 이성분계의 고-액 상평형과 과잉물성, 굴절률 및 점도 편차)

  • Gu, Ji-Eun;Oh, Ha-Young;Park, So-Jin
    • Korean Chemical Engineering Research
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    • v.57 no.1
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    • pp.78-84
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    • 2019
  • Recently, bio-butanol is being promoted as environmentally friendly sustainable energy. However, some problems are still obstacle for commercialization of bio-butanol: the development of cheap biomass and enhancement of fermentation ratio and preparation of economical separation process for fermented products. In the conventional ABE biobutanol fermentation process, organic acids with acetone, butanol, and ethanol are produced. Therefore, it is necessary to study phase equilibrium data and mixture properties for the design and operation of separation process. However, there is lack of design data for organic acids except acetic acid contained system. In this study, therefore, binary solid-liquid equilibria (SLE) and mixture properties: the excess molar volumes ($V^E$), molar refraction deviation (${\Delta}R$) and deviation of viscosity (${\Delta}v$) at 298.15 for $C_3-C_6$ organic acid were reported. The experimental SLE data were correlated with the NRTL and UNIQUAC activity coefficient model with less than 0.5 K of root mean square deviation (RMSD). In addition, $V^E$, ${\Delta}R$ and ${\Delta}v$ for the same binary systems were satisfactorily fitted using the Redlich-Kister polynomial with less than ca. 0.004 standard deviation.

Synthetic Experiment on the Pt-Sb-Bi System: Phase Equilibria and Mineralogical Significance (백금-안티모니-비스머스계의 합성실험적 연구: 상관계 및 광물학적 의의)

  • 김원사
    • Journal of the Mineralogical Society of Korea
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    • v.11 no.2
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    • pp.117-125
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    • 1998
  • Crystallization behavior of platinum minerals within Pt-Sb-Bi bearing ore magmas and mineralogical properties of the existing minerals were investigated at 1,00$0^{\circ}C$ by synthetic experiment. High purity reagents were used as starting materials and silica tubings as containers. Reaction products were analysed by reflecting microscopy, X-ray diffraction, electron probe microanalysis, and micro-hardness test. Stable minerals at 1,00$0^{\circ}C$ are platinum, electron probe microanalysis, and micro-hardness test. Stable minerals at $1,000^{\circ}C$ are platinum, stump-flite (PtSb) and geversite (PtSb2). They are in equilibrium with liquid (ore magma). Platinum contains considerable amount of Sb of 7.5 at.%, whereas Bi only up to 0.9 at.%. Pure stumpflite is hexagonal with space group P63/mmc, and unit cell parameters are a=4.1318(6), c=5.483(1)$\AA$. VHN50=417(2)$\AA$. Geversite has cubic structure with space group Pa3. Cell parameters are a=6.4373(2)$\AA$ and Vicker hardness values VHN50=663.5 (566~766). Both stumpflite and geversite show solid solution and their end-members are Pt48.8Sb40.7-Bi10.5, and Pt33.7-Sb59.8Bi6.5, respectively. Although stumpflite (m.p. $1,043^{\circ}C$) and unnamed PtBi (m.p. 7$65^{\circ}C$) do not form a complete solid solution at $1,000^{\circ}C$, they are known, at $600^{\circ}C$, to form a continuous solid solution. Geversit (m.p. $1,226^{\circ}C$) also forms complete solid solution with insizwaite (m.p. $660^{\circ}C$). Unit cell dimensions of the minerals above increases with the amount of Bi substituting for Sb.

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Purification of Naphthalene from Naphthalene and 2-methylnaphthalene System by Layer MelMelt-Crystallization (경막형 용융결정화에 의한 나프탈렌과 2-메틸나프탈렌 혼합물로부터 나프탈렌의 분리)

  • Koh, Joo-Young;Kim, Chul-Uog;Park, So-Jin
    • Clean Technology
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    • v.12 no.3
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    • pp.157-164
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    • 2006
  • In order to purify 2-methylnaphthalene as main impurity included in naphthalene, SLE (solid-liquid equilibria) on two components system including naphthalene and 2-methylnaphthalene were measured and a layered melt crystallization has been studied. SLE in the present system is shown a simple eutectic mixture and the experimental results using DSC method is similar to the static method. Purity and yield of naphthalene in crystal depended mainly on the cooling rate: Increasing cooling rate, the purity of naphthalene in crystal increase, whereas the yield of that decrease. The effective distribution coefficient (Keff) as the degree of impurity removal was observed to decrease with decreasing of cooling rate. Therefore, the purity of naphthalene by melt crystallization can be enhanced to 5~7 %.

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Purification of p-Dioxanone from p-Dioxanone and Diethylene Glycol Mixture by a Layer Melt Crystallization (경막형 용융결정화에 의한 파라디옥사논과 디에틸렌글리콜 혼합물로부터 파라디옥사논의 정제)

  • Kim, Sung-Il;Kim, Chul-Ung;Park, So-Jin
    • Korean Chemical Engineering Research
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    • v.43 no.5
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    • pp.595-602
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    • 2005
  • In order to purify diethylene glycol as main impurity included in p-dioxanone, SLE (solid-liquid equilibria) and mixture density on two components system of p-dioxanone and diethylene glycol were measured and a layered melt crystallization with seed has been applied. The SLE of p-dioxanone and diethylene glycol were a simple eutectic system and the temperature and PDX concentration at eutectic point were 0.08 and 246 K, respectively. Densities of their binary mixtures were well fitted by the best correlation equation, ${\rho}_l=0.405+1.361x+0.002T-0.004xT$. In the melt crystallization, the growth rate (G) was proportional to the 1.5th power of the subcooling degree. The effective distribution coefficient ($K_{eff}$) as the degree of impurity removal was observed to increase with increasing the growth rate and initial p-dioxanone concentration. And also, $K_{eff}$ was correlated with Z function using Wintermantel's model such as $K_{eef}=-0.0604+6.392{\times}Z$. Finally, PDX purity through the optimization of this process can be obtained over 99%.

Phase Equilibria of the System Pd-Sb-Te and Its Geological Implications (팔라듐-안티몬-테루르 계(系)의 상평형(相平衡)과 지질학적(地質學的) 의의(意義))

  • Kim, Won-Sa;Chao, George Y.
    • Economic and Environmental Geology
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    • v.26 no.3
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    • pp.327-335
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    • 1993
  • Phase relations in the system Pd-Sb-Te were investigated at $1000^{\circ}$, $800^{\circ}$, and $600^{\circ}C$, using the sealed-capsule technique; the quenched products were studied by reflected light microscopy, X-ray diffraction, and electron microprobe analysis. At $1000^{\circ}C$, the solid phases Pd, $Pd_{20}Sb_7$, $Pd_8Sb_3$, $Pd_{31}Sb_{12}$, and $Pd_5Sb_2$ are stable with a liquid phase that occupies most of the isothermal diagram. Additional solid phases at $800^{\circ}C$ are $Pd_5Sb_3$, PdSb, $Pd_8Te_3$, $Pd_7Te_3$, and a continuous $Pd_{20}Te_7-Pd_{20}Sb_7$ solid solution becomes stable. At $600^{\circ}$, $PdSb_2$, $Pd_{17}Te_4$, $Pd_9Te_4$, PdTe, $PdTe_2$, $Sb_2Te_3$, and Sb and continuous PdSb-PdTe and $PdTe-PdTe_2$ solid solutions are stable. All the solid phases exhibit solid solution, mainly by substitution between Sb and Te to an extent that varies with temperature of formation. The maximum substitution (at.%) of Te for Sb in the Pd-Sb phases is: 44.3 in $Pd_8Sb_3$, 52.0 in $Pd_{31}Sb_{12}$, 46.2 in $Pd_5Sb_2$ at $800^{\circ}C$; 15.3 in $Pd_5Sb_3$, 68.3 in $PdSb_2$ at $600^{\circ}C$. The maximum substitution (at.%) of Sb for Te in the Pd-Te phases is 34.5 in $Pd_5Sb_3$ at $800^{\circ}C$, and 41.6 in $Pd_7Te_3$, 5.2 in $Pd_{17}T_4$, 12.4 in $Pd_9Te_4$, and 19.1 in $PdTe_2$ at $600^{\circ}C$. Physical properties and X-ray data of the synthetic $Pd_9Te_4$, PdTe, $PdTe_2$, $Pd_8Sb_3$, PdSb, and $Sb_2Te_3$ correspond very well with those of telluropalladinite, kotulskite, merenskyite, mertieite II, sudburyite, and tellurantimony, respectively. Because X-ray powder diffraction data consistently reveal a 310 peak ($2.035{\AA}$), the $PdSb_2$ phase is most probably of cubic structure with space group $P2_13$. The X-ray powder pattern of a phase with PdSbTe composition, synthesized at $600^{\circ}C$, compares well with that of testibipalladite. Therefore, testibiopalladite may be a member of the $PdSb_2-Pd(Sb_{0.32}Te_{0.68})$ solid solution series which is cubic and $P2_13$ in symmetry. Thus the ideal fonnula for testibiopalladite, presently PdSbTe, must be revised to PdTe(Sb, Te). Borovskite($pd_3SbTe_4$) has not been found in the synthetic system in the temperature range $1000^{\circ}-600^{\circ}C$.

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