• Bulletin of the Korean Chemical Society
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• v.21 no.9
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• pp.882-890
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• 2000

Ab initio calculations are carried out on protonation equilibria of 5-memberedheteroaromatic aldehydes (5MHAs;heteroatom Y = NH, O, PH,and S and substituentZ = NH2, OCH3, SCH3, CH3, H, Cl, CHO, CN,NO2) at the $MP2}6-31G*$ level. Naturalbond orbital (NBO) analyses show that the optimal localized natural Lewis structures of the protonated aldehydes,(P), are ortho (C3) protonated (for Y = O, PH and S) and N-pro-tonated (for Y = NH) forms in contrast to the standard structural Lewis formula for aldehydes, (R). The delo-calizability of ${\pilone}-pairon$ the heteroatom $(n{\pi}(Y))$ is in the order Y = NH > O > S > PH. The transmission efficiency of (Z) substituent effects to the carbonyl moiety run parallel to the delocalizability of $n{\pi}(Y)$ for R,but is dominantly influenced by the cationic charge on $C{\alpha}(C{\alpha}+)$ for P, which is in the reverse order of thede-localizability of $n{\pi}(Y).$ The Hammett ${\rho}values$ for variation of Z in the protonation are determined by the dif-ference in the transmission efficiencies between Pand R stateat simple interpretation of their magnitude is not warranted. However,the magnitude of the gas-phase ${\rho}z+$ values decreases as the level ofcomputation is raised from RHF/3-21G* to RHF/6-31G* and to $MP2}6-31G*$ but increases again at the MP4SDQ/6-31G* level. Further decrease occurs when solvent effect (water) is accounted for by the SCRF method. Comparison of the SCRF ${\rho}z+values$ with those determined in the aqueous acid solution for Y = S and CHCH shows inadequacy of accounting for the solvent effects on the ${\rho}values$ by a continuum model. It is noteworthy that semiempirical calculations, especially theAM1 method, give even lower magnitude of the gas-phase ${\rho}values.

• Clean Technology
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• v.12 no.3
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• pp.128-137
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• 2006

The volume change of an ionic liquid and the phase separation behavior of room temperature ionic liquid(RTIL)/organic compound mixture in supercritical carbon dioxide were measured in a high pressure view cell. 1-Butyl-3-methylimidazolium hexafluorophosphate ([bmim][$PF_6$]) and 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][$BF_4$]) was used as ionic liquid(IL). and methanol and dimethyl carbonate were used as organic compound. For a fixed amount of [bmim][$PF_6$] the lower critical endpoint (LCEP) pressure, where the liquid phase is split, decreased as increasing the amount of organic compound. The LCEP pressure became higher as the water content of ionic liquid was higher. However, for water contents above a certain value, no LCEP was formed. LCEP appeared 1.0 MPa higher for a mixture with [bmim][$BF_4$] than with [bmim][$PF_6$]. There was almost no difference in the K-point pressures for different types of ionic liquid and for different amounts of organic liquid. When the concentration of ionic liquid([bmim][$PF_6$]) (IL/(IL+MeOH)) in the initial liquid mixture was larger than 5.9 mol% at the LCEP of the mixture, the volume of $L_1$ because larger than the volume of $L_2$. When it was smaller, however, the volume became smaller, too. The volume change of ionic liquid in the presence of carbon dioxide decreased as increasing the temperature, while it increased as increasing the pressure. For temperatures between 313.15 to 343.15K at 300 bar, it was about 123~125 % of the original volume.

• Applied Chemistry for Engineering
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• v.5 no.4
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• pp.573-579
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• 1994

1-O-oleoyl glycerol, 2-O-oleoyl myo-inositol and methyl 2-O-oleoyl-${\alpha}$-D-glucopyranoside were used as surfactants in this study. The solution properties and solubilization process of those nonionic surfactants were examined by the phase equilibria. As a result of this study, we have found that phase behavior of two component systems of surfactants/$H_2O$/cyclohexane depends on temperature respectively. The three phase regions of three component systems appeared in the temperature range of $27^{\circ}C{\sim}32^{\circ}C$, $36^{\circ}C{\sim}45^{\circ}C$ and $38^{\circ}C{\sim}52^{\circ}C$ and solubilization of water and oil was high in those three phase ranged As the temperature was varied in the two component systems, liquid crystals of hexagonal were observed to in the case of 1-O-oleoyl glycerol, and liquid crystal of lamella types were observed in the case of 2-O-oleoyl myo-inositol and methyl 2-O-oleoyl-${\alpha}$-D-glucopyranoside.

• Economic and Environmental Geology
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• v.16 no.1
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• pp.1-10
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• 1983

The Yeonhwa (I, II) and Keodo mines, neighboring in the middle part of the Taebaegsan mineral belt, contain three distinct classes of skarn deposits: the zinc-lead skarn at Yeonhwa (I, II), the iron skarn at Keodo south (Jangsan orebodies), and the copper skarn at Keodo north (78 orebodies). The present study characterizes the three classes of skarn deposits mainly in terms of skarn/ore associations examined from chemical compositional point of view, and applies existing quantitative phase diagrams to some pertinent mineral assemblages in these mines. At Yeonhwa I the Wolam I orebody shows a vertical variation in skarn minerals ranging from clinopyroxene/garnet zone on the lower levels through clinopyroxene (without garnet) zone on the intermediate levels, and finally to rhodochrosite veins on the upper levels and surface. Ore minerals, sphalerite and galena, associate most closely with the intermediate clinopyroxene zone. At Keodo, the Jangsan iron skarn hosted in quartz monzodiolite as a typical endoskarn, shows a skarn zoning, from center of orebody to outer side, magnetite zone, magnetite/garnet zone, garnet clinopyroxene zone, and clinopyroxene/epidote/plagioclase zone. The 78 copper skarn in the Hwajeol limestone indicates a zoning, from quartz porphyry side toward limestone side, orthoclase/epidote zone, epidote/clinopyroxene zone, and clinopyroxene/garnet zone; chalcopyrite and other copper sulfides tend to be in clinopyroxene/garnet zone. Mioroprobe analyses of clinopyroxenes and garnets from the various skarn zones mentioned above revealed that the Yeonhwa zinc/lead skarns are characterized by johansenitic clinopyroxene (Hd 25-78, Jo 15-23) and manganoan andraditic garnet (Ad 13-97, Sp 1-24), whereas the Jangsan iron skarn at Keodo by Mn-poor diopsidic clinopyroxene (Di 78-93, Jo 0.2-1.0) and Mn-poor grossularitic grandite (Gr 65-77, Sp 0.5-1.0). The 78 copper skarn at Keodo is characterized by Mn-poor diopsidic-salite (Di 66-91, Jo 0.2-1.1) and Mn-poor andraditic grandite(Ad 40-74, Sp 0.5-1.1). The compositional charateristics of iron, copper, and zinc-lead skarns in the Yeonhwa-Keodo mines are in good correlations with those of the foreign counterparts. Compiling a $T-XCO_2$ phase diagram for the Jangsan endoskarns, a potential upper limit of temperature of the main stage of skarn formation is estimated to be about $530^{\circ}C$, and a lower limit to be $400^{\circ}C$ or below assuming $XCO_2=0.05$ at P total=1kb. Applying a published log $fS_2$-log $fo_2$ diagram to the Keodo 78 and Yeonhwa exoskarns, it is revealed that copper sulfides and zinc-lead sulfides do not co-exist stably below log $fS_2=-4$ and log $fO_2=-23$ at $T=400^{\circ}C$ and ${\times}CO=1$ atm.

• 한국신재생에너지학회:학술대회논문집
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• 2008.10a
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• pp.213-215
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• 2008

최근 지구온난화가 국제적인 이슈화되면서 온실가스의 효과적인 처리에 많은 관심이 집중되고 있다. 냉매로 주로 사용되는 HFC-134a와 절연제로 주로 사용되고 있는 $SF_6$는 각각 이산화탄소의 11,700배와 23,900배의 지구온난화지수를 가지는 온실가스이다. 본 연구에서는 이 두 물질의 효과적인 분리/회수를 위하여 가스 하이드레이트 형성을 이용한 방법을 제안하였다. 하이드레이트 형성법을 이용 할 경우 공정이 단순하고 저압에서 분리가 가능하므로 타 분리공정과의 경쟁이 가능할 것으로 예상된다. 본 실험은 275-290 K의 온도범위와 3 - 30 bar의 압력범위에서 질소 + HFC-134a (20, 40, 60, 80%)와 질소 + $SF_6$ (10, 30, 50, 70%)의 혼합기체를 사용하여 각 조성에 따른 하이드레이트(H)-물($L_W$)-기상 (V)의 3상 평형점을 측정하였다. HFC-134a 또는 $SF_6$의 조성이 낮은 혼합기체의 3상 평형점은 순수 질소의 3상 평형점에 비하여 주어진 온도에서 평형압력이 현저히 낮은 것을 볼 수 있었으며 HFC-134a 또는 $SF_6$의 조성이 증가할 수록 순수한 HFC-134a 또는 $SF_6$의 3상 평형점에 근접하는 것을 볼 수 있었다. 특히 $SF_6$는 다른 기체와 달리 하이드레이트의 생성/해리에 긴 시간이 필요하다는 것을 알 수 있었다. 본 실험에서 얻어진 결과는 하이드레이트를 이용한 HFC-134a와 $SF_6$ 분리 공정의 중요한 기초 자료가 되며 다른 혼합 기체의 분리 공정에도 응용될 수 있을 것이다.

• Clean Technology
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• v.11 no.4
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• pp.165-170
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• 2005

The aim of this study is to provide vapor-liquid equilibrium (VLE) information for the study of process which directly synthesize dimethyl carbonate (DMC) from $CO_2$. For this study we collected some necessary VLE systems data of Methanol-Water, Methanol-DMC, $CO_2$-DMC, $CO_2$-Methanol, $CO_2$-Methanol, and performed VLE calculation with Peng-Robinson equation of state, Wong-Sandler mixing rules that widely used in chemical industry. These calculation results relatively agreed with VLE data well. Optimized Parameters of EoS given through this calculation will be used as some valuable information for fundamental study, process development and process optimization of DMC direct synthesis.

• 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.

• Resources Recycling
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• v.17 no.3
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• pp.29-34
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• 2008

Solvent extraction behaviors of iron(III) from chloride solution at high ionic strength condition between Alamine336 and TBP were compared by using MaCabe-Thiele diagram. Extraction isotherms of iron by the two extractants were obtained by calculating the equilibrium concentrations of iron in both phases from the initial extraction conditions. In calculating the equilibrium concentration of iron, chemical equilibria in the aqueous phase and mass balance together with the solvent extraction reaction were considered. MaCabe-Thiele diagram of iron by 1M Alamine336 indicated that two extraction stages could lead to complete extraction of 0.5M iron from 3M HCl solution at an A/O ratio of 6/5. The extraction power of 1M Alamine336 was found to be the same as 2-3M TBP. MaCabe-Thiele diagram together with the physical properties of the two extractants indicated that Alamine336 is superior to TBP in extracting ferric iron from chloride solution.

• Journal of the Korean Society of Mineral and Energy Resources Engineers
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• v.55 no.6
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• pp.670-687
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• 2018

This paper reviews the structures, physical and chemical properties, origins and global distribution, amount of energy resources, production technologies, and environmental impacts of gas hydrates to understand the gas hydrates as future energy sources. Hydrate structures should be studied to clarify the fundamentals of natural gas hydrates, hydrate distributions, and amount of energy sources in hydrates. Phase equilibria, dissociation enthalpy, thermal conductivity, specific heat, thermal diffusivity, and fluid permeability of gas hydrate systems are important parameters for the the efficient recovery of natural gas from hydrate reservoirs. Depressurization, thermal stimulation, inhibitor injection, and chemical exchange methods can be considered as future technologies to recover the energy sources from natural gas hydrates, but so far depressurization is the only method to have been applied in test productions of both onshore and offshore hydrates. Finally, we discuss the hypotheses of environmental impacts of gas hydrates and their contribution to global warming due to hydrate dissociation.

• Korean Chemical Engineering Research
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• v.55 no.5
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• pp.660-667
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• 2017

Equilibrium data of the mixture is essential in the design and operation of separation equipment such as distillation or extraction in chemical processes. These equilibrium data can be obtained through experiments or by calculations using the known binary parameters and the thermodynamic models. Generally, to obtain these parameters, phase equilibrium experimental data such as gas-liquid and liquid-liquid are used. In this study, the excess enthalpy of the mixture was measured using the flow type microcalorimeter which is a simpler method than phase equilibria experiments, and the parameters of various theories were obtained by using this data. In order to investigate the relationship between carbon chain length, enthalpy and binary parameters in the alkane system, excess enthalpies for the n-hexane + alkane (n-pentane, n-heptane, n-octane and n-dodecane) were measured at 298.15 K and the banary interaction parameters of Wilson, NRTL, and UNIQUAC were obtained from the experimental data. In addition, we wanted to obtain basic information on the interaction and association phenomena of the system including electrolyte applicable to various fields by using the excess enthalpy experimental data and the existing theory. First, we investigated the excess enthalpy for the NaOH / Water / Ethanol system as a basic experiment and examined the applicability using the electrolyte-NRTL (eNRTL) theory.