• 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.

• International Area Studies Review
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• v.14 no.2
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• pp.61-78
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• 2010

The paper is basically attempted to reveal a possibility of monetary unification and setting an anchor currency in North East Asian economies such as South Korea, China, and Japan. The Cobb-Douglas utility function is tentatively built by a Walrasian economic framework. Korean Won(KRW) is represented for a numeraire in a structural model, and the estimation of a parameter is performed by 2SLS and GARCH-M models. Empirical evidence is found that not only monetary unification itself in this regime seems not to be practicable, but also setting an anchor currency by Chinese Yuan(CNY) or Japanese Yen(JPY) is also inappropriated due to the fact that the estimated parameter is not converged to a unity. Walrasian equilibria are enhanced by the convergence to a unity in the model. It also has to be mentioned that a number of necessary and sufficient conditions should be fulfilled prior to discuss a monetary unification in North East Asian economies. Instead, Asia currency unit(ACU) is more feasible in reality.

• International Area Studies Review
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• v.15 no.1
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• pp.571-583
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• 2011

We use the properties of competitive location equilibrium to study the relationship between the demand for education and the choice of primary residential location. Consumers can work and live in a comparatively high wage place where there are few education opportunities, or live in a place where education is available and commute to work. If education and employment are each location-specific, there are pooling equilibria in which consumers locate according to their preference for education. In general, the stronger the taste for education, the greater the attraction of living close to the education site and the lower the demand for other goods, including housing. Exploring the effects of the model parameters on the spatial distribution of consumers, we find that a higher frequency of trips taken to the education site, a shorter distance between the work place and the education site, or a greater out-of-pocket education cost each leads to a wider range of consumer types selecting to reside at the education location. We also find that a higher wage lowers the range of consumers who select to live near the education site.

• Analytical Science and Technology
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• v.7 no.2
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• pp.213-224
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• 1994

Several isotopomers of cyclooctanone were prepared by selective deuterium substitution. Intrinsic isotope effects on $^{13}C$ NMR chemical shifts of these isotopomers were investigated systematically at low temperature. These istope effects were discussed in relation to the preferred boat-chair conformation of cyclooctanone. Deuterium isotope effects on NMR chemical shifts have been known for a long time. Especially in a conformationally mobile molecule, isotope perturbation could affect NMR signals through a combination of isotope effects on equilibria and intrinsic effects. The distinction between intrinsic and nonintrinsic effects is quite difficult at ambient temperature due to involvement of both equilibrium and intrinsic isotope effects. However if equilibria between possible conformers of cyclooctanone are slowed down enough on the NMR time scale by lowering temperature, it should be possible to measure intrinsic isotope shifts from the separated signals at low temperature. $^{13}C$ NMR has been successfully utilized in the study on molecular conformation in solution when one deals with stable conformers or molecules were rapid interconversion occurs at ambient temperature. The study of dynamic processes in general requires analysis of spectra at several temperature. Anet et al. did $^1H$ NMR study of cyclooctanone at low temperature to freeze out a stable conformation, but were not able initially to deduce which conformation was stable because of the complexity of alkyl region in the $^1H$ NMR spectrum. They also reported the $^1H$ and $^{13}C$ NMR spectra of the $C_9-C_{16}$ cycloalkanones with changing temperature from $-80^{\circ}C$ to $-170^{\circ}C$, but they did not report a variable temperature $^{13}C$ NMR study of cyclooctanone. For the analysis of the intrinsic isotope effect with relation to cylooctanone conformation, $^{13}C$ NMR spectra are obtained in the present work at low temperatures (up to $-150^{\circ}C$) in order to find the chemical shifts at the temperature at which the dynamic process can be "frozen-out" on the NMR time scale and cyclooctanone can be observed as a stable conformation. Both the ring inversion and pseudorotational processes must be "frozen-out" in order to see separate resonances for all eight carbons in cyclooctanone. In contrast to $^1H$ spectra, slowing down just the ring inversion process has no apparent effects on the $^{13}C$ spectra because exchange of environments within the pairs of methylene carbons can still occur by the pseudorotational process. Several isotopomers of cyclooctanone were prepared by selective deuterium substitution (fig. 1) : complete deuterium labeling at C-2 and C-8 positions gave cyclooctanone-2, 2, 8, $8-D_4$ : complete labeling at C-2 and C-7 positions afforded the 2, 2, 7, $7-D_4$ isotopomer : di-deuteration at C-3 gave the 3, $3-D_2$ isotopomer : mono-deuteration provided cyclooctanone-2-D, 4-D and 5-D isotopomers : and partial deuteration on the C-2 and C-8 position, with a chiral and difunctional case catalyst, gave the trans-2, $8-D_2$ isotopomer. These isotopomer were investigated systematically in relation with cyclooctanone conformation and intrinsic isotope effects on $^{13}C$ NMR chemical shifts at low temperature. The determination of the intrinsic effects could help in the analysis of the more complex effects at higher temperature. For quantitative analysis of intrinsic isotope effects, the $^{13}C$ NMR spectrum has been obtained for a mixture of the labeled and unlabeled compounds because the signal separations are very small.

• Journal of Korean Society of Environmental Engineers
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• v.30 no.7
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• pp.712-720
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• 2008

Sediment and interstitial water samples from ten lagoons in the Northeastern coastal part of South Korea were analyzed to obtain the concentrations of metals and inorganic ligand. These data, coupled with pH and ionic strength, were used to compute the aqueous speciation of the metals in the interstitial water using the MINTEQA2 equilibrium program. The K and Na were almost entirely present as the free aqua ions, but Co, Cd, Ni, Pb and Zn were existed as various metal-ligand complexes. Metals such as Al, As, and Cr formed 3$\sim$4 metal-ligand complexes. In the interstitial water with high chloride concentrations, almost all of the metals were dominated by free aqua ions. Metals of Cd, Co, Ni, Pb and Zn were bound as chloride-metal complexes of the type M$^{x+}$ + xCl$^-$, and Fe, Mn and Mg were dominated by sulfate equilibria(M$^{2+}$ + SO$_4{^{2-}}$). Hg(II) was speciated as HgCl$_2$(aq), HgCl$_3{^-}$ and HgCl$_4{^-}$. However, in the interstitial water with low chloride concentrations, Hg(II) and Cd(II) were existed as chloride-metal complexes, metals of Cu, Mg, Mn, Ni, Pb and Zn were dominated by sulfate equilibria, and the speciation of Fe(II) was bound as Fe(OH)$_2{^+}$, Fe(OH)$_3$(aq). However, Al, As and Cr were dominated by hydroxy-metal and oxide-metal species in nearly all of the lagoons.

• 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.

• Analytical Science and Technology
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• v.8 no.3
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• pp.321-334
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• 1995

Basic studies for the effective extraction of ammonium pyrrolidine dithiocarbamate(APDC) complexes of Co(II), Ni(II) and Cu(II) into a solvent have been performed. The maximum distribution ratio was appeared (log D=1.3543) at pH 2.0 and the partition coefficient was 2.489 in the extraction of $4{\times}10^{-5}M$ APDC itself into chloroform. From the UV/visible spectra of metal-chelates in aqueous and organic solutions, the pH to form stable 1:2 metal-ligand complexes were Co(II):5.0, Ni(II):8.0 and Cu(II):8.0, respectively and only 1 minute was enough to be partitioned into the chloroform. Besides, the partition and extraction equilibria of the complexes were investigated by back-extracting $10.0{\mu}g/ml$ metal-chelates from the solvent into an aqueous solution beacuse of their slight solubilities in the aqueous solution. The distribution coefficients and extractabilities were as follows : at pH 6.5~8.5 of the aqueous solution, log D=2.834 : E(%)=99.9% for $Co(PDC)_2$, at pH 11, log D=5.699 E%=100 for $Ni( PDC)_2$, and at pH 6.0, log D=2.025 : E(%)=99.1% for $Cu(PDC)_2$. And the extraction and formation constants were log $K_{ex}=9.671$ : log ${\beta}_2=6.938$ for $Co(PDC)_2$, log $K_{ex}=9.646$ : log ${\beta}_2=7.071$ for $Ni( PDC)_2$, and log $K_{ex}=9.074$ : log ${\beta}_2=7.049$ for $Cu(PDC)_2$, respectively. From these results, an optimum extraction procedure can be constructed for the separative concentration of trace metallic ions, and the quantitative determination of them in advanced materials and environmental samples will be expected without any influence of sample matrixes.

• Journal of the Korean Chemical Society
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• v.38 no.12
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• pp.898-907
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• 1994

The solvent extraction of an inorganic trace mercury in sea water samples was studied using zinc diethyldithiocabamate $Zn(DDC)_2$ as chelating agent. The $Zn(DDC)_2$ which maintained the stability of DDC- in the acidic aqueous solution in the course of extraction was synthesized from NaDDC and $ZnSO_4$ in this laboratory. The trace of mercury(Ⅱ) was extracted at pH 3.0 from 100 ml of sea water into 10ml of chloroform containing 0.05 M $Zn(DDC)_2$ by shaking for 5 minutes. And from the organic phase, the $Hg(DDC)_2$ was back-extracted into 10ml of 1 to 1 mixed acid of each 3% (v/v) nitric acid and hydrochloric acid by shaking for 25 minutes. The mercury back-extracted was determined by a cold vapor atomic absorption spectrophotometry. The trace mercury(Ⅱ) was so successfully extracted that this procedure could be applied to its determination in the sea water. That is, the recoveries of mercury in two kinds of samples into which as given amount of Hg(Ⅱ) was spiked were 90.0% and 93.3%, respectively.

• 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.

• Economic and Environmental Geology
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• v.45 no.1
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• pp.1-8
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• 2012

Copper-zinc-bearing skarns of the Kasihan area developed at limestone layers in the sedimentary facies of the Late Oligocene Arjosari Formation. The skarns consist mainly of fine-grained, massive clinopyroxene-garnet, garnet, garnet-epidote, and epidote skarns. Most copper and zinc(-lead) ore mineralization occur in the clinopyroxene-garnet and garnetepidote skarn, respectively. Clinopyroxene occurs as a continuous solid solution of diopside and hedenbergite (from nearly pure diopside up to ${\approx}34$ mole percent hedenbergite), with a maximum 28.2 mole percent johannsenite component. The early and late pyroxenes of Kasihan skarns are diopsidic and salitic, respectively. They fall in the fields typical Cu- and Zn-dominated skarns, respectively. Garnet displays a relatively wide range of solid solution between grossular and andradite with up to ${\approx}2.0$ weight percent MnO. Garnet in early pyroxene-garnet skarn ranges from 49.1 to 91.5 mole percent grossular (mainly ${\geq}78$ mole % grossular). Garnets in late garnet and garnet-epidote skarns range from 2.8 to 91.4 mole percent grossular (mainly ${\geq}70$ mole % for garnet skarn). Epidote compositions indicate solid solutions of clinozoisite and pistacite varying from 65.8 to 76.2 mole percent clinozoisite. Phase equilibria indicate that skarn evolution was the result of interaction of water-rich fluids ($X_{CO_2}{\leq}0.1$) with original lithologies at ${\approx}0.5$ kb with declining temperature (early clinopyroxene-garnet and garnet skarn, ${\approx}450$ to $370^{\circ}C$; late garnet-epidote and epidote skarn, ${\approx}370$ to $300^{\circ}C$).