• Title/Summary/Keyword: Equilibria

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Adsorption and Desorption Characteristics of Sr, Cs, and Na Ions with Na-A Zeolite Synthesized from Coal Fly Ash in Low-Alkali Condition (석탄 비산재로부터 저알칼리 조건에서 합성된 Na-A 제올라이트의 Sr, Cs 및 Na 이온의 흡탈착 특성)

  • Choi, Jeong-Hak;Lee, Chang-Han
    • Journal of Environmental Science International
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    • v.28 no.6
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    • pp.561-570
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    • 2019
  • A zeolitic material (Z-Y2) was synthesized from Coal Fly Ash (CFA) using a fusion/hydrothermal method under low-alkali condition (NaOH/CFA = 0.6). The adsorption performance of the prepared zeolite was evaluated by monitoring its removal efficiencies for Sr and Cs ions, which are well-known as significant radionuclides in liquid radioactive waste. The XRD (X-ray diffraction) patterns of the synthesized Z-Y2 indicated that a Na-A type zeolite was formed from raw coal fly ash. The SEM (scanning electron microscope) images also showed that a cubic crystal structure of size $1{\sim}3{\mu}m$ was formed on its surface. In the adsorption kinetic analysis, the adsorption of Sr and Cs ions on Z-Y2 fitted the pseudo-second-order kinetic model well, instead of the pseudo-first-order kinetic model. The second-order kinetic rate constant ($k_2$) was determined to be $0.0614g/mmol{\cdot}min$ for Sr and $1.8172g/mmol{\cdot}min$ for Cs. The adsorption equilibria of Sr and Cs ions on Z-Y2 were fitted successfully by Langmuir model. The maximum adsorption capacity ($q_m$) of Sr and Cs was calculated as 1.6846 mmol/g and 1.2055 mmol/g, respectively. The maximum desorption capacity ($q_{dm}$) of the Na ions estimated via the Langmuir desorption model was 2.4196 mmol/g for Sr and 2.1870 mmol/g for Cs. The molar ratio of the desorption/adsorption capacity ($q_{dm}/q_m$) was determined to be 1.44 for Na/Sr and 1.81 for Na/Cs, indicating that the amounts of desorbed Na ions and adsorbed Sr and Cs ions did not yield an equimolar ratio when using Z-Y2.

Overview of Gas Hydrates as a Future Energy Source and Their Physical/Chemical Properties (미래 에너지로서 가스 하이드레이트의 개관 및 물리/화학적 특성)

  • Cha, Minjun;Min, Kyoung-Won
    • 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.

Monetary Unification in North East Asian Economies and Setting an Anchor Currency by CNY and JPY (한중일 3개국의 화폐통합과 기축통화 설정에 관한 연구)

  • Rhee, Hyun-Jae
    • 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.

A Theoretical Analysis on the Demand for Education and Residential Location (교육수요와 거주지선택에 대한 이론적 분석)

  • Kim, Byung-Hyun
    • 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.

INTRINSIC NMR ISOTOPE SHIFTS OF CYCLOOCTANONE AT LOW TEMPERATURE (저온에서의 싸이클로옥타논에 대한 고유동위원소 효과)

  • Jung, Miewon
    • 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.

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Metal Speciation in the Lagoon Sediment Interstitial Water from the Northeast Coast, Korea (동해안 석호 퇴적물의 간극수에 함유된 금속류의 화학종 분포)

  • Kim, Dong-Jin;Kim, Min-Chul;Yoo, Jin-Yull;Kwon, Sang-Yong;Seo, Yong-Chan;Yang, Jae-E.;Oh, Seung-Yoon;Ok, Yong-Sik
    • 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.

Phase Equilibria of Ionic Liquid/Organic Compound/Supercritical CO2 Systems (이온성액체/유기화합물/초임계이산화탄소계의 상평형)

  • Lim, Bang-Hyun;Kim, Jong-Won;Paek, Sang-Min;Son, Bo-Kook;Lee, Yong-Rok;Lee, Chul Soo;Lee, Huen;Ra, Chun-Sup;Shim, Jae-Jin
    • 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.

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Studies on Partition and Extraction Equilibria of Metal-Dithiocarbamate Complexes(II). Metal Complexes of Ammonium Pyrrolidine Dithiocarbamate (Dithiocarbamate 금속착물의 분배 및 추출평형(제2보). Ammonium Pyrrolidine Dithiocarbamate의 금속착물)

  • Lee, Jong-Sun;Choi, Jong-Moon;Choi, Hee-Seon;Kim, Young-Sang
    • 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.

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Studies on Partition and Extraction Equilibria of Metal-Dithiocarbamate Complexes(Ⅰ). Solvent Extraction of Inorganic Trace Mercury(Ⅱ) (Dithiocarbamate 금속착물의 분배 및 추출평형 (제 1 보) 흔적량 무기수은(Ⅱ)의 용매추출)

  • Ho-Seong Choi;Jong-Moon Choi;Hee-Seon Choi;Young-Sang Kim
    • 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.

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Measurement and Calculation of Excess Enthalpies for n-Hexane/Alkane series and NaOH/Water/Ethanol System using Isothermal Microcalorimeter (등온 미세열량계를 이용한 n-Hexane-알칸계 이성분 혼합물 및 NaOH/Water/Ethanol계의 과잉 엔탈피 측정 및 계산)

  • Choi, In Kyu;You, Seong-sik
    • 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.