• Journal of the Korea Academia-Industrial cooperation Society
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• v.14 no.9
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• pp.4643-4651
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• 2013

In this study, we have surveyed the new technologies in the cryogenic distillation of ITER, equilibrium reactors and helium refrigeration cycle contained in the isotope separation system (ISS). We also have collected thermodynamic and transport properties for $H_2$, HD, $D_2$, HT, DT and $T_2$ components of which properties are not built in a general purpose chemical process simulators such as Aspen Plus and PRO/II with PROVISION. Verification works have been performed to compare between literature data and simulation results. For the simulation of ISS involving six hydrogen isotope components, four distillation columns and two equilibrium reactors are used for the separation of $D_2$ and DT from $T_2$.

• Economic and Environmental Geology
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• v.44 no.3
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• pp.193-201
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• 2011

The Geopung Cu deposit consists of two subparallel quartz veins that till the NE-trending fissures in Triassic Cheongsan granite. The quartz veins occur mainly massive with partially cavity and breccia. They can be followed along strike for about 500 m and varies in thickness from 0.2 to 2.2 m. Based on the mineralogy and paragenesis of veins, mineralization of quartz veins can be divided into hypogene and supergene stages. Hypogene stage is associated with hydrothermal alteration minerals such as sericite, pyrite, quartz, chlorite, clay minerals and sulfides such as pyrite, arsenopyrite, pyrrhotite, marcasite, sphalerite, stannite, chalcopyrite and galena. Supergene stage is composed of geothite. Fluid inclusion data from quartz indicate that homogenization temperatures and salinity of hypogene stage range from 163 to $356^{\circ}C$ and from 0.2 to 7.2 wt.% eq. NaCl, respectively. They suggest that ore forming fluids were progressively cooled and diluted from mixing with meteoric water. Sulfur (${\delta}^{34}S$: 4.3~9.2‰) isotope composition indicates that ore sulfur was derived from mainly magmatic source although there is a partial derivation from the host rocks. The calculated oxygen (${\delta}^{18}O$: 0.9~4.0‰) and hydrogen (${\delta}D$: -86~-69‰) isotope compositions suggest that magmatic and meteoric ore fluids were equally important for the formation of the Geopung Cu deposit and then overlapped to some degree with another type of meteoric water during mineralization.

• Journal of the Korean Chemical Society
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• v.38 no.5
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• pp.391-396
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• 1994

The hydrolysis of $\alpha-benzoxystyrene(1)$ in strong acidic solution has been investigated kinetically. In perchloric acid concentration lower than 5.5 M($H_o$ < -3.0), hydration paramer $\omega$ = + 7.6, and $\Phi$ = + 0.54 were obtained. The solvent isotope effect $k_{H_2O}/K_{D_2O}$ is 0.72. The substituent effect was found to conform to the Hammett $\sigma^+$ constant with $\rho$ = -0.60. On the basis of these results and other evidence, the hydrolysis of the enol ester proceeds by $A_{AL}$2 type mechanism. In concentration greater than 5.5 M($H_o$ > -3.0), isotope effect, $k_{H_2O}/_{D_2O}$ is 3.32, substituent effect, $\rho$ is -1.60 and the rate is linear with the acidity function, $H_o$. Thus, the mechanism changes one involving initial, and rate-determining olefin protonation.

• Bulletin of the Korean Chemical Society
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• v.28 no.6
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• pp.936-940
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• 2007

The aminolyses of diphenyl phosphinic chloride (1) with substituted anilines in acetonitrile at 55.0 oC are investigated kinetically. Large Hammett ρ X (ρnuc = ?4.78) and Bronsted β X (βnuc = 1.69) values suggest extensive bond formation in the transition state. The primary normal kinetic isotope effects (kH/kD = 1.42-1.82) involving deuterated aniline (XC6H4ND2) nucleophiles indicate that hydrogen bonding results in partial deprotonation of the aniline nucleophile in the rate-limiting step. The faster rate of diphenyl phosphinic chloride (1) than diphenyl chlorophosphate (2) is rationalized by the large proportion of a frontside attack in the reaction of 1. These results are consistent with a concerted mechanism involving a partial frontside nucleophilic attack through a hydrogen-bonded, four-center type transition state.

• Journal of the Korean Chemical Society
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• v.47 no.3
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• pp.191-198
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• 2003

The pairwise energy model (PEM) assumes that the cross section for the reaction cross section for the reaction A+BC$\{leftrightarrow}$B+C, where B and C are isotopes of hydrogen, depends on only the pairwise relative energy Es between A and B. Until now, the PEM has been used to interpret theoretically the isotope effect for the reactions such as $O(^3P)+HD,\;Ar^++(H_2,\;D_2,and\;HD)$. In this paper we carry out extensive quasiclassical trajectory calculations for the three possible reactions $Cl+H_2$ and HD and show that the PEM works very well at high energy. In particular we are able to accurately predict the intramolecular isotope effect at high energy for the reaction of Cl+HD using only the cross section data for $Cl+H_2$. To understand that the PEM works so well at high energy, the internal energy distributions for the products are examined. The distributions for three reactions are different at a fixed relative collision energy E but are approximately same at a fixed pairwise energy Es. This suggests that the PEM works very well at high energy. We believe the conclusions reached here will apply to other A+BC systems.

• Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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• 2000.11a
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• pp.87-90
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• 2000

The hydrogeochemical and isotopic studies on deep groundwater in the Munkyeong area, Kyeongbuk province were carried out. $CO_2$-rich groundwater (Ca-HC $O_3$ type) is characterized by low pH (5.8~6.5) and high TDS (up to 2,682 mg/L), while alkali groundwater (Na-HC $O_3$ type) shows a high pH (9.I~10.4) and relatively low TBS (72~116 mg/L). $CO_2$-rich water may have evolved by $CO_2$ added at depth during groundwater circulation. This process leads to the dissolution of surrounding rocks and Ca, Na, Mg, K and HC $O_3$ concentrations are enriched. The low Pc $o_2$ (10$^{-6.4}$atm) of alkali groundwaters seems to result from the dissolution of silicate minerals without a supply of $CO_2$. The $\delta$$^{18}$ O and $\delta$D values and tritium data indicate that two types of deep groundwater were both derived from pre-thermonuclear meteoric water. The carbon Isotope data show that dissolved carbon in the $CO_2$-rich water was possibly derived from deep-seated $CO_2$ gas. The $\delta$$^{18}$ S values of dissolved sulfate show that sulfate reduction occurred at great depths. The application of various chemical geothermometers on $CO_2$-rich groundwater shows that the calculated deep reservoir temperature is about 130~175$^{\circ}C$. Based on the geological setting, water chemistry and environmental isotope data, each of the two types of deep groundwater represent distinct hydrologic and hydrogeochemical evolution at depth and their movement is controlled by the local fracture system.m.

• Journal of Environmental Science International
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• v.17 no.5
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• pp.509-516
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• 2008

New functional surfactant, N,N-dimethyl-N-dodecyl-N-(2-methyl benzimidazoyl) ammonium chloride(DDBAC) having benzimidazole(BI) functional group have been synthesized and the critical micellar concentration of DDBAC measured by surface tentiometry and electric conductivity method was $8.9{\times}10^{-4}M$. Micellar effects in DDBAC functional surfactant solution on the hydrolysis of p-nitrophenylacetate(p-NPA), p-nitro-phenylpropionate(p-NPP) and p-nitrophenylvalerate(p-NPV) were observed with change of various pH (Tris-buffer). The pseudo first rate constants of hydrolysis of p-NPA, p-NPP and p-NPV in optimum concentration of DDBAC solution increase to about 160, 280 and 600 times, respectively, as compared with those of aqueous solution at pH 8.00(Tris-buffer). It is considered that benzimidazole functional moiety accelerates the reaction rates of hydrolysis because they act as nucleophile or general base. In optimum concentration of DDBAC solution, the rate constants of hydrolysis of p-NPP and p-NPV increase to about 1.5 and 3.0 times, respectively, as compared with that of p-NPA. It means that the more the carbon numbers of alkyl group of substrates, the larger the binding constants between DDBAC micelle and substrates are. To know the hydrolysis mechanism of p-NPCE(p-NPA, p-NPP and p-NPV), the deuterium kinetic isotope effects were measured in $D_2O$ solutions. Consequently the pseudo first order rate constant ratios in $H_2O$ and $D_2O$ solution, $k_{H_2O}/k_{D_2O}$, were about $2.8{\sim}3.0$ range. It means that the mechanism of hydrolysis were proceeded by nucleophile and general base attack in approximately same value.

• Bulletin of the Korean Chemical Society
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• v.33 no.3
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• pp.1037-1041
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• 2012

The nucleophilic substitution reactions of (2R,4R,5S)-(+)-2-chloro-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidine 2-sulfide (3) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $5.0^{\circ}C$. The anilinolysis rate of 3 involving a cyclic five-membered ring is considerably fast because of small negative value of the entropy of activation (${\Delta}S^\neq=-2cal\;mol^{-1}\;K^{-1}$) over considerably unfavorable enthalpy of activation (${\Delta}H^\neq=18.0\;kcal\;mol^{-1}$). Great enthalpy and small negative entropy of activation are ascribed to sterically congested transition state (TS) and bulk solvent structure breaking in the TS. A concerted $S_N2$ mechanism with a backside nucleophilic attack is proposed on the basis of the secondary inverse deuterium kinetic isotope effects, $k_H/k_D$ < 1.

• Bulletin of the Korean Chemical Society
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• v.34 no.4
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• pp.1096-1100
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• 2013

The kinetic studies on the reactions of O-methyl (1), O-propyl (3) and O-isopropyl (4) phenyl phosphonochloridothioates with substituted anilines and deuterated anilines have been carried out in acetonitrile at $55.0^{\circ}C$. A concerted $S_N2$ mechanism is proposed for the anilinolyses of 1, 3 and 4. The anilinolysis rates of the phosphonochloridothioates are predominantly dependent upon the steric effects over the inductive effects of the two ligands. The deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are primary normal with 1 and 3, while secondary inverse with 4. Primary normal and secondary inverse DKIEs are rationalized by frontside and backside nucleophilic attack transition state, respectively. The DKIEs of the phosphonochloridothioates do not have any consistent correlations with the two ligands.

• Journal of the Korean Magnetic Resonance Society
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• v.8 no.1
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• pp.55-61
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• 2004

Biosupramolecular systems such as biological membranes usually fluid under physiological conditions$^1$. Therefore, solid-state NMR has been used to investigate biosupramolecular systems. But solid-state NMR spectra contain a large number of overlapping resonances and are rather difficult to analyze. These problem has to be overcome by selective isotope labeling. We constructed a deuterium NMR probe for AM400 NMR spectrometer, which is mainly used for liquid samples. To overcome the fluidity problem, a saddle type coil was designed. The efficiency was systematically investigated for two kinds of coil geometry, solenoid and saddle types. Our results suggest that solenoids are superior to saddle type coils in the sensitivity. However, the letter fits better to fluid samples such as biosupramolecular systems.