• The Journal of Engineering Geology
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• v.19 no.2
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• pp.165-175
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• 2009

This study is concerned with creep characteristics of red shale in the Haman Formation by the single stage and multi stage loading tests. Creep constants in the Griggs's experiential equation, ${\epsilon}_t$= a+$b{\cdot}log$ t + $c{\cdot}t$, are determined by regression analysis on the total data obtained. The transition time between the primary and second creep means the time when the differential value of $b{\cdot}log$ t is equal to the differential value of $c{\cdot}t$. The correlation equation between loads (${\sigma}$%) and creep constants is deduced from the three times multi stage loading tests. Also a failure time under each loads is anticipated from creep constants and maximum strain at the failure.

• Nuclear Engineering and Technology
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• v.42 no.5
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• pp.552-561
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• 2010

This study investigates the solubility of neptunium (Np) in the deep natural groundwater of the Korea Atomic Energy Research Institute Underground Research Tunnel (KURT). According to a Pourbaix diagram (pH-$E_h$ diagram) that was calculated using the geochemical modeling program PHREEQC 2.0, the redox potential and the carbonate ion concentration both control the solubility of neptunium. The carbonate effect becomes pronounced when the total carbonate concentration is higher than $1.5\;{\times}\;10^{-2}$ M at $E_h$ = -200 mV and the pH value is 10. Given the assumption that the solubility-limiting stable solid phase is $Np(OH)_4(am)$ under the reducing condition relevant to KURT, the soluble neptunium concentrations were in the range of $1\;{\times}\;10^{-9}$ M to $3\;{\times}\;10^{-9}$ M under natural groundwater conditions. However, the solubility of neptunium, which was calculated with the formation constants of neptunium complexes selected in an OECD-NEA TDB review, strongly deviates from the value measured in natural groundwater. Thus, it is highly recommended that a prediction of neptunium solubility is based on the formation constants of ternary Np(IV) hydroxo-carbonato complexes, even though the presence of those complexes is deficient in terms of the characterization of neptunium species. Based on a comparison of the measurements and calculations of geochemical modeling, the formation constants for the "upper limit" of the Np(IV) hydroxo-carbonato complexes, namely $Np(OH)_y(CO_3)_z^{4-y-2z}$, were appraised as follows: log $K^{\circ}_{122}\;=\;-3.0{\pm}0.5$ for $Np(OH)_2(CO_3)_2^{2-}$, log $K^{\circ}_{131}\;=\;-5.0{\pm}0.5$ for $Np(OH)_3(CO_3)^-$, and log $K^{\circ}_{141}\;=\;-6.0{\pm}0.5$ for $Np(OH)_4(CO_3)^{2-}$.

• Journal of the Korean Chemical Society
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• v.53 no.6
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• pp.693-703
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• 2009

The complex formation of anti-inflamatory drug piroxicam (PX, 4-hydroxy-2-methyl-N-2--pridyl-2H-1,2-benzothiazine-3-carboxadiamide-1,1-dioxide) with transition metal ions Co(II), Ni(II), Cu(II) and Zn(II) in methanol(MeOH)/water binary mixtures were studied by spectrophotometric method at 25$^{\circ}C$, constant pH = 5.0 and I = 0.1 M. The computer program SQUAD was used to extract the desired information from the spectral data. The outputs of the fitting processes were stability constants, standard deviations of the estimated stability constants, concentration distribution diagrams and spectral profiles of all species. The sequence of the stability constants of PX complexes with Co(II), Ni(II), Cu(II) and Zn(II) follow the Cu(II) > Co(II) > Ni(II) ${\approx}$ Zn(II) order. This may be due to different geometry tendencies of these metal ions. The acidity constants of the PX were also determined under above condition from its absorption spectra at different pH values. The computer program DATAN was used for determination of acidity constants of PX. The validity of the obtained acidity constants was checked by a well known computer program SPECFIT/32. The effects of the different parameters like solvent nature, cations characteristics on the stability and acidity constants were thoroughly discussed.

• Journal of the Korean Chemical Society
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• v.31 no.5
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• pp.434-443
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• 1987

The formation constants of the complexes between Ln-EDTA 1 : 1 complex and IMDA have been investigated by a potentiometric titration method at 20.0${\pm}$0.2 degree C and ${\mu}$ = 0.1 (KNO$_3$). Unusually large stability in Ln(EDTA) mixed ligand complexes was found. Trends in the formation constants vs. atomic number of the lanthanide metals were discussed on the basis of coordination number and ionic radius of the metals.

• Journal of the Korean Chemical Society
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• v.32 no.5
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• pp.464-475
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• 1988

The complex formation of p-aminoazobenzene and its derivatives with Fe(III) and Mn(II) has been studied by UV and IR spectroscopy and conductometry. The effects of solvents, donor basicity, and other factors on the formation of these complexes have been examined. The vatio of metal to ligand for the complexes formed is 1 : 1, both in the solid state and in solution. The stability constants of Fe(III)-donor and Mn(II)-donor complexes are in the range of 10$^2$∼10$^4$ and 0.1∼1, respectively. The absorptivities are ~10$^4$ and ∼10$^3$ l/mol${\cdot}$cm respectively. Thermodynamic properties such as ${\Delta}H^{\circ}$, ${\Delta}G^{\circ}$ and ${\Delta}S^{\circ}$ are calculated from their stability constants utilizing Van't Hoff equation.

• Journal of the Korean Applied Science and Technology
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• v.8 no.1
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• pp.59-67
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• 1991

The reactions of semicarbazide hydrochloride with aliphatic and alicyclic ketones were studied kinetically at 15, 25, 35 and 45$^{\circ}C$ in 20% ethanol solution buffered at pH 2.9. The rate of cyclohexanone semicarbazone formation is 5.5 times as fast as that of cyclopentanone semicarbazone, while 3-pentanone semicarbazone is 4.7 times as slow as that of 2-pentanone, The activation energy of cyclohexanone, 2-pentanone, 2 hexanone, cyclopentanone, 4-methyl-2-pentanone and 3-pentanone semicarbazone formation are calculated 5.08, 7.52, 8.79, 9.59, 9.49, 11.59, respectively. It is concluded from the effect of ionic strength that the reaction is affected by not ion but neutral molecules being progressed hydrogen bond between oxygen atom of carbonyl group and hydrogen atom of acid-catalyst and concerted nucleophilic attack of free base on the carbonly compound. Dependence on pH of the rate of 2-pentanone semicarbozone formation is linear relationship below pH 4.60 and above pH 5.60. As a result of studing citric acid catalysis, second order constants increase linearly with citric acid concentration. As the catalyst concentration is varied from 0.025 to 0.10 mol/1 at pH 2.90, the rate constants increase 1.4 times, but slight increase is observed at pH 5.60. Conclusively, the rate-determining step is formation of tetrahedral interemediate below pH 4.65 and dehydration between pH 5.60 and pH 7.11. It is concluded that the formation reaction of cyclohexanone semicarbazone is faster than cyclopentanone semicarbazone due to the steric strain in the process of forming tetrahedral intermediate.

• The Korean Journal of Ceramics
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• v.4 no.2
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• pp.99-102
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• 1998

Cordierite ceramics with low dielectric constants were obtained through sol-gel techniques using as metal alkoxides. The powders for the sintered cordierite ceramics were prepared by hydrolysis of metal alkoxides with ethanol and distilled water. In the hydrolysis, the mole ratio of HCI/TEOS was controlled by changing the amount of HCI as a catalyst. The sol-gel derived powders were dried, pressed, and fired at $1300^{\circ}C$. The dried powders were calcined at $800{\circ}C$ for 3hours to remove residual organics. The fired bodies with different dielectric constants were obtained by using HCI adjusted to various mole ratios of HCI/TEOS in the process. The variation of the amount of HCI catalyst led to a significant influence on dielectric contant, which was attributed to the formation of pores in the sintered body. Especially, the porosity of the sintered body influenced the dielectric constants.

• Journal of the Korean Chemical Society
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• v.32 no.1
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• pp.53-59
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• 1988

Recently, the formation of the complexes between macrocyclic polyethers and alkali metal salts have been determined by several methods. It has been suggested that the specificity of the complexation be due to the nature of the surrounding solvent molecules. The formation constant values ($K_f$) of $K^+$ are shown to be the largest among the other alkali metal cations because the ionic diameter of $K^+$ is approximately the same with the hole size of 18-crown-6. In this study the formation constants of the 1 : 1 complexes of 18-crown-6 with potassium p-substituted phenoxide are calculated by the conductance measurement in organic solvents. As a result, the $K_f$ value series among organic solvents are given in the order of $CH_3$OH > DMF > DMSO. It seems that the donor number of the solvent is a main factor in the formation of the complex between $K^+$ metal ion and 18-crown-6 molecules. At the same time, the formation constants increase with increasing the electron-withdrawing power of substituents because the phenoxide ion is stabilized by the charge dispersion.

• Bulletin of the Korean Chemical Society
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• v.23 no.5
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• pp.688-692
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• 2002

The aminomethylation of phenols with para-substituents by the Mannich reaction has successfully been accomplished to produce the Mannich bases 2-6. The compounds 7-8 have also been synthesized in order to identify the effect of the side arms and t he macrocycle in the complex formation. Protonation constants and stability constants of the double armed diaza-18-crown-6 ethers 2-7 with metal ions have been determined by potentiometric method at 25 $^{\circ}C$ in 95 % methanol solution. Under a basic condition (pH > 8.0), the double-armed crown ethers 2-6 revealed stronger interaction with divalent metal ions than the simple diazacrown ether 1. The stability constants with these metal ions were Co 2+ < Ni2+ < Cu2+ > Zn 2+ in increasing order, which are in accordance with the order of the Williams-Irving series. The stability constants with alkali earth metal ions were Ca 2+ < Sr 2+ < Ba 2+ in increasing order, which may be explained by the concept of size effect. It is noteworthy that the hosts 2-6, which have phenolic side arms and a macrocycle, bind stronger with metal ions than the hosts 1 and 7. On the other hand, the host 8, which has phenolic side arms with a pyperazine ring,provided comparable stability constants to those with the host 3. These facts demonstrate that phenolic side arms play a more important role than the azacrown ether ring in the process of making a complex with metal ions especially in a basic condition. In particular, the log KML values for complexation of divalent metal ions with the hosts 2-6 had the sequence, i.e., 2 (R=OCH3) < 3 (R=CH3) < 4 (R=H) < 5 (R=Cl) < 6 (R=CF3). The stability constants of the hosts 5 and 6 containing an electron-withdrawing group are larger than those of the hosts 2 and 3 containing an electron-donating group. This substituent effect is attributed to the solvent effect in which the aryl oxide with an electron-donating group has a tendency to be tied strongly with protic solvents.

• Bulletin of the Korean Chemical Society
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• v.16 no.11
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• pp.1093-1099
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• 1995

The polycondensations of bis(2-hydroxyethyl) naphthalate were kinetically investigated in the presence of various metallic compounds as catalysts at 295 ℃. The effect of the catalyst nature in the polycondensation has been studied. The order of catalytic activity on the formation of poly(ethylene 2,6-naphthalate) was found to be related to the stability constants which are indicated in an index of the catalytic activity.