• Journal of the Korean Chemical Society
• /
• v.30 no.6
• /
• pp.526-531
• /
• 1986

The stability constants of 1,15-diaza-3,4:12,13-dibenzo-5,8,11-trioxacycloheptadecane (NenOdien H$_4$, L) with transition metal ions such as $Co^{2+},\;Ni^{2+},\;Cu^{2+},\;and\;Zn^{2+}$ have been determined by potentiometry in 95% methanol solution at 25$^{\circ}$C. The complex formation of the NenOdien $_4$ with the transition metal ions depends on the basicity of the donor atoms. The order of complex stability was Co(II) < Ni(II) < Cu(II) > Zn(II). The geometries of the complexes in solid state were discussed by visible-near infrared and infrared spectrophotometry, elemental analysis and electro-conductivity. The results suggest that the geometries of the solid complexes are octahedral for $[CoL_2(OH_2)Cl]Cl{\cdot}2H_2O$, $[NiL_2(OH_2)Cl]Cl{\cdot}2H_2O$, and $[ZnLCl_2]{\cdot}\frac{1}{2}H_2O$ and square pyramidal for [CuLCl]Cl, respectively.

• Journal of the Korean Chemical Society
• /
• v.17 no.6
• /
• pp.434-438
• /
• 1973

Distribution coefficients (C) of some transition metal ions such as Ni(II), Cu(II), Cd(II), Zn(II), and Hg(II) have been determined in methanol-, ethanol-, isopropanol-, acetone-, and dimethylsulfoxide-water mixtures by using Rexyn 101 (Na-form) resin and 0.2 M sodium chloride solution. The log C values of the metallic ions decrease almost straightly with the increase in reciprocal values of the dielectric constants of the mixed solvents. In the solvents having the same dielectric constants, the distribution coefficients of the metallic ions decrease with the increase in the basicity of the aprotic organic molecule and with the decrease in the molecular size of the protic organic molecule. The separation of the metallic ions has been accomplished with the eluting agent suggested by the C values.

• Journal of the Korean Chemical Society
• /
• v.34 no.6
• /
• pp.652-657
• /
• 1990

Primary amines react with 1,6-hexanediol at 180$^{\circ}C$ for 5 h under argon atmosphere in the presence of both $RuCl_3{\cdot}3H_2$O and $PR_3$ to give N-substituted perhydroazepine derivatives in good yields. For aromatic amines such as anilines, $RuCl_3{\cdot}3H_2$O combined with $PPh_3$ showed the highest catalytic activity. On the other hand, in the reaction of aliphatic amines, $RuCl_3{\cdot}3H_2$O combined with $PBu_3$ showed the highest catalytic activity. These differences may be attributed to the difference in the basicity of these amines. Less basic aromatic amines may require less basic phosphines, while more basic aliphatic amines may require more basic phosphines as the ligands.

• Bulletin of the Korean Chemical Society
• /
• v.27 no.12
• /
• pp.2011-2018
• /
• 2006

We have investigated the solvent effects on $\Delta log\;K_s $(the difference of stability constant of binding) and the different free energies of binding of $Nd^{3+}$ and $Eu^{3+}$ ions to 18-crown-6, i.e., the selectivity of $Nd^{3+}$ and $Eu^{3+}$ ions to 18-crown-6 using a Monte Carlo simulation of statistical perturbation theory (SPT) in diverse solvents. The stability constant ($\Delta log\;K_s $) of binding of $Nd^{3+}$ and $Eu^{3+}$ ions to 18-crown-6, in $CH_3OH$ was calculated in this study as -1.06 agrees well with the different experimental results of -0.44~-0.6, respectively. We have reported here the quantitative solvent-polarity relationships (QSPR) studied on the solvent effects the relative free energies of binding of $Nd^{3+}$ and $Eu^{3+}$ ions to 18-crown-6. From the calculated coefficients of QSPR, we have noted that solvent polarity (ET) and Kamlet -Tafts solvatochromic parameters (b ) dominate the differences in relative solvation Gibbs free energies of $Nd^{3+}$ and $Eu^{3+}$ ions but basicity (Bj) dominates the negative values in differences in the stability constant ($\Delta log\;K_s $) as well as the relative free energies of binding of $Nd^{3+}$ and $Eu^{3+}$ ions to 18-crown-6 and acidity (Aj) dominates the positive values in differences in the stability constant ($\Delta log\;K_s $) as well as the relative free energies of binding of $Nd^{3+}$ and $Eu^{3+}$ ions to 18-crown-6.

• Korean Chemical Engineering Research
• /
• v.45 no.6
• /
• pp.627-632
• /
• 2007

A fundamental study on the melt decontamination of metal wastes generated by dismantling the nuclear facility, the melting of metal wastes such as stainless steel and carbon steel have been carried out to investigate the distribution phenomena of the radioisotopes such as $^{60}Co$ and $^{137}Cs$ into the ingot, slag and dust phases by using the various slag types, slag concentration and basicity in an arc furnace. The $^{60}Co$ remained homogeneously in the ingot phase above 90 % and it was barely present in the slag below 10 %. The effect of the slag composition on the distribution for Co-60 was not considerable, but a basic slag former with high fluidity showed effective. $^{137}Cs$ was completely eliminated from the melt of the stainless steel as well as the carbon steel and distributed to the slag and the dust phase.

• Bulletin of the Korean Chemical Society
• /
• v.30 no.1
• /
• pp.214-218
• /
• 2009

Second-order rate constants ($k_N$) have been measured for nucleophilic substitution reactions of S-4-nitrophenyl thiobenzoate with a series of alicyclic secondary amines in $H_2O$ containing 20 mol % DMSO at 25.0 ${\pm}$ 0.1 ${^{\circ}C}$. The Br$\phi$nsted-type plot exhibits a downward curvature, i.e., $\beta_{nuc}$ decreases from 0.94 to 0.34 as the amine basicity increases. The reactions in the aqueous DMSO have also been suggested to proceed through a zwitterionic tetrahedral intermediate (T${\pm}$) with change in the RDS on the basis of the curved Br$\phi$nsted-type plot. The reactions in the aqueous DMSO exhibit larger $k_N$ values than those in the aqueous EtOH. The macroscopic rate constants ($k_N$) for the reactions in the two solvent systems have been dissected into the microscopic rate constants ($k_1\;and\;k_2/k_{-1}$ ratio) to investigate effect of medium on reactivity in the microscopic level. It has been found that the $k_2/k_{-1}$ ratios are similar for the reactions in the two solvent systems, while $k_1$ values are larger for the reactions in 20 mol % DMSO than for those in 44 wt % EtOH, indicating that the larger $k_1$ is mainly responsible for the larger $k_N$. It has been suggested that the transition state is more stabilized in 20 mol % DMSO through mutual polarizability interaction than in 44 wt % EtOH through H-bonding interaction.

• Bulletin of the Korean Chemical Society
• /
• v.34 no.8
• /
• pp.2251-2255
• /
• 2013

Second-order rate constants ($k_{HOO^-}$) for the nucleophilic substitution reactions of Y-substituted-phenyl diphenylphosphinates (4a-4i) with $HOO^-$ in $H_2O$ have been measured spectrophotometrically. The ${\alpha}$-nucleophile $HOO^-$ is 10-70 times more reactive than the reference nucleophile $OH^-$ although the former is ca. $4pK_a$ units less basic than the latter, indicating the ${\alpha}$-effect is operative. The Bronsted-type plot for the reactions of 4a-4i with $HOO^-$ is linear with ${\beta}_{lg}=-0.51$, a typical ${\beta}_{lg}$ value for reactions which were reported to proceed through a concerted mechanism. The Yukawa-Tsuno plot is also linear with ${\rho}=1.40$ and r = 0.47, indicating that a negative charge develops partially on the O atom of the leaving group, which can be delocalized to the substituent Y through resonance interactions. Thus, the reactions have been proposed to proceed through a concerted mechanism. The magnitude of the ${\alpha}$-effect (i.e., the $k_{HOO^-}/k_{HO^-}$ ratio) decreases linearly as the leaving-group basicity increases. It has been concluded that solvation effect is not solely responsible for the ${\alpha}$-effect found in this study but the transition-state stabilization through an intramolecular H-bonding interaction is also responsible for the ${\alpha}$-effect.

• Journal of the Korean GEO-environmental Society
• /
• v.11 no.11
• /
• pp.47-54
• /
• 2010

Nowadays, geosynthetics for reinforcement and protection are widely applied to the waste landfill site. Current research indicates the potential for progressive failure in geosynthetic-soil system depends on the interface shear strength governed by several intrinsic factors such as moisture, normal stress, chemical, etc. In particular, the effect of the acidity and basicity from the leachate is intensively reviewed to assess the chemical reaction mechanism of interface shear strength under the cyclic loading condition. New multi-purpose interface apparatus(M-PIA) has been manufactured and the cyclic direct shear tests using submerged geosynthetics and soils under the different chemical conditions have been performed, consequently, the thickness of interface and shear stress degradation are verified. The basic schematic of the Disturbed State Concept(DSC) is employed to estimate the shear stress degradation in the interface, then, normalized disturbed function is obtained and analyzed to describe the shear stress degradation of geosynthetic-soil interface with chemical influence factors under dynamic condition.

• Resources Recycling
• /
• v.5 no.1
• /
• pp.3-8
• /
• 1996

CZS(2Ca0 , SiO\ulcorner) phase of cement clinkcr was obtaincd by melting mixcd four indnstrial wasles of limestone sludge, waste Foundry sand, coal lly ash fiorn power plants and chernicas glasses. The effect ot mixing ratio of four rvastc mater~als ou the composnlg phascs in melled slag was investigated. Thc mixed wastes were meltcd to slag by heat under a constant basicity at 1370C. The shg consisted of p -CIS and C,AS(2CaO - A I P , . SiO,). The ratio of two phases was varied with mixing ~atioo f the waste materials. In order Lo increasc the amount ot j -C2S phase, the coal fly ash content should be reduced, while amount of the chemical glass be increased. The coal fly ash contcnt was the most imporlant factor in controlling phases of thc melted-slag.

• Applied Chemistry for Engineering
• /
• v.23 no.6
• /
• pp.604-607
• /
• 2012

Solid base catalysts for biodiesel production were synthesized by impregnating basic metal species on two support materials with large specific surface area : zeolite and pyrolysis char. KL zeolite and Undaria pinnatifida char were impregnated with KOH aqueous solution and calcium nitrate solution, respectively, to enhance the basic strength. The catalysts synthesized were characterized using Hammett indicators and $CO_2$-TPD analysis. Biodiesel was produced using soybean oil and methanol over the catalysts synthesized. The content of fatty acid methyl esters was measured to evaluate the catalytic activity. Generally, the catalytic activity increased with increasing quantity of basic metal impregnated but impregnation of excessive amount of metal could cause reduction in the activity.