• Journal of the Korean Chemical Society
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• v.29 no.5
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• pp.472-477
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• 1985

The rates for the aquation of $cis-[Co(en)(NH_3)_2Cl_2]Cl in acetone-water mixtures have been measured at various pressures and temperatures by the electric conductivity method. The rate constant measured at 25$^{\circ}$C in pure water solvent is 3.47 ${\times}10^{-4}$/sec. Rate constants are increased with increasing temperature, and decreased with increasing pressure and mole fraction of acetone. Activation volumes and other activation parameters are calculated from these rate constants. The activation volumes are all positive and lie in the limited range +2.82~+$8.2cm^3$/mole. The rate constants in aqueous acetone solution are analyzed with the solvent compositions. Plots of log $k_{obs}$ vs. Grunwald-Winstein Y values show that log $k_{obs}$ varies linearly and the gradients are about 0.25. The applications of a free energy cycle relating the process initial state ${\to}$ transition state in water to that in acetone-water mixture show that the changes in solvation of the transition state have a dominant effect on the rate. From these results the aquation of this complex would be discussed in terms of dissociative mechanism ($I_d$).

• Applied Chemistry for Engineering
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• v.10 no.5
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• pp.718-725
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• 1999

In order to investigate the interaction characteristics of poly(dimethylsiloxane) (PDMS) with various solvents such as water, ethanol, and iso-propanol, Inverse Gas Chromatography(IGC) at finite concentration, which is a very fast, accurate, and thus promising technique in thermodynamic study of polymer systems, is employed. By measuring the specific retention volumes of the probes, the interaction parameters are calculated by means of the Flory-Huggins equation. From the results, the interaction parameters of the probes are, as expected due to the hydrophobicity of the polymer, found to be of large positive values (2$2.0{\times}10^{-3}mol/g$. For the linear PDMS, interpretation of the space distribution of molecules is performed by the Kirkwood-Buff-Zimm(KBZ) integrals, which give intuitive information about physical properties. From the KBZ integrals, water does not show the tendency of preferential solvation with the PDMS but formed self-cluster. The larger solvent molecules show a stronger tendency to distribute more randomly in the mixture.

• Journal of the Korean Chemical Society
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• v.23 no.4
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• pp.237-242
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• 1979

The equivalent conductances of sodium, potassium, ammonium, tetramethylammonium, triethylammonium, diethylammonium and ethylammonium iodide, and picrate salts of sodium and potassium in ethylene carbonate have been measured at 40.0 $^{\circ}C. The limiting equivalent conductances of the salts have been computed by Fuoss-Onsager-Skinner equation. The limiting ionic equivalent conductances of $Na^+,\;K^+,\;and\;NH^+$ are in order of $Na^+ which is the reverse order of solvation for the ions in any solution, And the order of limiting ionic equivalent conductances for alkylammonium ions is $(C_2H_5)_4N^+<(C_2H_5)_3NH^+<(CH_3)_4N^+<(C_2H_5)_2NH_2^+<(C_2H_5)NH_3^+$ which coincides with the order of mass transfer. From the dissociation constants of the saltss determinde by Fuoss-Kraus method, it is found that ethyene carbonate is a good ionizing solvent for the salts. In addition, Stokes radii and effective fadii of ions have been calculated by Stokes law and Nightingale method, repectively. From the results, it appears tha alkylammonium ions and picrate ion seem to be not solvated, and tha iodide ion is fairly solvated in ethylene carbonate.

• Journal of the Korean Chemical Society
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• v.32 no.5
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• pp.443-451
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• 1988

New crown ether dye-Ⅰ and dye-Ⅱ having an azo group(-N=N-) were synthesized from monobenzo-15-crown-5 and dibenzo-18-crown-6. These dyes showed ${\lambda}_{max}$ of 377 and 383nm respectively. The complexes of alkali metal ions ($Na^+$, $K^+$, $Cs^+$) with dye ligands showed band shift (390~400nm) and intensity increased. For a given anion, the extraction constants are in the order of $K^+$ < $Cs^+$ < $Na^+$ for dye-Ⅰ and $Cs^+$ < $Na^+$ < $K^+$ for dye-Ⅱ. These results show that the selectivity of crown ethers toward the alkali metal ions is dependant on the charge density of cation and the size of crown ether cavity. For a given cation, the order of the extraction constant is $Cl^-$ < $Br^-$ < $I^-$ < picrate. This order coincides with the degree of anion solvation effect.

• Journal of the Korean Chemical Society
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• v.33 no.6
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• pp.588-595
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• 1989

Log K, ${\Delta}$H and ${\Delta}$S for the complexation of $La^{3+},\;Ce^{3+}$ and $Eu^{3+}$with various multidentate ligand containing crown ether, diaza crown ether and diamine ether have been determined in methanol and acetonitril solutions at $25^{\circ}C$ by solution calorimetric titration method. The greater stability constant of $La^{3+}$-15C5 than those of 18C6 diaza [2.2] in methanol are discussed in terms of the size of metal ion and the ligand cavity and of metal ion solvation. The stabilities of $Ce^{3+}$ and $La^{3+}$ ion complexes with a various multidentate ligand in acetonitril are in the order of (diamine ether)<18C6<15C5$Ce^{3+}$, $La^{3+}$ and $Eu^{3+}$-diaza [2.2] complexes in acetonitril are increased with the following order: $Eu^{3+}$ < $La^{3+}$ < $Ce^{3+}$, that is increasing order of the optimum size and of the charge density of metal ion.

• Analytical Science and Technology
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• v.18 no.3
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• pp.194-200
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• 2005

The N hyperfine coupling constants ($a_N$) of di-t-butyl nitroxide (DTBN) radicals in water-solvent system were measured with EPR spectroscopy. Various kinds of the solvents with different polarity such as acetone, dimethylsulfoxide (DMSO), methanol, ethanol and 1-propanol were applied and studied. Equilibrium constants for the solvation equilibrium and the solvent parameters ($E_T$, molar transition energy) of various water-solvent system were obtained from the experimental results and are presented. The $a_N$ values were plotted as a function of mole fraction of the solvent. In case of water-DMSO, water-ethanol and water-1-propanol system, slight negative deviations from the straight line were observed. In water-acetone system, the absorption wavelength (${\lambda}$) due to ${\eta}{\rightarrow}{\pi}^{\ast}$ transition increased linearly with the increase of mole fraction of acetone. The relationship between $a_N$ of DTBN and ${\lambda}$ due to ${\eta}{\rightarrow}{\pi}^{\ast}$ transition in water-acetone and water-DMSO system was examined. It was found that the electronic structure of the nitroxide radicals is stablized from the fact that the N hyperfine coupling constants of DTBN radicals are greatly unaffected in the environment of water-solvent system.

• Korean Chemical Engineering Research
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• v.50 no.2
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• pp.292-299
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• 2012

We made 8 wt% silica dispersion system with fumed silica and photo curable acrylic monomer by beads mill process. These dispersions could be applied in organic/inorganic hybrid coating systems. These dispersions could be applied in organic/inorganic hybrid coating systems. The 4 species of photo curable acrylic monomer which was presence of hydroxyl group, different solubility parameter, and different molecular size were used in the silica dispersions. Stability of polar solvent, isopropyl alcohol, in silica dispersions was investigated. We investigated the stability of silica dispersions by using steady-state and dynamic rheology. As the monomer has hydroxyl group increased in mono and binary monomer silica dispersions, they showed non flocculated stable sol (loss modulus (G")> storage modulus (G')). When polar solvent IPA was added into slightly flocculated silica dispersions, they changed to non flocculated stable sol.

• Journal of Environmental Science International
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• v.2 no.1
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• pp.61-72
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• 1993

Result of this study indicate that two criteria must be met in order to have effective macrocycle-mediated transport in these emulsionsystem. First, one must effective extraction of the post transition metals, $Cd^{2+}$. $Pb^{2+}$ and $Hg^{2+}$ , into toluene membrane. The effectiveness of this extraction is greatest if log K values for the metal-macrocycle interaction is large. Second, the ratio of the log K values for the metal ion-receiving phase to the metal ion-macrocycle interaction must be large enough to ensure quantitative stripping of the metal ion at the toluene phase interface. Control of the first step can be obtained by appropriate selection of macrocycle donor atom, substituents, and cavity radius. The second step can be controlled by selecting the proper complexing agent for inclusion in the receiving phase. The order of the transport, when using the several $A^-$ species such as $SCN^-$, $1^-$, $Br^-$ and $Cl^-$ is the order of the changing degree of solvation for $A^-$ and the transport of the metals is also affected by the control of concentration for receiving species because of solubility-differences. In this study, we can seperate each single metal ion from the mixture of $Cd^{2+}$, $Pb^{2+}$, and $Hg^{2+}$ ions by using the toluene membranes controlled by optimized conditions. Transport of the single metal is also very good, and alkaline and alkaline earth metals as interferences ions did not affect the seperation of the metals in this macrocycle-liquid membrances but transition metal ions were partially affected as interferences for the post transition metal ions.

• Journal of the Korean Chemical Society
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• v.38 no.10
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• pp.753-762
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• 1994

Dephosphorylation of diphenyl- or isopropylphenyl-4-nitrophenylphosphinate (DPNPIN or IPNPIN) mediated by $OH^-$ or o-iodosobenzoate ion ($IB^-$) are relatively slow in aqueous solution. The reactions in CTAX micellar solutions are, however, very accelerated, because CTAX micelles can accommodate both reactants in their Stern layer in which they can easily react, while hydrophilic $OH^-$(or $IB^-$) and hydrophobic phosphinates are not mixed in water. Even though the concentrations (> $10^{-3}$ M) of $OH^-$(or $IB^-$) in CTAX solutions are much larger amounts than those ($6{\times}10^{-6}$ M) of phosphinates, the rate constants of the dephosphorylations are largely influenced by change of the concentration of the ions, which means that the reactions are not followed by the pseudo first order kinetics. In comparison to effect of the counter ions of CTAX in the reactions, CTACl is more effective on the dephosphorylation of DPNPIN (or IPNPIN) than CTABr due to easier expelling of $Cl^-$ ion by $OH^-$(or $IB^-$) ion from the micelle, because of easier solvation $Cl^-$ ion by water molecules. The reactivity of IPNPIN with $OH^-$(or $IB^-$) is lower than that of DPNPIN. The reason seems that the 'bulky' isopropyl group of IPNPIN hinders the attack of the nucleophiles. The mechanism of reaction of IPNPIN with IB- ion concluded as 'nucleophilic' instead of 'general basic' by a trapping experiment and a measured kinetic isotope effect.

• Resources Recycling
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• v.31 no.1
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• pp.65-77
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• 2022

A study was conducted in Korea on the leaching behavior and possibility of recovery of vanadium and other valuable metals from domestic vanadium titanomagnetite (VTM) by direct acid leaching. In this study, a VTM concentrate containing 0.8% V₂O₅ was used, and the ratio of magnetite to ilmenite was calculated as 1.9:1 by using the HSC program. The leaching behavior of vanadium from the VTM was similar to that of iron, and it was affected by the concentration of sulfuric acid and temperature. Further, titanium could be leached in the form of TiOSO₄ at a temperature higher than 75℃. To improve the leaching efficiency of V, Fe, and Ti in VTM, reductive sulfuric acid and oxidative sulfuric acid leaching were performed. When Na₂SO₃ was used as a reducing agent, the leaching rate of vanadium was 80% of that in that case of leaching by sulfuric acid. Similarly, the leaching rate of titanium increased from 20% to 50%. When Na₂S₂O₈ was used as an oxidation agent, most of the vanadium was leached, and the main residue found by XRD analysis was ilmenite. In studies on the possibility of recovering valuable metals, the selective extraction of metals is hardly achieved by solvent extraction from oxidation leaching solutions; however, in this study, Cyanex 923, a solvation extractant from reductive leaching solutions, could selectively extract Ti.