• Bulletin of the Korean Chemical Society
• /
• v.30 no.7
• /
• pp.1535-1538
• /
• 2009

We present calculations for $S_N$2/E2 reactions in protic solvents (t-butyl alcohol, ethylene glycol). We focus on the role of the hydroxyl (-OH) groups in determining the $S_N$2/E2 rate constants. We predict that the ion pair E2 mechanism is more favorable than the naked ion E2 reaction in ethylene glycol. E2 barriers are calculated to be much larger (~ 9 kcal/mol) than $S_N$2 reaction barriers in protic solvents, in agreement with the experimental observation [Kim, D. W. et al. J. Am. Chem. Soc. 2006, 128, 16394] of no E2 products in the reaction of CsF in t-butyl alcohol.

• Journal of the Korean Chemical Society
• /
• v.17 no.4
• /
• pp.229-234
• /
• 1973

The dependence of ionic activity and electrode potential upon electrolyte concentration in ethylenediamine includes the effects of ion-pair formation involving all possible combinations of cations and anions represent in the solution and includes the ion-atmosphere effects of dissociated ions. For calculating activity coefficients, Debye-Huckel limiting law, extended Debye-Huckel,equation, and Marshall Grunwald equation were used in comparison of experimental and calculated plots of the electromotive force of the cell versus the logarithum of concentration. The fit of the experimental points to the theoretical curves was improved in case of the Marshall-Grunwald equation.

• Bulletin of the Korean Chemical Society
• /
• v.15 no.5
• /
• pp.357-360
• /
• 1994

The adsorption of cyanide ion on the gold electrode has been investigated by the subtractively normalized interfacial Fourier transform infrared spectroscopy (SNIFTIRS). The observations made by SNIFTIRS were consistent with those obtained by the polarization modulated Fourier transform infrared spectroscopy. According to the surface selection rule, cyanide ion appeared to adsorb on gold via either carbon or nitrogen lone pair electrons assuming a perpendicular orientation with respect to the metal surface. The possibility of presence of bridge-bound species seemed very infeasible. From the ab initio quantum mechanical calculation, adsorbate-to-metal bonding appeared to occur mainly via the $5{\sigma}$ donation from carbon to Au.

• Bulletin of the Korean Chemical Society
• /
• v.10 no.2
• /
• pp.155-158
• /
• 1989

The rates of complexation of the 18-C-6 (1,4,7,10,13,16-hexaoxacyclooctadecane) with $K^+,\;Ca^{2+},\;Sr^{2+},\;and\;Ba^{2+}$ in methanol solution have been determined at 25$^{\circ}C$ by a pressure-jump technique. The Eigen Winkler mechanism has been applied to interprete the kinetic data. The results suggest that the rate determining step of the complexation in methanol is the rearrangement of the ligand in the outer sphere ion-dipole pair to form a stable encapsulated complex of the metal ion by the crown ether.

• Proceedings of the PSK Conference
• /
• 2002.10a
• /
• pp.401.1-401.1
• /
• 2002

Potentiometric sensors are important and viable devices for use in pharmaceutical analysis. liquid polymeric membrane electrodes for many basic drugs and a few acidic drug were reported. The acidic drug-metal(Ⅱ)-triethylene tetramine ion pair complexes were prepared and used in poly(vinyl chloride) membrane electrodes to analyze anionic drugs such as mefenamic acid and ibuprofen. Metal ion used were Fe2＋. Co2＋. Ni2＋ and Cu2＋. Plasticizer used was o-nitrophenyl octyl ether.. (omitted)

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
• /
• v.18 no.4
• /
• pp.457-464
• /
• 2020

In this study, extraction of uranium(VI) from an aqueous nitric acid solution was investigated using tri-n-butyl phosphate (TBP) as an extractant in an ionic liquid, 1-alkyl-3-methylimidazolium bis (trifluoromethylsulfonyl)imide ([Cnmim][Tf2N]). The distribution ratio of U(VI) in 1.1 M TBP/[Cnmim][Tf2N] was significantly high when the concentration of nitric acid was low. The value of the distribution ratio decreased as the concentration of the nitric acid increased at lower acidities, and then increased with a nitric acid concentration of up to 8 M. This can be attributed to the different extraction mechanisms of U(VI) based on nitric acid concentrations. Thus, a cation exchange at low acidity levels and an ion-pair extraction at high acidity levels were suggested as the extraction mechanism of U(VI) in the TBP/[Cnmim][Tf2N] system.

• Macromolecular Research
• /
• v.11 no.5
• /
• pp.375-381
• /
• 2003

Silver salt complex membranes with glassy poly(methyl methacrylate) (PMMA) unexpectedly showed higher propylene permeance than those with rubbery poly(butyl methacrylate) (PBMA) where as neat PMMA is much less permeable to propylene than that of neat PBMA. Such unusual facilitated olefin transport has been systematically investigated by changing the side chain length of polymethacrylates (PMAs) from methyl, ethyl to butyl. The ab initio calculation showed almost the same electron densities of the carbonyl oxygens in the three PMAs, expecting very similar intensity of the interaction between carbonyl oxygen and silver ion. However, the interaction intensity decreases with the length of the alkyl side chain: PMMA > PEMA > PBMA according to wide angle X-ray scattering and FT-Raman spectroscopy. The difference in the interaction intensity may arise from the difference in the hydrophilicity of the three PMAs, as confirmed by the contact angle of water, which determines the concentrations of the ionic constituents of silver salts: free ion, contact ion pair and higher order ionic aggregate. However, propylene solubilities and facilitated propylene transport vary with the side chain length significantly even at the same concentration of the free ion, the most active olefin carrier, suggesting possible difference in the prohibition of the molecular access of propylene to silver ion by the side chains: the steric hindrance. Therefore, it may be concluded that both the hydrophilicity and the steric hindrance associated with the side chain length in the three PMAs are of pivotal importance in determining facilitated olefin transport through polymer/silver salt complex membranes.

• Analytical Science and Technology
• /
• v.19 no.1
• /
• pp.31-38
• /
• 2006

Micellar electrokinetic capillary chromatography(MECC) and HPLC with ion-pairing mechanism were applied for the separation of the well known environmental wastes from dye industry. These compounds include H-acid, J-acid, ${\gamma}$-acid, orthanilic acid, sulfanilic acid and 2-naphthylamine-1,5-disulfonic acid, and are known to be the diazo components of the azo dye. MECC method was also applied to separate few acid dyes including Acid Orange 7, Acid Orange 5 and Acid Blue 92 and direct dye such as Direct Red 80. Informations about the diazo components of any azo dye could be obtained by comparison of electropherogram of the reduction solution of a given dye with those obtained from standard materials such as H-acid, J-acid, ${\gamma}$-acid, orthanilic acid, sulfanilic acid and 2-naphthylamine-1,5-disulfonic acid. It has been concluded that MECC and HPLC with ion-pairing mechanism could be successfully applied for the analysis of unknown dyes and their diazo components.

• Journal of Korean Society of Water and Wastewater
• /
• v.12 no.1
• /
• pp.88-95
• /
• 1998

The Electron/Hole Pair is generated when the Activation Energy produces by Ultraviolet Ray illumination to the Semiconductor. And $OH^-$ ion produces by Water Photo-Cleavage reacts with Positive Hole. As a result, OH Radical acting as strong oxidant is generated and then Photocatalytic Oxidation Reaction occurs. The Photocatalytic Oxidation can oxidize the chlorophenol to Chloride and Carbon Dioxide easier, safer and shorter than conventional Water Treatment Process With the same degree of chlorination, the $Cl^-$ ion at para (C4) position is most easily replaced by the OH radical. And then, the blocking effect of $OH^-$ ion between the $Cl^-$ ions and $Cl^-$ ions at symmetrical location is easily replaced by the OH radical. For mono-, di-, tri-chlorophenols, there is no obvious difference in decomposition rate, decomposition efficiency and completeness of the decomposition reaction except for 2,3-dichloropheno, 2,4,5-, 2,3,4-trichlorophenol. The decomposition efficiency is higher than 75% and completeness of the decomposition reaction is higher than 70%. Therefore, continuous flow photocatalytic reactor is promising process to remove the chlorinated aromatic compounds which is more toxic than non-chlorinated aromatic compound.

• The Transactions of the Korean Institute of Electrical Engineers C
• /
• v.50 no.2
• /
• pp.79-85
• /
• 2001

A conventional electrolyzing cell has been made by an ion exchange membrane inbetween parallel plate electrodes. A low dc voltage is applied to the electrodes for electrolyzing and the efficiency is remained in low. in this study, a novel electrolyzing cell with a pair of slit-type third electrodes installed inbetween parallel plate electrodes has been proposed and investigated experimentally. And pulse power wa supplied to between each electrodes. This slit type of third electrodes can concentrate the strong electric fields at the every its edges to accelerate the electrolyzing powers, and to generate oxygen bubble discharges for generating oxidants. And moreover the slits eliminate the space charge limiting action and the temperature of the water by leaking out through the slits from electrolyzing region to outside of the main electrode region. As a result, it was found that a strong electorzed water of pH 2.8 and pH 10.5 and oxidants dissolved water of 1 [ppm] in acidic water were obtained with a tap water fed at the electric current of 2 [A], which however were several times higher oxidant and ion concentration quantity compared with the conventional cell.