• Journal of the Korean Chemical Society
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• v.24 no.1
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• pp.44-52
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• 1980

Ionic dissociation rates of $\alpha$-chlorobenzyl ethyl ether in each solvent of toluene-$d_8$ and carbon tetrachloride were measured by the method of dynamic NMR spectroscopy. The spin system of these 1H NMR spectra was $AB_3$. The theoretical spectrum was calculated by computer simulation of dynamic NMR spectra, which agreed very well with observed spectra. From this computer simulation, the ionic dissociation rate constant k was obtained, and by Eyring plot with it, slope and intercept length was gained, from which kinetic parameters were calculated.The easiness of ionic dissociation depended upon solvent polarity. Activation enthalpy was 4.7 kcal/mole in toluene-$d_8$, 10.7 kcal/mole in carbon tetrachloride, and activation entropy was -35. 8 e.u. in toluene-$d_8$, -14.4 e.u. in carbon tetrachloride. It was understood that though the ${\Delta}H^{neq}$ value was small, this ionic dissociation had an easier procession in nonpolar solvents with increasing temperatures. Considering that the ionic dissociation could be thought as the first step of $S_N1$ mechanism, attention might be paid to the results that the value of ${\Delta}S^{neq}$ had a large negative value in comparison with a small ${\Delta}H^{neq}$.

• Journal of the Korean Chemical Society
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• v.10 no.3
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• pp.114-118
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• 1966

The glass electrode was empirically calibrated in dioxane-and ethanol-water mixed solvents, by means of which the pH-meter reading could be converted to stoichiometric hydrogen ion concentration. By the potentiometric titration method, the thermodynamic dissociation constants of hydrogen cupferrate (HCup) with variations of ionic concentration in aqueous solution were determined, and by the extrapolation of the constants the new thermodynamic $pK_a$ value, 3.980${\pm}$0.006, at zero ional concentration was obtained. The thermodynamic dissociation constants of HCup in dioxane-and ethanol-water solution were also potentiometrically determined with the changes in composition of organic solvents at 0.01 and 0.05 of the ionic strength(${mu}$) and 25 $^{\circ}C$. The empirical formula of the constants with mole fraction(n) of the organic solvent are as follow: Dioxane-water solution. $pK_a$= 12.96n + 4.10 at ${\mu}$ = 0.01, n = 0.0228∼0.171 $pK_a$= 12.05n + 4.23 at ${\mu}$ = 0.05, n= 0.0228∼0.171 Ethanol-water solution, $pK_a$= 4.0ln + 4.26 at ${\mu}$= 0.01, n= 0.0395∼0.262 $pK_a$= 3.83n + 4.34 at ${\mu}$= 0.05, n= 0.0395∼0.262

• Applied Biological Chemistry
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• v.19 no.2
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• pp.75-81
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• 1976

High ionic strength is expected to enhance dissociation of Ca-DPA from spores and to contribute to a detrimental effect on spore stability or on spore heat resistance with a combined treatment of gamma-radiation. From this study, this hypothesis has become apparent as as follows; 1) Ca-DPA dissociation contributes to loss of stability of bacterial spores with respect to heat resistance, survival during storage, and 2) the cytoplasmic membrane plays a role in maintaining the stability of DPA-Ca-spore complex, apparently by serving as a permeability barrier.

• Bulletin of the Korean Chemical Society
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• v.6 no.5
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• pp.266-269
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• 1985

The dissociation constants(K) of m-chloroanilinium ion in water-ethanol mixture, where the volume percentage of water is 89.5%, were evaluated by UV-spectroscopic method at $20{\sim}50^{\circ}C$, up to 1500 bars with changing ionic strength from 0.04 to 0.10 mol $kg^{-1}$ by use of acetate buffer. K values enhance with increasing ionic strength and temperature, but decrease with elevating pressure. From K values, we obtained the partial molar volume change and some other thermodynamic parameters. From the values of enthalpy, entropy and isoequilibrium temperature (649 K), we concluded that the dissociation of m-chloroanilinium ion mentioned above is controlled by enthalpy.

• YAKHAK HOEJI
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• v.9 no.1_2
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• pp.4-7
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• 1965

Acid dissociation constants of sulfamethoxypyridazine, sulfadimethoxine, sulfamerazine, sulfathiazole and sulfadiazine, and stability constants for formation of copper chelate were calculated from their titration curves in 80% dimethylformamide with ionic strength 0.1 at $25{\deg}$ It was found that the acid dissociation constants (pKa) of sulfa-drugs were in the range of 9.33 - 10.05, and the stability constants (log $k_{1}$, $k_{2})$ of their copper chelates were in the range of 9.33-9.71.

• Bulletin of the Korean Chemical Society
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• v.33 no.9
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• pp.2999-3003
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• 2012

Various types of room temperature ionic liquids (RTILs) containing 1,1-dicyano-1-acetylmethanide anion ($[C(CN)_2(COCH_3)]^-$, $[DCNAcC]^-$) were prepared and their physical and electrochemical properties were studied. All of these ILs exhibited high thermal stabilities over $200^{\circ}C$ and relatively high ionic conductivities up to 29.4 $mS\;cm^{-1}$ at $80^{\circ}C$. Although the ionic conductivity of IL containing bis(trifluoromethanesulfonyl)-imide ($[Tf_2N]^-$) anion is higher than that of ILs bearing $[DCNAcC]^-$ anion, the specific capacitance of ILs bearing $[DCNAcC]^-$ anion are higher than that of IL containing $[Tf_2N]^-$ anion and showed high temperature dependence. Such favorable electrochemical properties of these ILs are likely to be attributed to the efficient dissociation of cation and anion at higher temperature and enhanced electrosorption of $[DCNAcC]^-$ anion at the electrode.

• Journal of the Korean Electrochemical Society
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• v.12 no.3
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• pp.271-275
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• 2009

Five novel lithium polyelectrolyte-ionic liquid systems, using poly (lithium 2-acrylamido-2-methyl propanesulfonate; PAMPSLi) were prepared and their electrochemical properties were measured. The ionic conductivity of the PAMPSLi/1-ethyl-3-methylimidazolium tricyano methanide (emImTCM) system was exhibited high conductivity (1.28 $\times$ $10^{-3}$ $S/cm^{-1}$). The high conductivity and low viscosity of PAMPSLi/emImTCM system is due to the high flexibility of imidazolium cation and dissociation of lithium cation from the polymer chains. The PAMPSLi/N,N-dimethyl-N-propyl-Nbutylammonium tricyanomethanide ($N_{1134}TCM$) and PAMPSLi/N, N-dimethyl-N-propyl-N-butylammonium dicyanamide ($N_{1134}DCA$) systems showed fairly high conductivity (6.3 $\times$ $10^{-4}$ $S/cm^{-1}$, 6.0 $\times$ 10.4 S/cm.1). PAMPSLi/Trihexyl (tetradecyl) phosphonium bis (trifluoromethane sulfonyl) amide ($P_{66614}TFSA$) exhibited low conductivity (2.22 $\times$ $10^{-5}$ $Scm^{-1}$) and thermally stable over 400$^{\circ}C$.

• Journal of the Korean Electrochemical Society
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• v.13 no.3
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• pp.198-202
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• 2010

Lithium co-polyelectrolyte-ionic liquid systems, using poly (lithium 2-acrylamido-2-methyl propanesulfonate; PAMPSLi) and polyvinyl formamid (PVF) were prepared and their electrochemical and physical properties were measured. The conductivity of co-polymer systems, PAMPSLi/PVF/N, N-dimethyl-N-propyl-N-butylammonium tricyanomethanide (PAMPSLi/PVF/$N_{1134}$TCM) and PAMPSLi/PVF/N, N-dimethyl-N-propyl-N-butylammonium dicyanamide (PAMPSLi/PVF/$N_{1134}$DCA) exhibited low viscosity ($N_{1134}$TCM:$N_{1134}$DCA 28.6cP, 28.7cP) and higher conductivity ($2.48{\times}10^{-3}Scm^{-1}$, $2.2{\times}10^{-3}Scm^{-1}$) than homopolymer system. The ionic conductivity PAMPSLi/PVF/1-ethyl-3-methyl imidazolium dicyanamide (PAMPSLi/PVF/emImDCA) exhibited $1.54{\times}10^{-3}Scm^{-1}$ and low viscosity (emImDCA: 28.09cP). High flexibility of imidazolium cation and dissociation of lithium cation from the co-polymer chains were affected by high conductivity and low viscosity.

• Journal of the Korean Chemical Society
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• v.30 no.2
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• pp.145-151
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• 1986

Using a new conductometric method, dissociation constants of 3-cyano, 4-cyano, 3-amino and 4-aminopyridine were measured in the temperature range 15 ∼ 40${\circ}C$ and pressure up to 2500bar in aqueous media. This method is convenient to apply to the low dissociative acid and base but have to do tedious extrapolating procedure for the ionic conductance in elaborated temperatures and pressures and have to know any reference dissociation constant. The measured dissociation constants were increased as the temperature increase but decreased as the pressure increase. From the constants, various thermodynamic properties were evaluated and discussed for the dissociation reactions.

• Bulletin of the Korean Chemical Society
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• v.19 no.6
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• pp.671-676
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• 1998

The formation and dissociation rates of $Ce^{3+}$ Complexes of the 1,4,7,10-tetraaza-13,16-dioxacyclooctadecane-NN', N",N"'-tetraacetic acid (1), 1,4,7,10-tetraaza-13,16-dioxacyclooctadecane-N,N',N",N"'-tetramethylacetic acid (2), and 1,4,7,10-tetraaza-13,16-dioxacyclooctadecane-N,N',N",N"'-tetrapropionic acid (3) have been measured by the use of stopped-flow spectrophotometry. Observations were made at 25.0±0.1 ℃ and at an ionic strength of 0.10 M $NaClO_4$. The complexation of $Ce^{3+}$ ion with 1 and 2 proceeds through the formation of an intermediate complex $(CeH_3L^{2+})^*$ in which the $Ce^{3+}$ ion is incompletely coordinated. This may then lead to be a final product in the rate-determining step. Between pH 4.76 and 5.76, the diprotonated $(H_2L^{2-})$ from is revealed to be a kinetically active species despite of its low concentration. The stability constants $(logK(CeH_3L^{2+}))$ and specific water-assisted rate constants $(k_{OH})$ of intermediate complexes have been determined from the kinetic data. The dissociation reactions of $Ce^{3+}$ complexes of 1, 2, and 3 were investigated with $Cu^{2+}$, ions as a scavenger in acetate buffer. All complexes exhibit acid-independent and acid-catalyzed contributions. The effect of buffer and $Cu^{2+}$ concentration on the dissociation rate has also been investigated. The ligand effect on the dissociation rate of $Ce^{3+}$ complexes is discussed in terms of the side-pendant arms and the chelate ring sizes of the ligands.