• 대한화학회지
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• 제24권1호
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• pp.44-52
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• 1980

동적 핵자기공명법에 대하여 toluene-$d_8$ 및 carbon tetrachloride 용매속에서의 $\alpha$-chlorobenzyl ethyl ether의 이온해리속도를 측정하였다. 먼저, 동적NMR spectra를 얻고 $J_{AB}, T_2,{\Delta}_{vAB}$ 값 등을 이용하여 computer simulation에 의한 이론spectra를 얻었는데 실측spectra와 매우 잘 일치하였으며, 이로부터 해리속도정수 k를 얻고 이 k의 Eyring plot에 의하여 기울기와 절편의 길이를 알고 이로부터 동력학적 parameter를 얻었다. 이온 해리의 난역도는 용매의 극성에 의존하였으며 활성화 enthalpy는 toluene-$d_8$ 용매중에서 4.7kcal/mole 이었고 carbon tetrachloride 용매중에서 10.7kcal/mole 이었다. 활성화 entropy는 toluene-$d_8$ 용매중에서 -35.8 e.u. 이었고 carbon tetrachloride 용매중에서 -14.4 e.u. 이었다. $S_N$ mechanism의 초기단계로 볼 수 있는 이 이온 해리는 ${\Delta}H^{neq}$ 값이 작아도 비극성 비양자성용매중에서 이온해리가 용역함을 알았으며 작은 ${\Delta}H^{neq}$에 비하여 ${\Delta}S^{neq}$는 음의 큰 값을 가졌음은 주목할 필요가 있다.

• 대한화학회지
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• 제10권3호
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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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• 제19권2호
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• pp.75-81
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• 1976

세균포자의 안정성과 관련하여 DPA-Ca-spore complex의 해리에 영향을 주는 여러 요인중 15%까지의 NaCl 농도에 의해서 이루어 지는 높은 이온 강도의 효과에 대하여 실험하고 다음과 같이 결론을 얻었다. 1) NaCl에 의한 포자 현탁액중의 이온강도의 변화는 포자로 부터 Ca-DPA의 해리를 촉진시켜 주며 이런 현상은 포자의 열 저항성을 감소시키고 따라서 보관중 포자의 안정성이 상당히 저하 되었다. 2) 세포질의 membrane은 포자내에서 Ca-DPA의 안정성을 유지하는데 permeability barrier로써 중요한 역할을 한다.

• Bulletin of the Korean Chemical Society
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• 제6권5호
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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.

• 약학회지
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• 제9권1_2호
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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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• 제33권9호
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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.

• 전기화학회지
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• 제12권3호
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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$^{\circ}C$.

• 전기화학회지
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• 제13권3호
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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.

• 대한화학회지
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• 제30권2호
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• pp.145-151
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• 1986

3-CN, 4-CN, $3-NH_2$ 및 $4-NH_2$ 치환피리딘의 해리상수를 온도(15 ∼ 40${\circ}C$)와 압력(1-2500bar)을 변화시키면서 측정하였다. 측정방법은 전도도법을 적용했으나 낮은 해리상수를 가진 물질에서도 적용되는 피리딘류의 염용액의 전도도를 측정하므로 계산가능한 방법을 모색하여 응용하였다. 이 방법은 어떤 조건에서의 해리상수를 알고 있어야 하는 것과 실험값을 외삽하여 피리딘염의 전도도를 알아야 하는 번거로움도 있으나 측정이 가능하다는 것을 확인할 수 있다. 이들 치환체의 해리상수는 온도가 증가하면 커지고 압력이 높아지면 해리상수는 작아진다는 것을 알 수 있었다. 또 반응의 열역학적 성질을 계산하여 반응성도 고찰하였다.

• Bulletin of the Korean Chemical Society
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• 제19권6호
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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.