• Journal of the Korean Chemical Society
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• v.31 no.6
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• pp.534-541
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• 1987

The study of reaction mechanism for the substitution of ethylenediamine (en) for Cl and Hedta from $[CoCl(Hedta)]^-$ in the presence of $Hg^{2+}$ ion was carried out by uv and CD spectra. From the kinetic data, we proposed that the first ethylenediamine be substituted through the associative reaction path by means of interaction of $Hg^{2+}$ ion with Co(III), and that the second and the third ethylenediamine be substituted stepwise. From the optical purities of $[Co(en)_3]^{3+}$ which was formed after reaction, we suggested the critical stereochemical step and new substitution reaction paths.

• Bulletin of the Korean Chemical Society
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• v.31 no.9
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• pp.2483-2487
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• 2010

Pseudo-first-order rate constants ($k_{obsd}$) were measured spectrophotometrically for nucleophilic substitution reactions of 4-nitrophenyl picolinate (6) with alkali metal ethoxides (EtOM, $M^+\;=\;K^+$, $Na^+$ and $Li^+$) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plot of $k_{obsd}$ vs. [EtOM] exhibits upward curvature regardless of the nature of $M^+$ ions. However, the plot for the reaction of 6 with EtOK is linear with significantly decreased $k_{obsd}$ values when 18-crown-6-ether (18C6, a complexing agent for $K^+$ ion) is added in the reaction medium. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ (i.e., the second-order rate constant for the reaction with dissociated $EtO^-$ and ion-paired EtOM, respectively) has revealed that ion-paired EtOM is 3~17 times more reactive than dissociated $EtO^-$. The reaction has been proposed to proceed through a 5-membered cyclic transition state, in which $M^+$ ion increases the electrophilicity of the reaction site. Interestingly, $Na^+$ ion exhibits the largest catalytic effect. The presence of a nitrogen atom in the pyridine moiety of 6 has been suggested to be responsible for the high $Na^+$ ion selectivity.

• Proceedings of the Membrane Society of Korea Conference
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• 2001.05a
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• pp.104-107
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• 2001

• Resources Recycling
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• v.27 no.4
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• pp.36-43
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• 2018

In order to recycle waste nickel-cadmium batteries, cadmium was selectively removed by ion substitution reaction so that cadmium and nickel could be separated efficiently. The electrode powder obtained by crushing the electrode in the waste nickelcadmium battery was leached with sulfuric acid. The cadmium in the nickel-cadmium solution was precipitated with cadmium sulfide by the addition of sodium sulfide. Ion substitution experiments were carried out under various conditions. At the optimum condition with pH = -0.1 and $Na_2S/Cd=2.3$ at room temperature, the residual Cd in the solution was about 100 ppm, and most of it was precipitated with CdS.

• Bulletin of the Korean Chemical Society
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• v.15 no.8
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• pp.654-658
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• 1994

Rate constants have been measured spectrophotometrically for the nucleophilic substitution reactions of p-and m-nitrophenyl 2-furoates (4 and 5, respectively) with alkali metal ethoxides ($EtO^-M^+$) in absolute ethanol at 25$^{\circ}$C. The reactivity of $EtO^-M^+$ toward 4 is in the order $EtO^-K^+$ > $EtO^-Na^+$> $EtO^-Li^+$ > $EtO^-K^+$+ 18-crown-6 ether. This is further confirmed by an ion pairing treatment method. The present result indicates that (1) ion paired $EtO^-M^+$ is more reactive than dissociated $EtO^-$ ; (2) the alkali metal ions ($K^+,\;Na^+,\;Li^+$) behave as a catalyst; (3) the catalytic effect increases with increasing the size of the metal ion. A similar result has been obtained for the reaction of 5, however, the catalytic effects shown by the metal ions are more significant in the reaction of 5 than in that of 4.

• Bulletin of the Korean Chemical Society
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• v.15 no.2
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• pp.161-167
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• 1994

Rate constants have been measured spectrophotometrically for the nucleophilic substitution reactions of aryl substituted benzenesulfonates (3) with alkali metal ethoxides ($EtO^-M^+$) and butane-2,3-dione monoximates ($Ox^-M^+$) in ethanol at $25^{\circ}C$. The reactivity of the alkali metal ethoxides decreases in the order $EtO^-K^+> EtO^- > EtO^-Li^+$, indicating that $K^+$ ion behaves as a catalyst and $Li^+$ ion acts as an inhibitor for all the substrates studied. For the corresponding reactions of 3 with Ox^-M^+$, $Li^+$ ion also exhibits inhibitory effect for all the substrates, while, $K^+$ ion shows catalytic or inhibitory effects depending on the nature of substituents on the acyl and phenyl moieties. A study of substituent effect on rate has revealed that both EtO^- $and Ox^-$ systems have the same reaction mechanism. The different behavior shown by $K^+$ ion for the reaction of 3 with $EtO^-$ and $Ox^-$ would be attributed to a difference in charge polarization of S=O bond in the transition state between the two systems and/or a change in conformation of Ox^-K^+$.

• Bulletin of the Korean Chemical Society
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• v.35 no.5
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• pp.1506-1510
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• 2014

A kinetic study on nucleophilic substitution reaction of 5-nitro-8-quinolyl picolinate (6) with alkali-metal ethoxides (EtOM; M = K, Na, and Li) in anhydrous ethanol is reported. The plot of $k_{obsd}$ vs. [EtOM] curves upward in the absence of crown ethers but is linear with significantly decreased reactivity in the presence of crown ethers. Dissection of $k_{obsd}$ into $k_{EtO}$- and $k_{EtOM}$ (i.e., the second-order rate constants for the reactions with the dissociated $EtO^-$ and ion-paired EtOM, respectively) has revealed that the ion-paired EtOM is significantly more reactive than the dissociated $EtO^-$ (e.g., $k_{EtOM}/k_{EtO^-}$ = 33.4-141). This indicates that the reaction of 6 is catalyzed by $M^+$ ions in the order $Na^+$ > $Li^+$ > $K^+$ and the catalytic effect disappears in the presence of a proper crown ether. Picolinate ester 6 is much more reactive and is more strongly catalyzed by $M^+$ ions than 5-nitro-8-quinolyl benzoate (5). It has been concluded that $M^+$ ions catalyze the reaction of 6 by increasing electrophilicity of the reaction center through a cyclic transition state, which is structurally not possible for the reaction of 5.

• Bulletin of the Korean Chemical Society
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• v.35 no.1
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• pp.225-230
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• 2014

A kinetic study on nucleophilic substitution reactions of 4-nitrophenyl X-substituted-benzoates (7a-i) with EtOK in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$ is reported. The plots of pseudo-first-order rate constants ($k_{obsd}$) vs. [EtOK] curve upward. Dissection of $k_{obsd}$ into the second-order rate constants for the reactions with the dissociated $EtO^-$ and ion-paired EtOK (i.e., $k_{EtO^-}$ and $k_{EtOK}$, respectively) has revealed that the ion-paired EtOK is more reactive than the dissociated $EtO^-$. Hammett plots for the reactions of 7a-i with the dissociated $EtO^-$ and ion-paired EtOK exhibit excellent linear correlations with ${\rho}_X$ = 3.00 and 2.47, respectively. The reactions have been suggested to proceed through a stepwise mechanism in which departure of the leaving-group occurs after the RDS. The correlation of the $k_{EtOK}/k_{EtO^-}$ ratio with the ${\sigma}_X$ constants exhibits excellent linearity with a slope of -0.53. It is concluded that the ion-paired EtOK catalyzes the reaction by increasing the electrophilicity of the reaction center rather than by enhancing the nucleofugality of the leaving group.

• 한국정보디스플레이학회:학술대회논문집
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• 2008.10a
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• pp.578-580
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• 2008

Blue-emitting $CaAl_2Si_2O_8:Eu^{2+}(CAS:Eu^{2+})$ phosphor, prepared by solid-state reaction, is described in this paper. We researched the effect of boron ion substitution in the host materials. The phase and luminescent properties were investigated using the powder X-ray diffraction(XRD) and photoluminescence(PL) spectra.

• Journal of the Korean Chemical Society
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• v.36 no.3
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• pp.405-411
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• 1992

The substitution reaction and structrue of products obtained from the reaction of Equatorial-Skew-[Co(TRDTRA)($OH_2$)] (TRDTRA = trimethylenediaminetriacetate) with $CN^-, NO^{-}_{2}$ and $NCS^-$ ions have been investigated by means of electronic absorption spectroscopy and theoretical calculation based on the Yamatera's theory. According to kinetic data, the substitution reaction order for the complexes such as $CN^-, NO^{-}_{2}$ and $NCS^-$ was the first order, respectively, and overall reaction order was second order. It has been determined that the structure of products having $CN^{-} and NO^{-}_{2}$ ions was Polar-Chair type complexes which were accompanying with isomerization and having $NCS^-$ ion was Equatorial-Skew type complex which was not accompanying with isomerization.