• Bulletin of the Korean Chemical Society
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• 제29권1호
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• pp.117-121
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• 2008

Pseudo-first-order rate constants (kobsd) have been measured spectrophotometrically for nucleophilic substitution reactions of 5-nitro-8-quinolyl benzoate (5) with alkali metal ethoxides, EtO?M+ (M+ = Li+, Na+ and K+) in anhydrous ethanol (EtOH) at 25.0 0.1 C. The plots of kobsd vs. [EtO?M+] exhibit upward curvatures, while the corresponding plots for the reactions of 5 with EtO?Na+ and EtO?K+ in the presence of complexing agents, 15-crown-5-ether and 18-crown-6-ether are linear with rate retardation. The reactions of 5 with EtO?Na+ and EtO?Li+ result in significant rate enhancements on additions of Na+ClO4, indicating that the M+ ions behave as a catalyst. The dissociated EtO and ion-paired EtOM+ have been proposed to react with 5. The second-order rate constants for the reactions with EtO (kEtO) and EtOM+ (kEtOM+) have been calculated from ion-pairing treatments. The kEtO and kEtOM+ values decrease in the order kEtONa+ > kEtOK+ > kEtOLi+ > kEtO, indicating that ion-paired EtOM+ species are more reactive than the dissociated EtO ion, and Na+ ion exhibits the largest catalytic effect. The M+ ions in this study form stronger complex with the transition state than with the ground state. Coordination of the M+ ions with the O and N atoms in the leaving group of 5 has been suggested to be responsible for the catalytic effect shown by the alkali metal ions in this study.

• Applied Biological Chemistry
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• 제20권3호
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• pp.300-309
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• 1977

The information related to the heavy metal pollution in the environment was obtained from studies on the effects of pH, phosphate and soil properties on the adsorption of metal ions (Cd, Cu, Ni, and Zn) by soils. Three soil materials; soil 1 with low CEC (8.2 me/100g) and low organic carbon content (0.34%); soil 2 with high CEC (36.4 me/100g) and low organic carbon content (1.8%) and soil 3 with high CEC (49.9 me/100g) and high organic carbon content (14.7%) were used. Soils were adjusted to several pH's and equilibrated with metal ion mixtures of 4 different concentrations, each having equal equivalents of each metal ion (0.63, 1.88, 3.12 and 4.38 micromoles per one gram soil with and without 10 micromoles of phosphate per one gram soil). Reported here are the results of the equilibrium study on soil I. The rest of the results on soil 2 and soil 3 will be repoted subsequeutly. Generally higher metal ion concentration solution resulted in higher final metal ion concentrations in the equilibrated solution and phosphate had minimal effect except it tended to enhance removal of cadmium and zinc from equilibrated solutions while it tended to decrease the removal of copper and nickel. In soil 1, percentages of added metal ions removed at pH 5.10 were; Cu 97, Ni 69, Cd 63, and Zn 55, while increasing pH to 6.40, they were increased to Cu 90.9, Zn 99, Ni 96, and Cd 92 per As initial metal ion concentration increased, final metal ion concentrations in the equilibrated solution showed a relationship with pH of the system as they fit to the equation $p[M^{++}]=a$ pH+b where $p[M^{++}]=-log$[metal ion concentration in Mol/liter]. The magnitude of pH and soil effects were reflected in slope (a) of the equation, and were different among metal ions and soils. Slopes (a) for metal ions in the aqueous system are all 2. In soil 1 they were; Zn 1.23, Cu 0.99, Ni 0.69 and Cd 0.59 at highest concentration. The adsorption of Cd, Ni, and Zn in soil 1 could be represented by the Iangmuir isotherm. However, construction of the Iangmuir isotherm required the correction for pH differences.

• 멤브레인
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• 제11권3호
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• pp.133-139
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• 2001

PVA/SSA-$H^{+}$으로 제조된 막은 1가 이온 $Li^{+}$, $Na^{+}$, $K^{+}$, 2가 이온 $Mg^{2+}$, $Ca^{2+}$, $Ba^{2+}$, 3가 이온 $Al^{+}$로 치환되었다. 각 금속이온이 치환된 막의 금속이온의 효과를 알아보기 위하여 물-에탄올 및 물-메탄올 혼합용액에 대하여 팽윤도 및 투과증발 실험을 수행하였다. 또한 이들의 치환정도를 알아보기 위해 부분적으로 ESCA 실험을 통하여 알아보았다. 물-에탄올 및 물-메탄올 혼합용액에 대한 팽윤도는 $Li^{+}$> $Na^{+}$>$K^{+}$의 순으로 감소하였는데 이는 금속이온의 `salting-out'효과에 기인하는 것으로 사료되었으며, 2가 및 3가이온의 경우의 팽윤도 결과는 `salting-out' 효과뿐만 아니라 electrostatic 가교 및 금속이온의 반응성에 의해 좌우되는 것으로 사료되었다. 투과증발실험을 통한 투과도면에서는 물-에탄올 용액에 대해 PVA/SSA-$Na^{+}$막에서 최소치를 보였다가 PVA/SSA-$K^{+}$막에서 다시 증가하는 결과를 얻은 반면에 선택도는 반대의 경향을 얻었다. 대표적 분리 결과는 $50^{\circ}C$에서 90%에탄올 수용액에 대하여 투과도는 59 g/$m^{2}$hr, 선택도는 44의 값을 얻었다. 물-메탄올 용액에 대해서는 1가이온의 경우 에탄올 용액과 같은 경향의 결과를 얻었으나 2가 및 3가 이온의 경우 팽윤도 실험 결과와 마찬가지로 `salting-out' 효과 그리고 electrostatic 가교 등에 의해 영향을 받는다고 할 수 있다.

• Bulletin of the Korean Chemical Society
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• 제31권2호
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• pp.303-308
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• 2010

Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for nucleophilic substitution reactions of 4-nitrophenyl benzoate (5a), 4-nitrophenyl 4-methoxybenzoate (5b), and 4-nitrophenyl 4-hydroxybenzoate (5c) with alkali metal ethoxides, $EtO^-M^+$ ($M^+=Li^+$, $Na^+$ and $K^+$) in anhydrous ethanol (EtOH) at $25.0{\pm}0.1^{\circ}C$. The plots of $k_{obsd}$ vs. [$EtO^-M^+$] exhibit upward curvatures in all cases, indicating that $M^+$ ions catalyze the reactions and ionpaired $EtO^-M^+$ species are more reactive than dissociated $EtO^-$. Second-order rate constants for reactions with dissociated $EtO^-$ and ion-paired $EtO^-M^+$ (i.e., $k_{EtO^-}$ and $k_{EtO^-M^+}$, respectively) have been calculated from ion-pair treatment for the reactions of 5a and 5b. However, such ion-pair treatment has failed to determine $k_{EtO^-}$ and $k_{EtO^-M^+}$ values for the reactions of 5c. It has been concluded that reactions of 5a and 5b are catalyzed by one metal ion, which increases electrophilicity of the reaction center through coordination on the carbonyl oxygen. In contrast, reactions of 5c have been suggested to involve two metal ions, i.e., the one coordinated on the carbonyl oxygen increases the electrophilicity of the reaction center while the other one associated on the phenoxy oxygen decreases the charge repulsion between the anionic reagents (i.e., $EtO^-$ and deprotonated 5c). It has been found that the rate equation derived from the mechanism involving two metal ions fits nicely to the kinetic results obtained for the reactions of 5c.

• 한국자기학회지
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• 제19권6호
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• pp.216-221
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• 2009

Y-type 바리움 페라이트 $Ba_2Co_2Fe_{12}O_{22}$를 고상반응법으로 제조하고 금속이온몰비($Fe^{3+}:\;Ba^{2+}:\;Co^{2+}$)와 열처리 온도가 자기적 성 질과 미세구조에 미치는 영향에 대하여 조사하였다. 상분석과 미세구조는 각각 XRD(X-ray diffractometer)와 FESEM(field effect scanning electron microscope)을 이용하여 조사하였으며 분말의 자기적 성질은 VSM(vibrating sample magnetometer)을 이용하여 조사하였다. 금속이온몰비($Fe^{3+}:\;Ba^{2+}:\;Co^{2+}$)가 6 : 1 : 1인 조성의 분말을 $1050\;{^{\circ}C}$에서 열처리하였을 때 단일 상이 합성되었으며 8 : 1 : 1인 조성의 분말을 $1200\;{^{\circ}C}$에서 열처리하였을 때 가장 높은 포화자화값(39.1 emu/g)을 나타내었다.

• Bulletin of the Korean Chemical Society
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• 제33권2호
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• pp.519-523
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• 2012

A kinetic study is reported on nucleophilic displacement reactions of benzyl 2-pyridyl carbonate 6 with alkalimetal ethoxides, EtOM (M = Li, Na, and K), in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plots of pseudo-firstorder rate constant $k_{obsd}$ vs. [EtOM] curve upward, a typical phenomenon reported previously for alkaline ethanolysis of esters in which alkali-metal ions behave as a Lewis-acid catalyst. The kobsd value for the reaction of 6 with a fixed EtOK concentration decreases rapidly upon addition of 18-crown-6-ether (18C6), a complexing agent for $K^+$ ion up to [18C6]/[EtOK] = 1.0 and then remains constant thereafter, indicating that the catalytic effect exerted by K+ ion disappears in the presence of excess 18C6. The reactivity of EtOM towards 6 increases in the order $EtO^-$ < EtOLi < EtONa < EtOK, which is contrasting to the reactivity order reported for the corresponding reactions of 2-pyridyl benzoate 4, i.e., $EtO^-$ < EtOK < EtONa < EtOLi. Besides, 6 is 1.7 and 3.5 times more reactive than 4 towards dissociated $EtO^-$ and ion-paired EtOK, respectively. The reactivity difference and the contrasting metal-ion selectivity are discussed in terms of electronic effects and transition-state structures.

• 한국염색가공학회지
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• 제18권3호
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• pp.31-41
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• 2006

Functional properties are available with sputtering. But sputtering treatment alone cannot got a good fastness performance to washing, rubbing and light. This research was objected to investigate optimum condition by sputtering on polyester through various processing conditions such as ion current and treatment time, and then various resin treated onto metal coated polyester fabrics in order to increase washing fastness of metal membrane. As the results, the optimum conditions revealed 1500 mA of ion current, 2 min of treatment time in sputter, and suitable resin concentrations were 2% of o.w.s (on the weight of solution) in resin treatment. Therefore, we could get enhanced anti-static effect and flex stiffness as well as washing fastness in sputtered polyester fabric with various resin treatment, for example, melamine and polyurethane.

• 공업화학
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• 제10권2호
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• pp.218-224
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• 1999

원자로 정지시 혼상 탈염기의 최적 운전방법을 제안할 목적으로 산성-산화성 분위기에서 저농도의 Ni, Co 및 Ag 이온이 함유된 모의 냉각재 용액의 연속식 이온교환특성을 연구하였다. 금속 이온의 제거 용량에 미치는 양이온 교환수지 형태의 효과로서 $H^+$형 수지의 성능은 $Li^+$형 수지의 성능보다 약 6% 정도 높은 것으로 나타났다. 혼합층 이온교환 방법인 양이온과 음이온 수지의 혼합은 비혼합시와 비교하여 금속 이온들의 제거 용량에는 영향을 미치지 않았으나 금속 이온들의 파과곡선의 기울기를 매우 조금 증가시켰다. 냉각재의 산성-산화성 분위기와 관계된 영향으로서 붕산의 첨가는 금속 이온들의 파과곡선의 기울기를 매우 작게 감소시킨 반면, 과산화수소의 첨가는 금속이온들의 제거 용량을 약간 감소시켰다.

• 한국공작기계학회논문집
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• 제15권1호
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• pp.49-55
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• 2006

The effect of coating temperature with regard to surface properties of TiN-coated layer on hard metal(WC-Co) are experimentally investigated. Hardness, surface roughness, TiN coating thickness and adsorption force were measured in order to evaluate the effect of coating temperature. The two-way ANOVA method is used in order to evaluate the experimental data. In AIP processing, It is concluded that the furnace temperature in the range of $400^{\circ}C\~500^{\circ}C$ affected to a little increasing the number of production with the coating temperature.

• 대한화학회지
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• 제67권4호
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• pp.222-225
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• 2023

Metallic salts of C10-18 aliphatic carboxylic acids were prepared and their scanning electron microscopic images were analyzed for the morphology dependency with the metal and the carboxylic acid. Regardless of metal ion, metal salts of dicarboxylic acids showed a high crystallinity with a fiber image (SuA-Na). The aromatic dicarboxylates also represented a morphology of a rectangular-rod or board shapes (IA-Li, IA-Ba). With Na ion, most aliphatic carboxylate (MA, PA, SA) showed a fiber-like crystallinity. However, other monovalent Li, K and multivalent Mg, especially Al ion resulted a glassy-amorphous in the metallic salts of acids (MA, PA, SA). With divalent Ba and Ca ions, the metal salt of aliphatic acids expressed a branched round cluster shape as in SA-Ca, SA-Ba. Both Li and Mg ions with a similar size showed a strong morphological similarity in the metallic salts of aliphatic acids MA, PA, SA. In the case of Na and Ca ions with a similar size (98, 106 pm), both ionic salts of stearic acid gave a branching effect for a fiber or round granular image. In the case of hydroxyl-aliphatic acids (HLA, HPA, HSA), the fiber images in HLA-Na and HSA-Na was appeared about 100 nm thicker than those of nonhydroxycarboxylates (LA-Na, SA-Na). The metallic salts of unsaturated C-18 carboxylic acids (OlA, LeA and LnA) showed an amorphous glassy image due to a kinked carbon chain.