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이심성,윤창주,김시중 聖心女子大學校 1981 論文集 Vol.12 No.2
수용액에서 Ag₂S 이온선택성전극의 특성은 잘 알려져 있다. 그러나 이 전극의 비수용매 또는 혼합용매계에서의 행동은 거의 알려진바 없다. 이 논문은 물-유기용매의 혼합용매계에서의 Ag₂S전극의 성질을 규명하려는 몇 가지 실험결과를 보이고 있다. 또한 Ag+이온의 선택성 용매화의 메카니즘에 관한 연구를 Ag₂S 전극을 이용하여 수행할 수 있음도 보이려고 한다. 할로겐화 이온 및 그들의 혼합물을 Ag₂S 전극을 사용하여 50%-MeOH용매계에서 분석하였다. 그 결과 은에 대한 전극 반응은 순수한 물에서의 것과 매우 유사하였다. The properties of Ag₂S ion-selective electrode in aqueous solvents well known. Very little is known, however, about the performance of this electrode in the systems of non-aqueous or mixed solvents. This paper presents the results of some experiments which is carried out to determine the properties of the silver sulfide electrode in water-organic mixed solvents. And it also shows the possibilities of studies on the selective solvation mechanism of silver ion by using the electrode. The halide ions and halide ion mixtures have been analyzed by potentionmetric titration using the electrode in 50% methanol system. As the result, the electrode response to silver ion in pure water and mixed solvent system is very similar.
Partial Molal Volumes of Cyclic Ethers in Aqueous Solutions
LEE, Shim-sung,KIM, Jae-sang,KWON,Soo-han 慶尙大學校 1986 論文集 Vol.25 No.2
수용액에서 고리형 에테르 화합물의 겉보기 몰랄부피(Φv)를 구하여 이로부터 분몰랄부피(V2u) 및 excess 몰랄부피(V20E)를 각기 구하였다. 도한 이를 비전해질의 관능기의 구성함으로부터 구한 V20값과 비교하였다. 이러한 결과들로부터 이 용액의 성질을 농도에 대한 Φv의 효과, V20E 및 사슬형 동종화합물과의 비교 등으로 고찰하였다. Φv는 용질농도의 증가에 대해 작은 음의 기울기를 가졌으며, 분자량이 증가할수록 그 값은 증가하였는데 이는 사슬형 동종화합물과 유사한 결과이나 그 값은 조금씩 작았다. 또한 V20E와 고리의 크기 효과 등으로부터 용질의 소수성 및 친수성기와 용매분자 사이의 구조적인 여러 용질-용매 상호작용이 있음을 알았다.
Potentiometric Analysis of Several Sulfur-Containing Compounds in Mixed Solutions
LEE, Shim-sung,KWON, Soo-han,KIM, Jae-sang 慶尙大學校 1985 論文集 Vol.24 No.2
50%물-메틸알콜 혼합용매에서 황을 포함하는 유기화합물인 시스테인, 티오아세트아미드 및 티오벤즈아미드를 황화은 전극을 사용하여 전위차적정업과 직접전위차법에 의해 정량하였다. 시스테인은 강염기 용액에서 적정이 불가능하였으나 직접전위차법에서는 반대로 더 좋운 감응을 보였다. 티오아세트아마드와 티오벤즈아미드는 모두 약산성, 중성 및 약염기성 용액에서 적정이 가능하였으나 강산 및 강염기 용액에서는 적정이 불가능 하였는데 이는 아미드 화합물의 tautomerization 및 은이온과의 비양론적인 반응에 기인된것으로 보인다.
Host-Guest Interactions Between Macrocycles and Methylsubstituted Anilinium Ions
Lee, Shim Sung,Jung, Jong Hwa,Chang, Duk Jin,Lee, Bu Yong,Kim, Si-Joong 慶尙大學校 기초과학연구소 1991 基礎科學硏究所報 Vol.7 No.-
The binding characteristics and analytical applications of anilinium ion complexes with 18-crown-6 were studied by polarography and NMR. First, the electrochemical reduction of the 10 species of mono and dimethylsubstituted anilinium ion complexes with 18-crown-6 as host in methanol are examined. The addition of 18-crown-6 to anilinium guest solution the polarographic waves remain well defined but shifted toward more negative potentials. indicating the complex formation. The values of formation constants, log K for 10 species of methylsubsituted anilinium ion complexes with 18-crown-6 varies form 2.7 to 4.8 in methanol at 25℃. The stability order of complexes for 18-crown-6 is anilinilum>4-methyl>3.4-dimethyl>3-methyl>3.5-dimethyl>2.4-dimethyl>2.5-dimethyl>2.3-dimethyl>2-methyl>2.6-dimethylanilinium ion. The steric hindrance shows significant effect. Second, Proton NMR was used to elucidate their interaction characteristics. From the results of so called NMR titration techniques. the behaviors of binding sites on complexation, and the stoichiometry and stability order of complex were obtained. And the later results show the satisfactory agreement with the quantitative values obtained by polarography. Finally, the individual determinations of anilinium ion mixtures were also accomplished by addition of 18-crown-6. In some mixtures of methyl or dimethylanilinium ions the reduction peaks of differential pulse method appeared into one unresolved wave attributed to the small difference of half-wave potential.ΔE_y2. In the presence of 18-crown-6, the polarographic waves were resolved into individual maxima because of the shift toward more negative direction by the difference of selectivity of anilinium ions with 18-crown-6. It may be concluded that quantitative analysis of methylanilinium ion mixture make possible because the half-wave potential shift by the selectivity difference due to the steric hindrance between methyl group and 18-crown-6 on complexation.
SOLUTION CHARACTERISTICS OF SOME PODANDS AS HOSTS FOR UNI-AND DIVALENT CATIONS
Lee, Shim Sung,Jung, Jong Hwa,Kim, Jineun,Shin, Young Kook,Kim, Si-Joong 慶尙大學校 기초과학연구소 1992 基礎科學硏究所報 Vol.8 No.-
The cation binding characteristics of 8 podands have been studied by NMR titration and potentiometry by using the Ag^+-ISE. We found that the most of podands form 1:1 complexes with cations examined and donor heteroatoms in aromatic group(nitrogen) and ether chain (sulfur) show the important roles to enhance the stability. but the effect of ether chain length was less important.
Lee, Shim Sung,Park, Sung Oh,Jung, Jong Hwa,Lee, Bu Yong,Kim, Si-Joong 慶尙大學校 기초과학연구소 1990 基礎科學硏究所報 Vol.6 No.-
The equivalent conductance of univalent cation (potassium, silver, thallium and ammonium) perchlorates in methanol containing 18-membered crown ethers, 18-crown-6(18C6) and 1,10-dithia-18-crown-6 (DT18C6) were measured at different temperatures. The equivalent conductances of ammonium perchlorate were increased by increasing content of DT18C6 exceptionally, due to more favorable solvations than complexations. From the equivalent conductance changes, the formation constants for 1:1 complexes have been determined, and the values of enthalpy and entropy changes have been calculated. The complexations of 18C6 and DT18C6 with the univalent cations under investigation are all exothermic and the ΔS values are all negative and no considerable differences around 50J/(K ㏖). The selectivity order of18C6 K^+>Tl^+>Ag^+>NH_4^+, while that of DT18C6 is Ag^+>Tl^+>NH_4^+>K^+ By sulfur substitutions in 18C6 result in significant decrease in stability, but the stability of Ag^+-DT18C6 complex are 10^4 times larger than those of K^+. This increase of stabilities for Ag^+-DT18C6 complex are primary due to the result of favorable exothemic heat of reaction between the polarizable soft cation and soft sulfur centers. In NMR experiment. the stepwise additions of cation perchlorates into crown ether solutions induced two major spectral changes. First, the resonance all shift down field and the cation induced shifts were linear up to 1:1 cation/crown ratio, above which no further changes were observed. On the basis of these results, it could be concluded that 1:1 complex is formed. Second, the magnitudes of cation induced shifts were different each other in same ligand. By addition of silver ion to the solution of DT18C6, the largest shift of proton peak near the sulfur atom was observed. These effects are also arisen from the results of covalent bonding between "soft-soft" interactions.
마크로고리 화합물을 운반체로 하는 액체막을 통한 이온의 운반에 관한 연구 (제2보). 유기액체막 운반체를 통한 수소이온의 운반
윤창주,이심성,김영희,김시중,Yoon, Chang-Ju,Lee, Shim-Sung,Kim, Young-Hee,Kim, Si-Joong 대한화학회 1984 대한화학회지 Vol.28 No.3
Dibenzo-18-crown-6(DBC) 및 dicyclohexyl-18-crown-6(DCC)를 이온의 운반체로 하는 여러 유기액체막을 통해 수소이온의 운반속도를 25$^{\circ}$C에서 측정하였다. 운반속도는 용매의 유전상수에 크게 영향을 받는데 이를 액체막 내부에서 이온 화학종이 가진 Born의 포텐셜 에너지 장벽을 들어 고찰하였다. 또한 음이온의 크기도 운반속도에 영향을 주었는데 이는 Born식으로 부터 새로이 유도된 이론적인 결과와 잘 일치하였다. The transport rates of $H^+$ ion by DBC and DCC as carrier molecules through organic liquid membranes were determined at 25$^{\circ}$C. The transport rates depend highly on the dielectric constants of membrane solvents and these results were discussed in terms of Born's potential energy barrier methods. The sizes of anions also affect the transport rates and these results were well explained theoreticlly by extended Born's equation.