1-(2-pyridylazo)-2-naphthol을 킬레이트제로 사용한 Co(Ⅱ)의 염석추출법적 정량

서무룡,하광수,장미경 경상대학교 환경보전연구소 1996 環境保全硏究所報 Vol.4 No.1

As a part of analytical application of 1-(2-pyridylazo)-2-naphthol(PAN), the extraction method with salting-out technique was applied to the determination of cobalt(Ⅱ) ion in aqueous solution. After cobalt(Ⅱ) was extracted from the buffered aqueous solution into acetonitrile layer as a Co(Ⅱ)-PAN chelate by salting-out technique, the visible absorption spectrum was recorded. In this experiment, ammonium sulfate was used as a salting-out reagent. The effects of amount of ammonium sulfate and extracting reagent, PAN on the extractability, the relationship between pH of the aqueous phase and extractability of Co(Ⅱ)-PAN chelate, and the calibration curves for the determination of Co(Ⅱ) by spectrophotometry and differential pulse polarograph have been evaluated. The effects of diverse ion on the determination of Co(Ⅱ) by these methods have also been investigated.

아세토니트릴 용액속에서 Ni(II)-1-(2-thiazolylazo)-2-naphthol 착물의 전기화학적 환원

서무룡 慶尙大學校 1988 論文集 Vol.27 No.1

반양자성 용매인 아세토니트릴 용액에서 Nickel-1-(2-thiazolylazo)-2-naphthol 착물의 전기화학적 환원을 직류 폴라로그래프법, 일정전위 전기분해법 및 자외선 분광광도법으로 수행하였다. Ni(II)-(TAN)2 착물은 아세토니트릴 용매 속에서 3단계의 환원과정을 거치며 제1단계에서는 비교적 안정한 anion radical 이 생성되는 1전자 환원 단계이며 제2단계에서는 dianion이 생성되는 1전자 환원단계로 생각된다. 그리고 최종 환원생성물은 amine 화합물이 될 것으로 추측된다. 모든 환원단계는 화산지배적이었으며 제1단계의 가역성은 비교적 좋았으나 제2단계의 가역성은 비교적 나쁜편이었다.

$NH_4^+$ 정량을 위한 Amperometric Enzyme Electrode

서무룡,김재상,이심성,배준웅,이흥락,박태명,Moo Lyong Seo,Jae Sang Kim,Shim Sung Lee,Zun Ung Bae,Heung Lark Lee,Tae Myung Park 대한화학회 1993 대한화학회지 Vol.37 No.11

Immobilon-AV Affinity membrane에 L-glutamate dehydrogenase를 고정하여 유리질 탄소전극에 부착시킨 전극을 사용하여 암모니아를 전류법으로 정량하였다. 이때 환원형의 NADH가 $NAD^+$로 산화될 때 전류를 +1.0 volt vs. Ag/AgCl에서 측정하였다. 효소 고정화된 membrane을 부착시킨 전극의 감응 특성은 다음과 같다. 곧 직선 감응 농도 범위는 $4.0\;{\times}\;10^{-5}\;{\sim}\;4.0\;{\times}\;10^{-4}$ M이었으며, 정량한계는 2.0 ${\times}\;10^{-6}$ M이었다. 또한 감응 시간은 2분이었으며 효소 고정화된 막의 최적 pH와 수명은 각각 pH 7.3∼7.6 (Dulbecco's buffer 용액)과 25일이었다. 그리고 다른 생리활성 물질의 방해는 없었다. Enzyme electrodes for amperometric measurement of ammonia was prepared by immobilization of L-glutamate dehydrogenase on an Immobilon-AV Affinity membrane and attachment to a glassy carbon electrode. Reduced nicotinamide adenine dinucleotide (NADH) was used as the electroactive species. The electrochemical oxidation of NADH was monitored at +1.0 volt vs. Ag/AgCl. Response was linear from $4.0\;{\times}\;10^{-5}\;to\;4.0\;{\times}\;10^{-4}$ M. The detection limit was 2.0 ${\times}\;10^{-6}$ M. Response time, the optimum pH and life time of enzyme immobilized membrane were 2 min, pH 7.3∼7.6 (Dulbecco's buffer solution) and about 25 days respectively. When the enzyme electrode was applied to the $NH_4^+$ determination with amperometric method, other physiological materials had no interference.

아세토니트릴 용매 중에서 Copper-1,5,9,13-Tetrathiacyclohexadecane착물의 전기화학적 거동과 그 분석적 응용

서무룡,이부영,최명자,배준웅,박태명,Moo-Lyong Seo,Bu-Yong Lee,Myung-Ja Choi,Bae Jun Ung,Park Tae Myeong 대한화학회 1992 대한화학회지 Vol.36 No.3

비수용매인 아세토니트릴 중에서 Cu(Ⅱ)와 1,5,9,13-tetrathiacyclohexadecane[16-ane-$S_4$]의 착물에 대한 전기화학적 거동으로서 직류폴라로그램과 미분펄스폴라로그램으로부터 환원전류의 유형과 가역성을 조사하고, 이들 화합물의 분석적 응용으로서 수용액에 있는 Cu(Ⅱ) 이온을 염석추출법으로 정량하였다. 또한 아세토니트릴 용매 중에서 착물의 안정도 상수를 구하고, 분석적 응용으로 수용액 중의 Cu(Ⅱ)를 염석추출법으로 정량하기 위하여 추출조건, 곧 킬레이트와 염석제의 효과, pH 범위를 구하고 또한 Cu(Ⅱ) 이온을 정량하는데 있어서의 검량성과 공존이온 효과를 조사하였다. 실험결과로부터 환원 과정은 비가역적이었으며 환원전류는 확산지배적임을 알았다. 또한 아세토닐트릴 용매 중에서 착물의 log $K_f$의 값은 3.51이었으며 Cu(Ⅱ) 이온을 정량하는데 있어 공존하는 이온의 영향을 별로 받지 않아 선택성이 좋았으며 본 실험방법에 의한 정량한계는 60ppb 이었다. The electrochemical behaviors and analytical application of copper-1,5,9,13-tetrathiacyclohexadecane[16-ane-$S_4$] complex in acetonitrile(AN) solution have been investigated by the use of DC polarography and differential pulse polarography. Thus the formation constant of copper complex was $10^{3.51}$. Copper (Ⅱ) ion was found to form complex of 1-to-1 composition with [16-ane-$S_4$]. In addition, reduction step was irreversible and the reduction current was diffusion controlled. And the effect of concentration of the salting-out reagent and chelating agent and pH of aqueous phase on the determination of copper (Ⅱ) was investigated and diverse ion effect was discussed. By salting-out extraction technique, we can be determined until the concentration of copper (Ⅱ) of 60 ppb.

5원자 헤테로고리 화합물을 이용한 $Mg^{2+}$의 정량

서무룡,이심성,김재상,박태명,Seo, Moo Lyong,Lee, Shim Sung,Kim, Jae Sang,Park, Tae Myung 한국분석과학회 1993 분석과학 Vol.6 No.3

5원자 헤테로고리를 포함하는 열린고리형의 ionophore를 합성하였다. 이 때 합성한 ionophore를 착화제로 이용하여 수용액 중의 $Mg^{2+}$을 염석추출법으로 추출하여 원자 흡광 광도법으로 정량하였다. Acetate 완충용액으로 pH를 4.2로 조절한 $Mg^{2+}$를 포함하는 수용액에 ionophore-AN 용액을 넣어 $Mg^{2+}$-ionophore 착물을 형성시킨 다음, 염석제를 첨가하여 유기층으로 추출하고, 유기층의 착물의 흡광도를 원자 흡광 광도계로서 측정하여 $Mg^{2+}$를 정량하였다. 최적 추출 조건을 조사해 본 결과, 최적 pH는 2.5~5.0이었으며, 염석제인 황산암모늄[$(NH_4)_2SO_4$]의 양은 5g 이상이면 정량적으로 추출되었다. 또한 $Mg^{2+}$과 ionophore의 착물 조성비는 1:2이었다. $Mg^{2+}$의 정량범위는 0.24ppm~2.4ppm이었으며 $Ca^{2+}$이온 및 EDTA의 방해효과가 크게 나타났다. Ionophore, which contains 5-membered heterocyclic compound, was prepared. $Mg^{2+}$ was determined by salting-out technique using ionophore as a chelating reagent. After $Mg^{2+}$ was extracted into the acetonitrile layer as a Mg-$(Ionophore)_2$ complex from acetate buffered aqueous solution by salting-out extraction technique, absorbance of complex was recorded by atomic absorption spectrophotometry. Optimum pH was between 2.5 and 5.0 for extraction and 1:2([$Mg^{2+}$]/[ionophore]) complex were formed. The range of detection was 0.24ppm~2.4ppm and $Ca^{2+}$ and EDTA were interfered in the determination of $Mg^{2+}$.

염석추출법에 의한 칼륨(Ⅰ)의 미분펄스폴라로그래프법적 정량

서무룡,이심성,박태명 慶尙大學校 기초과학연구소 1991 基礎科學硏究所報 Vol.7 No.-

비수용매인 아세토니트릴과 거대고리화합물인 dibenzo-18-crown-6(DB18C6)의 분석적 응용으로서 수용액에 있는 K(I) 이온을 염석추출법으로 정량하였다. 곧 borax 완충용액으로 수용액의 pH를 9.2로 조절하고, DB18C6를 포함하는 아세토니트릴용액을 넣어 K(I)-DB18C6 착물을 형성시킨 다음 염석추출법으로 추출분리하고 유기용매층의 K(I)-DB18C6 착물의 미분 펄스폴라로그램을 측정하였다. 이 때 -1.97volt vs. Ag/Ag^+ [0.1M AgNO_3(AN)]에서 피이크 전류를 측정하여 추출조건, 곧 적당한 염석제의 양, pH 범위, 적당한 킬레이트의 양을 구하고 K(I) 이온을 정량하는데 있어서의 정량성과 공존이온 효과를 조사하였다. 실험결과로부터 공존하는 이온의 영향을 별로 받지 않아 선택성이 좋았으며 본 실험방법에 의한 정량한계는 0.1ppm이었다. As one of the analytical application of dibenzo-18-crown-6 (DB18C6) and aprotic solvent, the extraction method with a salting-out technique was applied for the determination of potassium (I) in the aqueous solution. After potassium(I) was extracted into the acetonitrile (AN) layer as a K(I)-DB18C6 complex from the aqueous solution of borax buffer at pH 9.2 by the salting-out technique, the differential pulse polarograms for the K(I)-DB18C6 complex was recorded. In this case magnesium chloride was used as a salting-out reagent. The peak potential of the K(I)-DB18C6 complex in the organic phase was -1.97 volt vs. Ag/Ag^+[0.1M Ag/AgNO_3(in AN)]. The effect of concentration of the salting-out reagent and chelating reagent and pH of aqueous phase on the extractability were investigated. And the calibration curve for the determination of potassium (I) was obtained and diverse ion effect was discussed. By salting-out extraction technique, we can be determined until the concentration of potassium (I) of 0.1 ppm.

아세토니트릴 용매 중에 1-(2-Thiazolylazo)-2-naphthol의 전기화학적 거동

서무룡,박태영 慶尙大學校 1990 論文集 Vol.29 No.1

The electrochemical behaviors of l-(2-thiazolylazo)-2-naphthol(TAN) in acetonitrile(AN) solution were studied by cyclic voltammetry, controlled potential coulometry. In order to investigate the type of reducion current at each reduction step, dependence of limiting current on the scan rates and concentration of TAN have been examined. And in order to investigate the reduction mechanism of TAN in AN solution, the effect of proton donor such as water on cyclic voltammogram of TAN and the revrisbillty of each reduction step have been studied. And we measured the number of the electrons involving in each reduction step by controlled potential coulometry. The electrochemical reduction of TAN in AN solution occurs in four one-electron steps. The product of the first and third electron transfer to the dianion is followed by a chemical reaction producing a protonated species which is oxidizable to the parent compound. The product of the fourth electron transfer also produces the corresponding amine compounds.

1-(-2 Thiazolylazo)-2-naphthol을 킬레이트제로 사용한 Cu(Ⅱ)의 염석추출법적 정량

서무룡,박태명 국립경상대학교 공과대학 부설 첨단소재연구소 1991 尖端素材 Vol.1 No.-

As a part of analytical application of 1-(2-thiazolylazo)-2-naphthol (TAN), the extraction method with salting-out tachnique was employed for the determination of Cu(II) ion acetonitrile-water solution. After the extraction of Cu(II) ion into acetonitrile layer as a Cu(II)-TAN complex from the buffered aqueous solution, the visible absorption spectra and differential polarograms were recorded. In this experiment, ammonium sulfate was used as a salting-out agent. Not only the relationship between pH of aqueous phase and extractabilities of TAN chelate, but also the effect of concentraction of ammonium sulfate and chelating agent(TAN) on extractability have been evaluted. And the calibration curves and diverse ion effect for the determination of Cu(II) ion have been investigated by spectrophotometric and polarographic method.

[화학]5원자 헤테로고리 화합물을 이용한 Mg²+의 정량

서무룡(Moo Lyong Seo),이심성(Shim Sung Lee),김재상(Jae Sang Kim),박태명(Tae Myung Park) 한국분석과학회 1993 분석과학 Vol.6 No.3

아세토니트릴 溶媒중에서 1-(2-Thiazolylazo)-2-naphthol 의 폴라로그래프적 거동

배준웅,서무룡,Zun Ung Bae,Moo Lyong Seo 대한화학회 1988 대한화학회지 Vol.32 No.1

반양성자성 용매인 아세토니트릴 중에서 1-(2-thiazolylazo)-2-naphthol (이하 TAN으로 줄임)의 폴라로그래프적 성질을 조사하였다. 직류폴라로그램으로부터 환원전류의 유형과 양성자 주게 인물의 첨가에 따른 영향을 검토하였다. 그리고 환원반응에 관여한 전자수는 정전위분해법으로 구하였다. 또 일정전위전해생성물의 UV-Vis Spectrum과 IR-Spectrum으로부터 전해생성물을 확인하였다. 이상의 실험결과로부터 아세토니트릴 용매중에서 TAN은 1전자 4단계의 환원과정을 거쳐 최종적으로 아민화합물이 됨을 알았다. 또 각 환원과정은 모두 가역적이었으며, 각 단계의 환원전류는 확산지배적이었다. The Polarographic behavior of 1-(2-thiazolylazo)-2-naphthol (TAN) in acetonitrile solution was studied. From the DC polarograms of TAN in acetonitrile solution, the type of reduction current and the effect of proton donor such as water have been investigated. In order to explain the reduction mechanism, the number of the electrons for each reduction step was measured by controlled potential coulometric technique and the electrolysis products were identified by UV-Vis spectroscopy and IR spectroscopy. The results were shown that the reduction of TAN in acetonitrile solution occurred with four-one electron steps. In addition, each reduction step was considerably reversible and the reduction current was diffusion controlled.