Methylthymolblue(MTB)에 依한 Ti(IV)의 吸光光度分析

박두원,이종남,Doo Won Park,Chong Nam Lee 대한화학회 1963 대한화학회지 Vol.7 No.4

A method of the colorimetric determination of titanium has been developed, based on the fact (IV) forms a stable blue complex with methylthymolblue(MTB) which is suitable for spectrophotometric determination of titanium in the concentration range of 0.2 to 22 $\mu$g per ml as $TiO_2$. The determination was carried out in the solution of pH range of 2.6 to 3.6, and the absorbancy of complex was at 600m$\mu$ with Coleman spectrophotometer. Titanium forms a 1:1 complex with MTB, which has a molar absorptivity, $1.1{\times}10^4$ at 600m\mu$. The effects of hydrogen ion concentration, reagent concentration, stability of complex, and hydrolysis were studied. Most of cations do not interfere seriously; however, many of anions such as oxalate, citrate, phosphate, chloride interfere in this determination.

물아닌 용매속에서의 요오드의 전기화학적 환원

박두원,최원형,Park Doo Won,Choi Won Hyung 대한화학회 1975 대한화학회지 Vol.19 No.2

요오드의 전기화학적 환원과정을 여러가지 특성을 가진 물아닌 용매 속에서 polarography, chronopotentiometry, cyclic voltammetry, controlled potential coulometry 등의 전기분석적 방법을 이용하여 적하수은전극, 백금, 금 및 백금아말감전극등을 사용하여 상세히 조사하였다. 메탄올, 에탄올, 이소프로판올 및 피리딘과 같은 양쪽성 용매 속에서는 $I_2{\longrightarrow}I^-$의 I단계 환원과정을 거치며 아세톤, 디메틸포름아미드, 메틸에틸케톤, 디메틸술폭시드, 아세토니릴과 같은 반양성자 용매속에서는 $I_2{\longrightarrow}I_3^-{\longrightarrow}I^-$의 2단계 환원과정을 거쳤다. 적하수은전극, 고인 수은전극, 백금, 금 그리고 백금아말감전극등 전극조건을 다르게 하였을 때에도 $^'I_2$의 환원과정은 같았으며 사용한 모든 전극에서 확산지배적이었다. 반양성자용매에 물을 첨가하여 그 영향을 걸토한 결과 물의 첨가량이 약 $50v/v{\%}$ 이상일때 2단계의 환원과정이 1단계의 환원과정으로 줄어들었다. 또 chronopotentiometric data와 Send의 식으로부터 계산한 각 용매 속에서의 요오드의 확산계수는 $D_{I2}^{AN}=5.96{\times}10^{-6}cm^2/sec,\;D_{13-}^{AN}=9.63{\times}10^{-6}cm^2/sec,\;D_{I2}^{MeOH}=5.30{\times}10^{-6}cm^2/sec$이였다. 전기화학적 환원과정의 stoichiometry를 알아 보고저 controlled potential coulometry로 使用하였으며, 얻은 생성물은 은법적정으로 확인 및 정량하였다. The electrochemical reduction of iodine in non-aqueous media have been studied by polarography, chronopotentiometry, cyclic voltammetry and controlled potential coulometry at dropping mercury electrode and platinum, gold and amalgamated platium electrodes. In amphiprotic solvents such as methanol, ethanol, isopropanol and pyridine, iodine were reduced to iodide ions via one step reduction involving 1 electron and in aprotic solvents such as acetonitrile, dimethylformamide and dimethylsulfoxide via two step reduction involving all 3 electrons. The reductions of iodine give well defined polarograms at dropping mercury electrode and irreversible chronopotentiograms at platinum electrode, but less defined irreversible chronopotentiograms at gold and amalgamated platinum electrodes, those are all diffusion controlled. The diffusion coefficients of iodine in various solvents were estimated from the chronopotentiometric data and Sand equation.

有機溶媒中에서 옥신, 아닐린 및 피라딘을 포함하는 텅스텐錯物의 合成

박두원,오대섭,Doo Won Park,Tae Sub O 대한화학회 1975 대한화학회지 Vol.19 No.6

六鹽化 텅스텐(WCl6)을 여러가지 有機溶媒 속에서 리간드로서 옥신과 아닐린 및 피리딘을 각각 반응시켜서 不溶性인 텅스텐 錯化合物을 合成하였다. Dichloromethane과 DMF와 같이 서로 성질이 다른 溶媒속에서의 옥신 錯物을 合成해 보면 溶媒에 따라서 다른 錯物이 生成되었다. 아닐린의 錯物은 dichloromethane溶媒에서 合成되고 피리딘의 錯物은 아세톤溶液에서 合成되었다. 元素分析과 赤外線 스펙트럼 및 熱分析結果 錯化合物들은 組成이$[WCl_2(Hox)_2]와\;[WO_2(Ox)_2],[WCl_3A_3]\;및\;[WO_2ClPy]$임을 알아냈다. The insoluble tungsten complexes with 8-hydroxy quinoline (oxine=Hox), aniline (A), and pyridine(Py) in several organic solvents have been synthesized. Using the different solvents with oxine, two different complexes have been synthesized in dichloromethane and dimethylformamide(DMF), respectively. Only one kind of complex has been synthesized with aniline in dichloromethane and with pyridine in acetone. The complexes may be formulated as $WCl_2(Hox)_2,\;[WO_2(Ox_2)],\;[WCl_3A_3],\;and\;[WO_2ClPy]$ by the results of elemental analysis, infrared spectral data, and thermogravimetric analysis.

Acetonitrile에서의 Mg-EBT$^-$ 착물에 관한 연구

박두원,최원형,이흥락,Doo Won Park,Won Hyung Choi,Heung Lark Lee 대한화학회 1973 대한화학회지 Vol.17 No.4

Mg(II)과 Eriochrome Black T가 Acetonitrile용액속에서 반응하여 만든 착물을 일정한 이온의 세기와 일정한 수소이온농도에서 분광광도법으로 연구했다. 유리전극과 Ag/0.1 M $AgNO_3$기준전극쌍을 써서 Acetonitrile 용액속에서 측정한 pH 값은 표준완충용액으로 검정했으며 그 결과는 다음과 같다. Picric acid$-10^{-3}M$ tetramethylammonium picrate 완충용액에 있어서는 은기준전극에 대한 유리 전극의 $25^{\circ}C$에서의 전위는 $E_{glass}=716+59.1logA_{H+}[mv]$이고, 1,3-Diphenylguanidine$-3{\times}10^{-3}M $1,3-diphenylguanidine perchlorate 완충용액에서는 $E_{glass}=1,193+59.1 logA_{H+}[mv]$이다. 리간드 Eriochrome Black T의 산해리지수$ pK_{H,EBT-}$는 9.1이었으며, 반응 $H_mEBT^{(3-m)-} + Mg^{2+} {\leftrightarrow}MgEBT^{-} + mH^{+}$ 으로 생성된 착물 $MgEBT^{-}$의 조건안정도상수를 log-ratio method으로 구하니 m이 2일때는 $logK_{MgEBT^-} + 3.97$이고, m이 1일 때는 $logK_{MgEBT^-} + 5.02$이었다. 착물의 조성은 수용액에서 Schwarzenbach씨 등이 구한 결과와 같이 비수용매 Acetonitrile속에서도 한 종류의 착물 $MgEBT^{-}$만이 생성됨을 알 수 있었다. Complex formation of magnesium-Eriochrome Black T at constant ionic strength and hydrogen ion concentration have been studied spectrophotometrically in acetonitrile solution. The measured pH values were calibrated with standard buffer solutions by using a glass electrode Ag/0.1M $AgNO_3$ reference electrode couple. The results are as follows;$E_{glass}=716+59.1\;logA_{H+}[mv]$+(in mv. vs. Ag reference electrode for picric acid $-10^{-3}M$ tetramethylammonium picrate buffer), and $E_{glass}=1,193+59.1\;logA_{H+}[mv]$(in mv. vs. Ag reference electrode for 1,3-diphenylguanidine $-3{\times}10^{-3}M $ 1,3-diphenylguanidine perchlorate buffer). The acid dissociation exponent of ligand, $ pK_{H,EBT-}$was found to be 9.1. The conditional formation constants of $MgEBT^{-}$complex by log-ratio method were 3.97 (when m = 2) and 5.02 (when m = 1) as $log K_n$, respectively, for the reaction of $H_mEBT^{(3-m)-} + Mg^{2+} {\leftrightarrow}MgEBT^{-} + mH^{+}$. The present study showed that$MgEBT^{-}$ has the composition of 1:1 which agrees with the result of Schwarzenbach et al. in aqueous solution.

Ethylenediamine Tetrabutylacetate (EDTA butyl ester)에 依한 Co의 吸光光度分析

박두원,Park, Doo-Won 대한화학회 1966 대한화학회지 Vol.10 No.1

A new method of cobalt determination has been developed by employing ethylenediamine tetrabutyl acetate(EDTA-butyl ester) synthesized from EDTA and Butyl alcohol. The synthesized EDTA ester dissolved in butyl alcohol extracts various metal ions from aqueous solutions. Cobaltous ion extracted into organic phase containing EDTA ester to form Co (II)-EDTA butyl ester complex is back extracted into alkaline aqueous phase forming a stable pink colored complex of Co (III). The optimum condition for spectrophotometric determination of cobalt via the new complex has been established. The absorption peak occurs at 540$m{\mu}$ and Beer's law was obeyed over the concentration range of 0∼50 ${\mu}g/ml$ of cobalt.

추출폴라로그래프법에 의한 Cr (Ⅵ) 의 정량

박두원,배준웅,Park Doo Won,Bae Zun Ung 대한화학회 1976 대한화학회지 Vol.20 No.6

The extraction-polarographic method applied to the determination of micro amount of chromium (Ⅵ). Chromium(Ⅵ) was extracted into methylisobuthylketone(MIBK) layer containing diethyldithiocarbamate(DDTC) as Cr(Ⅲ)-DDTC complex from acetate buffered aqueous, solution of pH 5.4 and the direct current polarogram for the extract was recorded after addition of sodium perchlorate as supporting electrolyte. The reduction current was diffusion controlled. And the half wave potential of this reduction wave was -0.81 volt vs. SCE. The diffusion current was proportional to the chromium concentraticn in aqueous solution in the range of 8∼160 ppm. And the chromium(Ⅵ) could be selectively determined in the presence of chromium(Ⅲ), since the chromium(Ⅲ) did not interfere up to twice the amount of chromium(Ⅵ). Many of other metals such as Mn(Ⅱ), Cu(Ⅲ), Zn(Ⅱ), Mg(Ⅱ), Ni(Ⅱ) and Ag(Ⅰ) were found to have no effect even when present in 1000 times the amount of chromium (Ⅵ). 추출폴라로그래프법을 이용하여 6가 크롬을 정량하는 방법에 대하여 검토하였다. 수용액중의 Cr(Ⅵ)을 초산완충용액 (pH = 5.4)에서 diethyldithiocarbamate를 킬레이트제로 사용하여 methylisobuthylketone용매로 추출하여, 이 추출액에 지지전해제로 sodium perchlorate를 넣어 직류 폴라로그램을 얻었다. 이 추출착물의 환원파는 확산지배적이었으며, 이 파의 반파전위는 -0.81 volts vs. SCE 였다. 이 환원파의 확산전류는 Cr(Ⅵ)의 양이 8 ppm 에서 160 ppm 까지의 농도범위에서 Cr(Ⅵ)의 농도에 비례하였다. 더욱이 2배량의 Cr(Ⅲ)이 공존해도 Cr(Ⅵ)의 정량에 별 영향이 없으므로 Cr(Ⅲ)와 Cr(Ⅵ)의 분별정량이 가능하며 또 Mn(Ⅱ), Cu(Ⅱ), Zn(Ⅱ), Ag(Ⅰ), Mg(Ⅱ), Ni(Ⅱ) 등이 약 1000배 정도 공존하여도 Cr(Ⅵ)의 정량에는 별 영향이 없었다

Silver Halide의 均一沈澱法에 關한 硏究

박두원,오상오,Park, Doo-Won,Oh, Sang O. 대한화학회 1962 대한화학회지 Vol.6 No.2

The silver halide precipitate tends to separate in curdy form of flocculated colloid when it is precipitated by direct mixing of reactant solutions. This type of precipitate has a great tendency to adsorb or occlude foreign ions in the solution.When silver halide in precipitated from homogeneous solution using the slow hydrolysis of Alkyl halide or Ally halide, the precipitate becomes dense, filterable and uniform in particle size which is very advantageous in gravimetric analysis.We found that silver halide precipitates obtained from homogeneous solution with hydrogen halide formed by the hydrolysis of alkyl halide do not give the color change with fluorescein as adsorption indicater, while silver halide precipitates obtained by direct mixing method give sharply pink color which appear to be uniformly distributed through the solution in silver ion excess.

고층건물에서의 피난 엘리베이터의 효율성에 관한 연구

박두원(Park, Doo-Won),노삼규(Roh, Sam-Kew),김종훈(Kim, Jong-Hoon),김운형(Kim, Woon-Hyung) 한국화재소방학회 2006 한국화재소방학회 학술대회 논문집 Vol.2006 No.춘계

고층건물에서의 피난 엘리베이터의 효율성

박두원(Park, Doo-Won),노삼규(Roh, Sam-Kew) 한국화재소방학회 2007 한국화재소방학회 학술대회 논문집 Vol.2007 No.춘계

경주 방사성 폐기물 처분장 주변 논에 대한 방사성 요오드와 테크네튬의 토양-쌀알 전이계수

최용호,임광묵,전인,박두원,금동권,한문희,Choi, Yong-Ho,Lim, Kwang-Muk,Jun, In,Park, Doo-Won,Keum, Dong-Kwon,Han, Moon-Hee 한국방사성폐기물학회 2010 방사성폐기물학회지 Vol.8 No.4

Radiotracer experiments were performed over two years using pot cultures in a greenhouse to investigate soil-torice seeds transfer factors of radioiodine and technetium for paddy fields around the radioactive-waste disposal site in Gyeongju. Before transplanting rice seedlings, the top about 20 cm soils were thoroughly mixed with $^{125}I$ (2007) and $^{99}Tc$ (2008), and the pots were irrigated to simulate flooded rice fields. Transfer factors were determined as the ratios of the radionuclide concentrations in dry rice seeds (brown rice) to those in dry soils. Transfer factors of radioiodine and technetium were in the ranges of $1.1{\times}10^{-3}{\sim}6.4{\times}10^{-3}$ (three soils) and $5.4{\times}10^{-4}{\sim}2.5{\times}10^{-3}$ (four soils), respectively, for different soils. It seems that the differences in the clay content among soils played a more important role for such variations than those in the organic matter content and pH. As the representative values of radioiodine and technetium transfer factors for rice seeds, $2.9{\times}10^{-3}$ and $1.1{\times}10^{-3}$, respectively, were proposed. In order to obtain more highly representative values in the future, investigations for the sites of interest need to be carried out continuously.