Metal Cupferrate Complex에 관한 硏究 : 混合溶媒中에서 Ce(Ⅲ)-Cupferrate Complex의 安定度常數決定

申斗淳 단국대학교 1968 論文集 Vol.2 No.-

Al ion 의 Paper electrophoresis 에 關한 硏究

신두순,한만운,Shin, Doo-Soon,Han, Man-Un 대한화학회 1962 대한화학회지 Vol.6 No.1

電壓條件 永動時間 및 支持電解質溶液의 pH가 Al ion의 paper electrophoresis에 미치는 影響을 closed horizontal type의 泳動裝置를 써서 Michaelis buffer soln.으로 飽和시킨 paper strip에서 實驗的으로 檢討하였다. 그 結果 Al ion에 가장 適合한 pH, 電壓 및 泳動時間을 決定하였으며 pH=2.38에서 Al ion의 mobility는 $(1.004{\pm}0.0020){\times}10^{-4}\;cm^2\;sec^{-1}\;volt^{-1},\;Al(NO_3)_3\;soln.$의 isoelectric point는 pH=3.23 임을 알았다. Paper electrophoresis of aluminium ion was studied using a closed horizontal type apparatus. The optimal conditions of voltage, pH of electrolytic supporting solution and migration time were determined for the electrophoretic migration of the ion on the paper strip saturated by Michaelis buffer solution. The mobility of the ion and the isoelectric point of $Al(NO_3)_3$ solution were $(1.004{\pm}0.0020){\times}10^{-4}\;cm^2\;sec^{-1}\;volt^{-1}$ at pH = 2.38 and pH = 3.23 respectively.

${\beta}-Ag_3SI$ 단결정막 전극에 관한 연구

신두순,이선천,Sin Doo-Soon,Seon-Cheon Lee 대한화학회 1984 대한화학회지 Vol.28 No.2

${\beta}-Ag_3SI$의 단결정을 만들어 막전극으로의 응용을 살펴보았다. 그 결과 할로겐 이온들에 대해 감응함을 알았고, 분리용액법과 혼합용액법으로 할로겐 이온들에 대한 선택계수를 얻어 이론값과 비교검토 하였으며, 전위시간 곡선으로 부터 이 전극이 유리 전극기구에 의해 전도함을 알았고, 넓은 pH 범위에서 전위가 일정한 값을 가짐을 알았다. 한편 분석화학에의 응용을 살펴 본 결과 할로겐이온의 혼합용액에서 좋은 지시전극으로 사용할 수 있음을 알았다 The single crystal ion-selective electrode,$ {\beta}-Ag_3SI/PVC-THF $membrane electrode has showed a linear potential response to the activities of iodide ion (10-1${\sim}$10-7M). The $ {\beta}-Ag_3SI$ membrane electrode was compared with AgI/PVC-THF membrane and copper metal plate membrane electrodes. In order to measure the selectivity coefficient of the electrodes toward $Cl^-$ and $Br^-$, the separation and mixed solution method were employed. The potential-time curve was obtained by the usual immersion technique and pH effect was also examined. The orders of selectivity for $Br^-$, $Cl^-$ and stability of response time are ${\beta}-Ag_3SI/PVC-THF $membrane > AgI/PVC-THF membrane > copper metal plate membrane. These electrodes could be used as indicating electrodes in the potentiometric titration of a single halide and mixed halides with the standard solution of silver nitrate.

(Bakelite-A)-(2,2'-Bipyridine)-Ni(Ⅱ) 착물의 질산이온 선택성 막전극

신두순,정기원,Doo-Soon Shin,Chung Ki-Won 대한화학회 1992 대한화학회지 Vol.36 No.3

(Bakelite-A)-(2,2'-Bipyridine)-Ni(Ⅱ) Nitrate 착물 막전극이 질산 이온 선택성 막전극이 됨을 확인하였다. 이 막전극은 수소 이온이나 2가 및 3가 음이온에는 감응하지 아니하였고, 특히 이 막전극의 수명, 감응 농도 범위, 감응 시간 및 이온 선택성 등 전기 화학적 성질과 착물 리간드의 유성도 크기 사이의 관계를 비료 고찰하였고, 또한 막의 최적 조건의 착물조성 구조로부터 막의 이온교환 메카니즘을 고찰하였다. (Bakelite-A)-(2,2'-Bipyridine)-Ni(Ⅱ) Nitrate complexes were tested as ion exchanger for nitrate ion-selective electrode. The experimentally observed selectivity and electrode characteristics were relatively in good agreement with the exchanger lipophilicity in the membrane phase. Based on chemical composition, mechanisms for exchange with nitrate ion and internal electrical conduction were postulated. Analytical application to the determination of nitrate were studied.

용매성 유기분자와 니트로벤젠 및 그의 유도체와의 전하전이 착물에 관한 연구

신두순,김시중,Doo-Soon Shin,Si-Joong Kim 대한화학회 1973 대한화학회지 Vol.17 No.2

니트로 벤젠의 세가지 유도체, 즉 1.3.5-트리니트로벤젠(1.3.5-TNB), m-디니트로벤젠(m-DNB) 및 니트로벤젠(NB)등이 11종의 염기성 유기 용매 즉, ${\alpha}$-피콜린, 피리딘, 디메틸술포옥시드(DMSO), NN′-디메틸초산아미드(NN′-DMA), 테트라히드로퓨란(THF), 1,4-디옥산, 디에틸에테르, 시안화메틸, 프로필렌옥시드, 에피클로로히드린, 초산메틸등과 사염화탄소용액중에서 전하전이착물을 형성함을 자외선분광광도법에 의해 확인하고, 이들 전하전이착물의 안정도 상수를 결정하였다. Drago 와 Wayland 의 이중척도엔탈피식(double-scale-enthalpy)을 수정하여 $logK = E_AC_A+E_DC_D$식을 얻고, 이것을 써서 정전기적효과 $E_D$와 공유성효과 $C_D$값을 11종의 유기 용매에 대해 얻었다. 이 두 효과는 전하전이착물의 안정도 상수 K와 그리고 적외선 흡수 스펙트럼의 신축진동수변화 ${\Delta}{\nu}_C=O$에 영향을 주며, 특히 $C_D$ sms 안정도 상수에 비례하였고, 신축진동수변화 ${\Delta}{\nu}_{C=O}= 37.4-5.47E_D+12.1C_D$의 실험식을 얻었다. ${\pi}$결합을 가진 분자들이 전이착물을 이룰 때 정전기적효과와 공유성효과와 공유성효과가 모두 관여하며, 그밖에 결합하는 분자의 ${\pi}$궤도함수도 중요한 역할을 한다는 것을 알았다. The stability constants of the charge-transfer complexes formed between three derivatives of nitrobenzene, i.e., 1,3,5-trinitrobenzene, m-dinitrobenzene, nitrobenzene and eleven organic molecules such as $\alpha-picoline$, pyridine, dimethylsulfoxide, N, N'-dimethylacetamide, tetrahydrofurane, 1, 4-dioxane, diethyl ether, acetonitrile, propylene oxide, epichlorohydrine, and methyl acetate, have been determined by ultraviolet absorption spectroscopy in carbon tetrachloride solution at 25.0$^{\circ}C$. The parameters of the electrostatic effect ($E_D$) and covalent effect ($C_D$) for the eleven organic compounds have been calculated from the modified equation of the double-scale enthalpy,$logK = E_AC_A+E_DC_D$ and also the shift of C=O vibrational frequency in infrared spectra for N,N'-dimethylacetamide have been measured from the solutions of above organic compounds. The empirical equation, ${\Delta}{\nu}_{C=O} = 37.4-5.47E_D+12.1C_D$, related to the parameters and the frequency shift has been derived. It seems that the stabilities of the complexes principally depend on the covalent effect. Especially it is found that $\pi$ orbitals in molecules, in addition to the parameters, play the important role in forming the charge-transfer complexes.

(Phenol-Formaldehyde-Aniline 중합체)-Nickel(Ⅱ) Nitrate 구조에 관한 연구

신두순,박봉근,Doo Soon Shin,Bong Keun Park 대한화학회 1988 대한화학회지 Vol.32 No.5

In this study, an aniline modified Bakelite-A resine was synthesized by polymerizing phenol, formaldehyde and aniline. Structural properties of the polymer were examined by IR spectroscopy, elemental analysis and vapour pressure osmometry. By visible spectroscopy, it was found that nitrogens of amine groups in the polymer are strongly coordinated to Ni(Ⅱ). Also a nitrate ion-selective PVC membrane electrode based on the polymer-Ni(Ⅱ) complex as ion carrier was preparaed. The electrode gave a linear response with a Nernstian slope within the concentration range $10^{-1}$ M∼$10^{-4}$M $KNO_3$.

Metal Cupferrate Complex 에 關한 硏究 (第 2 報) Spectrophotometry 에 의한 Fe(III)-Cupferrate의 化學組成의 決定

김시중,신두순,Si-Joong Kim,Doo-Soon Shin 대한화학회 1963 대한화학회지 Vol.7 No.4

Spectrophotometry에 의한 몰比法, 運續變化法 및 傾科比法으로 chloroform phase에 存在하는 Fe(III)-cupferrate의 組成을 決定하였는데, 그 황化合物은 325m$\mu$에서와 385m$\mu$에서 모두 $FeCupf_3^인 化學式을 갖는 것이었다. Fe (III)-cupferrate composition in chloroform phase was determined by molar ratio method, continuous variation method and slope ratio method spectrophotometrically at 325m$\mu$ and 385m$\mu$ wavelength. At both wavelength, compositions of the complex were Fe$Cupf_3$.

Metal Cupferrate Complex 에 關한 硏究 (第 3 報) $H_2O$-Chloroform 系에서의 Hydrogen Cupferrate 의 分配係數에 關한 硏究

김시중,신두순,Si-Joong Kim,Doo-Soon Shin 대한화학회 1963 대한화학회지 Vol.7 No.4

$H_2O$-chloroform系에서의 hydrogen cupferrate의 分配係數와 水溶液相의 pH, 이온强度 및 cupferron의 濃度와의 關係를 살폈는데, 分配係數는 pH(1.50∼3.00사이)와 이온强度(0.1∼2.0사이)에는 無關하지만 cupferron의 濃度가 커질수록 分配係數는 增加했으며, 熱力學的인 分配係數의 完全한 값으로 120.0이란 새로운 값을 얻었다. 한편 cupferron의 濃度가 커짐에 따라 分配係數가 增加하는 까닭은 chloroform相에 monomer로서의 HCup. 의 活動度의 감소로 간주하고, chloroform相에서의 HCup. 의 濃度와 chloroform相에서의 HCup. 의 活動度係數와의 關係를 表示하는 實驗式 $-logf_{CHCl3}=0.1285C_{CHCl3}+{7.775C^2}_{CHCl3}$를 얻었으며, 이 式은 HCup. 의 chloroform 溶液 0.1mole/l order 以下의 濃度에서 大端히 잘 맞는다. The distribution ratio of hydrogen cupferrate in $H_2O-CHCl_3$ system was considered as a function of pH ($HClO_4$), ionic strength ($NaClO_4$), and cupferron concentration in perchloric acid media, respectively. The values were independent upon pH (1.50∼3.00 range) and ionic strength (0.1∼2.00 range), but they increased as increasing the cupferron concentration in the acidic media. At the infinite dilution, the thermodynamic distribution ratio between chloroform and aqueous phase was 120. 0. The activity coefficients of hydrogen cupferrate in chloroform solution were determined by the distribution ratio. This activity coefficient may be calculated by using the empirical equation, $-log\;f_{CHCl3}=0.1285C_{CHCl3}+{7.775C^2}_{CHCl3}$ which represents the experimental data quite well for the solution in 0.1 mole/l order of hydrogen cupferrate concentration.

Dimethyl Sulfoxide 에서의 용매와 용질사이의 상호작용

김시중,신두순 고려대학교 공학기술연구소 1970 고려대학교 생산기술연구소 연구보고 Vol.1 No.1

Solute-solvent interactions in dimethy sulfoxide(DMSO), a polar aprotic solvent, were studied. The cryoscopic constant of the solvent, 4.40±0.01℃/molal, was determined, and also the osmotic and activity coefficients of ten electrolytes and six nonelectrolytes in the solvent were determined by freezing point depression method. The coethcients were compared and discussed with those in water and ethylene carbonate. As the results, the behaviors of nonelectrolytes in DMSO were alike them in aqueous solutions, and the solvent-structure-breaking effects of cations were in the order of Li^+$gt;Na^+$gt;K^+$gt;Cs^+NH₄^+$gt; (C₂H_5)₄N^+]+(CH₃)₃ N-CH₂-CH₂-N(CH₃)₃^+. It was observed that the larger iodide ion was highly polarized than the smaller chloride ion, and ammonium ion was not solvated through hydrogen bond by DMSO. It was concluded that DMSO has the behavior of the normal polar liquid.

Bakelite A-Ni(II) 착물의 질산이온 선택성 막전극

김환기,신두순,Kim, Hwan-Ki,Shin, Doo-Soon 대한화학회 1987 대한화학회지 Vol.31 No.3

Amine기를 가진 Bakelite A와 Ni(II) 사이의 착물을 이용한 ${NO_3}^-$이온 선택성 막전극을 만들었다. 이 막전극은 $H^+$ 이온 및 2가 3가 음이온에는 감응하지 않으며, 특히 이 막전극의 재현성, 감응시간 및 이온선택성등 전기화학적 성질을 조사하여 다른 실용화된 막전극과 비교 고찰하였으며 분석화학에의 응용을 고찰하였다. A nitrate ion-selective PVC membrane electrode based on ammonia modified bakelite A-Ni$(NO_3)_2$ complex as ion exchanger was prepared. The electrode gave a linear response with a Nernstian slope of 60mV per decade within the concentration range $1{\sim}10^{-4}$ M $KNO_3$ but nonresponse to hydrogen ion and multivalent anions. The selectivity, response time and life time of the electrode were investigated and it was found that the electrode exhibited good selectivity for four univalent anions ($Cl^-,\;Br^-,\;I^-,\;{ClO_4}^-$). Analytical application to the determination of nitrate were also studied.