• Bulletin of the Korean Chemical Society
• /
• 제27권9호
• /
• pp.1329-1334
• /
• 2006

The electrochemical reduction of coumarin, 7-acetoxy-4-methyl coumarin (AMC), and 7-acetoxy-4-bromomethyl coumarin (ABMC), in 0.1 M tetraethyl ammonium perchlorate/acetonitrile solution was carried out by direct current, differential pulse polarography, cyclic voltammetry, and controlled potential coulometry. The electrochemical reduction of ABMC was proceeded through three steps of electron transfer coupled with the chemical reactions. The color of solution was changed to yellow when the carbonyl group was reduced during 2nd step (-1.8 volts) and independented with cleavage of bromo group. Highest fluorescence intensity showed when the electrochemical reduction of AMC was controlled at near the potential (-2.3 volts vs. Ag/AgCl).

• 분석과학
• /
• 제18권1호
• /
• pp.89-95
• /
• 2005

Studies on the electrochemical reduction of 7-acetoxy-4-bromomethyl-coumarin (ABMC), 7-acetoxymethyl coumarin (AMC), and coumarin in 0.1 M tetraethyl ammonium perchlorate acetonitrile solution were carried out with direct current, differential pulse polarography, cyclic voltammetry, and controlled potential coulometry. The electrochemical reduction of ABMC was proceeded through three irreversible steps coupled with the chemical reactions. The solution color was changed to yellow when the carbonyl group was reduced during second step and the color change was independent with bromo group of ABMC. Fluorescent intensity was highest when the electrochemical reduction was controlled at near the overpotential of supporting electrolyte (-2.3 volts).

• 대한화학회지
• /
• 제35권2호
• /
• pp.165-171
• /
• 1991

6,6-dibromopenicillanic acid 1,1-oxide(DBPA)의 6위치 dibromo기의 전기화학적 환원을 direct current, differential pulse polarography, cyclic voltammetry, 조절전위 전기량법으로 연구하였다. DBPA 환원과정은 2단계-0.48, -1.62 volts)에서 모두 완전비가역으로 2전자씩 이동하는 EC, EC 반응기구로 진행하였다. 조절전위 전기분해를 이용하여 6-bromo-PA와 6,6-dihydro-PA를 단계적으로 합성하였으며, pH 변화에 다른 폴라로그램의 해석과 생성물 분석의 결과를 바탕으로 전기화학적 반응기구도 제안하였다.

• 농업과학연구
• /
• 제11권2호
• /
• pp.315-321
• /
• 1984

0.1M tetraethylammoniumperchlorate (TEAP)를 지지전해질로 한 acetonitrile속에서 direct current (DC), differential pulse (DP) polarography 및 cyclo voltammetry (CV) 방법에 의한 Sumithion의 전기화학적 환원반응은 -1.0~-2.50volt vs. Ag-AgCl 범위에서, 제1단계로 P-Oph 결합의 분열에 의하여 dimethylthiophosphonyl radical과 p-nitro-m-cresol이 생성되는 1전자 유사가역반응이 일어나고, 제2단계는 전형적인 1전자 비가역 반응으로 dimethylthiophosphonyl radical이 dimethylthiophosphonate가 되며, 제3단계 반응은 2.7volt vs. Ag-AgCl의 높은 음전위에서 p-nitro-m-cresol은 4전자 비가역반응에 의한 nitro group의 환원으로 p-hydroxy-amino-m-cresol이 생성되는 총 3단계의 비가역적인 electron-transfer chemical reaction (EC) 메카니즘으로 전극반응이 진행됨을 알았다.

• 대한화학회지
• /
• 제32권3호
• /
• pp.195-202
• /
• 1988

Acetonitrile 용액중에서 3-phenyl-4-nitrosydnone의 전기화학전 환원을 direct current, differential pulse polarography, cyclic voltammetry 그리고 controlled potential coulometry 방법으로 연구하였다. Phenyl-N 단일 결합의 분리 이전에 nitro 기능기의 비가역적 전자 전달-화학반응(EC)기구의 진행으로 다전자 이동에 의한 amino(또한 hydroxylamino)기를 형성하고, 높은 음 전위 영역에서 2,3 비가역성 환원파의 일전자전달-화학반응에 의한 phenyl hydrazine을 생성하였다. 음극 반파 전위들은 cetyltrimethyl ammonium bromide의 억제 효과에 의해 음의 값으로 이동하였고 한편, sodium lauryl sulfate micelle은 높은 음전위 영역에서 제 2,3 환원파의 가역성산화 peaks를 보였다.

• 약학회지
• /
• 제22권4호
• /
• pp.201-206
• /
• 1978

The analysis of elemental sulfur by polarography has already been reported in the literature. Only a discussion of the more important factors influencing the analysis is here presented. (1) The effects of pH on the reduction of elemental sulfur are pronounced and the use of buffered solutions for the analysis of elemental sulfur is necessary. The authors found that a pH of 4-6 was found to be reproducible polarograms by use of D.C. polarograph. However, in alkali solvents the plateau of elemental sulfur has a pronounced dip if the concentration of sulfur is as much as 30ppm. (2) A.C. polarographic method shows a very high sensitivity in the case of sulfur reduction, so that the very low concentration of sulfur can easily be determined (about 1ppm). (3) The characteristics of sulfur wave can be formulated according to Stackelberg-Hauck-Hans equation. It was found that the curve of the peak potential of elemental sulfur in A.C. polarography versus logarithm of sulfur concentration was obtained to be straight line with the slope of 29.6 millivolts. This result was well agreed with theoretical consideration. (4) It was assumed that this polarographical methods were applicable to micro-analysis of elemental sulfur in crude oil and its petrochemical products, precipitated sulfur, and sulfur ointments with accuracy and rapidity.

• 분석과학
• /
• 제13권1호
• /
• pp.1-4
• /
• 2000

로듐이 미량으로 존재할 때 펄스차이 폴라로그래피로 정량할 수 있는 용액조건을 확립하였다. 포름알데히드 0.004%(w/v)-염산 0.75M의 조건에서 가장 예민한 수소촉매파를 얻을 수 있었다. 이 조건에서 검출한계는 $7.0{\times}10^{-12}M$이고 봉우리 전류가 선형인 농도범위는 $1.0{\times}10^{-11}{\sim}1.0{\times}10^{-8}M$이었다. 이 농도범위에서 다른 백금족 원소가 500배까지 존재하여도 방해를 받지 않았다.

• Bulletin of the Korean Chemical Society
• /
• 제11권6호
• /
• pp.497-505
• /
• 1990

The function exp$(x^2)$erfc(x), which is often encountered in studies of electrode kinetics, is evaluated to an extended precision with 32 significant decimal digits in order to find theoretical relationships used in derivative polarography/voltammetry for a chemically-coupled electrode process. Computations with a lower precision are not successful. Evaluation of the function is accomplished by using three types of expansions for the function. Best ranges of arguments are selected for each equation for particular precisions for efficiencies. The method is successfully applied to calculate higher-order derivatives of the current-potential curves in all potential ranges for a reversible electron transfer reaction coupled with a prior chemical equilibrium (i.e., a CE type process). Various parameters that characterize the peak asymmetry (such as ratios of peak-heights, ratios of half-peak-widths, and separations in peak-potentials) are analyzed to find how kinetic and thermodynamic parameters influence shapes of the derivatives. The results from the CE process is compared with those from an EC process in which a reversible electron transfer is coupled with a follow-up homogeneous chemical reaction. The two processes exibit quite contrasting differences for values of the parameters.

• Bulletin of the Korean Chemical Society
• /
• 제21권7호
• /
• pp.685-689
• /
• 2000

The complexation reaction between Pb2+,TI and Cd2+ions and macrocyclic ligands, 18-crown-6 ( 18C6) and dibenzo- 18-crown-6 (DB 18C6), was studied in dimethylsulfoxide (DMSO)-nitromethane (NM) and dimethyl-formamide (DMF)-nitromethane binary system s by square wave polarography (SWP) technique. The stoichiometry and stability of the complexes were determined by monitoring the shifts in half-waves or peak potentials of the polarographic waves of metal ions against the Iigand concentration. In most cases, the stability constants of complexes increase with increasing amounts of the nitromethane in mixed binary solvents used in this study. The complexes formed between 18C6 and DB18C6 and these metal cations in all cases had a stoichiometry of 1 : 1. The results obtained show that there is an inverse relationship between the formation constant of complexes and the donor number of solvents based on a Gatmann donocity scale and the stability constants show a high sensitivity to the composition of the mixed solvent systems. A linear behavior was observed for variation of log Kf of I8C6 complexes vs the composition of the mixed solvent systems in NM/DMSO and NM/DMF,but a non-linear behavior was observed in the case of DB 18C6 complexes in these binary systems. In most of the systems investigated, the Pb2+ cation forms a more stable complex with the 18C6 than other two cations and the order of selectivity of this Iigand for cations is: Pb2+ > TI+,Cd2+.

• 자연과학논문집
• /
• 제11권1호
• /
• pp.33-39
• /
• 1999

$Sm^3+$과 Alizarin red S(ARS)가 반응하여 생성한 착물의 전기화학적 성질을 직류폴라로그래피, 펄스차이폴라로그래피 및 순환전압전류법으로 연구하였다. $Sm^3+$과 ARS는 1 : 3 착물을 형성하였다. 0.1M LiCl 지지전해질 용액에서 착물의 환원파는 확산지배적이며 흡착성 착물파임을 확인하였다. 착물파의 환원전위는 ARS의 환원전위보다 음전위에서 나타났으며 $Sm^3+$의 농도를 증가시키면 ARS의 봉우리전류($P_1$)는 감소하고 착물의 봉우리 전류($P_2$)는 증가하였다. ARS의 농도 $2{\times}$$10^-4$ M에서 $Sm^3+$의 농도 $2{\times}$$10^-6$ M~$3.2{\times}$$10^{-5}$ M 범위에서 직선적으로 변하였다.