• Title/Summary/Keyword: polarography

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Polarographic Determination of Iron(Ⅱ), Iron(Ⅲ) and Total Iron in the Presence of DTPA (DTPA 존재하에서 폴라로그래피법에 의한 2가 철, 3가 철 및 전체 철의 정량)

  • Se Chul Sohn;Moo yul Suh;Tae Yoon Eom
    • Journal of the Korean Chemical Society
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    • v.37 no.12
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    • pp.1053-1059
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    • 1993
  • The determination of iron(Ⅱ), iron(Ⅲ) and total iron was studied by differential-pulse and Tast polarography in 0.1 M acetate buffer solution at pH 4.60, Half wave potentials of iron(Ⅱ)-DTPA and iron(Ⅲ)-DTPA complexes were -0.150V vs. SCE reference electrode. In the presence of DTPA the redox process of iron(Ⅱ) and iron(Ⅲ) was reversible. Linear calibration plots were obtained for iron(Ⅱ) and iron(Ⅲ) concentration of 0.2∼1.0 mM. The detection limits of iron(Ⅱ) and iron(Ⅲ)by Tast polarographic method were 0.05 mM and 0.07 mM, respectively.

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Polarographic Studies on the Kinetics of Cu(II)-thiocyanate and the Adsorption Wave of Cu(I)-thiocyanate (Polarography에 依한 Cupric-thiocyanate의 Kinetics와 Cuprous-thiocyanate의 Adsorption Wave에 關한 硏究)

  • Hwang, Jung-Euy;Chung, Chong-Jae;Son, Moo-Young;Park, Yu-Chul
    • Journal of the Korean Chemical Society
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    • v.14 no.3
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    • pp.213-219
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    • 1970
  • In the presence of hydrogen peroxide, the effects of temperature and pH to the catalytic reaction velocity of cupric -thiocyanate and the quantities of reduction products adsorbed on the D.M.E. have been studied by polarographic method. According to these experiments, the following empirical equation has been derived for the relation among temperature $T_i$, concentration of hydrogen ion $pH_i$ and adsorbed cuprous-thiocyanate in moles/$cm^2Z_{ij}$, and rate constant log$K_{ij}$ $$log\;K_{ij}=\frac{1}{T_i}\{A(pH_j)+B\}+C(pH_j)+D$$ $$Z_{ij}=\frac{1}{T_i}\{{\alpha}(pH_j)^{\frac{1}{2}}+{\beta}\}+{\gamma}(pH_j)^{\frac{1}{2}}+{\delta}$$ where, A,B,C,D and {$\alpha},{\beta},{\gamma},{\delta}$ are constants. The Calculated values by both equations are well agreed with empirical values within 8% in the error.

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Electrochemical Behaviors of Copper-1-(2-pyridylazo)-2-naphthol Complex in Acetonitrile (아세토니트릴 용매 중에서 Copper-1-(2-pyridylazo)-2-naphthol 착물의 전기화학적 성질)

  • Zun-Ung Bae;Sang-O Oh;Hee-Bong Song;Tae-Myung Park
    • Journal of the Korean Chemical Society
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    • v.37 no.10
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    • pp.888-894
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    • 1993
  • The electrochemical behaviors of copper-1-(2-pyridylazo)-2-naphthol(Cu-PAN) complex in acetonitrile (AN) solution have been investigated by the use of cyclic voltammetry, DC-polarography, controlled potential coulometry and UV-Vis spectroscopy. Cu-PAN complex in acetonitrile exhibit three reduction waves at -1.27 V, -1.64 V and -2.08 V vs. Ag/AgNO$_3$(AN). The numbers of electron involved in each reduction step was calculated with controlled potential coulometry, and reduction product was identified with UV-Vis spectrum. As the result, we proposed the reduction mechanism of the Cu-PAN complex in acetonitrile.

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Electrochemical Behavior of Zn(II)-Bilirubin Complex in N,N-Dimethylformamide (N,N-Dimethylformamide 용액 중에서 Zn(II)-Bilirubin 착물의 전기화학적 거동)

  • Zun-Ung Bae;Heung-Lark Lee;Tae-Myung Park;Moo-Lyong Seo
    • Journal of the Korean Chemical Society
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    • v.37 no.7
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    • pp.672-676
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    • 1993
  • The complexation of bilirubin with zinc(II) and copper(II) ions was studied spectrophotometrically. In the zinc(II)-bilirubin (Zn-BR) system, complex is formed, but the copper(II) ion oxidizes bilirubin to biliverdin and then to the further oxidation products. The electrochemical reduction behavior of ZN-BR complex has been investigated with DC polarography and cyclic voltammetry. The three polarographic waves were obtained for the reduction of ZN-BR complex in DMF solution. Thde reduction current of the third wave was diffusion current, but that of the first and the second waves contained a little kinetic current.

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Electrochemical Behavior of Mordant Red 19 and its Complexes with Light Lanthanides

  • Sang Kwon Lee;Taek Dong Chung;Song-Ju Lee;Ki-Hyung Chjo;Young Gu Ha;Ki-Won Cha;Hasuck Kim
    • Bulletin of the Korean Chemical Society
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    • v.14 no.5
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    • pp.567-574
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    • 1993
  • Mordant Red 19(MR19) is reduced at mercury electrode at -0.67 V vs. Ag/AgCl with two electrons per molecule in pH 9.2 buffer by differential pulse polarography and linear sweep voltammetry. The peak potential is dependent on the pH of solution. The exhaustive electrolysis, however, gives 4 electrons per molecule because of the disproportionation of the unstable hydrazo intermediate. The electrochemical reduction of lanthanide-MR19 complexes is observed at more cathodic potential than that of free ligand. The difference in peak potentials between complex and free ligand varies from 75 mV for $La^{3+}$ to 165 mV for $Tb^{3+}$ and increases with increasing the atomic number of lanthanide. The electrochemical reduction of lanthanide complexes with MR19 is due to the reduction of ligand itself, and it can be potentially useful as an indirect method for the determination of lanthanides. The shape of i-E curves and the scan rate dependence indicates the presence of adsorption and the adsorption was confirmed by potential double-step chronocoulometry and the effect of standing time. Also the surface excess of the adsorbed species and diffusion coefficients are determined. The composition of the complex is determined to be 1 : 2 by spectrophotometric and electrochemical methods.

Polarographic Behavior of Oxovanadium (IV) Complex of Mercaptopyridine N-Oxide

  • Shim, Yoon-Bo;Choi, Sung-Nak
    • Bulletin of the Korean Chemical Society
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    • v.8 no.4
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    • pp.225-230
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    • 1987
  • The redox properties of 2-mercaptopyridine N-oxide (mpno) and its oxovanadium complex, $VO (mpno)_2$ have been studied by the use of polarography and cyclic voltammetry. The radical anion of mpno is generated in acetone and is adsorbed to the electrode to form an adsorption wave at -0.21 V vs Ag/AgCl electrode. The normal wave appeared at -0.50 V is attributed to the formation of radical anion. The $VO (mpno)_2$ exhibits one oxidation wave at +0.57 V, and two reduction waves at -1.07 V and -1.76 V vs. Ag/AgCl electrode; the oxidation is fully reversible one-electron process ($VO (mpno)_2\;{\leftrightarrow}\;VO(mpno)_2^+ + e).$ The reduction wave at -1.07 V is quasireversible and is arised from the formation of $VO (mpno)_2^-.$ The second reduction wave at -1.76 V is irreversible and this reduction process consists of two one-electron steps. The sulfur containing ligands seem to enhance the stability of lower oxidation state of vanadium while the oxygen or nitrogen donor of the ligands stabilize the higher oxidation state of vanadium when comparisons are made among several oxovanadium complexes.

Electrode Kinetics for Mixed Ligand Complexes of Cobalt (III) with Bis (ethylenediamine) and Monodendate Ligands (한자리 배위자와 에틸렌디아민의 코발트 (III) 착물에 대한 전극반응 속도론)

  • Jung-Ui Hwang;Jong-Jae Chung;Jae-Duck Lee
    • Journal of the Korean Chemical Society
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    • v.33 no.2
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    • pp.225-231
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    • 1989
  • The heterogeneous rate constants for the electrochemical reduction by $trans-[Co(en)_2X_2](ClO_4)_n$(where X is cyanide, nitrite, ammonia, and isothiocyanate) at mercury and glassy carbon electrode were investigated by cyclic voltammetry, DC polarography, and by using rotating disk electrode. The good linear relationship was obtained between the activation energy of reduction and absorption wave number of complexes on glassy carbon electrode. At mercury electrode, $NO_2^-$ ligated complex showed the large deviation from the linear relationship. The difference in the value of rate constants for $NO_2^-$ ligated complex between mercury and glassy carbon electrode was about three order of magnitude which was much larger than the other complexes. It was suggested that $NO_^-$ ligated complex was reduced by inner-sphere mechanism on mercury electrode from the larger value of activation energy and entropy on mercury than carbon electrode.

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Quantitative Determination of Vitamin $B_1$ (Thazole Derivatives) (Vitamin $B_1$ (Thiazole 유도체(誘導體))의 정량법(定量法)에 관(關)한 연구(硏究))

  • Kim, Yong-Jin
    • Korean Journal of Food Science and Technology
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    • v.12 no.1
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    • pp.41-44
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    • 1980
  • The model compounds of Vitamin $B_1$ 3-benzyl-4-methylthiazolium bromide, (1), 3, 4-dimethylthiazolium iodide (2) and 2-($\alpha$-hydroxyethyl)-3-benzyl-4-methylthiazolium bromide (3) were prepared by the organic synthesis. Colorimetric determination with phosphotungstic acid showed an increase of $1.1{\sim}1.2$ folds with compound (1) and $1.5{\sim}1.9$ folds with compound (3) when readings were carried out after an overnight, compared with immediate readings. Colorimetry with 2.6-dibromoquinone chloroimide yielded the compound (1) being $2.2{\sim}2.5$ folds higher than the compound (3). The half wave potentials and diffusion currents of anodic and cathodic waves of polarography with the same concentration of the compounds (1), (2) and (3) also resulted in different values of their waves. Therefore, it was a firm conclusion that any values obtained from quantitative analysis with this model compounds (1), (2) and (3) were not directly applicable to those of $B_1$.

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Determination of a Trace Amount of Copper, Lead, Cadmium and Zinc in Water by Solvent Extraction and Square Wave Polarography (溶媒抽出-矩形波폴라로그래피에의 물중의 미량 구리, 납, 카드뮴 및 아연의 定量)

  • Moon Su-Chan
    • Journal of the Korean Chemical Society
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    • v.21 no.5
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    • pp.372-378
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    • 1977
  • The following new techniques have been developed: (A); To a 500ml of sample water, it was adjusted pH 10 with ammonia-anmonium citrate, added 10ml of 1${\%}$ sodium diethyldithiocarbamate and extracted three times with 10ml of CHCl3. The extract was shaken with 10ml of 0.05N $HCl-4{\times}10^{-4}M\;HgCl_2$. The aqueous solution was added 2ml of 2N KCl and washed two times with 10ml of pure $CHCl_3$, and then recorded square wave polarograms. (B); To a 500ml of sample water adjusted pH 10 with ammonia-ammonium citrate, it was added 2ml of 1${\%}$ 8-hydroxyquinoline and extracted three times with 10ml $CHCl_3$. The separated $CHCl_3$ phase was shaken with 10ml of 0.2 N HCl. The aqueous solution was recorded polarograms directly. These methods can be used for determination of the ppb order of metal in water with an error of ${\pm}10{\%}$. The method (B) can not be used for the determination of zinc on account of the free 8-hydroxyquinoline.

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Electrochemical Reduction on the -S-N= Bond of N-Tert-butylbenzothiazole-2-sulfenamide (N-Tert-butylbenzothiazole-2-sulfenamide의-S-N = 결합에 대한 전기화학적 환원)

  • Kim, Hae-Jin;Jung, Keun-Ho;Choi, Qw-Won;Kim, Il-Kwang;Leem, Sun-Young
    • Journal of the Korean Chemical Society
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    • v.35 no.6
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    • pp.673-679
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    • 1991
  • The electrochemical reduction of N-tert-butylbenzothiazole-2-sulfenamide (TBBS; vulcanization accelerator) was investigated by direct current, differential pulse polarography, cyclic voltammetry and controlled potential coulometry. The electrode reduction of TBBS proceeded E-C-E-C reaction mechanism by four electrons transfer at irreversible one wave (-2.31 volts vs. Ag/0.1M AgN$O_3$ in AN). As the results of controlled potential electrolysis, mercaptobenzothiazole (MBT), benzothiazole disulfide (MBT dimer) and extricated sulfur were products which followed by cleavage of the sulfenamide (-S-N=) bond. Upon the basis of products analysis and polarogram interpretation with pH variable, electrochemical reaction mechanism was suggested.

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