• Journal of the Korean Chemical Society
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• v.53 no.6
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• pp.693-703
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• 2009

The complex formation of anti-inflamatory drug piroxicam (PX, 4-hydroxy-2-methyl-N-2--pridyl-2H-1,2-benzothiazine-3-carboxadiamide-1,1-dioxide) with transition metal ions Co(II), Ni(II), Cu(II) and Zn(II) in methanol(MeOH)/water binary mixtures were studied by spectrophotometric method at 25$^{\circ}C$, constant pH = 5.0 and I = 0.1 M. The computer program SQUAD was used to extract the desired information from the spectral data. The outputs of the fitting processes were stability constants, standard deviations of the estimated stability constants, concentration distribution diagrams and spectral profiles of all species. The sequence of the stability constants of PX complexes with Co(II), Ni(II), Cu(II) and Zn(II) follow the Cu(II) > Co(II) > Ni(II) ${\approx}$ Zn(II) order. This may be due to different geometry tendencies of these metal ions. The acidity constants of the PX were also determined under above condition from its absorption spectra at different pH values. The computer program DATAN was used for determination of acidity constants of PX. The validity of the obtained acidity constants was checked by a well known computer program SPECFIT/32. The effects of the different parameters like solvent nature, cations characteristics on the stability and acidity constants were thoroughly discussed.

• Journal of the Korean Chemical Society
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• v.9 no.1
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• pp.45-48
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• 1965

Stability constant, composition of copper (II)-oxamidoxime complex were determined by spectrophotometric method. The ratio of copper (II) and oxamidoxime in the above complex was 1 : 1, and its stability constant was calculated to be $2.4{\times}10^{22}$. The complex solution gave constant absorbancy between the pH range of 4.5 to 6 at 600 $m{\mu}$ in which Beer's law applicable in the concentration range of 0.3 to 2.0 ppm studied in this work. It was noted that some metals such as Fe(III), Ni(II), Co(II), U(VI) interfere copper determination by this method.

• Bulletin of the Korean Chemical Society
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• v.26 no.6
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• pp.943-946
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• 2005

An effective spectrophotometric determination of palladium with 4-(2-pyridylazo)-resorcinol (PAR) using molten naphthalene as a diluent has been studied. A red complex of palladium with PAR is formed at 90 ${^{\circ}C}$. In the range of pH 9.0-11.0, the complex is quantitatively extracted into molten naphthalene. The organic phase is anhydrously dissolved in $CHCl_3$ to be determined spectrophotometrically at 520 nm against the reagent blank. Beer’s law is obeyed over the concentration range of 0.1-2 ${\mu}g{\cdot}mL^{-1}$. The molar absorptivity and Sandell’s sensitivity are 8.0 ${\times}\;10^5\;L{\cdot}mol^{-1}{\cdot}cm^{-}1\;and\;0.49\;{\mu}g{\cdot}cm^{-2}$ respectively. From the results of tolerance limits, it was found that there was no interferences were observed for most of the ions examined and those somewhat high interferences by Co(II), Fe(II) and Bi(III) could be effectively masked by EDTA.

• Journal of the Korean Chemical Society
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• v.50 no.2
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• pp.99-106
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• 2006

The electronic absorption spectra of [3-(2-thenoyl) 3-(p-NO2-phenylhydrazone) ethyl pyruvate] (I), p-Br (II) and p-CH3 (III) were studied in ethanol and the spectra comprise four absorption bands which assigned to the corresponding electronic transition. The pK values of these compounds have been determined spectrophotometrically and pH-metrically, the results shown that the interval range for color change of compound (I) is (8-10) similar to that of phenolphethalin indicator, indicating that this compound can be used as acid-base indicator. The successive stability constants of the compounds under study with some transition elements (Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), UO2(II), La(III) and Zr(IV) have been determined pH- metrically. Stoichiometric complexes with ratios 1:1 and 1:2 (M: L) were formed for all metals. The pK of the three derivatives and the values of the stability constant (logK) of the complexes have the order; III > II > I. Also conductometric titrations have been carried out and the results show that this titration can be used for determination of both the metal ion and the ligand concentrations by each others.

• Journal of Environmental Science International
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• v.15 no.8
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• pp.799-809
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• 2006

Hydrobromic acid salts of new N, N, O tridentate ligands containing phenol, 2-[(2-Methylamino- ethyl- amino)-methyl]-phenol(H-MMP. 2HBr), 5-Bromo-2-[(2-Methylamino-ethylamino)-methyl]-phenol (Br- MMP. 2HBr), 5-Chloro-2-[(2-Methylamino-ethylamino)-methyl]-phenol(Cl-MMP. 2HBr), 5-Methyl-2-[(2-Methylamino-ethylamino)-methyl]-phenol(Me-MMP. 2HBr), 5-Methoxy-2-I(2-Methylamino-ethylamino)- methyl]-phenol(MeO- MMP. 2HBr) and. 1-[(2-Methylamino-ethylamino)- methyl]-naphthalen-2-ol(Nap- MMP. 2HBr) were synthesized. The synthesized ligands were confirmed by C. H. N. atomic analysis, UV-visible and IR spectroscopies, $^1$H NMR, $^{13}$C NMR and mass analysis. The potentiometry study revealed that the proton dissociation constants(logK$_n^H$) of the synthesized ligands and stability constants (logK$_{ML}$, logK$_{LM2}$) of transition metal complexes of Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Pb(II) ions occurred in three steps and the order of the calculated overall proton dissociation constants(log$\beta_p$) and stability constants (logK$_{ML}$) of ligands was Br-MMP. 2HBr < Cl-MMP 2HBr < H-MMP. 2HBr < Nap-MMP. 2HBr < Me-MMP. 2HBr < MeO-MMP. 2HBr. The order showed a similar trend to that of Hammett substituent constants($\delta_p$). The synthesized ligands usually form 2:1(ML$_2$) complexes with transition metal ions. The order of the stability constants of each transition metal ions was Co(II) < Ni(II) < Cu(II) ;> Zn(II) ;> Cd(II) ;> Pb(II).

• Journal of the Korean Chemical Society
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• v.37 no.8
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• pp.723-729
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• 1993

Cu(II) ion-responsive chemically modifed electrodes (CMEs) were constructed by incorporating 1-(2-pyridylazo)-2-naphthol (PAN) into a conventional carbon-paste mixture of graphite powder and Nujol oil. Cu(II) ion was chemically deposited on the surface of the PAN-chemically modified electrode in the absence of an applied potential by immersion of the electrode in a buffer solution (pH 3.2) containing Cu(II) ion, and then reduced at a constant potential in 0.1 M KNO$_3$. And a well-defined voltammetric peak could be obtained by scanning the potential to the positive direction. The electrode surface could be regenerated with exposure to acid solution and reused for the determination of Cu(II) ion. In 5 deposition / measurement / regeneration cycles, the response could be reproduced with 6.1${\%}$ relative standard deviation. In case of using the differential pulse voltammetry, the calibration curve for Cu(II) was linear over the range of 2.0 ${times}$ 10$^{-7}$ ∼ 1.0 ${times}$ 10$^{-6}$ M. And the detection limit was 6.0 ${times}$ 10$^{-8}$ M. Studies of the effect of diverse ions showed that Co, Ni, Zn, Pb, Mg and Ag ions added 10 times more than Cu(II) ion did not influence on the determination of Cu(II) ion, except EDTA and oxalate ions.

• Bulletin of the Korean Chemical Society
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• v.27 no.4
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• pp.563-567
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• 2006

The application of a synergistic solvent extraction by the formation of ternary complex with pyrocatechol violet (PV) and benzalkonium chloride (BC) was studied for determination of trace Zn(II) in water samples. The pH of sample solution and the amount of PV and BC added were optimized for the formation of the stable complex, a proper solvent was selected for the effective extraction, and the concentration of nitric acid was fixed for the back extraction of the complex from the solvent. After the ionic strength of 100 mL sample solution was adjusted to 0.1 M by adding NaCl and the pH was fixed at 9 with a carbonate buffer, 1.0 mL of 2% PV solution was added to form Zn(II)-PV complex then the Zn(II)-PV/BC ternary complex was made by adding 1.0 mL of 10% BC solution. The ternary complex was extracted into 10 mL of MIBK. And the ternary complex was back-extracted with 10 mL of 1.0 mol/L nitric acid to determine Zn(II) by a flame atomic absorption spectrophotometer (flame-AAS). The interference of concomitant ions on the extraction of Zn(II) was investigated. This procedure was applied to the analysis of three real samples such as Dalbang-dam water, laboratory tap water and Jungnajin seawater. The recoveries of Zn(II) in spiked samples were 86.58-104.1%.

• Analytical Science and Technology
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• v.10 no.4
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• pp.256-263
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• 1997

The new naphthol-containing hexadentate ligands, 1,12-bis (2-naphthol)- 2,5,8,11-tetraazadodecane 4HCl (nptr) and 1,14-bis(2-naphthol)- 2,6,9,13- tetraazatetradodecane .4HCl (npptr) were synthesized and characterized by elemental analysis, IR, NMR, and mass spectrometry. Acid dissociation constants and stability constants of Co(II), Ni(II). Cu(II), and Zn(II) complexes were determined at $25.0^{\circ}C$ and ionic strength ($\mu$)=0.10M($KNO_3$) by potentiometry. The relationship between basicity and stability constants of ligands containing aliphatic amines and 2-naphthol were studied.

• Journal of the Korean Chemical Society
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• v.37 no.10
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• pp.881-887
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• 1993

A cobalt(II) ion-selective carbon-paste electrode (CPE) was constructed with ${\iota}$-sparteine. Cobalt(II) ion in aqueous solution was chemically deposited through the complexation with ${\iota}$-sparteine onto the CPE. The surface of CPEs were characterized by cyclic voltammetry and differential pulse voltammetry in an acetate buffer solution, separately. Exposure of the CPEs to an acid solution could regenerate surface to reuse it for the deposition. In more than 5 deposition / measurement / regeneration cycles, the response was reproducible and linear up to $5.0{\times}10^{-6}$M with linear sweep voltammetry. The peaks at 0.17V / 0.27V were correspond to the redox of Co(II)-SP complex deposited on CPE. The anodic peak of which appeared after scan over the cathodic peak of 0.17 V to more negative scan. In case of using the differencial pulse voltammetry (DPV), we have obtained the linear response $2.0{\times}10^{-7}$M with relative standard deviation ${\pm}5.6%$. The detection limit was $1.0{times}10^{-7}$M for 20 minutes of the deposition. We have also investigated the interference effect of various metal ions, which are expected to form the complex with the ligand on the electrode.

• Journal of the Korean Chemical Society
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• v.33 no.3
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• pp.273-280
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• 1989

The spectra of the $Co^{II}CyDTA$(CyDTA: cyclohexyldiaminetetraacetic acid) complex have been measured in aqueous solution of pH = 6-13.2. The red shift of the spectrum in the more basic solution was ascribed to the transformation of $CoCyDTA^{2-}$ into $CoCyDTA(OH)^{3-}$. The equilibrium constant, $K_{OH} = [CoCyDTA(OH)^{3-}]/[CoCyDTA^{2-}][OH^-]$ was $75M^{-1}$ at $40^{\circ}C$. The electron transfer reactions of $CoCyDTA^{2-}$ and $CoCyDTA(OH)^{3-}$ with $Fe(CN)_6^{3-}$ have been studied using spectrophotometric technique in the range of pH applied to the determination of equilibrium constant. The pseudo first-order rate constants observed ($k_{obs}$) were not changed upto pH = 10.8, but increased with increasing pH in the range of pH = $10.8{\sim}13.0$. The rate law reduced in the range of pH = 6-13 was $k_{obs} = (k_3[CoCyDTA^{2-}] + k_4[CoCyDTA(OH)^{3-}])/(1+K_1[CoCyDTA^{2-}])$. The rate constants of the reactions (3a) and (3b), $k_3$ and $k_4$ respectively have been determined to be 0.529 and $4.500M^{-1}sec^{-1}$ at $40^{\circ}C$. The activation entropies (147{\pm}1.1JK^{-1} mol^{-1}$ at pH = 10.8) and activation volumes $(6.25cm^3mol^{-1}, pH = 10.8)$ increased with increasing pH, while the activation enthalpy (12.44 ${\pm}$ 0.20 kcal/mole) was independent of pH. Using the pH effect on the rate constants, the activation entropies and the activation volumes, the mechanism of the electron transfer reaction for $Co^{II}-Fe^{III}$ system was discussed.