• Title/Summary/Keyword: Potentiometry $Pb^{2+}$ analysis

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Synthesis of New N,N,O Tridentate Ligands and Determination of Stability Constants of Transition Metal Complexes by Potentiometry (새로운 N,N,O계 세 자리 리간드의 합성과 전위차적정법에 의한 전이금속 착물의 안정도상수의 결정)

  • Kim, Sun-Deuk;Lee, Do-Hyub
    • 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).

Lead-Selective Poly(vinyl chloride) Membrane Electrode Based on 1-Phenyl-2-(2-quinolyl)-1,2-dioxo-2-(4-bromo) phenylhydrazone

  • Zare, Hamid Reza;Ardakani, Mahammad Mazloum;Nasirizadeh, Navid;Safari, Javad
    • Bulletin of the Korean Chemical Society
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    • v.26 no.1
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    • pp.51-56
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    • 2005
  • A PVC membrane electrode for lead ion based on 1-phenyl-2-(2-quinolyl)-1,2-dioxo-2-(4-bromo) phenylhydrazone (PQDBP) as ionophore was demonstrated. The optimum composition of the membrane was 30 wt% poly(vinyl chloride), 60 wt% dibutyl phthalate as a plasticizer, 4 wt% ionophore and 6 wt% sodium tetraphenylborate as additive. The electrode exhibits a Nernstian response (28.7 mV decade$^{-1}$) for Pb$^{2+}$ over a wide concentration range (1.0 ${\times}$ 10$^{-1}$ to 1 ${\times}$ 10$^{-6}$ M) with a detection limit of 6.0 ${\times}$ 10$^{-7}$ M. This sensor has a short response time and can be used for at least 2 months without any divergence in potentials. The proposed electrode could be used in a pH range of 3.0-6.0 and revealed good selectivities for Pb$^{+2}$ over a wide variety of other metal ions. It was successfully applied as an indicator electrode for the potentiometric titration of lead ion with potassium chromate and for the direct determination of lead in mine.

Complex Formation of Transition and Post-Transition Metal Ions with 1,15-Diaza-3,4 : 12,13-dibenzo-5,8,11-trioxacyclooctadecane (전이 및 중금속이온과 1,15-diaza-3,4 : 12,13-dibenzo-5,8,11-trioxa-cyclooctadecane과의 착물형성)

  • Kim, Si-Joong;Lee, Myung-Jae;Koo, Chang-Hyung;Woo, Kyoun-Ja
    • Journal of the Korean Chemical Society
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    • v.35 no.6
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    • pp.645-652
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    • 1991
  • The stability constants$(K_f)$ of the complexes of some transition and post-transition metal ions (Co(Ⅱ), Ni(Ⅱ), Cu(Ⅱ), Zn(Ⅱ), Cd(Ⅱ), Pb(Ⅱ), Hg(Ⅱ)) with $N_2O_3$-donor macrocyclic ligand, 1,15-diaza-3,4 : 12,13-dibenzo-5,8,11-trioxacyclooctadecane ($NtnOdienH_4$), have been determined by potentiometry in aqueous solution at $25^{\circ}C$. Log $K_f$ values of the complexes were : Co(Ⅱ): 3.83, Ni(Ⅱ) : 4.56, Cu(Ⅱ) : 7.74, Zn(Ⅱ) : 4.98, Cd(Ⅱ) : 3.91, Pb(Ⅱ) : 6.65, and Hg(Ⅱ) : 14.87. The order of stabilities of transition metal complexes was the same as the natural order of stability proposed by Williams-Irving. In post-transition metal complexes, the order of stabilities was Cd(Ⅱ) < Pb(Ⅱ) < Hg(Ⅱ), and the covalent character in metal ion-donor atoms bonds appeared a dominant factor in the stability. In methanol solution, each metal ion forms 1 : 1 complex, while Ni(Ⅱ) ion forms both 1 : 1 and 1 : 2 complexes. It was confirmed by $^1H-$ and $^{13}C-$NMR spectral study that the nitrogen atoms in the ligand were major contributors for the complexation of post-transition metal ions with the ligand. It was shown, by elementry analysis, electrical conductivity and magnetic susceptibility measurements, and spectral analysis, that solid Cu(Ⅱ)-and Zn(Ⅱ)-complexes have a distorted octahedral and a tetrahedral structure, respectively.

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