• Journal of Environmental Science International
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• v.19 no.7
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• pp.849-860
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• 2010

A new $N_3O_2$ pentadentate ligand, N,N'-Bis(2-hydroxybenzyl)-ethylenetriamine(H-BHET 3HCl) was synthesized. The hydrochloric acid salts of Br-BHET 3HCl, Cl-BHET 3HCl, $CH_3O$-BHET 3HCl and $CH_3$-BHET 3HCl containing Br-, Cl-, H-, $CH_3O-$ and $CH_3-$ groups at the para-site of the phenol group of the H-BHEP were synthesized. The structures of the ligands were confirmed by C. H. N. atomic analysis and $^1H$ NMR, $^{13}C$ NMR, UV-visible and mass spectra. The calculated stepwise protonation constants(${\logK_n}^H$) of the synthesized $N_3O_2$ ligands showed six steps of the proton dissociation. The orders of the overall protonation constants($\log{\beta}_p$) of the ligands were Br-BHET < Cl-BHET < H-BHET < $CH_3O$-BHET < $CH_3$-BHET. The orders agreed well with that of para Hammett substituent constants(${\delta}_p$). The calculated stability constants($\logK_{ML}$) between the ligands and heavy metal ions (Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Pb(II)) agreed well with the order of the overall proton dissociation constants of the ligands but they showed a reverse order in para Hammestt substituent constants(${\delta}_p$). The order of the stability constants between the heavy metal ions with the synthesized ligands were Co(II) < Ni(II) < Cu(II) > Zn(II) > Cd(II) > Pb(II).

• Analytical Science and Technology
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• v.6 no.5
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• pp.443-451
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• 1993

Pentaethylenehexaamine(penten) was reacted with a chloromethylated polystyrene resin on the purpose of the synthesis of polyamine chelating resin, $(P)_c$-penten. The stepwise dissociation constants of the synthesized polyamine chelating resin and the stability constants with metal ions were determined by Bjerrum's method. These stability constants were compared with those of the free penten. The adsorptivities and eluting tendencies of several metal ions on the chelating resin were studied.

• Journal of the Korean Chemical Society
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• v.54 no.5
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• pp.541-550
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• 2010

A new $N_4O_3$ heptadentate ligand, N,N'-Bis(2-hydroxybenzyl)-1,3-bis[(2-aminoethyl)amino]-2-propanol(H-BAP 4HCl)was synthesized. The hydrochloric acid salts of Br-BAP 4HCl, Cl-BAP 4HCl, $CH_3O$-BAP 4HCl and $CH_3$-BAP 4HCl containing Br-, Cl-, H-, $CH_3O-$ and $CH_{3^-}$ groups at the para-site of the phenol group of the H-BAP were synthesized. The structures of the ligands were confirmed by C. H. N. atomic analysis and $^1H$ NMR, $^{13}C$ NMR, UV-visible and mass spectra. The elemental stepwise protonation constants(${logK_n}^H$) of the synthesized $N_4O_3$ ligands showed six steps of the proton dissociation. The orders of the overall dissociation constants($log{\beta}_p$) of the ligands were Br-BAP < Cl-BAP < H-BAP < $CH_3O$-BAP < $CH_3$-BAP. The orders agreed well with that of Hammett substituent constants($\sigma_p$). The calculated stability constants($logK_{ML}$) between the ligands and transition metal ions agreed well with the order of the overall proton dissociation constants of the ligands but they showed a reverse order in Hammestt substituent constants($\sigma_p$). The order of the stability constants between the transition metal ions with the ligands were Co(II) < Ni(II) < Cu(II) > Zn(II) > Cd(II) > Pb(II).

• Analytical Science and Technology
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• v.9 no.4
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• pp.345-354
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• 1996

Algal(II) Multidentate N, O-Schiff base ligands, such as bis(salicylaldehyde) ethylenediimine(SED), bis(salicylaldehyde) propylenediimine(SPD), bis(salicylaldehyde) diethylenetriimine(SDT), bis (salicylaldehyde) triethylenetetraimine(STT) and bis(salicyl-aldehyde)tetraethylenepentaimine(STP) were prepared. Stepwise proton dissociation constants of the Schiff base were measured potentiometrically in ethanol and a mixture of 70% dioxane and 30% $H_2O$. The stability constants of copper(II)-Schiff base complexes were in the order of Cu(II)-SPD${\leq}$Cu(II)-SED~STT${\leq}$Cu(II)-STP. Oxidation-reduction process of the Cu(II)-Schiff base complexes was involved with one-electron reaction.

• Journal of the Korean Chemical Society
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• v.36 no.5
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• pp.652-660
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• 1992

The polyamine resins were synthesized by reacting amines such as diethylenetriamine(dien), triethylenetetramine(trien), tetraethylenepentamine(tetren), and pentaethylenehexamine(penten). Stepwise dissociation constants of amines, enthalpy and free energy of metal chelate were determined. Formation constants $(log k_1) of metal chelates were in order of Cu(Ⅱ) > Ni(Ⅱ) > Cd(Ⅱ) > Zn(Ⅱ) > Co(Ⅱ) and tendency of stabilities were proportional to nitrogen numbers of ligand such as dien < trien < tetren > penten. Elutional selectivites of metal ions on resin were agreed to formation constants of metal chelates. {\Delta}H and {\Delta}G were calculated by Van't Hoff equation. Stability constants (log k1) of metalic complexes were in order Cu(Ⅱ) > Ni(Ⅱ) > Cd(Ⅱ) > Zn(Ⅱ) > Co(Ⅱ), and tendency of stabilities were {\circledP}_L-Dien < {\circledP}_L-Trien < {\circledP}_L-Tetren < {\circledP}_L-Penten. The elutional selectivities of metal ions were agreed to stability constants of metal chelates.

• Journal of the Korean Chemical Society
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• v.33 no.4
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• pp.366-370
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• 1989

A new macrocyclic ligand 1,15,18-triaza-3,4;12,13-dibenzo-5,8,11-cycloeicosane (NdienOdien$H_4$ = $N_3O_3$) has been synthesized and identified by element analysis, NMR and IR spectrophotometry. Stepwise protonation constants of ligand are determined by potentiometry in 95% methanol solution(I = 0.1 mol $dm^{-3}$, $Me_4$NCl). log $K_1$;log $K_2$;log $K_3$ = 9.1;8.1;3.6.The kinetics of the acid-promoted dissociation reactions of complex cations of nickel(II) and copper(III) with NdienOdien and NdienOen macrocyclic ligands having, respectively, 17 and 20 ring members, have been studied spectrophotometrically in HCl$O_4$ NaCl$O_4$ aqueous solutions. From the temperature effect on kinetic constant ($k_{obs}$), the parameters of activation(${\Delta}H^{\neq}$, ${\Delta}S^{\neq}$) of dissociation reaction for $ML^{2+}$ with $H^+$ ion have been determined. We have proposed the possible mechanism of the reaction from the data obtained.