Chelating agents, such as ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), and nitrilotriacetic acid (NTA) are widely used in industry and agriculture as water softeners, detergents, and metal chelating agents. In wastewater treatment plants, a significant amount of chelating agents can be discharged into natural waters because they are difficult to degrade. Since those compounds affect the mobility of radionuclides or heavy metals in decontamination operations at nuclear facilities and radioactive waste disposal, quantification of the amount of ligand is very important for safe nuclear waste management. To predict the behavior of the main complexation in sample matrices of radioactive wastes, it is essential to evaluate the distribution of the metal-chelating species and their stabilities in order to develop analytical techniques for quantifying chelating agents. We have investigated to collect information on the pH speciation of metal chelation and the stability constants of metal complexes depending on three chelating agents (EDTA, DTPA, and NTA). For example, Zhang’s group recently reported that the initial coordination pH of Cu(II) and EDTA4− is delayed with the addition of Fe(III), and the pH range for the stable existence of [Cu(EDTA)]2− is narrowed compared to when it is alone in the sample matrix. The addition of Fe(III) clearly impacts the chemical states of the Cu(II)-EDTA solution. Additionally, Eivazihollagh’s group demonstrated differences in the speciation and stability of Cu(II) species between Cu(II) and three chelating ligands (EDTA, DTPA, and NTA). This study will be greatly helpful in identifying the sample matrix for binding major chelating agents and metals as well as developing chemically sample pretreatment and separation methods based on the sample matrix. Finally, these advancements will enable reliable quantitative analysis of chelating agents in decommissioning radioactive wastes.

Novel N2O2 tetradentate ligands, H-3BPD and H-2BPD were synthesized. Hydrochloric acid salts of Br-3BPD, Cl-3BPD, Br-2BPD and Cl-2BPD having Br and Cl substituents at the para position of the phenol hydroxyl group, were synthesized. The ligands were characterized by C. H. N atomic analysis, 1H NMR, 13C NMR, UV-visible, and mass spectra. The proton dissociation constants (logKn H) of the phenol hydroxyl group and secondary amine of the synthesized N2O2 ligands were shown by four step wise values. The orders of the calculated overall proton dissociation constants (logβp) were Br-3BPD < Cl-3BPD < H-3BPD in case of 3BPD and Br-2BPD < Cl-2BPD < H-2BPD in case of 2BPD respectively. The order agreed well with that of para Hammett substituent constants(δp). The stability constants(logKML) of the complexes between the synthesized ligands and transition metal(II) ions agreed with the order of logβp of the ligands. The order of the logKML value of the each transition metal (II) ion was Co(Ⅱ) < Ni(Ⅱ) < Cu(Ⅱ) > Zn(Ⅱ) > Cd(Ⅱ) > Pb(Ⅱ), which agreed well with that of Iriving-Williams series.

new N3-O2 pentadentate ligand, H-BHPT, was synthesized. Hydrochloric acid salts of Br-BHPT, Cl-BHPT, CH3O-BHPT and CH3-BHPT, having Br-, Cl-, CH3- and CH3O- substituents at the para position of the phenol hydroxyl group of H-BHPT were synthesized. Hydrochloric acid salts of 3OH-BHPT and 4OH-BHPT, having different position of the phenol hydroxyl group of H-BHPT were also synthesized. The synthesis of each ligand was confirmed by C. H. N. atomic analysis and 1H NMR, 13C NMR, UV-visible, and mass spectra. The calculated proton dissociation constants (logKn H) of the phenol hydroxyl group and secondary amine group of the synthesized N3-O2 ligands showed five steps of the proton dissociations. The order of the overall proton dissociation constants (logβp) of the ligands was Br-BHPT < Cl-BHPT < H-BHPT < CH3O-BHPT < CH3-BHPT. The order agreed with that of Hammett substituent constants (δp). However, dissociation steps of 3OH-BHPT were four and that of 4OH-BHPT was three. The calculated stability constants (logKML) between the ligands and transition metal ions agreed with the order of logβp values of the ligands. The order of the stability constants between the transition metal ions with the synthesized ligands was Co(Ⅱ) < Ni(Ⅱ) < Cu(Ⅱ) > Zn(Ⅱ) > Cd(Ⅱ) > Pb(Ⅱ). The order agreed well with that of the Iriving-Williams.

A new N3O2 pentadentate ligand, N,N'-Bis(2-hydroxybenzyl)-ethylenetriamine(H-BHET․3HCl) was synthesized. The hydrochloric acid salts of Br-BHET․3HCl, Cl-BHET․3HCl, CH3O-BHET․3HCl and CH3-BHET․3HCl containing Br-, Cl-, H-, CH3O- and CH3- 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, 13C NMR, UV-visible and mass spectra. The calculated stepwise protonation constants(logKnH) of the synthesized N3O2 ligands showed six steps of the proton dissociation. The orders of the overall protonation constants(logβp) of the ligands were Br-BHET < Cl-BHET < H-BHET < CH3O-BHET < CH3-BHET. The orders agreed well with that of para Hammett substituent constants(δp). The calculated stability constants(logKML) 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(δp). 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).

Hydrochloric acid salt of a new N2O3 pentadentate ligand, N,N'-Bis(2-Hydroxybenzyl)-1,3-diamino-2-propanol(H-BHDP․2HCl) was synthesized. Br-BHDP․2HCl, Cl-BHDP․2HCl, CH3-BHDP․2HCl and CH3O- BHDP․2HCl having Br, Cl, CH3 and CH3O substituents at 5-position of the phenol group of H-BHDP․2HCl were also synthesized. The potentiometry study in aqueous solution revealed that the proton dissociations of the synthesized ligands occurred in four steps and their order of the calculated overall proton dissociation constants(logβp) was Br-BHDP〈 Cl-BHDP〈 H-BHDP〈 CH3O-BHDP〈 CH3-BHDP. The order showed a similar trend to that of Hammett substituent constants(δp). The order of the stability constants(logKML) was Co(Ⅱ)〈 Ni(Ⅱ)〈 Cu(Ⅱ)〈 Zn(Ⅱ)〈 Cd(Ⅱ)〈 Pb(Ⅱ). The order in their stability constants (logKML) of each transition metal complex agreed with that of the overall proton dissociation constants (logβp).

Hydrochloride acid salts of new N2O2 tetradentate ligands containing amine and phenol N,N'-bis(2-hydroxybenzyl)-o-phenylenediamine(H-BHP), N,N'-bis(5-bromo-2-hydroxybenzyl)-o-phenylenediamine(Br-BHP), N,N'-bis (5-chloro-2-hydroxybenzyl)-o-phenylene-diamine(Cl-BHP), N,N'-bis(5-methyl-2-hydroxybenzyl)-o-phenylene-diamine (Me-BHP) and N,N'-bis(5-methoxy-2-hydroxybenzyl)-o-phenylenediamine(MeO-BHP) were synthesized. The ligands were characterized by elemental analysis, mass and NMR spectroscopy. The elemental analysis showed that the ligands were isolated as dihydrochloride salt. The potentiometry study revealed that the proton dissociation constants(logKnH) of ligands and stability constants (logKML) of transition and heavy metals complexes. The order of the stability constants of each metal ions for ligands was Br-BHP < Cl-BHP < H-BHP < MeO-BHP < Me-BHP.

Hydrobromic acid salts of new N, N, O tridentate ligands containing phenol, 2-[(2-Methylamino- ethylamino)-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-[(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, 1H NMR, 13C NMR and mass analysis. The potentiometry study revealed that the proton dissociation constants(logKnH) of the synthesized ligands and stability constants (logKML, logKML2) 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(logβp) and stability constants (logKML) 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(δp). The synthesized ligands usually form 2:1(ML2) 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).

N,N-bis(2-salicylaldehyde)dipropylenetriamine(5-Hsaldipn), N,N-bis(5-bromosalicyl-aldehyde) dipropylenetriamine (5-Brsaldipn), N,N-bis(5-chlorosalicylaldehyde)dipropylene-triamine(5-Clsaldipn), N,N-bis(2-hydroxy-5-methoxybenzaldehyde)dipropylenetriamine(5-OCH3saldipn) and N,N-bis (2-hydroxy-5-nitrobenzaldehyde)dipropylenetriamine (5-NO2saldipn) were synthesized and characterized by elemental analysis, infrared spectrometry, NMR spectrometry and mass spectrometry. Their proton dissociation constants were determined in 70% dioxane/30% water solution by potentiometric. Stability constants of the complexes between these ligands and the metal ions such as Cu(Ⅱ), Ni(Ⅱ) and Zn(Ⅱ) were measured in dimethyl sulfoxide by a polarographic method. Stability constants for the ligands were in the order of 5-OCH3 ＞ 5-H ＞ 5-Br ＞ 5-Cl ＞ 5-NO2saldipn. Enthalpy and entropy changes were obtained in negative values.

The thiophene or furan-containing hexadentate ligands 1,12-bis (2-theophene)-2,5,8,11-tetraazadodecane(Thiotrien ․4HCl) and 1,12-bis (2-furan)-2,5,8,11-tetraazadodecane(Furatrien․4HCl) were synthesized as their tetrahydrochloride salt and characterized by EA, IR, NMR, and Mass spectrum. Their protonation constants (logKnH) and stability constants (logKML) for Cd2+, Pb2+, Zn2+ and Cu2+ ions were determined in aqueous solution by potentiometry and compared with 1,12-bis(2-pyridyl)-2,5,8,11-tetra-azadodecane(Pytrien) of pyridyl-containing ligand. The effect stability constants of ligands and metal ion for removal of heavy metals in aqueous solution were described.