• Environmental Engineering Research
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• v.13 no.3
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• pp.131-135
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• 2008

In this study, Fe(VI) was employed as a multi-functional agent to treat the simulated industrial wastewater contaminated with Cu(II)-EDTA through oxidation of EDTA, decomplexation of Cu(II)-EDTA and subsequent removal of free copper through precipitation. The decomplexation of $10^{-4}\;M$ Cu(II)-EDTA species was performed as a function of pH at excess concentration of Fe(VI). It was noted that the acidic conditions favor the decomplexation of Cu(II)-EDTA as the decomplxation was almost 100% up to pH 6.5, while it was only 35% at pH 9.9. The enhanced degradation of Cu(II)-EDTA with decreasing the pH could be explained by the different speciation of Fe(VI). $HFeO_4^-$ and $H_2FeO_4$, which are relatively more reactive than the unprotonated species $FeO_4^{2-}$, are predominant species below neutral pH. It was noted that the decomplexation reaction is extremely fast and within 5 to10 min of contact, 100% of Cu(II)-EDTA was decomplexed at pH 4.0. However, at higher pH (i.e., pH 10.0) the decomplexation process was relatively slow and it was observed that even after 180 min of contact, maximum ca 37% of Cu(II)-EDTA was decomplexed. In order to discuss the kinetics of the decomplexation of Cu(II)-EDTA, the data was slightly fitted better for the second order rate reaction than the first order rate reaction in the excess of Fe(VI) concentration. On the other hand, the removal efficiency of free Cu(II) ions was also obtained at pH 4.0 and 10.0. It was probably removed through adsorption/coagulation with the reduced iron i.e., Fe(III). The removal of total Cu(II) was rapid at pH 4.0 whereas, it was slow at pH 10.0. Although the decomplexation was 100% at lower pH, the removal of free Cu(II) was relatively slow. This result may be explicable due to the reason that at lower pH values the adsorption/coagulation capacity of Fe(III) is greatly retarded. On the other hand, at higher pH values the decomplexation of Cu(II)-EDTA was partial, hence, slower Cu(II) removal was occurred.

• Bulletin of the Korean Chemical Society
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• v.16 no.3
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• pp.265-269
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• 1995

Complexation of ortho-xylyl-17-crown-5 (X17C5) with alkali metal ions in acetonitrile was studied by 7Li and 23Na NMR spectroscopy. The complex formation constants of X17C5 with LiI, LiSCN, NaI, and NaSCN were determined by investigating the changes in the chemical shifts as a function of the concentration ratio of X17C5 to metal ion. It was found that X17C5 forms 1:1 complex with Li+ and Na+ ions and the log Kf's for the complexation with LiI, LiSCN, NaI, and NaSCN were determined to be 2.88, 2.43, 2.53, and 2.30, respectively. In particular, the kinetics of complexation of X17C5 with Na+ was investigated by the method of 23Na NMR lineshape analysis. Activation energies were determined from Arrhenius plot of the resultant rate constant data to be 25.4 kJ/mol for NaI and 15.1 kJ/mol for NaSCN. Other kinetic parameters were also calculated by employing the Eyring equation. The decomplexation rates measured were 1.82 × 104 M-1s-1 for NaI and 1.50 × 104 M-1s-1 for NaSCN. It is concluded that the decomplexation mechanism is predominantly a bimolecular cation exchange for both cases.

• Bulletin of the Korean Chemical Society
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• v.28 no.1
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• pp.95-98
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• 2007

Polyethylenimine (PEI) has been widely investigated for delivery of DNA into cells. It was previously reported that there were at least two types of cytotoxicity in PEI-mediated gene delivery, immediate and delayed toxicities. PEI-mediated gene delivery protocols use net cationic complexes with an excess of PEI to maintain equilibrium between the complexed and dissociated forms in solution. In this study, toxicity of free PEI or PEI/ DNA complex was investigated. Human embryonic kidney 293 cells were incubated with free PEI or PEI/DNA complex for 4 hrs. Then, the cells were analyzed at 6, 24, 48, and 96 hrs after the incubation. In MTT assay, the viability of the cells incubated with PEI/DNA complex was continuously decreased with time, while that of the cells incubated with free PEI was not. On the contrary, the expression level of the luciferase gene increased gradually along with time. Release of DNAs from the complexes for transcription produces free PEIs in the cells. This process may proceed slowly due to high charge density of PEI and may be related to delayed toxicity. In addition, apoptotic cells were observed only in the cells incubated with the PEI/DNA complex from 24 hrs after the incubation. The results suggest that PEI/DNA complex contributes to the delayed toxicity by inducing apoptosis and that the delayed toxicity may be related to decomplexation of the complexes in the cells.

• Journal of Korean Society on Water Environment
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• v.21 no.1
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• pp.66-72
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• 2005

Effect of the pH, molar ratio of Cu(II)/EDTA, concentration of Cu(II)-EDTA and ionic strength on the photocatalytic oxidation(PCO) of Cu(II)-EDTA in solar light was studied in this work. Experimental results in this work were compared with previous results obtained with UV-lamp. In the kinetics, Cu(II)-EDTA decomposition was favorable below neutral pH. The removal of Cu(II) and DOC was favorable as $TiO_2$ dosage increased. The initial rate for the decomplexation of Cu(II)-EDTA linearly increased as the concentration of Cu(II)-EDTA increased. The removal of Cu(II) and DOC was not much affected by variation of ionic strength with $NaClO_4$ as a background ion while much reduction was observed in the presence of background ions having higher formal charges. The removal trend of Cu(II) and DOC with variation of ionic strength and concentration of Cu(II)-EDTA in solar light was similar with that in UV light. Variation of the molar ratio of Cu(II)/EDTA showed a negligible effect on the removal of both Cu(II) and DOC. However, removal of both Cu(II) and DOC was two-times greater than that previous results obtained with UV light.

• Journal of Korean Society of Environmental Engineers
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• v.30 no.7
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• pp.729-734
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• 2008

The higher valence state of iron i.e., Fe(VI) was employed for the treatment of Cu(II)-EDTA in the aqueous/waste waters. The ferrate(VI) was prepared through wet oxidation of Fe(III) by sodium hypochlorite. The purity of prepared Fe(VI) was above 93%. The stability of Fe(VI) solution decreased as solution pH decreased through self decomposition. The reduction of Fe(VI) was obtained by using the UV-Visible measurements. The dissociation of Cu(II)-EDTA complex through oxidation of EDTA using Fe(VI) and subsequent treatment of organic matter and metal ions by Fe(III) reduced from Fe(VI) in bench-scale of continuous flow reactor were studied. The removal efficiencies of copper were 69% and 79% in pH control basin and reactor, respectively, at 120 minutes as retention time. In addition, Cu(II)-EDTA in the reactor was decomplexated more than 80% after 120 minutes as retention time. From this work, a continuous treatment process for the wastewater containing metal and EDTA by employing Fe(VI) as muluti-functional agent was developed.

• Journal of Korean Society of Environmental Engineers
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• v.27 no.8
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• pp.844-851
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• 2005

The purpose of this study was to determine feasibility of application of regenerated or recycled $TiO_2$ on the successive treatment of Cu(II)-EDTA. The recovery of copper, the reuse of $TiO_2$ and the assessment of acute toxicity was studied in the total eight successive photocatalytic reactions. Aqueous solution of $10^{-4}\;M$ Cu(II)-EDTA was treated using an illuminated $TiO_2$ at pH 6 in a circulating reactor. Two different procedures were applied in the reuse of $TiO_2$: i) recycle of $TiO_2$ without acid wash ii) regeneration of $TiO_2$ with acid wash to remove adsorbed copper in a previous experiment. The averaged decomplexation rate constant($k'_{obs}$) of Cu(II)-EDTA in recycle of $TiO_2$ without acid wash was approximately 45% less than that in regeneration of $TiO_2$ with acid wash. Removal of Cu(II) was near complete after 180 minutes in the total eight successive photocatalytic reactions using the regenerated $TiO_2$ after acid wash. In contrast, removal of Cu(II) was minimum at total fifth successive photocatalytic oxidation using the recycled $TiO_2$ without arid wash. The recovered $TiO_2$ was approximately 86% in average in each procedure. The recovered Cu(II) was 67.9% in average. The acute relative toxicity of the treated water rapidly declined at an initial reaction time up to 60 minutes but little declination was observed after 60 minutes due to little degradation of DOC. Relative toxicity of treated water using the recycled $TiO_2$ without acid wash we some what well correlated with the concentration of dissolved Cu(II). From this work, it is suggested that Cu(II)-EDTA can be effectively treated using an integrated cyclic photocatalytic oxidation with recovery of $TiO_2$ and Cu(II).