• Analytical Science and Technology
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• v.8 no.3
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• pp.321-334
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• 1995

Basic studies for the effective extraction of ammonium pyrrolidine dithiocarbamate(APDC) complexes of Co(II), Ni(II) and Cu(II) into a solvent have been performed. The maximum distribution ratio was appeared (log D=1.3543) at pH 2.0 and the partition coefficient was 2.489 in the extraction of $4{\times}10^{-5}M$ APDC itself into chloroform. From the UV/visible spectra of metal-chelates in aqueous and organic solutions, the pH to form stable 1:2 metal-ligand complexes were Co(II):5.0, Ni(II):8.0 and Cu(II):8.0, respectively and only 1 minute was enough to be partitioned into the chloroform. Besides, the partition and extraction equilibria of the complexes were investigated by back-extracting $10.0{\mu}g/ml$ metal-chelates from the solvent into an aqueous solution beacuse of their slight solubilities in the aqueous solution. The distribution coefficients and extractabilities were as follows : at pH 6.5~8.5 of the aqueous solution, log D=2.834 : E(%)=99.9% for $Co(PDC)_2$, at pH 11, log D=5.699 E%=100 for $Ni( PDC)_2$, and at pH 6.0, log D=2.025 : E(%)=99.1% for $Cu(PDC)_2$. And the extraction and formation constants were log $K_{ex}=9.671$ : log ${\beta}_2=6.938$ for $Co(PDC)_2$, log $K_{ex}=9.646$ : log ${\beta}_2=7.071$ for $Ni( PDC)_2$, and log $K_{ex}=9.074$ : log ${\beta}_2=7.049$ for $Cu(PDC)_2$, respectively. From these results, an optimum extraction procedure can be constructed for the separative concentration of trace metallic ions, and the quantitative determination of them in advanced materials and environmental samples will be expected without any influence of sample matrixes.

• Journal of the Korean Chemical Society
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• v.12 no.2
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• pp.47-50
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• 1968

Two methods for separation of the impurities from bismuth metal have been found by the use of Dowex $1{\times}4,$ anion exchange resins. The first method is that Dowex $1{\times}4$ resins are packed into the two stage columns (height of under stage is 22cm and upper stage is 3cm, and diameter of columns are 1.5cm), and the impurities of Pb(II), Ag(I) and Cu(II) are separated by the eluent of 7.5M HCl soln, Zn(II), Fe(III) by 0.5M HCl solns, and Te(IV) in the upper stage by 2M NaOH soln. Remained Au(III) in the upper stage is determined by the ignition with resins. The 2nd method is that for the separation of all the impurities simultaneously the same resins are packed into single stage column(height is 10cm and diameter is 1.5cm), and all the impurities of Pb(II), Zn(II), Cu(II), Fe(III) and Ag(I) are eluted by the eluent of 0.5M HCl soln. Separated impurities are determined by the colorimetry.

• Journal of Environmental Science International
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• v.21 no.4
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• pp.421-435
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• 2012

Novel $N_2O_2$ 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, $^{13}C$ NMR, UV-visible, and mass spectra. The proton dissociation constants ($logK_n{^H}$) of the phenol hydroxyl group and secondary amine of the synthesized $N_2O_2$ ligands were shown by four step wise values. The orders of the calculated overall proton dissociation constants ($log{\beta}_p$) 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(${\delta}_p$). The stability constants($logK_{ML}$) of the complexes between the synthesized ligands and transition metal(II) ions agreed with the order of $log{\beta}_p$ of the ligands. The order of the $logK_{ML}$ 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.

• YAKHAK HOEJI
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• v.42 no.2
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• pp.149-152
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• 1998

A high performance liquid chromatographic method was developed for the determination of DA-6034 in biological fluids using internal standard. Plasma containing DA-6034 and inter nal standard was extracted by liquid-liquid extraction at an acidic pH. After evaporation of the organic layer, the drug and internal standard were reconstituted with mobile phase and injected into the column. They were separated by high performance liquid chromatography on inertsil ODS II column at 334 nm. The detection limit of DA-6034 in plasma was 0.02 ${\mu}$g/ml. In this method, the range of recovery and coefficients of variation were 96-110% and 0.40-3.78%, respectively. There was no interference from endogenous substances. Urine and bile were analysed using the deproteinization method and the detection limit of DA-6034 was 1${\mu}$g/l.

• Analytical Science and Technology
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• v.9 no.4
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• pp.336-344
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• 1996

The extraction of trace cobalt, copper, nickel, cadmium, lead and zinc in urine samples of organic and alkali metal matrix into chloroform by the complex with a dithizone was studied for graphite furnace AAS determination. Various experimental conditions such as the pretreatment of urine, the pH of sample solution, and dithizone concentration in a solvent were optimized for the effective extraction, and some essential conditions were also studied for the back-extraction and digestion as well. All organic materials in 100 mL urine were destructed by the digestion with conc. $HNO_3$ 30 mL and 30% $H_2O_2$ 50 mL. Here, $H_2O_2$ was added dropwise with each 5.0 mL, serially. Analytes were extracted into 15.0 mL chloroform of 0.1% dithizone from the digested urine at pH 8.0 by shaking for 90 minutes. The pH was adjusted with a commercial buffer solution. Among analytes, cadmium, lead and zinc were back-extracted to 10.00 mL of 0.2 M $HNO_3$ from the solvent for the determination, and after the organic solvent was evaporated, others were dissolved with $HNO_3-H_2O_2$ and diluted to 10.00 mL with a deionized water. Synthetic digested urines were used to obtain optimum conditions and to plot calibration-eurves. Average recoveries of 77 to 109% for each element were obtained in sample solutions in which given amounts of analytes were added, and detection limits were Cd 0.09, Pb 0.59, Zn 0.18, Co 0.24, Cu 1.3 and Ni 1.7 ng/mL, respectively. It was concluded that this method could be applied for the determination of heavy elements in urine samples without any interferences of organic materials and major alkaline elements.

• Journal of Environmental Science International
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• v.18 no.7
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• pp.735-746
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• 2009

Hydrochloric acid salt of a new $N_2O_3$ pentadentate ligand, N,N'-Bis(2-Hydroxybenzyl)-1,3-diamino-2-propanol(H-BHDP 2HCl) was synthesized. Br-BHDP 2HCl, CI-BHDP 2HCl, $CH_3-BHDP$ 2HCl and $CH_3O$-BHDP 2HCl having Br, Cl, $CH_3$ and $CH_3O$ 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($log{\beta}_p$) was Br-BHDP < Cl-BHDP < H-BHDP < $CH_3O-BHDP$ < $CH_3-BHDP$. The order showed a similar trend to that of Hammett substituent constants(${\delta}_p$). The order of the stability constants($logK_{ML}$) was Co(II) < Ni(II) < Cu(II) < Zn(II) < Cd(II) < Pb(II). The order in their stability constants ($logK_{ML}$) of each transition metal complex agreed with that of the overall proton dissociation constants ($log{\beta}_p$).

• Journal of Environmental Science International
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• v.20 no.6
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• pp.687-700
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• 2011

A new $N_3-O_2$ pentadentate ligand, H-BHPT, was synthesized. Hydrochloric acid salts of Br-BHPT, Cl-BHPT, $CH_3O$-BHPT and $CH_3$-BHPT, having Br-, Cl-, $CH_{3-}$ and $CH_3O-$ 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, $^{13}C$ NMR, UV-visible, and mass spectra. The calculated proton dissociation constants ($log{K_n}^H$) of the phenol hydroxyl group and secondary amine group of the synthesized $N_3-O_2$ ligands showed five steps of the proton dissociations. The order of the overall proton dissociation constants ($log{\beta}_p$) of the ligands was Br-BHPT < Cl-BHPT < H-BHPT < $CH_3O$-BHPT < $CH_3$-BHPT. The order agreed with that of Hammett substituent constants (${\delta}_p$). However, dissociation steps of 3OH-BHPT were four and that of 4OH-BHPT was three. The calculated stability constants ($logK_{ML}$) between the ligands and transition metal ions agreed with the order of $log{\beta}_p$ 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.

• Proceedings of the KSME Conference
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• 2003.11a
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• pp.1222-1227
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• 2003

Pitting wear is a dominant form of polyethylene surface damage in total knee replacements, and may originate from surface cracks that propagate under repeated tribological contact. In this study, stress intensity factors, $K_{I}$ and $K_{II}$, were calculated for a surface crack in a polyethylene - CoCr - bone system under the rolling and/or sliding contact pressures. Crack length and load location were considered in determination of probable crack propagation mechanisms and fracture modes. Positive $K_{I}$ values were obtained for shorter cracks in rolling contact and for all crack lengths when the sliding load was apart from the crack. $K_{II}$, was the greatest when the load was directly adjacent to the crack $(g/a={\pm}1)$. Sliding friction caused a substantial increase of both $K_{I}^{max}$ and $K_{II}^{max}$. The effective Mode I stress intensity factors, $K_{eff}$, were the greatest at $g/a={\pm}1$, showing the significance of high shear stresses generated by loads adjacent to surface cracks. Such behavior of $K_{eff}$ suggests mechanisms for surface pitting by which surface cracks may propagate along their original plane under repeated rolling or sliding contact.

• Journal of the Korean Chemical Society
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• v.40 no.12
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• pp.724-732
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• 1996

The organic precipitate flotation using Cu(II)-pyrrolidinedithiocarbamate complex as a coprecipitant was studied for the preconcentration and determination of trace Cd, Pb, Bi and Co in several water samples. Experimental conditions such as pH of solution, amounts of Cu(II) and ammonium pyrrolidinedithiocarbamate(APDC), stirring time, the type and amount of surfactant, etc. were optimized for the effective flotation of analytes. After 3.0 mL of 1,000 ${\mu}g/mL$ Cu(II) solution was added to 1.00 L water sample, the pH of the solution was adjusted to 2.5 with HNO3 solution. Trace amounts of analytes were coprecipitated by adding 2.0% APDC solution. And the precipitates were flotated onto the surface of solution with the aid of nitrogen gas and sodium lauryl sulfate. The floats were collected from mother liquor, and filtered through the micropore glass filter by suction. The precipitates were dissolved with 4 mL conc. HNO3, and then diluted to 25.00 mL with deionized water. The analytes were determined by graphite furnace atomic absorption spectrophotometry. This flotation technique was applied to the analysis of some water samples, and the 90 to 120% of recoveries were obtained from the spiked samples, this procedure could be concluded to be simple and applicable for the trace element analysis in various kinds of water.

• Journal of the Korean Chemical Society
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• v.38 no.9
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• pp.667-675
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• 1994

The precipitate flotation using $La(OH)_3$ as a coprecipitant was studied for the simultaneous determination of trace three elements in a sea water. Several experimental conditions such as pH, coprecipitant and surfactant were investigated with an artificial sea water. To remove the influence of Cr(VI) the Cr(VI) was reduced to Cr(III) using $NaBH_4$ prior to the flotation. Trace amounts of Cu(II), Co(II) and total Cr in 1.0 l sea water was coprecipitated together with the precipitation of $La(OH)_3$ in the solution of pH 9.8 adjusted with 3.OM NaOH solution. The precipitate was floated by using a mixed surfactant (1 to 8 of each 0.5% ethanolic sodium oleate and sodium dodecylsulfate solution) by bubbling a nitrogen gas. The floats was separated and filtrated from the mother liquor by suction. The precipitate was dissolved in 7.0 M $HNO_3$ solution and then marked to 25.0 ml with a deionized water. These elements were determined by graphite fumace atomic absorption spectrophotometry. This method was applied to determine the elements in the sea water of the Eastern and Western coasts. And the recoveries were over 90.0% in the samples into which given amounts of the analyte elements were spiked.