• Journal of the Korean Chemical Society
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• v.44 no.5
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• pp.403-409
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• 2000

The formation and dissociation rates of $Zn^{2+}$ Complexes with l,4,7,10-tetraaza-13,16-diox-acyclooctadecane-N,N',N",N'"-tetraacetic acid (1), 1,4,7,10-tetraaza-13,16- dioxacyclooctadecane-N,N',N",N'"-tetramethylacetic acid (2), and 1,4,7,10-tetraaza-13,16- dioxacyclooctadecane-N,N',N",N'"-tetrapropionic acid(3) have been measured by stopped-flow and conventional spectrophotometry. Observations were made at 25.0$\pm$0.1 $^{\circ}C$ and at an ionic strength of 0.10 M NaClO$_4$. The formation reactions of $Zn^{2+}$ ion with 1 and 2 took place by the rapid formation of an intermediate complex (ZnH$_3L^+$) in which the $Zn^{2+}$ ion is incompletely coor-dinated. This might then lead to be a final product in the rate-determining step.ln the pH range 4.76-5.76, the diprotonated (H2L2-) form is the kinetically active species despite of its low concentration. The stability con-stants (log$K_{(ZnH$_3$3$L^+$)}$) and specific water-assisted rate constants (koH) of intermediate complexes have been deter-mined from the kinetic data. The dissociation reactions of $Zn^{2+}$ complexes of 1,2, and 3 were investigated with $Cu^{2+}$ ions as a scavenger in acetate buffer. All complexes exhibit acid-independent and acid-catalyzed con-tributions. The effect of buffer and $Cu^{2+}$ concentration on the dissociation rate has also been investigated. The ligand effect on t dissociation rate of $Zn^{2+}$ complexes is discussed in terms of the side-pendant armsand the chelate ring sizes of the ligands.

• Journal of Korean Society on Water Environment
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• v.25 no.6
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• pp.979-983
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• 2009

The mean pH of wastewater discharged from the plating process is 2, so a less amount of alkali is required to raise pH 2 to 5. In addition, if sodium sulfite is used to raise pH 5 to 9 in the secondary treatment, caustic soda or slaked lime is not necessary or only a small amount is necessary because sodium sulfite is alkali. Thus, it is considered desirable to use only $FeSO_4{\cdot}7H_2O$ in the primary treatment. At that time, the free cyanide removal rate was highest as around 99.3%, and among heavy metals, Ni showed the highest removal rate as around 92%, but zinc and chrome showed a low removal rate. In addition, the optimal amount of $FeSO_4{\cdot}7H_2O$ was 0.3g/L, at which the cyanide removal rate was highest. Besides, the free cyanide removal rate was highest when pH value was 5. Of cyanide removed in the primary treatment, the largest part was removed through the precipitation of ferric ferrocyanide: $[Fe_4(Fe(CN)_6]_3$, and the rest was precipitated and removed through the production of $Cu_2[Fe(CN)_6]$, $Ni_2[Fe(CN)_6]$, CuCN, etc. Furthermore, it appeared more effective in removing residual cyanide in wastewater to mix $Na_2SO_3$ and $Na_2S_2O_5$ at an optimal ratio and put the mixture than to put them separately, and the optimal weight ratio of $Na_2SO_3$ to $Na_2S_2O_5$ was 1:2, at which the oxidative decomposition of residual cyanide was the most active. However, further research is required on the simultaneous removal of heavy metals such as chrome and zinc.

• 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.

• Economic and Environmental Geology
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• v.25 no.4
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• pp.417-433
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• 1992

Lead-zinc-copper deposits of the Jeonheung and the Oksan mines around Euiseong area occur as hydrothermal quartz and calcite veins that crosscut Cretaceous sedimentary rocks of the Gyeongsang Basin. The mineralization occurred in three distinct stages (I, II, and III): (I) quartz-sulfides-sulfosalts-hematite mineralization stage; (II) barren quartz-fluorite stage; and (III) barren calcite stage. Stage I ore minerals comprise pyrite, chalcopyrite, sphalerite, galena and Pb-Ag-Bi-Sb sulfosalts. Mineralogies of the two mines are different, and arsenopyrite, pyrrhotite, tetrahedrite and iron-rich (up to 21 mole % FeS) sphalerite are restricted to the Oksan mine. A K-Ar radiometric dating for sericite indicates that the Pb-Zn-Cu deposits of the Euiseong area were formed during late Cretaceous age ($62.3{\pm}2.8Ma$), likely associated with a subvolcanic activity related to the volcanic complex in the nearby Geumseongsan Caldera and the ubiquitous felsite dykes. Stage I mineralization occurred at temperatures between > $380^{\circ}C$ and $240^{\circ}C$ from fluids with salinities between 6.3 and 0.7 equiv. wt. % NaCl. The chalcopyrite deposition occurred mostly at higher temperatures of > $300^{\circ}C$. Fluid inclusion data indicate that the Pb-Zn-Cu ore mineralization resulted from a complex history of boiling, cooling and dilution of ore fluids. The mineralization at Jeonheung resulted mainly from cooling and dilution by an influx of cooler meteoric waters, whereas the mineralization at Oksan was largely due to fluid boiling. Evidence of fluid boiling suggests that pressures decreased from about 210 bars to 80 bars. This corresponds to a depth of about 900 m in a hydrothermal system that changed from lithostatic (closed) toward hydrostatic (open) conditions. Sulfur isotope compositions of sulfide minerals (${\delta}^{34}S=2.9{\sim}9.6$ per mil) indicate that the ${\delta}^{34}S_{{\Sigma}S}$ value of ore fluids was ${\approx}8.6$ per mil. This ${\delta}^{34}S_{{\Sigma}S}$ value is likely consistent with an igneous sulfur mixed with sulfates (?) in surrounding sedimentary rocks. Measured and calculated hydrogen and oxygen isotope values of ore-forming fluids suggest meteoric water dominance, approaching unexchanged meteoric water values. Equilibrium thermodynamic interpretation indicates that the temperature versus $fs_2$ variation of stage I ore fluids differed between the two mines as follows: the $fs_2$ of ore fluids at Jeonheung changed with decreasing temperature constantly near the pyrite-hematite-magnetite sulfidation curve, whereas those at Oksan changed from the pyrite-pyrrhotite sulfidation state towards the pyrite-hematite-magnetite state. The shift in minerals precipitated during stage I also reflects a concomitant $fo_2$ increase, probably due to mixing of ore fluids with cooler, more oxidizing meteoric waters. Thermodynamic consideration of copper solubility suggests that the ore-forming fluids cooled through boiling at Oksan and mixing with less-evolved meteoric waters at Jeonheung, and that this cooling was the main cause of copper deposition through destabilization of copper chloride complexes.