• Journal of Korean Society of Environmental Engineers
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• v.30 no.5
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• pp.524-533
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• 2008

Industrial wastewater generated in the electroplating and metal finishing industries typically contain toxic free and complex metal cyanide with various heavy metals. Alkaline chlorination, the normal treatment method destroys only free cyanide, not complex metal cyanide. A novel treatment method has been developed which destroys both free and complex metal cyanide as compared with Practical Plant(I). Prior to the removal of complex metal cyanide by Fe/Zn coprecipitation and removal of others(Cu, Ni), Chromium is reduced from the hexavalent to the trivalent form by Sodium bisulfite(NaHSO$_3$), followed by alkaline-chlorination for the cyanide destruction. The maximum removal efficiency of chromium by reduction was found to be 99.92% under pH 2.0, ORP 250 mV for 0.5 hours. The removal efficiency of complex metal cyanide was max. 98.24%(residual CN: 4.50 mg/L) in pH 9.5, 240 rpm with 3.0 $\times$ 10$^{-4}$ mol of FeSO$_4$/ZnCl$_2$ for 0.5 hours. The removal efficiency of Cu, Ni using both hydroxide and sulfide precipitation was found to be max. 99.9% as Cu in 3.0 mol of Na$_2$S and 93.86% as Ni in 4.0 mol of Na$_2$S under pH 9.0$\sim$10.0, 240 rpm for 0.5 hours. The concentration of residual CN by alkaline-chlorination was 0.21 mg/L(removal efficiencies: 95.33%) under the following conditions; 1st Oxidation : pH 10.0, ORP 350 mV, reaction time 0.5 hours, 2nd Oxidation : pH 8.0, ORP 650 mV, reaction time 0.5 hours. It is important to note that the removal of free and complex metal cyanide from the electroplating wastewater should be employed by chromium reduction, Fe/Zn coprecipitation and, sulfide precipitation, followed by alkaline-chlorination for the Korean permissible limit of wastewater discharge, where the better results could be found as compared to the preceding paper as indicated in practical treatment(I).

• Journal of the Korean Chemical Society
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• v.35 no.5
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• pp.512-519
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• 1991

The axial ligations of nitrogenous bases (pyridine, imidazole, 1-methylimidazole and 2,6-lutidine) to Zn(II)-, Cu(II)-, and Ni(II)-tetrakis(o-chlorophenyl)porphyrin(o-ClTPP), and -tetraphenylporphyrin (TPP) were investigated in organic solvents $(CH_2Cl_2,\;C_6H_6,\;CH_3NO_2,\;(CH_3)_2CO,\;CHCl_3,\;DMF\;and\;DMSO)$ and at 0.01M of ionic strength. The equilibrium constants for the ligation reactions of methalloporphyrins were determined using spectrophotometric method at 15∼35${\circ}C$. In case of M(II)-TPP the equilibrium constants K were considerably larger than those of M(II)-(o-Cl)TPP, depending on steric effect of the porphyrin. The linear relationships between logK of the axial ligation and $pK_a$ of nitrogenous base were shown in M(II)-TPP, but not in M(II)-(o-Cl)TPP. The stabilities of MTPP(L) were controlled by the reation enthalpy and entropy, while those of M(o-Cl)TPP almost by the reaction entropy. The coordinating power of solvent to the methalloporphyrin were also studied in $CHCl_3,\;(CH_3)_2CO$, DMF and DMSO. From those results the solvent effects on the equilibrium constants were discussed.

• Journal of the Korean Chemical Society
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• v.35 no.6
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• pp.645-652
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• 1991

The stability constants$(K_f)$ of the complexes of some transition and post-transition metal ions (Co(Ⅱ), Ni(Ⅱ), Cu(Ⅱ), Zn(Ⅱ), Cd(Ⅱ), Pb(Ⅱ), Hg(Ⅱ)) with $N_2O_3$-donor macrocyclic ligand, 1,15-diaza-3,4 : 12,13-dibenzo-5,8,11-trioxacyclooctadecane ($NtnOdienH_4$), have been determined by potentiometry in aqueous solution at $25^{\circ}C$. Log $K_f$ values of the complexes were : Co(Ⅱ): 3.83, Ni(Ⅱ) : 4.56, Cu(Ⅱ) : 7.74, Zn(Ⅱ) : 4.98, Cd(Ⅱ) : 3.91, Pb(Ⅱ) : 6.65, and Hg(Ⅱ) : 14.87. The order of stabilities of transition metal complexes was the same as the natural order of stability proposed by Williams-Irving. In post-transition metal complexes, the order of stabilities was Cd(Ⅱ) < Pb(Ⅱ) < Hg(Ⅱ), and the covalent character in metal ion-donor atoms bonds appeared a dominant factor in the stability. In methanol solution, each metal ion forms 1 : 1 complex, while Ni(Ⅱ) ion forms both 1 : 1 and 1 : 2 complexes. It was confirmed by $^1H-$ and $^{13}C-$NMR spectral study that the nitrogen atoms in the ligand were major contributors for the complexation of post-transition metal ions with the ligand. It was shown, by elementry analysis, electrical conductivity and magnetic susceptibility measurements, and spectral analysis, that solid Cu(Ⅱ)-and Zn(Ⅱ)-complexes have a distorted octahedral and a tetrahedral structure, respectively.

• Journal of the Korean Geotechnical Society
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• v.16 no.2
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• pp.91-102
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• 2000

자연점토지반에서의 중금속 흡착시 온도변화에 따른 영향은 지금까지 2차적인 것으로 간주되었다. 그러나 최근 몇몇 연구자들에 의하면 온도변화가 중금속 흡착 거동에 큰 영향을 미친다고 보고하였다. 따라서 본 연구에서는 자연점토 지반에 대한 중금속 아연(Zn) 흡착시 온도변화에 따른 흙의 각 구성성분별 흡착거동을 살펴보기 위해 혼합 흡착-연속추출법(combined absorption-sequential extraction analysis, CASA)을 사용하였다. 실험결과 중금속 아연의 농도가 저농도(50mg/L 미만)일 경우 자연지반에서의 분배양상은 주로 탄산염 형태로 존재하고, 또한 온도의 증가에 따라 탄산염 형태의 흡착량이 증가하는 것을 알 수 있다. 하지만 고농도(50mg/L 이상)의 경우 분배양상은 주로 이온교환형태로 존재한다는 것을 알 수 있다. 그러나 고농도에서의 이러한 분배형태는 온도의 증가에 따라 탄산염형태의 흡착량이 약 20%정도 증가하는 결과를 얻었다. 결론적으로 중금속 아연의 자연점토지반의 각 구성성분 별 흡착거동은 이온교환 형태를 제외하고 온도증가에 따라 증가하는 흡열반응(ΔH0>0)인 것으로 나타났고, 또한 고농도에서의 분배형태는 이온교환 형태에서 탄산염 형태로 변화되는 것을 알 수 있다. 그리고 이온교환 형태의 경우 온도변화에 따라 독립적인 거동을 보였다.

• Proceedings of the Korean Society of Applied Pharmacology
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• 1995.04a
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• pp.130-130
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• 1995

AM, SM 및 ASA는 수용액중에서 겉보기 1차반응에 따라 분해되었으며 보존온도가 높을수록 분해가 촉진되는 온도 의존성을 나타내었다. AM의 분해경로는 pH 1.22 및 pH 7.0 이상에서는 AM$\longrightarrow$ SM $\longrightarrow$ SA의 경로로 주로 분해되었으며 pH 2.01 - 6.08의 범위에서는 AM $\longrightarrow$ASA$\longrightarrow$SA의 경로로 분해되는 양상을 보였다. 또 pH가 분해에 미치는 영향을 pH-rate profile로 나타낸 결과 AM, SM 및 ASA의 최대안정 pH는 각각 4.0, 3.0, 2.0 부근이 있고 이 조건에서의 분해 반감기는 114, 168, 113 hr로 나타났다. 전체적으로 보면 pH 2.0 이하에서는 ASA가 AM 보다 약간 안정한 편이나 pH 2.0-8.0 사이에서는 AM의 분해속도가 ASA보다 현저히 낮았다. 또 AM은 pH 7.0 이상에서, SM은 pH 6.0 이상에서, ASA는 9.0 이상에서 특수염기촉매반응에 따라 분해가 이루어지는 것을 알 수 있었다. 이온강도($\mu$)의 영향으로는 pH 7.0에서 이온강도가 0.115에서 1.0으로 증가할수록 $\mu$$^{1}$2/에 대해 AM의 분해속도정수가 직선적으로 완만하게 감소되었다. 또 완충수용액 중 AM의 가수분해 억제효과를 검토하기 위해 시클로덱스트린류를 첨가하였을 때, $\beta$-시클로덱스트린과 히드록시프로필기-$\beta$-시클로덱스트린은 AM의 분해를 각각 1.6배 및 1.1배 촉진시켜 촉매적으로 작용하였으며 디메칠-$\beta$-시클로덱스트린은 약 3.2배 분해속도를 억제시켜 안정화제로 작용하였다.Zn^{2+}$, soybean trypsin inhibtor에 의해 25～50% 정도, serine proteinase inhibitor인 phenylmethylsulfonyl floride에 의해 80%정도 활성이 억제되는 특성이 있음을 규명하였다.면역환성 (immunoreactivity)이 나타났고 pyramidal cell layer (PCL)와 glia에 SOD-1이 강하게 염색되었다. APT 병용 투여로 상당수의 경련이 일어나지 않은 흰쥐는 해마의 DG에 FRA가 경미하게 염색되었고, PCL에 SOD-1도 경미하게 나타났으나, 경련이 나타난 쥐에서는 KA만을 투여한 흰쥐와 구별되지 않았다. 이상의 APT의 항산화 효과는 KA로 인한 뇌세포 변성 개선에 중요한 인자로 작용할 것으로 사료되나, 보다 명확한 APT의 기전을 검색하고 직접 임상에 응응하기 위하여는 보다 다양한 실험 조건이 보완되어야 찰 것으로 생각된다. 항우울약들의 항혈소판작용은 PKC-기질인 41-43 kD와 20 kD의 인산화를 억제함에 기인되는 것으로 사료된다.다. 것으로 사료된다.다.바와 같이 MCl에서 작은 Dv 값을 갖는데, 이것은 CdCl$_{4}$$^{2-}$ 착이온을 형성하거나 ZnCl$_{4}$$^{2-}$ , ZnCl$_{3}$$^{-}$같은 이온과 MgCl$^{+}$, MgCl$_{2}$같은 이온종을 형성하기 때문인것 같다. 한편 어떠한 용리액에서던지 NH$_{4}$$^{+}$의 경우 Dv값이 제일 작았다. 바. 본 연구의 목적중의 하나인 인체유해 중금속이온인 Hg(II), Cd(II)등이 NaCl같은 염화물이 함유된 시료용액에 공해이온으로 존재할 경우 흡착에 의한 제거가 가능하다. 한편 이같

• Clean Technology
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• v.20 no.2
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• pp.108-115
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• 2014

Various metal chlorides and acid catalysts in ionic liquid solvent were investigated to directly convert cellulose into 5-hydroxymethylfurfural (5-HMF). Metal chlorides containing Sn(II), Zn(II), Al(III), Fe(III), Cu(II), and Cr(III) were used and acidic ionic liquid immobilized on silica gel as an acid catalyst and commercial acid catalysts (sulfuric acid, chloric acid, Amberlyst-15,DOWEX50x8) were used for comparison studies. The acid strength and amount of acid catalysts were probed with Hammett indicator. The selectivity and yield of 5-HMF were determined with reaction temperature, reaction time and catalyst ratio. A catalyst containing $CrCl_3-6H_2O$ and $SiO_2-[ASBI]HSO_4$ showed the highest selectivity and it was found that this catalyst had higher activity than commercial solid acid catalysts such as Amberlyst-15 and DOWEX50x8. The selectivity of 5-HMF appeared to be mainly dependent on the acid strength and catalyst ratio, it was found that levulinic acid was produced from 5-HMF by rehydration.

• Journal of the Korean Chemical Society
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• v.50 no.2
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• pp.99-106
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• 2006

The electronic absorption spectra of [3-(2-thenoyl) 3-(p-NO2-phenylhydrazone) ethyl pyruvate] (I), p-Br (II) and p-CH3 (III) were studied in ethanol and the spectra comprise four absorption bands which assigned to the corresponding electronic transition. The pK values of these compounds have been determined spectrophotometrically and pH-metrically, the results shown that the interval range for color change of compound (I) is (8-10) similar to that of phenolphethalin indicator, indicating that this compound can be used as acid-base indicator. The successive stability constants of the compounds under study with some transition elements (Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), UO2(II), La(III) and Zr(IV) have been determined pH- metrically. Stoichiometric complexes with ratios 1:1 and 1:2 (M: L) were formed for all metals. The pK of the three derivatives and the values of the stability constant (logK) of the complexes have the order; III > II > I. Also conductometric titrations have been carried out and the results show that this titration can be used for determination of both the metal ion and the ligand concentrations by each others.

• Journal of the Korean Chemical Society
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• v.8 no.2
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• pp.62-64
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• 1964

The cation exchange chromatographic studies for the analysis of transition metals have been described. The quantitative separation of a mixture of Fe(Ⅲ), Cu(II), Zn(II), Ni(II), Cd(II), Co(II) and Mn(II) has been obtained by elution, through a 28cm column of the resin, Dowex 50 ${\times}$ 4 (100∼200 mesh), using 0.45 M $NaNO_3$+0.05 M Na-tartrate solution as eluent, starting with the eluent of pH 3.5, followed stepwise by pH 4.0 and 4.5. A comparison between the calculated and the observed peak positions in the elution curve has been shown. The relative stability constants for tartrate complexes of some transition metals have been calculated by using distribution ratios obtained in this separation procedure.

• 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).

• Journal of Environmental Health Sciences
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• v.14 no.2
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• pp.65-71
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• 1988

In this study, the method of adsorption by activated carbon in the removal of Hg(II) ion in waste water was treated. The influence of kinds of activated carbon and effect of temperature and the influence of coexistent salt on adsorption rates, the influence of pH in the adsorption, equilibrium and adsorption of mercury from activated carbon were investigated. From the adsorption on activated carbon of mercury(II) ion in the presence of cyanide or thiocyanate ion was found that mercury(II) was easily adsorved onto the activated carbon in the form of complex artion such as Hg(CN)$_4^{2-}$, Hg(SCN)$_4^{2-}$ respectively. ZnCl$_2$ activation method had a higher adsorptive ability than steam activation method in adsorption of Hg on activated carbon. Activated carbon adsorbed iodide ion is very effective on adsorption of Hg.