• Journal of the Korean Electrochemical Society
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• v.18 no.2
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• pp.81-85
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• 2015

A method for degradation of the perchlorate anion ($ClO{_4}^-$) has been studied using electrochemically generated zero-valent iron (ZVI) deposited on a porous carbon electrode. The first strategy of this study is to produce the ZVI via the electrochemical reduction of iron (II) on a porous carbon electrode coated with a conducting polymer, instead of employing expensive $NaBH_4$. The present method produced well distributed ZVI on conducting polymer (polypyrrole thin film) and increased surface area. ZVI surface can be regenerated easily for successive reduction. The second strategy is to apply a mild reducing condition (-0.3 V) to enhance the efficiency of the degradation of perchlorate with ZVI without the evolution of hydrogen. The electrochemically generated ZVI nanoparticles may offer an alternative means for the complete destruction perchlorate without evolution of hydrogen in water with high efficiency and at low cost.

• Journal of Korean Society of Environmental Engineers
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• v.30 no.1
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• pp.37-44
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• 2008

In this study, we tried to establish analysis methods of perchlorate with ion chromatography(IC) and liquid chromatography/mass spectrometry(LC/MS) and monitored perchlorate levels in various kinds of water and soil samples. The obtained method detection limit(MDL) of IC was 1 ppb and that of LC/MS was 0.005 ppb in water sample. We monitored the ground and spring water in Busan and the average perchlorate level in ground water was 0.031 $\pm$ 0.011 ppb and that of spring water was 0.013 $\pm$ 0.014 ppb. Wastewater samples were also examined and the levels of perchlorate ranged from 0.007 to 0.380 ppb. The perchlorate levels in all water samples investigated in this study were below the EPA guideline.

• Journal of the Korean Chemical Society
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• v.14 no.1
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• pp.119-122
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• 1970

In those six kinds of diamine salt crystal of which their structures had already been determined up to date, commonly one molecule of diamine and two molecules of acid were combined; although the crystal of benzidine perchlorate, only one molecule each of benzidine and perchloric acid were combined. At the case of benzidine perchlorate, one molecule acts as the role of two molecules by coincidence of the center of symmetry point of both the lattice and molecule, and perchlorate ion is locating symmetrically between two -$NH_2$ groups of different benzidine molecule, therefore benzidine and acid could be combined together with 1:1 by mole ratio. When forming the salt with diamine and acid, the combining mole ratio would be determined in accordance with the relationship between the symmetry element that presented by the space group and the symmetry element of diamine salt melecule.

• Journal of Korean Society on Water Environment
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• v.26 no.5
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• pp.768-774
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• 2010

This study was conducted to provide a technical solution to treat effectively perchlorate from inorganic wastewater of zinc smelting. Despite an inhibition dissolved inorganic substances in the wastewater discharged from zinc smelting has demonstrated with the activity of microbes, biological treatment technology could reduce perchlorate to a satisfactory level under such stressful conditions. It was found that either conductivity or $SO{_4}^{2-}$ concentration of the wastewater was able to be used as the adequate index and the values were $2,450{\mu}S/cm$ and 1,200 ppm respectively. When $SO{_4}^{2-}$ increased from 0 to 16,000 ppm (conductivity : $428{\rightarrow}24,800{\mu}S/cm$), perchlorate biodegradation rate was reduced due to 1/10 times from 0.0365 to 0.0033/h, however, most of perchlorate was removed under the condition of hydraulic retention time (HRT) at 0.5day and mixed liquor volatile suspended solid (MLVSS) at 2,000 ~ 3,000 ppm.

• Membrane Journal
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• v.3 no.3
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• pp.126-135
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• 1993

Perchlorate ion-selective PVC membrane electrode responsive to $10^{-6}M$ was developed by incorporating the ion-pair complex of perchlorate with the quaternary ammonium salts as a active material. The effect of chemical structure, the content of active material, the kinds of plasticizers, and the membrane thickness on the electrode characteristics such as the linear response range and Nernstian slope of the electrode were studied. With the results, the useful pH range and the selectivity coefficients to various interfering anions were compared and investigated. It was obtained that the effect of the chemical structure of an active material on the electrode characteristics was improved with increasing the alkyl chain length of the quarternary ammonium salts in the ascending order of Aliquat 336P, TOAP, TDAP, and TDDAP. The electrode characteristics was improved with the decrease of the active material content below the optimum membrane composition, and DBP was the best as a plasticizer. The optimum membrane composition was 9.09wt% of TDDAP, 30.3wt% of PVC, and 60.6wt% of ptasticizer(DBP). And the optimum membrane thickness was0.45mm at this composition. Under the above condition, thelinear response ranger was $10^{-1}~1.2 {\times} 10^{-6}M$, and the detection limit was $5.1{\times}10^{-7}M$ with the Nernstian slope of 57mV/decade of activity of perchlorate ion. The electrode potential was stable within the pH range from 4 to 11. The selectivity coefficient was as shown below : $SCN^->I^->NO_3^->Br^->ClO_3^->F^->Cl^->SO_4^{2-}$

• Analytical Science and Technology
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• v.8 no.4
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• pp.511-517
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• 1995

A cationic water soluble porphyrin (5,10,15,20-tetrakis (l-methyl-pyridinium-4-yl)porphyrin, $H_2tmpyp^{4+}$) and its metalloporphyrins (MP) were easily extracted into acetonitrile separated by addition of sodium chloride ($4mol\;dm^{-3}$) in the presence of sodium perchlorate, where M denotes $Zn^{2+}$, $Cu^{2+}$, $Co^{3+}$, $Fe^{3+}$, and $Mn^{3+}$ and $P^{2-}$ is porphyrinate ion. The extracted ion-pair complexes were completely dissociated to $[MP(ClO_4)_3]^+$, and $[MP(ClO_4)_2]^{2+}$. The extraction and the dissociation constants were determined by taking into account of the partition constant of sodium perchlorate ($K_D=1.82{\pm}0.01$). The chemical properties of the separated acetonitrile phase as $E_{T(30)}$ and $D_{II,I}$ were determined and compared with other water miscible solvents (acetone, actonitrile, 1,4-dioxane, tetrahydrofuran, 1-propanol and 2-propanol). Furthermore, a sensitive and selective method was proposed for the determination of a subnanogram amount of copper(II) in natural water samples by using the present salting-out method and the porphyrins.

• Environmental Engineering Research
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• v.17 no.4
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• pp.185-190
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• 2012

Rejection characteristics of perchlorate ($ClO_4^-$) were examined for commercially available reverse osmosis (RO) and nanofiltration (NF) membranes. A bench-scale dead-end stirred-cell filtration system was employed to determine the toxic ion rejection and the membrane flux. Model water solutions were used to prepare $ClO_4^-$ solutions (approximately, $1,000{\mu}g/L$) in the presence of background salts (NaCl, $Na_2SO_4$, and $CaCl_2$) at various pH values (3.5, 7, and 9.5) and solution ionic strengths (0.001, 0.01, and 0.01 M NaCl) in the presence of natural organic matter (NOM). Rejection by the membranes increased with increasing solution pH owing to increasingly negative membrane charge. In addition, the rejection of the target ion by the membranes increased with increasing solution ionic strength. The rejection of $ClO_4^-$ was consistently higher for the RO membrane than for the NF membrane and $ClO_4^-$ rejection followed the order $CaCl_2$ < NaCl < $Na_2SO_4$ at conditions of constant pH and ionic strength for both the RO and NF membranes. The possible influence of NOM on $ClO_4^-$ rejection by the membranes was also explored.

• Journal of the Korean Society of Safety
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• v.10 no.4
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• pp.47-59
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• 1995

The perchlorate, thiocyanate, and nitrate ion-selective PVC membrance electrode for measuring hazardous anion in waste water were developed by incorporating the quaternary ammonium salts as active material. Ion-selective characteristics in waste water were studied by the useful pH range, the selective coefficients to various interfering anions, and the stability of electrode potential. DBP was best as a plasticizer. The effect of the membrane thickness on the electrode characteristics was improved with decreasing the membrane thickness, but below the optimum membrane thickness the electrode exhibited an inverse trend. The electrode potential of perchlorate, thiocyanate, and nitrate electrode with TDDA, as active material, was stable within the pH range 4-11, 3-12, and 4-10 repectively. And the long-term potential stability of these electrodes were 3.0, 3.5, and 3.5 months respectively. The order of the selectivity coefficients was as shown below ; $ClO_4{^-}$ > $SCN^-$ > $I^-$ > $NO_3{^-}$ > $Br^-$ > $CN^-$ > $F^-$ > $Cl^-$ > $Ac^-$ > $H_2PO_4{^-}$, $SO_4{^-}$.

• Journal of the Korean Chemical Society
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• v.26 no.2
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• pp.107-113
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• 1982

Addition of dimedone to thioxanthylium ion generated from the oxidation of thioxanthene by thianthrene cation radical perchlorate in acetonitrile gave 9-(4,4-dimethylcyclohexane-2,6-dionyl)thioxanthylium perchlorate (2), whereas from the reverse addition between two reactants was obtained initially 9-(4,4-dimethylcyclohexane-2,6-dionyl)thioxanthene (1), which then underwent further reaction to give 2. The compound 2 was readily deprotonated in aq acetone to give 9-(4,4-dimethylcyclohexane-2,6-dionylidene)thioxanthene (3). However, 3 turned out to be in equilibrium with 2 in which three isosbestic points at 219, 289, and 348 nm were recorded in aq acetonitrile. The intensity and the position of the maximum absorption of 3 near 380 nm vary depending on the solvents which has been explained in terms of the solvent-solute interactions.

• Bulletin of the Korean Chemical Society
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• v.20 no.10
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• pp.1213-1217
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• 1999

Hydrolysis reactions of 2-phenyl-4H,5H,6H-3-methyl-3-thiazinium perchlorate (PTP) and its derivatives at various pH have been investigated kinetically. The hydrolysis is quantitative, producing N-3-mercaptopropyl-N-methylbenzamide as the only product in the all pH ranges. The observed rate of hydrolysis of PTP was always of the first-order. For hydrolysis from PTP, Hammett ρvalues were 0.53, 0.84 and 1.13 for pH 5.0, 8.0, and 10.0, respectively. Bronsted βvalue was 0.53 for general base catalysis. This reaction is catalyzed by general w acetate concentration. However, as the amount of base becomes larger, the rate of hydrolysis reaction approaches the limiting values. The plot of log k vs. pH shows that the rate constants (kt) are two different regions in the profile; one part is directly proportional to hydroxide ion concentration and the other is not. On the bases of these result, the plausible hydrolysis mechanism and a reaction equation were proposed: Below pH 4.5, the hydrolysis was initiated by the addition of water to α-carbon. Above pH 9.0, the hydrolysis was proceeded by the addition of hydroxide ion to α-carbon. However, in the range of pH 4.5-8.0, these two reactions occured competitively.