• 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 : $SCN^->I^->NO_3^->Br^->ClO_3^->F^->Cl^->SO_4^{2-}$

• Journal of the Korean Chemical Society
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• v.28 no.5
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• pp.309-314
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• 1984

The species and equilibria of uranium and vanadium have been investigated in the various concentration of perchloric, hydrochloric and sulfuric acid by anion exchange chromatography. In the concentration range of $0.01\;{\sim}\;0.5M$ hydrochloric and $0.01\;{\sim}\;0.5M$ perchloric acid, uranium seems to be $UO_2^{2+}$species and in higher concentration than 0.5M hydrochloric acid $UO_2^{2+}$seems to form the chloride complex ion as $UO_2Cl^+$, $UO_2Cl_2$, $UO_2Cl_3^-$ and $UO_2Cl_4^{2-}$ according to the increase of the hydrochloric acid concentration. In the dilute(0.01N) sulfuric acid the adsorbability of uranium on anion exchange resin is strong and then decreases with increasing the sulfuric acid concentration. From this result we conclude that $UO_26{2+}$ formed the complex ion as $UO_2(SO_4)_2^{2-}$. In the perchloric acid of $0.01\;{\sim}\;0.5N$ concentration the existing equilibrium of vanadium and its constant calculated at $20^{\circ}C$ is $1.9{\times}108$ for $H_2V_{10}O_{28}^{4-}$ + $14H^+$ = $10VO_2^+ + 8H_2O$. The elution behaviors of vanadium in the hydrochloric and sulfuric acid are smiliar to those in perchloric acid.

• Journal of the Korean Chemical Society
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• v.42 no.5
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• pp.565-569
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• 1998

• Proceedings of the Korea Air Pollution Research Association Conference
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• 2007.10a
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• pp.509-510
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• 2007

See Full Text

• Journal of the Korean Chemical Society
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• v.28 no.1
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• pp.54-61
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• 1984

The species and equilibrium of molybdate and tungstate have been investigated from the elution behaviors of those in various concentrations of nitric acid and the UV spectra obtained at the various Z values. In higher concentrations than 0.05M nitric acid, the nitarte complex species of $MoO_2(NO_3)_2$ seems to form from the $MoO_2^{2+}$ ions formed by the following equation: $Mo_8O_{26}^{4-} + 20H^+$ ${\rightleftharpoons}$ $8MoO_2^{2+}$ + $10H_2O$. In the case of tungstate, the elution behaviors of tungstate in nitric acid medium are similar to those of perchloric acid, so we think the equilibrium of tungstate existed in perchloric acid could be also existed in nitric acid. These elution behaviors of tungstate are compared with the UV spectra obtained at the various Z values.

• Analytical Science and Technology
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• v.25 no.6
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• pp.435-440
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• 2012

A liquid chromatography-electrospray ionization-tandem mass spectrometry method (LC-ESI-MS/MS) was used for determining perchlorate in the Gum-River surface water. Sample was directly injected into LC-ESI-MS/MS after the filtrations using PTFE filter paper. The coefficient of variation of perchlorate was less than 3% and the limit of quantification was 0.17 ${\mu}g/L$. Water samples were collected from thirty-five basins of Gum-River on February, April and June 2012, respectively. As a result, perchlorate was detected in the concentration range of 0.23-3.73 ${\mu}g/L$ (mean 0.20 ${\mu}g/L$) in the frequency of 15% in general surface water and in the concentration range of 0.36-25.10 ${\mu}g/L$ (mean 1.69 ${\mu}g/L$) in the frequency of 36% in surface water samples near industry area.

• Journal of the Korean Chemical Society
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• v.38 no.5
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• pp.391-396
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• 1994

The hydrolysis of $\alpha-benzoxystyrene(1)$ in strong acidic solution has been investigated kinetically. In perchloric acid concentration lower than 5.5 M($H_o$ < -3.0), hydration paramer $\omega$ = + 7.6, and $\Phi$ = + 0.54 were obtained. The solvent isotope effect $k_{H_2O}/K_{D_2O}$ is 0.72. The substituent effect was found to conform to the Hammett $\sigma^+$ constant with $\rho$ = -0.60. On the basis of these results and other evidence, the hydrolysis of the enol ester proceeds by $A_{AL}$2 type mechanism. In concentration greater than 5.5 M($H_o$ > -3.0), isotope effect, $k_{H_2O}/_{D_2O}$ is 3.32, substituent effect, $\rho$ is -1.60 and the rate is linear with the acidity function, $H_o$. Thus, the mechanism changes one involving initial, and rate-determining olefin protonation.

• Journal of the Korean Chemical Society
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• v.36 no.5
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• pp.632-637
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• 1992

Standard transfer free energies of sodium and cupric perchlorates in water-acetylacetone solvent system have been determined by electromotive force measurements of galvanic cell and these energies of sodium and cupric ions in this solvent system have been evaluated by the tetrabutylammonium tetraphenylborate assumption as the extrathermodynamic procedure. Standard transfer free energy values of sodium and cupric ions from water to acetylacetone solvent were 5.09 and 4.16 kcal/mol at 25${\circ}C$, respectively. These values mean that acetylacetone is much weaker donor solvent to sodium and cupric ions than water. The standard transfer free energy value of cupric ion from water to mixture solvents which contain small amount of acetylacetone is changed by an unusual form. This is because of the chelate formation effect of acetylacetone to cupric ion.

• Membrane Journal
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• v.9 no.4
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• pp.230-239
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• 1999

Perchlorate ion-selective electrodes in PVC membranes that respond linearly to concentration 106 M were developed by incorporating the quaternary phosphonium salts as a canier. The effects of the chemical structure, the contents of canier, the kind of plasticizer and the membrane thickness on electrode characteristics such as the electrode slope, the linear respone range and the detection limit were studied. With this results, the detectable pH range, selectivity coefficients and AC impedance characteristics were compared and investigated. The perchlorate ion substituents of the quaternary phosphonium salts like tetraoctylphosphonium perchlorate (TOPP) , tetraphenylphosphonium perchlorate(TPPP), and tetrabutylphosphonium perchlorate(TBPP) as a canier were used. The electrode characteristics were better in the ascending order of TBPP < TPPP < TOPP, with the increase of carbon chain length of the alkyl group. Dioctylsebacate(OOS) was best as a plasticizer, the canier contents were better with 11.76 wt% and the optimum membrane thickness was 0.19 mm. Under the above condition, the electrode slope was 56.58 mV/$^P{ClO}_4$,the linear response range was $10^{-1}$\times$10^{-6}$ M, the detection limit was 9.66 x $10^{-7}$ M. The performance of electrode was better than Orion electrode. The electrode potential was stable within the pH range from 3 to 11. The order of the selectivity coefficients for the perchlorate ion was sol < F < Br < 1. With the result of impedance spectrum, it was found that the equivalent circuit for the electrode could be expressed by a series combination of solution resistance, parallel circuit consisting of the double layer capacitance and bulk resistance and Warburg impedance. And solution resistance was almost not appeared and Warburg impedance was highly appeared by diffusion. Then Warburg coefficient was 1.32$\times$$10^74 $\Omega$ $\cdot$ ${cm}^2/s^{1/2}$.

• Journal of the Korean Chemical Society
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• v.24 no.1
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• pp.34-43
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• 1980

The reaction of thianthrene cation radical perchlorate with thioxanthene in acetonitrile gave thianthrene and dark reddish thioxanthylium ion instead of thioxanthene cation radical. Addition of aromatic nucleophiles such as anisole, aniline, N,N-diethylaniline, catechol, ethylbenzene, to the above mixture yielded the corresponding thioxanthenes with substituent at 9 position. Reactions with dibenzo-18-crown-6-ether, diphenylmercury, and triphenylphosphine gave similar products. However, reactions with aromatics with electron-withdrawing group were either too slow or inert to such a reaction.