• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.11 no.4
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• pp.298-305
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• 1998

The PVC membrane electrode for measuring perchlorate ion was developed by incorporating various quaternary ammonium sallts. The effect of chemical structure, the content of active material, the kind of plasticizers, and the membrane thickness on the electrode characteristic such as the linear response range and Nernstian slope of the electrode were studied. 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 optimum membrane composition was 9.09wt% of TDDAP, 30.3wt% of PVC, and 60.6wt% of plasticizer(DBP). And the optimum membrane thickness was 0.45mm at this composition. Under the above condition, the linear response range was $10^{-1}~1.2\times10^{-6}$M, and the detection limit was $5.1\times10^{-7}$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 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 ; $ClO_4{^-}$ > $SCN^-$ > $I^-$ > $NO_3{^-}$ > $Br^-$ > $CN^-$ > $F^-$ > $Cl^-$ > $Ac^-$ > $H_2PO_4{^-}$, $SO_4{^-}$.

• Bulletin of the Korean Chemical Society
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• v.25 no.2
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• pp.172-176
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• 2004

A highly selective membrane electrode based on1,3,5-triphenylpyrylium perchlorate (TPPP) is presented. The proposed electrode shows very good selectivity for sulfate ions over a wide variety of common inorganic and organic anions. The sensor displays a nice Nernstian slope of -29.7 mV per decade. The working concentration ranges of the electrode is 1.0{\times}10^{-1}-6.3{\times}10^{-6} $M with a detection limit of $4.0{\times}10^{-6}$ M (480 ng per mL). The response time of the sensor in whole concentration ranges is very short (< 6 s). The response of the sensor is independent on the pH range of 2.5-9.5. The best performance was obtained with a membrane composition of 32% PVC, 59% benzyl acetate, 5% TPPP and 4% hexadecyltrimethylammonium bromide. It was successfully used as an indicator electrode for titration of sulfate ions with barium ions. The electrode was also applied for determination of salbutamol sulfate and paramomycine sulfate.

• Bulletin of the Korean Chemical Society
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• v.29 no.9
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• pp.1774-1780
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• 2008

New PVC based polymeric membrane electrodes (PME) and coated glassy carbon electrodes (CGCE) based on synthesized Schiff base complexes of Co(III); [Co(Salen)$(PBu_3)_2$]$ClO_4$, [Co($Me_2$Salen)$(PBu_3)_2$]$ClO_4$, [Co(Salen)$(PBu_3)H_2O$]$ClO_4$; as anion carriers for potentiometric determination of $ClO_4\;^-$were studied. The PME and also CGCE electrodes prepared with [Co(Me2Salen)$(PBu_3)_2$]$ClO_4$ showed excellent response characteristics to perchlorate ions. The electrodes exhibited Nernstian responses to $ClO_4\;^-$ ions over a wide concentration range with low detection limits ($1.0 {\times} 10^{-6}\;mol\;L^{-1}$ for PME and $9.0 {\times} 10^{-7}\;mol\;L^{-1}$ for CGCE). The electrodes possess fast response time, satisfactory reproducibility, appropriate lifetime and, most importantly, good selectivity toward $ClO_4\;^-$ relative to a variety of other common inorganic anions. The potentiometric response of the electrodes is independent of the pH in the pH range 2.5-8.5. The proposed sensors were used in potentiometric determination of perchlorate ions in mineral water and urine samples. The interaction of the ionophore with perchlorate ions was shown by UV/Vis spectroscopy.

• 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 $\Omega$ $\cdot$ ${cm}^2/s^{1/2}$.

• Bulletin of the Korean Chemical Society
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• v.27 no.12
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• pp.1985-1988
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• 2006

The polymeric membrane electrodes based on urea derivative as an ionophore were prepared and studied for the iodide-ion selective electrode. This membrane exhibits a linear stable response over a wide concentration range ($1.0\;{\times}\;10^{-5}\sim1.0\;{\times}\;10^{-2}$) with a slope of -57.7 mV/decade, a detection limit of log[$I^-$] = -5.63, and a selectivity coefficient for iodide against perchlorate anion (log$K^{pot}_{I^-,j}$ = -1.42). The selectivity series of the membrane gives the follow as $I^-$ > $SCN^-$, $Sal^-$ > $ClO_4^-$ > $NO_3^-$ > $Br^-$ > $NO_2^-$ > $Cl^-$ > $F^-$. The proposed electrode showed good selectivity and response for iodide anion over a wide variety of other anions in pH 5.0 buffer solutions.

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

• Proceedings of the Membrane Society of Korea Conference
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• 1998.04a
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• pp.49-52
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• 1998

1. 서론 : 화약이나 고체 충진제, 고체로\ulcorner 추진제의 산화제, slurry blasting agent 및 동물사료의 식품첨가제로 사용되고 있는 과염소산은 발화나 폭발성이 매우 강한 산화제로 정확한 순도를 측정하는 것은 중요하다. 용량분석법과 중량분석법에 비교하여 조작이 간단하고 편리한 과염소산이온의 농도를 직접 측정할 수 있는 PVC막 전극에 대한 많은 연구가 진행되고 있다. (생략)

• Journal of the Korean Applied Science and Technology
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• v.25 no.1
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• pp.65-72
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• 2008

The ion exchangers supported on silica gel containing primary, secondary, or tertiary amine groups show a behaviour that is weakly acidic, while the quaternary salts are strongly acidic. These properties change according to the hydrophilicities of the modifier functional groups. Ammonium salt derivatives supported on silica gel were prepared from silica modified with 3-Aminopropyltriethoxysiliane and N-3-(Trimethoxysilyl)propylehtylene diamine. The preparation and the ion exchange properties of two systems were discussed. Two systems have different hydrophilicities and contain ammonium chloride derivatives of 3-amminopropyltriethoxysilane and N-3-(triehtoxysilyl)propyl ethylene diamine supported on silica gel, $SA^+/Cl^-$ and $SA^+/Cl^-$, respectively. The high affinity to perchlorate ion presented by the $SA^+/Cl^-$ through the equilibrium studies of ion exchange led us to its application as an ion selective electrode for the perchlorate ion. The determination of the perchlorate ion in the presence of other anions and in complexes is very difficult. Few analytical methods are available and most of them are indirect. Both materials showed potential use as an ion exchanger; they are thermically stable, achieve equilibrium rapidly in the presence of suitable exchanger ions, and are easily recovered.

• Bulletin of the Korean Chemical Society
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• v.35 no.11
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• pp.3175-3180
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• 2014

A potentiometric sensor based on the 1-benzyl-3-(4-nitrophenyl) thio-urea was synthesized and tested as an ionophore in PVC based membrane sensor towards $SCN^-$ ions. This membrane exhibits a linear stable response over a wide concentration range ($1.0{\times}10^{-5}$ to $1.0{\times}10^{-2}M$) with a slope of -59.2 mV/dec., a detection limit of ${\log}[SCN^-]=-5.05$, and a selectivity coefficient for thiocyanate against perchlorate anion of ${\log}K^{pot}_{SCN^-j}=-0.133$. The selectivity series of the membrane is as follows: $SCN^-$ > $ClO_4{^-}$ > $I^-$ > $NO_3{^-}$ > $HSO_3{^-}$ > $Cl^-$ > $HSO_4{^-}$ > $F^-$ > $CH_3COO^-$ > $HCO_3{^-}$ > $Br^-$ > $H_2PO_4{^-}$ > $SO{_3}^{2-}$ > $SO{_4}^{2-}$ > $CO{_3}^{2-}$. The proposed electrode showed good selectivity and a good response for the $SCN^-$ ion over a wide variety of other anions in pH 6.0 buffer solutions and has a fast response time of about < 5s. The influences of the membrane by pH, ionophore, and plasticizer were studied.