• 한국전기전자재료학회논문지
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• 제11권4호
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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: $SCN^->I^-NO_3^->Br^->ClO_3^->F^->Cl^->SO_4^{2-}$

• 한국안전학회지
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• 제10권4호
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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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• 제25권2호
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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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• 제29권9호
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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.

• 멤브레인
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• 제9권4호
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• pp.230-239
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• 1999

운반체(감응물질)로 제 4급 인산염을 사용하여 PVC를 지지체로 하여 과염소산이온의 농도 $10^{-6}$ M까지 선형적인 이온선택성 전극을 제작하였다. 운반체의 화학적구조와 함량 가소제의 종류 및 막 두께에 따른 전극의 기울기 선형응답범위 및 한계측정농도 등 전극전위특성을 고려하여 최적의 과염소산 이온선택성 PVC막 전극을 제조한 다음 측정 가능한 pH 범위 선택계수 및 전극의 교류임피던스 특성을 비교 검토하였다 운반체로 tetraoctyl-phosphonium perchlorate(TOPP) tetraphenylphosphonium perchlorate(TPPP) 및 tetrabutylphosponium perchlorate (TBPP)_ 등의 제 4급 인산염의 과염소산 이온 치환체를 사용하였다 알킬기의 탄소고리 수가 증가할수록 전극특성은 TBPP$^P{ClO}_4$, 선형응답범위 $10^{-1}$\times$10^{-6}$ M 및 한계측정농도는 9.66$\times$$10^{-7}$ M 이었으며 시판되고 있는 Orion 전극특성보다 좋은 결과를 나타내었다 전극전위는 pH3~11범위에서 ph의 영향을 받지 않았으며 ${CIO}_4$ 에 대한 방해이온의 선택계수 서열은 ${SO}^2_4$ < F < Br < I 이었다 임피던스 측정결과 TOPP의 경우 등가회로는 용액저항 이중층용량과 벌크저항의 병렬 및 Warburg 임피던스의 직렬이었다 이 경우 용액저항은 거의 나타나지 않았고 확산에 의한 Warburg 임피던스는 크게 나타났으며 Warburg 계수는 1.32$\times$$10^74 $\Omega$ $\cdot$ ${cm}^2/s^{1/2}$이었다.

• Bulletin of the Korean Chemical Society
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• 제27권12호
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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.

• 멤브레인
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• 제3권3호
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• pp.126-135
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• 1993

감응물질로 제4급 암모늄염을 사용하여 PVC를 지지체로 과염소산이온의 농도 $10^{-6}M$까지 측정가능한 이온 선택성 전극을 제작하였다. 감응물질의 화학적 구조와 함량, 가소제의 종류 및 막 두께에 따른 선형응답 범위와 Nernst의 기울기 등 전극특성을 검토하여, 최적 막조건을 구한 다음 측정가능 pH범위와 여러 방해이온에 대한 선택계수를 비교 검토하였다. 과염소산 이온선택성 전극에서 감응물질의 화학적 구조 즉, 알킬기의 탄소고리수가 증가할수록 선형응답 범위 등 전극 특성은 Aliquat 336P, TOAP, TDAP 및 TDDAP의 순서로 좋아졌다. 가소제는 DBP가 가장 좋았고, 감응물질의 양은 최적 함량 이상에서 적을수록 좋았다. 최적 막 조성은 TDDAP 9.09, PVC 30.3 및 DBP 60.61wt%이었고, 막두께 0.45mm이었다. 이 조건에서 선형응답 범위 $10^{-1}~1.2 {\times} 10^{-6}M$, 검출한계 $5.1{\times}10^{-7}M$ 및 Nernst기울기 $57mV/pClO_4$이었다. 막전위는 pH 4~11 범위에서 pH의 영향을 받지 않았으며, 선택계수 서열은 다음과 같았다. $SCN^->I^->NO_3^->Br^->ClO_3^->F^->Cl^->SO_4^{2-}$

• 한국막학회:학술대회논문집
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• 한국막학회 1998년도 춘계 총회 및 학술발표회
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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)

• 한국응용과학기술학회지
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• 제25권1호
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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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• 제35권11호
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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.