• Journal of the Korean Chemical Society
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• v.11 no.4
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• pp.159-164
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• 1967

An exact expression of the titration fraction as a function of the potential is derived for the cases where the coefficients of the both half reactions involved in the titration are homogeneous. It shows that the potential is independent of the concentration of the reagents not only at the equivalence point but also at all titration fractions. The sharpness of the end point detection by potentiometric method is shown to depend not only on the difference of the normal potentials involved but also strongly on the number of electrons transferred in each half reaction. The inflexion point of the potentiometric titration curve is shown to be slightly off from the equivalence point, including the cases where the number of electrons involved are equal. Completeness of the reaction in the course of titration is analyzed, too, mostly in terms of equilibrium constant, thus most of the results are applicable to any type of equilibrium in a single phase with particular relationship of coefficients of chemical equation.

• Bulletin of the Korean Chemical Society
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• v.23 no.10
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• pp.1394-1398
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• 2002

A novel copper(II) membrane electrode based on diphenylisocyanate bis(acetylacetone) ethylenediimine (DIBAE), as a new hexadentates Schiff's base was prepared. The electrode exhibited a Nernstian response for Cu$^{2+}$ ions over a wide concentration range (1.0 ${\times}$ 10$^{-1}$ to 1.0 ${\times}$ l0$^{-6}$ M) with a limit of detection of 6.0 ${\times}$ 10$^{-7}$ M (39 ppb). The sensor shows a fast response time (15s) and the membrane can be used for more than 4 months without observing any major deviation. The electrode revealed very good selectivity with respect to many cations including alkali, alkaline earth, transition and heavy metal ions. The proposed sensor could be used in a pH range of 3.0-7.5. It was applied to the direct potentiometric determination of copper in black tea, and in wastewater of copper electroplating samples. The electrode was also used in potentiometric titration of the copper(II) ion with EDTA.

• Bulletin of the Korean Chemical Society
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• v.24 no.1
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• pp.37-44
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• 2003

We examined the effect of polyether-type nonionic surfactants (Brij 35, Triton X-100, Tween 20 and Tween 80) on the potentiometric properties of sodium-, potassium- and calcium-selective membranes which are prepared with widely used ionophores and four kinds of polymer matrices [poly(vinyl chloride) (PVC), polyurethane (PU), PVC/PU blend, and silicone rubber (SR)]. It was found that the PVC-based membranes, which provide the best performance among all other matrix-based membranes in the absence of nonionic surfactants, exhibited larger change in their potentiometric properties when nonionic surfactants are added to the sample solution. On the other hand, the sodium-selective SR-based membrane with calix[4]arene, potassium-selective PVC/PU- or SR-based membrane with valinomycin, and the calcium-selective SR-based membrane with ETH 1001 provide almost identical analytical performance in the presence and absence of Tween 20 or Tween 80 surfactants. The origin of nonionic surfactants effect was also investigated by interpreting the experimental results obtained with various matrices and ionophores. The results suggest that the nonionic surfactant extracted into the membrane phase unselectively form complexes with the primary and interfering ions, resulting in increased background potential and lower binding ability for the ionophore. Such effects should result in deteriorated detection limits, reduced response slopes and lower selectivity for the primary ions.

• Bulletin of the Korean Chemical Society
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• v.32 no.10
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• pp.3592-3596
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• 2011

A novel poly(vinylchloride)-based membrane sensor using $N^1$,$N^3$,$N^5$-tris(2-(2,3-dihydroxybenzylamino)-ethyl)cyclohexane-1,3,5-tricarboxamide (CYCOENCAT, L) as ionophore has been prepared and explored as $Fe^{3+}$ selective electrode. The membrane electrode composed of ionophore, poly(vinylchloride) and o-nitropheyloctyl ether in the optimum ratio 4:33:63 gave excellent potentiometric response characteristics, and displayed a linear log[$Fe^{3+}$] versus EMF response over a wide concentration range of $1.0{\times}10^{-5}-1.0{\times}10^{-1}$ M with super nernstian slope of 28.0 mV/decade and the detection limit of $8.0{\times}10^{-6}$ M. The proposed ion selective electrode showed fast response time (< 15 s), wide pH range (3.0-7.0), high non-aqueous tolerance (up to 20%) and adequate long life time (120 days). It also exhibited very good selectivity for $Fe^{3+}$ relative to a wide variety of alkali, alkaline earth, transition and heavy metal ions. Further, the analytical applicability of the sensor was tested as an indicator electrode in the potentiometric titration of $Fe^{3+}$ with EDTA.

• Bulletin of the Korean Chemical Society
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• v.28 no.1
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• pp.68-72
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• 2007

A new PVC membrane potentiometric sensor that is highly selective to Hg2+ ions was prepared, using bis(2-hydroxybenzophenone) butane-2,3-dihydrazone (HBBD) as an excellent hexadendates neutral carrier. The sensor works satisfactorily in the concentration range of 1.0 × 10-6 to 1.0 × 10-1 mol L-1 (detection limit 4 × 10-7 mol L-1) with a Nernstian slope of 29.7 mV per decade. This electrode showed a fast response time (~8 s) and was used for at least 12 weeks without any divergence. The sensor exhibits good Hg2+ selectivity for a broad range of common alkali, alkaline earth, transition and heavy metal ions (lithium, sodium, potassium, magnesium, calcium, copper, nickel, cobalt, zinc, cadmium, lead and lanthanum). The electrode response is pH independent in the range of 1.5-4.0. Furthermore, the developed sensor was successfully used as an indicator electrode in the potentiometric titration of mercury ions with potassium iodide and the direct determination of mercury in some binary and ternary mixtures.

• Journal of Electrochemical Science and Technology
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• v.10 no.3
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• pp.321-328
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• 2019

A new miniaturized all solid-state contact Fe (III)-selective PVC membrane electrode based on Fe (II) phthalocyanine as a neutral carrier was described. The effects of the membrane composition and foreign ions on the electrode performance was investigated. The best performance was obtained with a membrane containing 32% poly (vinyl chloride), 64% dioctylsebacate, 3% Fe (II) phthalocyanine, and 1% potassium tetrakis (p-chlorophenyl) borate. The electrode showed near Nernstian response of $26.04{\pm}0.95mV/decade$ over the wide linear concentration range $1.0{\times}10^{-6}$ to $1.0{\times}10^{-1}M$, and a very low limit of detection $1.8{\pm}0.5{\times}10^{-7}M$. The potentiometric response of the developed electrode was independent at pH 3.5-5.7. The lifetime of the electrode was approximately 3 months and the response time was very short (< 7 s). It exhibited excellent selectivity towards Fe (III) over various cations. The miniaturized all solid-state contact Fe (III)-selective membrane electrode was successfully applied as an indicator electrode for the potentiometric titration of $1.0{\times}10^{-3}M$ Fe (III) ions with a $1.0{\times}10^{-2}M$ EDTA and the direct determination of Fe (III) ions in real water samples.

• Bulletin of the Korean Chemical Society
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• v.27 no.10
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• pp.1581-1586
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• 2006

A La (III) ion-selective membrane sensor has been fabricated from poly vinyl chloride (PVC) matrix membrane, containing 3-hydroxy-N'-(pyridin-2-ylmethylene)-2-naphthohydrazide (HPMN) as a neutral carrier, potassium tetrakis (p-chlorophenyl) borate (KTpClPB) as an anionic excluder and ortho-nitrophenyloctyl ether (NPOE) as a plasticizing solvent mediator. The effects of membrane composition and pH as well as the influence of the anionic additive on the response properties were investigated. The sensor with 30% PVC, 62% solvent mediator, 6% ionophore and 2% anionic additive, shows the best potentiometric response characteristics. It displays a Nernstian behavior (19.2 mV per decade) across the range of $1.0{\times}10^{-2}-1.0{\times}10^{-7}$ M. The detection limit of the electrode is $7.0{\times}10^{-8}$ M ($\sim$10 ng/mL) and the response time is 15 s from $1.0{\times}10^{-2}$ up to $1.0{\times}10^{-4} $M and 30 s in the range of $1.0 {\times}10^{-5}-1.0{\times}10^{-7}$ M. The sensor can be used in the pH values of 3.0-9.0 for about seven weeks. The membrane sensor was used as an indicator electrode in the potentiometric titration of lanthanum ions with EDTA. It was successfully applied to the lanthanum determination in some mouth wash preparations.

• YAKHAK HOEJI
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• v.40 no.2
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• pp.135-140
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• 1996

Ion-selective poly(vinyl chloride)(PVC) membrane electrodes for the determination of the calcium antagonist verapamil and its pharmaceutical preparations were described. Verapam il-superchrome garnet Y(SGY), lumogallion(LG), acid red 97(AR97), Dragendorff(DD) and Meyer reagent ion pairs were inverstigated as an electroactive compound for membrane electrode. Stable potentiometric response was obtained with azo dye at pH 6.5-4.0 and with DD, and Meyer reagent at pH 6.5-3.0. The best plasticizer was 49w/w% 2-nitrophenyl octyl ether for azo dye, and 65.3w/w% tri(n-butyl) citrate for DD and Meyer reagent. Potentiometric response slopes of optimized membrane electrodes based on SGY, LG, AR97, DD, and Meyer complex for verapamil were 52.49, 54.88, 50.81, 54.13 and 49.31 mV/dec., respectively. Lower limits of linear range were $1.0{\times}10^6M$ for SGY, LG, and AR97, while those for DD and Meyer reagent were $4{\times}10^{-6}M$. Detection limits for all these electrodes were $1{\times}10^{-5}M,\;4{\times}10^{-6}M,\;1.8{\times}10^{-6}M,\;8{\times}10^{-7}M,\;and\;1{\times}10^{-6}M$ with relative standard deviation of 2.56, 3.6, 3.96, 2.56, 3.20%, respectively.

• Bulletin of the Korean Chemical Society
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• v.30 no.10
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• pp.2303-2308
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• 2009

A thiocyanate poly(vinyl chloride) (PVC) membrane electrode based on [1,2-bis(diphenylphosphino)ethane]dihalopalladium( II), [(dppe)$PdX_2$, X = Cl ($L^1$), X = I ($L^2$)] as active sensor has been developed. The diiodopalladium complex, [(dppe)$PdI_2](L^2$) displays an anti-Hofmeister selectivity sequence: $SCN^-\;>\;I^-\;>\;{ClO_4}^-\;>\;Sal^-\;>\;Br^-\;>\;{NO_2}^-\;>\;{HPO_4}^-\;>\;AcO^-\;>\;{NO_3}^-\;>\;{H_2PO_4}^-\;>\;{CO_3}^{2-}$. The electrode exhibits a Nernstian response (-59.8 mV/decade) over a wide linear concentration range of thiocyanate ($(1.0\;{\times}\;10^{-1}\;to\;5.0\;{\times}\;10^{-6}$ M), low detection limit ($(1.1\;{\times}\;10^{-6}$ M), fast response $(t_{90%}$ = 24 s), and applicability over a wide pH range (3.5∼11). Addition of anionic sites, potassium tetrakis[p-chlorophenyl] borate (KTpClPB) is shown to improve potentiometric anion selectivity, suggesting that the palladium complex may operate as a partially charged carrier-type ionophore within the polymer membrane phase. The reaction mechanism is discussed with respect to UV-Vis and IR spectroscopy. Application of the electrode to the potentiometric titration of thiocyanate ion with silver nitrate is reported.

• Bulletin of the Korean Chemical Society
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• v.32 no.3
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• pp.800-804
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• 2011

A potentiometric sensor based on the Schiff base $(N^2E,N^{2'}E)-N^2,N^{2'}$-bis(thiophen-2-ylmethylene)-1,1'-binaphthl-2,2'-diamine has been synthesized and explored as an ionophore PVC-based membrane sensor selective for the silver ($Ag^+$) ion. Potentiometric investigations indicate a high affinity of this receptor for the silver ion. Seven membranes have been fabricated with different compositions, with the best performance shown by the membrane with an ionophore composition (w/w) of: 1.0 mg, PVC: 33.0 mg, DOA: 66.0 mg in 1.0 mL THF. The sensor worked well within a wide concentration range of $1.0{\times}10^{-2}$ to $1.0{\times}10^{-7}$ M, at pH 5, at room temperature (slope 57.4 mV/dec.), and with a rapid response time of 9 s; the sensor also showed good selectivity towards the silver ion over a huge number of interfering cations, with the highest selectivity coefficient for $Hg^{2+}$ at -3.7. Thus far, the best lower detection limit was $4.0{\times}10^{-8}$ M.