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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 30, Number 10
BKCSDE 30(10)
October 20, 2009

Title	Organopalladium(II) Complexes as Ionophores for Thiocyanate Ion-Selective Electrodes
Author	Dong Wan Kim, So Hyun Lee, Junghwan Kim, Jineun Kim, Jong Keun Park, Jae Sang Kim*
Keywords	[(dppe)PdI₂], Thiocyanate ion-selective electrode, Fixed interference method, PVC membrane
Abstract	A thiocyanate poly(vinyl chloride) (PVC) membrane electrode based on [1,2-bis(diphenylphosphino)ethane]dihalopalladium( II), [(dppe)PdX2, X = Cl (L¹), X = I (L²)] as active sensor has been developed. The diiodopalladium complex, [(dppe)PdI₂](L²) displays an anti-Hofmeister selectivity sequence: SCN^- > I^- > ClO^4- > Sal^- > Br^- > NO^2- > HPO^4- > AcO^- > NO^3- > H₂PO^4- > CO₃^2-. The electrode exhibits a Nernstian response (-59.8 mV/decade) over a wide linear concentration range of thiocyanate (1.0 × 10^-1 to 5.0 × 10^-6 M), low detection limit (1.1 × 10^-6 M), fast response (t90% = 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.
Page	2303 - 2308
Full Text	PDF

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