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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 

Organopalladium(II) Complexes as Ionophores for Thiocyanate Ion-Selective Electrodes
Dong Wan Kim, So Hyun Lee, Junghwan Kim, Jineun Kim, Jong Keun Park, Jae Sang Kim*
[(dppe)PdI2], Thiocyanate ion-selective electrode, Fixed interference method, PVC membrane
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- > ClO4- > Sal- > Br- > NO2- > HPO4- > AcO- > NO3- > H2PO4- > CO32-. 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.
2303 - 2308
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