Bis(2-mercaptobenzoxazolato)mercury(II) and bis(2-pyridinethiolato)mercury(II) complexes as carriers for thiocyanate selective electrodes

Highly selective poly(vinyl chloride) (PVC) membrane electrodes based on bis(2-mercaptobenzoxazolato)mercury(II) [Hg(MBO)(2)] and bis(2-pyridinethiolato)mercury(II) [Hg(PT)(2)] complexes as new carriers for thiocyanate-selective electrodes are reported. The electrodes were prepared by coating the membrane solution containing PVC, plasticizer, carriers and additives on the surface of graphite electrodes. Influence of the membrane composition, pH and possible interfering anions were investigated on the response properties of the electrodes. Both sensors exhibited Nernstian responses towards thiocyanate over a wide concentration range of 1 x 10(-6) to 0.1 M, with slopes of 60.6 +/- 0.8 and 57.5 +/- 1.2 mV per decade of thiocyanate concentration for Hg(MBO)2 and Hg(PT)2 carriers, respectively, over a wide pH range of 3-11. The limit of detection for both electrodes was similar to6 x 10(-7) M. The sensors have response times of less than or equal to 5 s and can be used for at least 2 months without any considerable divergence in their potential response. The proposed electrodes show fairly good discrimination of thiocyanate over several inorganic and organic anions. The electrodes were successfully applied to direct determination of thiocyanate in saliva and as indicator electrodes in precipitation titrations. (C) 2003 Elsevier B.V. All rights reserved.