• Membrane Journal
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• v.9 no.4
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• pp.230-239
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• 1999

Perchlorate ion-selective electrodes in PVC membranes that respond linearly to concentration 106 M were developed by incorporating the quaternary phosphonium salts as a canier. The effects of the chemical structure, the contents of canier, the kind of plasticizer and the membrane thickness on electrode characteristics such as the electrode slope, the linear respone range and the detection limit were studied. With this results, the detectable pH range, selectivity coefficients and AC impedance characteristics were compared and investigated. The perchlorate ion substituents of the quaternary phosphonium salts like tetraoctylphosphonium perchlorate (TOPP) , tetraphenylphosphonium perchlorate(TPPP), and tetrabutylphosphonium perchlorate(TBPP) as a canier were used. The electrode characteristics were better in the ascending order of TBPP < TPPP < TOPP, with the increase of carbon chain length of the alkyl group. Dioctylsebacate(OOS) was best as a plasticizer, the canier contents were better with 11.76 wt% and the optimum membrane thickness was 0.19 mm. Under the above condition, the electrode slope was 56.58 mV/$^P{ClO}_4$,the linear response range was $10^{-1}$\times$10^{-6}$ M, the detection limit was 9.66 x $10^{-7}$ M. The performance of electrode was better than Orion electrode. The electrode potential was stable within the pH range from 3 to 11. The order of the selectivity coefficients for the perchlorate ion was sol < F < Br < 1. With the result of impedance spectrum, it was found that the equivalent circuit for the electrode could be expressed by a series combination of solution resistance, parallel circuit consisting of the double layer capacitance and bulk resistance and Warburg impedance. And solution resistance was almost not appeared and Warburg impedance was highly appeared by diffusion. Then Warburg coefficient was 1.32$\times$$10^74 $\Omega$ $\cdot$ ${cm}^2/s^{1/2}$.