Composite electrodes made of graphite, paraffin and metal hexacyanoferrates exhibit a voltammetric response of the hexacyanoferrate ions, the potential of which depends linearly on the logarithm of concentration of alkali and alkaline-earth metal ions. This behaviour has been observed on account of the fact that the electrochemical reaction is accompanied by an exchange of these ions between the solution and the zeolitic lattice of the hexacyanoferrates for charge compensation. The voltammetric determination of the formal potential of these electrodes in a solution allows the quantitative analysis of the ions which are exchanged between the metal hexacyanoferrates and the aqueous solutions. Iron(III), copper(II), silver(I), nickel(II) and cadmium(II) hexacyanoferrates have been studied for the determination of H(+), Li(+), Na(+), K(+), Rb(+), Cs(+), NH(+)(4), Mg(2+), Ca(2+) and Ba(2+). In some cases, the selectivity constants are as low as 3.10(-4), or even so small that their exact value is inaccessible. Electrodes made of iron (III), copper (II), silver (I), nickel (II) and cadmium (II) hexacyanoferrates are most suitable for the determination of potassium ions. Electrodes with nickel (II) and cadmium (II) hexacyanoferrates are also suitable for the determination of caesium ions. The working range of the electrodes also depends on the conductivity of the solutions and can range from 10(-5) to 1 mol l(-1). Typical standard deviations of the potential measurements are 3 mV.
A solid composite pH sensor can be made from quinhydrone, solid paraffin and surface-modified graphite powder. It exhibits an almost theoretical slope of the potential-pH dependence (-57.7mV at 25"C), a formal potential Eo' = 0.6922V (vs. NHE), low standard deviations for repeated measurements (0.04 pH units), fast potential response (15 s) and a working range up to pH 9.5. The sensor can be used in moderately concentrated mineral acids and, unlike the conventional quinhydrone electrode, it is also applicable for measurements in milk. The sensor shows the same salt effect and sensitivity towards strong oxidants and reductants as the conventional quinhydrone electrode. The surface modified graphite was prepared by boiling graphite powder with concentrated nitric acid. By voltammetry it was shown that the surface of the modified graphite contains surface-confined redox centers similar to those in quinhydrone, which can catalyze the electron transfer of the quinhydrone on the surface of the sensor.
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