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A new approach to the mechanism of chlorine evolution: Separate examination of the kinetic steps using ac impedance on a rotating thin ring electrode

1992; Elsevier BV; Volume: 37; Issue: 15 Linguagem: Inglês

10.1016/0013-4686(92)85198-t

1873-3859

Fengbin Li, A. Robert Hillman, S. D. Lubetkin,

Water Treatment and Disinfection

In the absence of a bulk diffusion effect, it is shown for the first time that the impedance spectra for the chlorine evolution reaction on a rotating thin ring electrode comprise three consecutive semicircles in the capacitive half of the complex plane. The first (highest frequency) semicircle is due to the charge-transfer resistance for chloride discharge and the simultaneous chlorine adsorption coupled to the double-layer capacitance. The second semicircle (around 5 Hz) is due to the adsorption and desorption of a chlorine intermediate. The third (lowest frequency, around 0.5 Hz) semicircle is due to the relaxation of surface oxygen species. The impedance data allow the steps of the overall reaction to be examined individually. On a Pt surface the rate of chloride discharge and simultaneous chlorine adsorption (the admittance of the first semicircle) is first order with respect to chloride concentration and has a potential-dependence close to 58 mV/decade. The rate of the adsorption and desorption process (the admittance of the second semicircle) is second order with respect to chloride concentration, and has a potential dependence close to 30 mV/decade. The time constant for the adsorption/desorption processes is ca 20 ms, independent of electrode potential in the range studied. These features are consistent with a mechanism in which a faster discharge reaction (Cl− ⇌ Clad + e) is followed by a slower surface combination reaction (2Clad → Cl2), but inconsistent with mechanisms in which ion + atom desorption is predominant, the initial chloride discharge is slow, or a unipositively charged chlorine species is involved.