The chlorine evolution reaction has been studied at highly boron-doped diam
ond thin film electrodes. The comparison of this carbonaceous material with
graphite and glassy carbon points out the similar behavior in terms of dia
gnostic parameters and related mechanisms, without the mechanical fragility
of these materials. Tafel slopes at different chloride concentrations in s
olution (from 0.1 to 4 M NaCl in 0.01 M HClO4) and at different pHs have be
en determined. together with the reaction orders with respect to Cl- and H.All measurements were carried out at a constant ionic strength. The electr
ode characterization has been done by means of cyclic voltammetry, showing
a detailed picture for the chloride oxidation and the reduction of the evol
ved chlorine. Significant surface modifications occur when the electrode wo
rks as an anode for oxygen evolution, while chlorine evolution does not see
m to cause severe changes. As shown by tests carried out following a method
suggested in the literature, the faradaic yield for chlorine production is
expected to be very high. In dilute chloride media and at neutral-weakly a
lkaline pH, a faradaic yield of about 65% has been found; this makes use of
highly doped diamond electrodes in, e.g., seawater electrolysis, quite pro
mising. (C) 2000 The Electrochemical Society.