The formation of O2/O3 on PbO2 from the electrolysis of water in neutral solutions is shown here to present some analogies and some differences with respect to the same process in acid media. The electrolyte composition affects the current efficiency for O3 formation (.eta.) and the cell potential (E) of a Membrel type electrochemical assembly. An improvement in .eta. and a decrease in E is observed upon addition of relatively low amounts of Na2SO4 or NaClO4 in pure water. We observe no effect of NaNO3 on either parameters. In agreement with literature data in acid solutions, F- causes an increase in both .eta. and E. The results of electrochemical kinetic investigations with electrodes of PbO2 electrodeposited on Ti confirm the above data. Current-potential curves constructed from measurements in NaNO3 show a region of Tafel linearity with slopes of 2RT/F and RT/F in the low and high currents range, respectively. Addition of Na2SO4 and NaClO4 to NaNO3 has an effect on the process at more positive potentials only: the RT/F slope decreases toward a value of RT/2F as the concentration of the "foreign" salt is increased. As an explanation of the observed behavior, the possibility is advanced that a step following the discharge of water is rate determining at high positive potentials with the adsorption of intermediates described by Temkin conditions. The composition of the electrolyte is expected to influence the yield of ozone formation by affecting the coverage and free energy of adsorbed oxygen intermediates
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