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Citation: Jin Shi-Xiong, Wen Qing. The Kinetics of the Anodic Oxidation of Ce(III) Ion at Pt Electrode in Sulfuric Acid Solution[J]. Acta Physico-Chimica Sinica, ;1995, 11(08): 688-693. doi: 10.3866/PKU.WHXB19950804 shu

The Kinetics of the Anodic Oxidation of Ce(III) Ion at Pt Electrode in Sulfuric Acid Solution

Jin Shi-Xiong ,
Wen Qing

1.
Department of Chemistry,Nankai University,Tianjin 300071

Received Date: 27 June 1994
Available Online: 15 August 1995

The kinetic data related respectively to Ce4+ anodic formation and O2 anodic evolution at Pt anode in 0.5mol•L-1H2SO4+x mol•L-1 Ce2(SO4)3 (x=0.01-0.1) and 0.025mol•L-1 Ce2(SO4)3 + xmol•L-1H2SO4 (x=1.09 - 4.20) solutions were obtained by method of resolving the steady-state polarization curve. From steady-state φ ~ lgi relationships for Ce4+ anodic formation reaction the Tafel slope is close to 2 ×2.303RT/βF, whereas for O2 anodic evolution it is close to 2.303RT/βF (with β = 0.5).
It was shown by experiments that the anodic formation of Ce4+ and O2 anodic evolution at Pt anode in mixed H2SO4-Ce2(SO4)3 solutions can be described by
i(O2)=k1aw4exp(βφF/RT)
i(Ce4+)=k2aw2[Ce3+]exp(βφF/2RT)
at high polarization region.
The experimental results of the high polarization region may be explained by the following scheme of electrode reactions
M+Ce3+=MCead3+
MCead3++4H2O→MCe(OH)4ad+4H++e
MCe(OH)4ad= MCe(OH)3Oad+H++e
2 MCe(OH)3Oad→2MCe(OH)3ad+O2
MCe(OH)3Oad+3H+= MCead3+3H2O
MCe(OH)3Oad+Ce3+→M+2CeO2+3H+
CeO2+4H+=Ce4++2H2O
where M is an adsorption site on the Pt-oxide.
- Pt anode,
- Ce(III) ion,
- Ce(IV) ion
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