Journal of Physical Chemistry A, Vol.102, No.38, 7353-7361, 1998
Intermittencies and related phenomena in the oxidation of formaldehyde at a constant current
In the galvanostatic oxidation of formaldehyde on Pt at 43 degrees C, we have found type LII intermittency (in the Pomeau-Manneville classification) as well as type I intermittency. Potential oscillation patterns change with time, and type I intermittency is usually observed after a periodic oscillation in a sequence of periodic oscillations, which appear in decreasing order of their periods and are interposed between chaotic states. At a comparatively low current density (e.g., 0.23 mA cm(-2) or less for a 1 mol dm(-3) formaldehyde solution) in a solution with a formaldehyde concentration of I mol dm-3 or more, we observe type III intermittency before a periodic oscillation in the sequence. Under other conditions we observe a type-III-like intermittent pattern followed by a reverse period-doubling cascade. We confirm the characteristics of type III intermittency with a period-k laminar flow by the shape of kth and (2k)th return maps, by the relation between a laminar duration and the time from the period-k pattern, and by the relation between a maximal Lyapunov exponent and that same time. Here we regard time as a parameter related to some surface states. We also observe that type I and type III intermittencies coexist. We sometimes observe a randomly alternating sequence of period-(n+1) and period-n patterns without any intermittencies. When the sequence of periodic oscillations appear in increasing order of their periods, the order in which type I and type In intermittencies appear is also reversed.
Keywords:FORMIC-ACID, ELECTROCHEMICAL OXIDATION, POTENTIAL OSCILLATION;DYNAMICAL-SYSTEMS, MECHANISM, PLATINUM