Spatially distributed current oscillations with electrochemical reactions in microfluidic flow cells.

The formation of spatiotemporal patterns is investigated by using a chemical reaction on the surface of a high-aspect-ratio metal electrode positioned in a flow channel. A partial differential equation model is formulated for nickel dissolution in sulfuric acid in a microfluidic flow channel. The model simulations predict oscillatory patterns that are spatially distributed on the electrode surface; the downstream portion of the metal surface exhibits large-amplitude, nonlinear oscillations of dissolution rates, whereas the upstream portion displays small-amplitude, harmonic oscillations with a phase delay. The features of the dynamical response can be interpreted by the dependence of local dynamics on the widely varying surface conditions and the presence of strong coupling. The patterns can be observed for both contiguous and segmented metal surfaces. The existence of spatially distributed current oscillations is confirmed in experiments with Ni electrodissolution in a microfluidic device. The results show the impact of a widely heterogeneous environment on the types of patterns of chemical reaction rates.

Resonance tongues in a system of globally coupled FitzHugh-Nagumo oscillators with time-periodic coupling strength.

We investigate the dynamics of a population of globally coupled FitzHugh-Nagumo oscillators with a time-periodic coupling strength. While for synchronizing global coupling, the in-phase state is always stable, the oscillators split into several cluster states for desynchronizing global coupling, most commonly in two, irrespective of the coupling strength. This confines the ability of the system to form n:m locked states considerably. The prevalence of two and four cluster states leads to large 2:1 and 4:1 subharmonic resonance regions, while at low coupling strength for a harmonic 1:1 or a superharmonic 1:m time-periodic coupling coefficient, any resonances are absent and the system exhibits nonresonant phase drifting cluster states. Furthermore, in the unforced, globally coupled system the frequency of the oscillators in a cluster state is in general lower than that of the uncoupled oscillator and strongly depends on the coupling strength. Periodic variation of the coupling strength at twice the natural frequency causes each oscillator to keep oscillating with its autonomous oscillation period.

Two-dimensional electrochemical turbulence during the electrodissolution of metal disk electrodes: Model calculations.

We present numerical studies of the spatio-temporal dynamics of disk electrodes with local limit cycle oscillations. The simulations are done with a realistic 3-D geometry of the electrochemical cell and disk-shaped working electrodes (WE). Spatio-temporal chaos is shown to exist from a critical electrode size onwards. It is analyzed by Karhunen-Loève decomposition and Hilbert transform. The former shows that the chaos becomes more complex with increasing system size, the latter allows features that generate the spatio-temporal complexity to be identified, namely, spatially extended 1-D phase defects and topological defects.

Effect of the interface on separation in multicapillary gas chromatography-based hyphenated techniques for speciation analysis of organometallic compounds.

This paper reports the effect of transfer line (TL) internal diameter (i.d.) on gas chromatographic separation characteristics such as efficiency and speed, when a multicapillary (MC) column is used for speciation analysis of mercury. Five different TL consisting of fused-silica capillaries with 0.15, 0.20, 0.25, 0.32, and 0.53 mm i.d. are compared. The separation efficiency and total chromatographic run time are critically affected by the i.d. of the TL. Narrow capillaries (i.d.< or =0.20 mm) produce minimum peak dispersion whereas wide capillaries result in narrow peaks and shorter chromatographic analysis times. A thermodynamic approach is proposed to describe the motion of the analytes through the separation column and TL. The model provides good agreement with the experimental data for high pressures (> or =35 psig) and wide TL (> or =0.25 mm i.d.).

Evolution of spatiotemporal patterns during the electrodissolution of metals: Experiments and simulations.

Spatiotemporal patterns including accelerating fronts, rotating waves, and homogeneous oscillations evolve during the electrodissolution of metals like cobalt and iron that exhibit passivity under potentiostatic control. The nature of the patterns is determined by long-range (nonlocal) coupling through the electric field which in turn is influenced by the geometry of the electrochemical cell, the applied potential, and the conductivity of the electrolyte. A two-variable model in a three-dimensional geometry is presented which is able to simulate the essential features of the experimental system.(c) 2002 American Institute of Physics.