Chaotic variations of electrical conductance in powdered Pd correlating with oscillatory sorption of D₂

A microcalorimetric method has been combined with a potentiostatic method to measure simultaneously the rate of heat evolution and the electrical current in a powdered sample of palladium during thermokinetic oscillations accompanying the sorption of deuterium in the metal. Deterministic chaos has been confirmed in the temporal variations in current (of ca. 1-4 mA) on the onset of both the sorption and the desorption of deuterium from Pd. It has been found that the first derivative of the current in time, dI/dt, turns out to be correlated precisely with the periodicity of thermokinetic oscillations. The dI/dt curves consist of regularly timed outbursts of aperiodic, high frequency (HF) fluctuations, interlinked by calm periods. The calm periods correlate with the descending slopes of thermokinetic oscillations (i.e., with decrease in the rate of heat evolution) and their lengths depend on the frequency of thermokinetic oscillations. In turn, the outbursts of aperiodic HF fluctuations in the dI/dt derivatives correlate with the ascending slopes of thermokinetic oscillations (i.e., with increasing rate of heat production), but their length is practically constant, irrespective of the thermokinetic frequency. We propose a periodic mechanism of sorption including a collective action of adsorbed deuterium taking place on the Pd surface. The periodicity of this mechanism arises from the temporal separation of its two sub-processes. The sub-process (1) involves only the adsorption of molecular D₂ on the Pd surface and proceeds with little heat evolution until a critical coverage of D₂ is achieved. The sub-process (2) initiates the dissociation of the adsorbed D₂ and the penetration of the dissociated atomic D species into the Pd lattice. It is the more energetic of the two, but it only begins after a threshold coverage of D₂ on the Pd surface has been achieved. We suggest that these sub-processes occurring alternatingly may provide a kernel for the oscillatory behavior observed in Pd/H(D) systems.