Journal of Physical Chemistry A, Vol.103, No.16, 2934-2940, 1999
Propagating fronts and chaotic dynamics in Co(OH)(2) Liesegang systems
This paper presents a study of some features and characteristics of the Co2+/NH4OH Liesegang system. The pattern of parallel Co(OH)(2) bands displays peculiar properties that are unique among other Liesegang systems. First, the process of dissolution of bands at the top of the pattern coupled to, the formation of new ones at the bottom results in a propagating pattern that moves down the tube. Second, the total number of bands N varies erratically with time, unlike other Liesegang systems in which N increases monotonically with time. These random oscillations in the variable N are related to the dissolution/precipitation scenario. New experiments are designed to obtain a rigorous measurement of the total number of bands. Image analysis software (SigmaScan) is used to accurately determine N and the distance of:the:first band from the junction between the two solutions, based on a cutoff zero absorbance criterion. A time series for N is obtained by monitoring the pattern for 40 consecutive days. This time series is then analyzed numerically using a "Chaos Data Analyzer" software. All the characterization tools (such as power spectra, phase portraits, Lyapunov exponents and fractal dimensions) suggest a chaotic behavior of deterministic nature. The distance of the first band from the interface is plotted versus time. The velocity of dissolution is determined by obtaining a functional fit from the time variation curve and then calculating a derivative curve of that fit. The derivative is particularly evaluated at t = 10 and 15 days (taken as reference days), thus yielding the velocity of the dissolution front. A;similar method is used for the distance of the last band from the interface, to determine the velocity of the precipitation front. The measurements are performed for five different concentrations (C) of cobalt chloride and the dependence of the two front velocities on Cis investigated. Both front velocities are found to decrease monotonically with increasing C with a linear correlation existing between them.
Keywords:PERIODIC PRECIPITATION PROCESSES;CONCENTRATION GRADIENTS;SPATIAL BIFURCATION;PATTERN-FORMATION