Thursday, 26 October 2006 - 9:50 AM
OLCC-Lindsay (Oakley-Lindsay Center)
77

A new batch chemical oscillator: the bromate-bromide-sulfuric acid system

Glen A. Frerichs1, Chong L. Park1, Daniel J. Shaughnessy1, and Richard C. Thompson2. (1) Westminster College, Fulton, MO, (2) University of Missouri-Columbia, Columbia, MO

 

The Belousov-Zhabotinsky (BZ) reaction is known to oscillate both in batch and in a continuous-flow stirred tank reactor (CSTR).  The classical BZ system is the most studied chemical oscillator, and consists of bromate ions, malonic acid, and cerium ions as a catalyst in sulfuric acid solution.  A simpler chemical system known as the minimal bromate (MB) oscillator has been found to oscillate in a CSTR over an extremely narrow range of conditions.  The MB oscillator consists of bromate, bromide, and either cerium or manganese ions in sulfuric acid.  We report here the discovery of a new batch chemical oscillator obtained simply by combining BrO3-, Br-, and H2SO4.  Periodic oscillations in the potential of a Pt electrode have been observed at 25 oC for [BrO3-]0 ranging from 1.5 x 10-3 M to 6.4 x 10-2 M.  The optimal [Br-]0 corresponds to a [BrO3-]0/[Br-]0 ratio of 3.5-4, a commonly used ratio in studies of the BZ oscillator.  Optimal [H2SO4]0 is consistent with the rate law for the apparently rate-determining initial step:  R = 2.1[BrO3-][Br-][H+[2 = (2-4) x 10-11 M s-1.  The peaks have a maximum amplitude of 15 mV and typically a period of 7 min at a stirring rate of about 500 rpm; oscillations have been found to continue for several hours.  Stirring rate appears to affect the specific nature of the oscillations.  Complex dynamical behavior has been observed, including period 2 oscillations and apparent chaos.  A possible mechanism for the oscillator will be discussed.


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