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Title: Thermodynamic analysis of critical limits in Belousov-Zhabotinskii reaction system
Authors: Rastogi, R P
Syal, V
Misra, G P
Issue Date: Mar-1991
Publisher: NISCAIR-CSIR, India
Abstract: Stability of the Belousov-Zhabotinskii (B-Z) reaction system containing bromate, ceric ammonium sulphate, sulphuric acid and mixed organic substrates (oxalic acid + acetone) has been examined using the thermodynamic theory of Glansdorff and Prigogine at the two critical limits of [acetone] and also in the oscillatory domain. The sign of excess entropy production due to perturbation in [HBrO2] has been estimated by taking into account the subset of reactions involving HBrO2. Numerical estimates of sign of relative excess entropy production for different reactions have been made using the latest accepted values of the rate constants (Field and Forsterling) as well as values of Field and Boyd. The thermodynamic analysis suggests that the reaction system is stabilized either when (i) the contribution to the excess entropy production due to destruction of HBrO2 by Br- exceeds the negative contribution due to autocatalytic reaction step or when (ii) the contribution of disproportionation of HBrO2 to the excess entropy production exceeds or becomes comparable to the negative contribution due to autocatalytic reaction step. Situation (i) corresponds to lower limit of [acetone] while (ii) corresponds to upper limit of [acetone]. Instability can occur when the negative contribution due to the autocatalytic reaction exceeds the sum of contributions of disproportionation of HBrO2 and its destruction by Br-.
Page(s): 203-208
ISSN: 0975-0975(Online); 0376-4710(Print)
Appears in Collections:IJC-A Vol.30A(03) [March 1991]

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