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Zusammenfassung:
The effect of temperature on a network of chemical reactions is not obvious, especially when compared to the effect exerted on elementary steps. There are few reports regarding the estimation of parameters such as activation energies for oscillating chemical systems. Still less investigated is the importance of the relative distance from thermodynamic equilibrium on the way in which temperature influences the oscillators' dynamics – a crucial aspect for the understanding of chemical and bio-chemical oscillating networks. In this paper we use the bromate–oxalic acid–acetone–cerium oscillatory system to study the influence of temperature under close and far-from-equilibrium regimes. The research was carried out under identical conditions for batch and flow (in a continuous flow stirred tank reactor, CSTR) regimes, and the main oscillation features were preserved, so that it was possible to isolate the effect of flow. Overall, increasing the flow results in an increase of the oscillatory frequency. The apparent oscillatory activation energy was found to decrease from 72 ± 6 kJ mol−1, for the system operated in batch, to 50 ± 2 kJ mol−1, under the flow regime. The role of the distance from the thermodynamic equilibrium on the temperature dependence is generalized and discussed in connection with other systems. Numerical simulations using the Brusselator model under batch and flow regimes further helped the discussion of the main experimental results.
