Essentials of kinetics and thermodynamics for understanding chemical oscillations

• Published in: Foundations of chemistry Vol. 17; no. 2; pp. 93 - 106
• Main Author: Barragan, Daniel
• Format: Journal Article
• Language: English
• Published: Dordrecht Springer Netherlands 01-07-2015; Springer
• Subjects: Chemical engineering; Chemical engineering research; Chemical reaction, Rate of; Chemistry/Food Science; Education; History; Oscillation; Philosophy; Philosophy of Science; Physical Chemistry; Thermodynamics; Gibbs energy; Oscillating reactions; Entropy generation; Thermodynamics of irreversible processes; Kinetic instabilities
• ISSN: 1386-4238; 1572-8463
• DOI: 10.1007/s10698-015-9221-4

This paper presents a numerical study of the reaction
A
 ↔ 
B
in the presence of an intermediate and destabilizing step in its dynamics. After introducing a direct autocatalytic destabilizing process, namely quadratic autocatalysis (
X
+
Y
→
2
Y
) and cubic autocatalysis (
X
+
2
Y
→
3
Y
), a thermodynamic analysis of the evolution of the reaction in closed and open systems was performed. In addition, the Gibbs free energy, the thermodynamic affinity, and the entropy generation of the overall reaction were evaluated for each of the autocatalytic steps, in order to analyze the behavior of these thermodynamic quantities when the system moved towards equilibrium or towards oscillatory non-equilibrium states.