Concepts Relevant for the Kinetic Analysis of Reversible Reaction Systems.

Area of Science:

• Chemical Kinetics and Thermodynamics
• Physical Chemistry
• Reaction Engineering

Background:

• Net reaction rates conflate unidirectional kinetics and thermodynamics.
• Traditional rate descriptors (e.g., reaction orders) lack intrinsic kinetic information.
• Multistep reversible reactions involve distinct forward and reverse pathways.

Purpose of the Study:

• To provide tools for deconvoluting kinetics and thermodynamics in reversible reactions.
• To precisely identify rate- and reversibility-controlling species and steps.
• To disambiguate unidirectional reaction trajectories.

Main Methods:

• Utilizing equation-based formalisms, such as De Donder relations.
• Interpreting thermodynamic principles within modern chemical kinetics theories.
• Applying analytical and conceptual tools to bidirectional reaction systems.

Main Results:

• Developed formalisms to distinguish kinetic and thermodynamic contributions.
• Enabled precise identification of rate-limiting steps in reversible reactions.
• Provided a framework applicable to both thermochemical and electrochemical reactions.

Conclusions:

• Separating kinetics and thermodynamics is crucial for understanding reversible reactions.
• The presented methods offer a unified approach across chemical physics and engineering.
• This work advances mechanistic insights in catalysis and kinetic modeling.