Kinetics and Mechanisms of Oxidation Reactions in Aqueous Systems

Oxidation reactions in aqueous systems underpin a multitude of natural and engineered processes, from the detoxification of water contaminants to the synthesis of fine chemicals and the metabolic pathways of living organisms. The rate at which these reactions proceed and the pathways they follow are governed by factors such as pH, temperature, ionic strength and the presence of catalytic or inhibitory species. Elementary steps frequently involve proton-coupled electron transfers, acid–base equilibria and the transient formation of reactive intermediates such as halonium or radical species. Over the past two decades, advances in time-resolved spectroscopic methods, stop-flow techniques and high-performance liquid chromatography have facilitated the direct observation of rapid kinetics and short-lived intermediates. These experimental insights, coupled with refined kinetic modelling, allow for the deconvolution of complex reaction networks and the prediction of rate behaviour under varied environmental conditions. A mechanistic understanding is crucial not only for optimising industrial processes such as advanced oxidation in water treatment but also for illuminating fundamental pathways in atmospheric chemistry and biological redox systems. Recent efforts have particularly highlighted the interplay between inhibitory effects, autocatalytic loops and clock phenomena, revealing how slight variations in reagent concentration or pH can dramatically alter both rates and product distributions. The global significance of these studies lies in their potential to mitigate environmental pollution, drive green chemistry innovations and enhance the efficiency of energy conversion processes.

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Kinetics and Mechanisms of Oxidation Reactions in Aqueous Systems publication trend

The graph below shows the total number of articles in kinetics and mechanisms of oxidation reactions in aqueous systems across all publications each year (not limited to Nature Index journals).

Technical terms

Rate coefficient: Constant quantifying the intrinsic speed of an elementary chemical reaction step.

Acid–base equilibrium: Reversible proton transfer between acid and base species in solution.

Autocatalysis: Process in which a reaction product accelerates its own formation, often yielding sigmoidal kinetics.

Substrate-depletive clock reaction: System in which a visible indicator appears only after complete consumption of a key substrate.

Landolt time: Induction period preceding the sudden appearance of a reaction product in a clock reaction.

Reactive intermediate: Transient species formed during a reaction pathway, often central to understanding mechanism.

References

1. Kinetics and Mechanism of Selenium(IV) Oxidation by Aqueous Bromine Solution. ACS Omega (2023).
2. Compatible Kinetic Model for Quantitative Description of Dual-Clock Behavior of the Complex Thiourea–Iodate Reaction. Inorganic Chemistry (2023).