A Comprehensive Review on the Oxidation of Inorganic Compounds by Cerium (IV): Kinetic and Mechanistic Perspectives

Abstract

: The oxidation studies with cerium(IV) is important because cerium(IV) is a significant single electron oxidant in aqueous acidic medium. This review paper investigated the kinetic and mechanistic perspective of oxidation of some inorganic compounds by cerium(IV) in aqueous medium. The present article highlights the different type of reactive species of cerium(IV) in various oxidation studies. The nature of these reactive species depends on the concentration and nature of medium used in the reaction. The order of reaction were identified with the respect of substrate, oxidants and metal ions i.e. catalyst.

Introduction

The review discusses the kinetics and mechanisms of oxidation reactions involving cerium(IV) [Ce(IV)], emphasizing its importance as a versatile and environmentally friendly oxidizing agent in both organic and inorganic chemistry. Kinetic studies help explain reaction mechanisms, identify factors affecting reaction rates, and determine reactive intermediates. Ce(IV) is widely used because it readily undergoes the reversible Ce(IV)/Ce(III) redox cycle and can oxidize a broad range of substrates, often in the presence of transition metal catalysts.

Ce(IV) is most stable in strongly acidic media, particularly sulfuric acid, where it exists as several sulfate complexes such as Ce(SO?)²?, Ce(SO?)?, Ce(SO?)?²?, and HCe(SO?)??. The identification of the kinetically active Ce(IV) species remains controversial because multiple equilibria involving sulfate, bisulfate, and hydrogen ions make speciation difficult. Different researchers have proposed different active species—including Ce(SO?)?, Ce(SO?)²?, Ce(SO?)?²?, and H?Ce(SO?)??—depending on the reaction conditions and substrates studied.

The review summarizes numerous oxidation studies of inorganic compounds such as antimony(III), arsenic(III), selenium(IV), tellurium(IV), mercury(I), thallium(I), palladium(II), titanium(I), hypophosphite, iron(II), chromium(III), chloride, and bromide. Most reactions follow first-order kinetics with respect to Ce(IV), while the order with respect to the substrate is often fractional due to intermediate complex formation. Reaction rates are influenced by factors such as acid concentration, sulfate and bisulfate ions, reaction products, and catalysts including Mn(II), Ru(III), Pd(II), Cr(III), and Os(VIII).

Overall, the review highlights that Ce(IV) is a powerful oxidant for mechanistic and synthetic studies, but its reaction behavior strongly depends on the nature of the reactive Ce(IV) species, acid medium, and catalytic conditions. Despite extensive research, the exact identity of the active cerium species remains unresolved, making the kinetics and mechanisms of Ce(IV)-mediated oxidation an important area for continued investigation.

Conclusion

Cerium (IV) in redox reactions reacts as an outer sphere or inner sphere mechanism in agreement with the type of the reluctant. This review study has correlated the different factors to control the mechanistic paths of catalysis in the title oxidation reactions. Several kinetically active cerium(IV) species like Ce(SO4)2, CeSO42+, Ce(SO4)32-, HCe(SO4)3-, H3Ce(SO4)4 were involved in the oxidation reaction of different type of inorganic and organic compounds. The effect of substrates, oxidants, metal ions (as catalyst) and added products on the rate of reaction have been reported and observed that reaction rate varies with varying the concentration of these reagents.

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