Rate constants have been compiled for reactions of various inorganic radicals produced by radiolysis or photolysis, as well as by other chemical means in aqueous solutions. Data are included for the reactions of ⋅CO2 −, ⋅CO3⋅−, O3, ⋅N3, ⋅NH2, ⋅NO2, NO3⋅, ⋅PO32−, PO4⋅2−, SO2⋅ −, ⋅SO3 −, SO4⋅−, ⋅SO5⋅−, ⋅SeO3⋅ −, ⋅(SCN)2⋅ −, ⋅CL2⋅−, ⋅Br2⋅ −, ⋅I2⋅ −, ⋅ClO2⋅, ⋅BrO2⋅, and miscellaneous related radicals, with inorganic and organic compounds.

Rate Constants for Reactions of Inorganic Radicals in Aqueous Solution

This review summarizes direct and indirect analytical methods for the detection and quantification of the reactive oxygen species (ROS): 1O2, O2·−/HOO·, H2O2, HO·, and CO3·− in aqueous solution. Each section briefly describes the chemical properties of a specific ROS followed by a table (organized alphabetically by detection method, i.e., absorbance, chemiluminescence, etc.) summarizing the nature of the observable (associated analytical signal) for each method, limit of detection, application notes, and reaction of the probe molecule with the particular ROS.

Methods for reactive oxygen species (ROS) detection in aqueous environments

Rates of reactions of OH and HO/sub 2/ with organic and inorganic molecules, ions and transients in aqueous solution have been tabulated, as well as the rates for the corresponding radical ions in aqueous solution (O/sup -/ and O/sub 2//sup -/). Most of the rates have been obtained by radiation chemistry methods, both pulsed and steady-state; data from photochemistry and thermal methods are also included. Rates for over one thousand reactions are listed.

/pdf/selected-specific-rates-of-reactions-of-transients-from-49nf7lpceh.pdf

Selected specific rates of reactions of transients from water in aqueous solution. III. Hydroxyl radical and perhydroxyl radical and their radical ions

Degradation and transformation of bisphenol A in UV/Sodium percarbonate: Dual role of carbonate radical anion.

Even in the absence of microbiological mediation, oxidation is one of the most important chemical processes contributing to the degradation of organic contaminants in the aquatic environment. The oxidants that are responsible for these reactions include hydroxyl radical, carbonate radical, organic oxyl and peroxyl radicals, peroxides, excited triplet states of organic chromophores, singlet molecular oxygen, ozone, chlorine dioxide, permanganate, and chromate. Some of these oxidants contribute to natural attenuation of organic contaminants, but many are of greater interest because of their role in engineered remediation technologies. Kinetic studies of these processes have lead to numerous quantitative structure-activity relationships (QSARs). Many of these QSARs are simple empirical correlations to common convenient descriptor variables like Hammett constants (sigma), half-wave oxidation potentials (E1/2), energies of the highest occupied molecular orbital (E(HOMO)) or rate constants for other oxidation reactions. However, several environmentally relevant, aqueous-phase oxidation reactions have been described with QSARs based on theoretical models for electron transfer that were developed by Marcus-Hush and Rehm-Weller. This review summarizes many of the reported QSARs for aquatic oxidations of organic compounds with emphasis on the interrelation between traditional empirical models and the potential for future development of QSARs based on theoretical models.

https://setac.onlinelibrary.wiley.com/doi/pdf/10.1897/01-237

Quantitative structure-activity relationships for oxidation reactions of organic chemicals in water

Reaction of the carbonate radical anion with substituted phenols.

Pulse radiolysis and steady-state X-radiolysis have been used to investigate the radiation inactivation of aldolase from rabbit muscle. Both eaq-and OH readily react with aldolase, and contribute to inactivation. The radical anions (CNS)2-and (Br)2-react with aldolase at neutral pH. The progressive addition of alkali results in an increase in the second-order rate constants, with an apparent pK approximately 10 +/- 0-3, and with the formation of an unstable intermediate, lambdamax approximately 400 nm resembling a phenoxyl radical. Steady-state radiolysis in the presence of (CNS)2-and (Br)2- at alkaline pH results in increased aldolase inactivation, with a pK of enzyme inactivation similar to that observed for reaction of the radical anions. We propose that a reaction of the radical anoins with tyrosine residues accounts for the resultant inactivation.

A. Sosnowski

Papers

Reaction of the carbonate radical anion with substituted phenols.

Radiation inactivation of rabbit muscle aldolase.

Reaction of radical probes with substituted phenols as models for the investigation of tyrosine in aldolase and chemically modified aldolase.