The Carbonate Radical (HCO3·/CO3–·) as a Reactive Intermediate in Water Chemistry: Kinetics and Modelling

Results from kinetic laboratory studies of reactions of the carbonate radical anion (CO₃^–·) with aromatic compounds in aqueous solution at T = 298 K are presented. Data were obtained in using a laser photolysis laser long-path absorption (LP-LPLA) apparatus which was designed for direct time-resolved studies of radical reactions. For the reactions of CO₃^–· with hydroquinone dimethyl ether (2), methyl anisole (3), benzene (4), p-xylene (5), toluene (6), chlorobenzene (7), nitrobenzene (8), and benzonitrile (9), rate coefficients of k₂ = (3.0 ± 0.6)·10⁷ M^–1 s^–1, k₃ = (9.7 ± 1.7)·10⁵ M^–1 s^–1, k₄ = (3.2 ± 0.7)·10⁵ M^–1 s^–1, k₅ = (3.8 ± 0.9)·10⁴ M^–1 s^–1, k₆ = (6.8 ± 2.3)·10⁴ M^–1 s^–1, k₇ = (2.7 ± 0.6)·10⁵ M^–1 s^–1, k₈ = (1.4 ± 0.5)·10⁴ M^–1 s^–1, and k₉ < 1.3·10² M^–1 s^–1 were obtained. In further studies the effect of temperature on the reactions (2), (4), and (5) has been studied. The kinetic data obtained for the reaction of the carbonate radical anion with aromatic compounds were compared to the corresponding reactions of the hydroxyl radical. Finally, these kinetic data were used within a simple model system to investigate the implications of carbonate radical anion kinetics within water treatment processes. It is shown that the degradation of organic pollutants in ^·OH-radical based water treatment may proceed via the CO₃^–·/HCO_3· radical under certain conditions.     

Products and Kinetics of the OH‐radical‐induced Dealkylation of Atrazine

Hydroxyl radicals, generated radiolytically in N₂O/O₂‐saturated solutions, yield in their reaction with atrazine equal amounts of deethylatrazine and acetaldehyde (40% of OH radical yield) and deisopropylatrazine and acetone (16%), respectively. The precursors of deethylatrazine and acetaldehyde is their Schiff base which hydrolyzes slowly (OH^–‐catalyzed: k = 5.2 dm³ mol^–1 s^–1). The hydrolysis of the Schiff base of deisopropylatrazine and acetone is too fast to be detected. In a pulse radiolysis experiment, the intermediate formed upon OH‐radical attack (k = 3·10⁹ dm³ mol^–1 s^–1) has a strong absorption at 440 nm. It decays in the presence of oxygen (k = 1.3·10⁹ dm³ mol^–1 s^–1), and upon deprotonation [pK_a(peroxyl radicals) ≈ 10.5] the peroxyl radicals thus‐formed eliminate superoxide radicals (k = 2.9·10⁵ s^–1). s‐Triazine itself reacts much more slowly with OH radicals (k = 9.7·10⁷ dm³ mol^–1 s^–1). This can explain, why in the case of atrazine in comparison to other aromatic compounds, e.g. toluene, the addition of the OH radical to the ring (estimated at ca. 40%) is of relatively little importance as compared to an H‐abstraction from (activated) positions of the side groups.     

Formation of Dibenzodioxins and Dibenzofurans in the Photochemical Transformation of Polychlorinated Phenols

It is shown that in the direct photolysis of polychlorinated phenols (2,4,5-TCP, PCP) in aqueous solution, under the action of solar light or UV-radiation from artificial sources, polychlorinated dibenzodioxins (PCDD) and dibenzofurans (PCDF) are found among the products of transformation. A mechanism is suggested of formation of these toxic compounds via the intermediate formation of free radicals. In the oxidation of chlorophenols by singlet oxygen, free radicals are not formed. Addition of fulvic acids prevents formation of PCDD and PCDF in solar light, possibly as a result of trapping of intermediate radicals.     

Modelling the Kinetics of Calcium Hydroxide Dissolution in Water

In water treatment calcium hydroxide is used in softening and decarbonization techniques as well as in stabilization processes. Due to its slight solubility calcium hydroxide is applied as suspension. The dissolution kinetics plays a major role in these processes. For the characterization of calcium hydroxide dissolution empirical methods exist. These methods allow relative comparison of different calcium hydroxide products. Thus in this study a dissolution rate model is presented that is based on the chemical reactions determining the dissolution. This model allows to predict the dissolution with respect to particle diameter and temperature. However, the most important factor is the particle diameter i.e. the total surface of particles in solution. Furthermore an effect of the dosed amount of calcium hydroxide particles on the solubility was found.