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

Th. Umschlag  H. Herrmann 《洁净——土壤、空气、水》1999,27(4):214-222

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.  相似文献   

The Impact of Human Activities on Freshwater Aquatic Systems     

Yu. I. Skurlatov  L. S. Ernestova 《洁净——土壤、空气、水》1998,26(1):5-12

The roles of oxygen and its activated species (superoxide radicals, hydrogen peroxide, hydroxyl radicals), as well as that of sulfur compounds, are considered in relation to biological quality and the self-cleaning capacity of freshwater aquatic systems. The effects on the aquatic redox-processes are discussed in terms of atmospheric fallout of sulfur compounds, bottom sediment composition, and input of wastewaters containing reducing substances. It is shown that the totality of anthropogenic influences, and/or unfavourable natural geochemical conditions, as well as climatic effects in a region can increase the significance of one-electron transfer processes in bio-geochemical cycles of oxygen, sulfur and manganese, compared with the significance of two-electron transfer processes. The resulting, reactive intermediate products of one-electron transfer processes are very important with respect to the composition and properties of aquatic systems. Examples are given of practical applications of wastewater treatment, using hydrogen peroxide and UV-irradiation, and of regulation of consumers’ activities which affect natural waters.  相似文献   

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

Yu. I. Skurlatov  L. S. Ernestova  E. V. Vichutinskaya  D. P. Samsonov  R. I. Pervunina  I. V. Semenova  V. O. Sjvydly 《洁净——土壤、空气、水》1998,26(1):31-35

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.  相似文献