Superoxide ion (O2•–) is of great significance as a radical species implicated in diverse chemical and biological systems. However, the chemistry knowledge of O2•– is rather scarce. In addition, numerous studies on O2•– were conducted within the latter half of the 20th century. Therefore, the current advancement in technology and instrumentation will certainly provide better insights into mechanisms and products of O2•– reactions and thus will result in new findings. This review emphasizes the state-of-the-art research on O2•– so as to enable researchers to venture into future research. It comprises the main characteristics of O2•– followed by generation methods. The reaction types of O2•– are reviewed, and its potential applications including the destruction of hazardous chemicals, synthesis of organic compounds, and many other applications are highlighted. The O2•– environmental chemistry is also discussed. The detection methods of O2•– are categorized and elaborated. Special attention is given to the f...

Superoxide Ion: Generation and Chemical Implications

Plasma–liquid interactions represent a growing interdisciplinary area of research involving plasma science, fluid dynamics, heat and mass transfer, photolysis, multiphase chemistry and aerosol science. This review provides an assessment of the state-of-the-art of this multidisciplinary area and identifies the key research challenges. The developments in diagnostics, modeling and further extensions of cross section and reaction rate databases that are necessary to address these challenges are discussed. The review focusses on non-equilibrium plasmas.

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Plasma-liquid interactions: A review and roadmap

The application of strong electric fields in water and organic liquids has been studied for several years, because of its importance in electrical transmission processes and its practical applications in biology, chemistry, and electrochemistry. More recently, liquid-phase electrical discharge reactors have been investigated, and are being developed, for many environmental applications, including drinking water and wastewater treatment, as well as, potentially, for environmentally benign chemical processes. This paper reviews the current status of research on the application of high-voltage electrical discharges for promoting chemical reactions in the aqueous phase, with particular emphasis on applications to water cleaning.

/pdf/electrohydraulic-discharge-and-nonthermal-plasma-for-water-bcogyk507r.pdf

Electrohydraulic Discharge and Nonthermal Plasma for Water Treatment

Chemical Science Division, Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99352; Department of Chemistry, ShelbyHall, University of Alabama, Box 870336, Tuscaloosa, Alabama 35487-0336; Notre Dame Radiation Laboratory, University of Notre Dame,Notre Dame, Indiana 46556; Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 0520-8107; Argonne NationalLaboratory, 9700 South Cass Avenue, Argonne, Illinois 60439; Department of Computer Science and Department of Physics, 2710 University Drive,Washington State University, Richland, Washington 99352-1671; Lawrence Berkeley National Laboratory, 1 Cyclotron Road Mailstop 1-0472,Berkeley, California 94720; Department of Chemistry and Biochemistry, University of Texas at Austin, 1 University Station A5300,Austin, Texas 78712; Office of Basic Energy Sciences, U.S. Department of Energy, SC-141/Germantown Building, 1000 Independence Avenue,S.W., Washington, D.C. 20585-1290; Department of Physics and Engineering Physics, Stevens Institute of Technology, Castle Point on Hudson,Hoboken, New Jersey 07030; Department of Chemistry, Johns Hopkins University, 34th and Charles Streets, Baltimore, Maryland 21218;Department of Chemistry, University of Southern California, Los Angeles, California 90089-1062; Department of Chemistry, The Ohio StateUniversity, 100 West 18th Avenue, Columbus, Ohio 43210-1185; Department of Chemistry, Columbia University, Box 3107, Havemeyer Hall,New York, New York 10027; Department of Chemistry, University of Pittsburgh, Parkman Avenue and University Drive,Pittsburgh, Pennsylvania 15260; Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973-5000; Department of Physics andAstronomy, Rutgers, The State University of New Jersey, 136 Frelinghuysen Road, Piscataway, New Jersey 08854-8019; Department of Chemistry,516 Rowland Hall, University of California, Irvine, Irvine, California 92697-2025; Stanford Synchrotron Radiation Laboratory, Stanford LinearAccelerator Center, 2575 Sand Hill Road, Mail Stop 69, Menlo Park, California 94025; School of Chemistry and Biochemistry, Georgia Institute ofTechnology, 770 State Street, Atlanta, Georgia 30332-0400; Geology Department, University of California, Davis, One Shields Avenue,Davis, California 95616-8605; Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue,Cambridge, Massachusetts 02139-4307; Department of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, Indiana 47907-2084Received July 23, 2004

http://casey.brown.edu/chemistry/research/LSWang/publications/194.pdf

Role of water in electron-initiated processes and radical chemistry: issues and scientific advances.

Liquid cell electron microscopy enables direct in situ imaging of processes in liquids and objects suspended in liquids with nanoscale resolution. However, the irradiating electrons affect the chemistry of the suspending medium, typically an aqueous solution, producing molecular and radical products such as hydrogen, oxygen, and hydrated (solvated) electrons. These may impact the imaged structures and phenomena. A good understanding of the interactions between the electrons and the irradiated medium is necessary to correctly interpret experiments, minimize artifacts, and take advantage of the irradiation. We predict the composition of water subjected to electron irradiation in the electron microscope. We reinterpret available experimental data, such as beam-induced variations in pH and colloid aggregation, in light of our predictions and show new observations of crystallization and etching as functions of dose rate, resolving conflicting reports in the scientific literature. We make our computer code avai...

Electron–Water Interactions and Implications for Liquid Cell Electron Microscopy

Rate constants measured over the temperature range 20–200 °C are reported for the following reactions: (a) reaction of the hydrated electron with oxygen, the proton, hydrogen peroxide, nitrate, nitrite, nitrobenzene and methyl viologen; (b) reaction of the hydroxyl radical with another hydroxyl radical and ferrocyanide; (c) reaction of the hydrogen atom with permanganate and oxygen. To evaluate methods of estimating rate constants at high temperatures these rate constants and others in the literature have been fitted to the following equation: kobs=kdiff/(1 +kdiff/kreact), where kobs is the measured rate constant for the bimolecular reaction in solution, kdiff is the encounter rate constant of the two reacting species, and kreact is the rate constant that would be measured if diffusion of the species was not rate influencing. With the exception of reactions of the hydrated electron with nitrate and nitrite ions and nitrous oxide, good fits have been obtained to the above equation, and the results demonstrate that few, if any, of the reactions which are pertinent to water radiolysis are truly diffusion controlled at elevated temperatures.

Estimation of rate constants for near-diffusion-controlled reactions in water at high temperatures

Rate constants for the reactions OH + O–2 and OH + HO2 have been determined in water up to 200 °C by pulse radiolysis of O2-saturated solutons at pH 7.9 (O–2) and pH 2 (HO2) as measured at room temperature. The rate constants were obtained by using the computer code FACSIMILE to simulate the measured absorbance–time profiles. Good agreement between simulation and experiment could be achieved only by including HO–3 and H2O3 as long-lived weakly absorbing products, and using values of the molar absorption coefficients of O–2 and HO2 that have been redetermined in this work to be ca. 15% lower than the recommended values in the literature. The temperature dependence of each rate constant is less than that expected for diffusion-controlled reactions, with the effect being more marked for OH + HO2.

A. John Elliot

Papers

Estimation of rate constants for near-diffusion-controlled reactions in water at high temperatures

Temperature dependence of the reactions OH + O–2 and OH + HO2in water up to 200 °C

Computer modelling of the radiolysis in an aqueous lithium salt blanket : suppression of radiolysis by addition of hydrogen

The radiolysis of aqueous solutions containing dithiothreitol and oxidized dithiothreitol

Solubilities of hydrogen and oxygen in concentrated lithium salt solutions