Environmental chemistry, photochemical reaction importance

A molecule may absorb electromagnetic (em) radiation and, in the process, break down into its atomic or molecular components. Unstable atoms and molecular fragments may also combine to form more stable molecules, disposing of their excess energy in the form of em radiation. These chemical reactions are called photochemical, and the process by which a photochemical reaction occurs is called photolysis. Photochemical reactions play very important roles in many aspects of environmental chemistry. Therefore, this book concludes with a brief account of some of the basic principles of photochemistry, which we will then apply to ozone in the Earth s stratosphere and the problem of the stratospheric ozone hole. 

Much of environmental chemistry and water chemistry are concerned with electrons in atoms. In the atmosphere, the absorption of electromagnetic radiation, primarily ultraviolet radiation, promotes electrons to higher energy levels, forming reactive excited species and reactive free radicals with unpaired electrons. These phenomena can result in photochemical reactions such as the formation of stratospheric ozone, which is an essential filter for solar ultraviolet radiation. Atomic absorption and emission methods of elemental analysis, important in the study of pollutants, involve transitions of electrons between energy levels. 

Another area that has received increased attention is environmental organic chemistry. Reactions that organic compounds undergo when they are released to the environment are becoming as significant as the reactions by which the compounds are prepared or the reactions that lake place in the use of the compounds. Some environmentally important types of reactions arc hydrolysis, oxidation, sunlight-initiated photochemical decomposition, and biodegradation by microbes. 

We and others have used pulse radiolysis methods to clarify a number of complex photochemical mechanisms. In the course of these studies we have also been able to learn a great deal of new chemistry, including the electronic absorption spectra, thermodynamics, and reaction mechanisms of highly reactive transition-metal centers in both unusually high and low oxidation states. As these data pertain to aqueous media, they contribute in an important way to future work on solar photoconversion in water (the ideal medium from both economic and environmental points of view) and to catalysis in aqueous media in general. 

Free radicals are important in many environmentally significant reactions (see the Chemistry in the Environment box on free radicals in this chapter). For example, photochemical smog— smog that results from the action of sunlight on air pollutants— forms in part by these two steps ... 

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