Organic chemistry oxidation-reduction reactions

Oxidation-reduction reactions in water are dominated by the biological processes of photosynthesis and organic matter oxidation. A very different set of oxidation reactions occurs within the gas phase of the atmosphere, often a consequence of photochemical production and destruction of ozone (O3). While such reactions are of great importance to chemistry of the atmosphere - e.g., they limit the lifetime in the atmosphere of species like CO and CH4 - the global amount of these reactions is trivial compared to the global O2 production and consumption by photosynthesis and respiration. 

The quinone-hydroquinone system represents a classic example of a fast, reversible redox system. This type of reversible redox reaction is characteristic of many inorganic systems, such as the interchange between oxidation states in transition metal ions, but it is relatively uncommon in organic chemistry. The reduction of benzoquinone to hydroquinone... 

It is convenient to divide organic chemical reactions between acid-base and oxidation-reduction reactions as in inorganic chemistry. In acid-base reactions the oxidation states of carbon do not change, e.g. in hydrolysis, where reaction is, for example,... 

Electron Transfer (ET) is a basic chemical process and is the fundamental step in oxidation-reduction reactions. Therefore it can be found in organic chemistry, inorganic chemistry, material science and biochemistry. The study of the structure and reactivity of radical ions, the primary species formed upon electron transfer of parent closed-shell systems, has been a topic of interest for several years. Initially, the research in this field focused on the experimental exploration of molecular structures in terms of their hyperfine structure. However, the interest has shifted during the past decade to the mechanistic studies of these reactive intermediates. 

There are several pathways by which one ligand may replace another in a square planar complex, including nucleophilic substitution, electrophilic substitution, and oxidative addition followed by reductive elimination. The first two of these are probably familiar from courses in organic chemistry. Oxidative addition and reductive elimination reactions will be covered in detail in Chapter 15. All three of these classes have been effectively illustrated by Cross for reactions of PtMeCItPMe-Ph),.-... 

Classification of Solvents. Solvent classification helps to identify properties useful in solvent selection for individual applications for example, the study of acid-base reactions, oxidation-reduction reactions, inorganic coordination chemistry, organic nucleophilic displacement reactions, and electrochemistry. 

Enamines have been recognized in organic chemistry as useful synthetic reagents since the early reports from Stork s laboratory1. At almost the same time similar chemical moieties were being implicated in biochemical systems. Because of their intrinsic instability in water, the biochemical enamines exist primarily as intermediates, although, some well-known coenzymes that participate in oxidation-reduction reactions also incorporate enamine structures in one of their oxidation states. The electronic structure of enamines involves two extreme resonance contributions as shown in equation 1. 

The transfer of a single electron between two chemical entities is the simplest of oxidation-reduction processes, but it is of central importance in vast areas of chemistry. Electron transfer processes constitute the fundamental steps in biological utilization of oxygen, in electrical conductivity, in oxidation reduction reactions of organic and inorganic substrates, in many catalytic processes, in the transduction of the sun s energy by plants and by synthetic solar cells, and so on. The breadth and complexity of the subject is evident from the five volume handbook Electron Transfer in Chemistry (V. Balzani, Ed.), published in 2001. The most fimdamental principles that govern the efficiencies, the yields or the rates of electron-transfer processes are independent of the nature of the substrates. The properties of the substrates do dictate the conditions for apphcability of those fimdamental... 

There are no sharp dividing lines between subfields in chemistry. Many of the subjects in this book, such as acid-base chemistry and organometallic reactions, are of vital interest to organic chemists. Others, such as oxidation-reduction reactions, spectra. 

A. Oxidation-reduction reactions versus electron transfer reactions in organic chemistry and electrochemistry... 

A. Oxidation-Reduction Reactions Versus Electron Transfer Reactions in Organic Chemistry and Electrochemistry... 

Because every chemical reaction involves charge transfer (or at least partial electron shifts), the distinction between an acid-base reaction and an oxidation-reduction reaction becomes meaningless unless defined in terms of changes in conventionally assigned oxidation number.21 This point of view also has been expressed before, but still is not discussed in contemporary textbooks of general, organic, and inorganic chemistry. 

The oxidation numbers given in Table 3 can be used to classify organic reactions as either oxidation-reduction reactions or metathesis reactions. Because electrons are neither created nor destroyed, oxidation cannot occur in the absence of reduction, or vice versa. It is often useful, however, to focus attention on one component of the reaction and ask Is that substance oxidized or reduced Assigning oxidation numbers to the individual carbon atoms in a complex molecule can be difficult. Fortunately, there is another way to recognize oxidation-reduction reactions in organic chemistry. 

In this chapter we will examine oxidation-reduction stoichiometry, equilibria, and the graphical representation of simple and complex equilibria, and the rate of oxidation-reduction reactions. The applications of redox reactions to natural waters will be presented in the context of a discussion of iron chemistry the subject of corrosion will provide a vehicle for a discussion of the application of electrochemical processes a presentation of chlorine chemistry will include a discussion of the kinetics of redox reactions and the reactions of chlorine with organic matter finally, the application of redox reactions to various measurement methods will be discussed using electrochemical instruments as examples. 

Chromium can exist in several oxidation states from Cr(0), the metallic form, to Cr(Vl). The most stable oxidation states of chromium in the environment are Cr(lll) and Cr(Vl). Besides the elemental metallic form, which is extensively used in alloys, chromium has three important valence forms. The trivalent chromic (Cr(lll)) and the tetravalent dichromate (Cr(Vl)) are the most important forms in the environmental chemistry of soils and waters. The presence of chromium (Cr(Vl)) is of particular importance because in this oxidation state Cr is water soluble and extremely toxic. The solubility and potential toxicity of chromium that enters wetlands and aquatic systems are governed to a large extent by the oxidation-reduction reactions. In addition to the oxidation status of the chromium ions, a variety of soil/sediment biogeochemical processes such as redox reactions, precipitation, sorption, and complexation to organic ligands can determine the fate of chromium entering a wetland environment. 

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