Reactions Involving Organic Substances

Like inorganic substances, organic substances can be anodicaUy oxidized and/or cathodicaUy reduced. Such reactions are widely used for the synthesis of various organic compounds (electroorganic synthesis). Moreover, they are of importance for the qualitative and qnantitative analysis of organic substances in solutions, as for instance in polarography (see Lund and Baizer, 1991). 

Reactions involving organic substances have some special features. Many of these substances are poorly soluble in aqueous solutions. Sometimes their solubilities can be raised by adding to the solution the salts of aromatic sulfonic acids with cations of the type [NHJ or alkali metal ions. These salts have a salting-in effect on poorly soluble organic substances. In many cases solutions in mixed or nonaque-ous solvents (e.g., methanol) are used. Suspensions of the organic substances in aqueous solutions are also useful for electrosynthesis. 

Electrochemical reactors are inferior to chemical reactors in their productivity. Hence, electrosynthesis is used when chemical ways to synthesize a given substance 

Most often, these radicals are unstable and can exist only while adsorbed on the electrode, although in the case of polycyclic aromatic compounds (e.g., the derivatives of anthracene), they are more stable and can exist even in the solution. The radicals formed first can undergo a variety of chemical or electrochemical reactions. This reaction type is the analog of hydrogen evolution, where electron transfer as the first step produces an adsorbed hydrogen atom, which is also a radical-type product. 

The chemical mechanism rests on the effect of intervening redox systems (see Section 13.6). Here intermediate reactants such as species on a cathode surface, species on an anode surface, or reducing and oxidizing agents in the solution layer next to the electrode are first produced electrochemicaUy from solution components. The further interaction of these reactants with the organic substance is purely chemical in character, for example, following a reaction 

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The degree to which an electrode will influence the reaction rates is different for different electrochemical reactions, hi complex electrochemical reactions having parallel pathways, such as a reaction involving organic substances, the electrode material might selectively influence the rates of certain individual steps and thus influence the selectivity of the reaction (i.e., the overall direction of the reaction and the relative yields of primary and secondary reaction products). 

Each system considered in this section has a space of overall reactions whose dimension exceeds one. In many industrial reactions involving organic substances a major product is formed, but a side reaction contributes to loss in selectivity or yield of the desired product. Such cases may be said to exhibit a multiple overall reaction, unless the ratio of desired product to by-product remains constant over a range of operating conditions, so that a simple chemical equation might be employed to express the stoichiometry. 

NUCLEOPHILE-ELECTROPHILE INTERACTIONS AND REDOX REACTIONS INVOLVING ORGANIC SUBSTANCES... 

Reactions of organic substances at the dropping electrode usually involve hydrogen ions a typical reaction can be represented by the equation... 

In addition to the direct absorption as a biological hazard, UV can have additional indirect effects on organisms.26,27 A number of UV photochemical reactions occur in solutions, both within cells and in the external aquatic environment. In the presence of UV, water itself is hydrolyzed, producing hydroxyl ions. Related reactions involving dissolved substances and mediated by UV lead to the formation of peroxides, super oxide, and other radicals. These reactive products are toxic by causing oxidative damage to biological molecules.28-31... 

At first sight, it may appear that a discussion of nucleophile-electrophile interactions does not fit into a chapter on redox processes, but the transfer of electron pairs from a nucleophile to an electrophile, such as in hydrolysis or in chlorination of a phenol, may be looked at as a reaction between an oxidant and reductant, although we are aware that mechanistically, in many real redox processes involving organic substances, the electron transfers often occur in one-electron steps. 

This is an essential topic for biochemists and biochemical engineers. Biochemical reactions involve both cellular and enzymatic processes, and the principal differences between biochemical and chemical reactions lie in the nature of the living systems. Biochemists and biochemical engineers can stabilize most organic substances in processes involving microorganisms. 

As a cautionary note PTC should not be considered a panacea for all of the problems associated with green chemistry. Two-phase reactions involving water are often difficult to deal with industrially, particularly if the water is contaminated with trace amounts of hazardous organic substances. In some cases it may be more practical, cost effective and environmentally prudent to avoid production of aqueous waste in favour of a recyclable less benign solvent. 

Both these conversion processes involve the addition of electrons to the toxic substances. The trichloroethylene molecule is electrically neutral and must gain electrons in reactions that generate negatively charged chloride anions, hi addition, water or hydronium ions must supply hydrogen atoms that replace the chlorine atoms in the organic substance. The detailed reaction is complicated, but the net reaction is relatively simple CI2 C I CHCl + 3 H3 + 6 H2 C CH2 + 3 Cr + 3 H2 O... 

In the past it had been a popular belief that the electrochemical reduction of any inorganic or organic substance involves the primary electrochemical formation of a special, active form of hydrogen in the nascent state (in statu nascendi) and subsequent chemical reaction of this hydrogen with the substrate. However, for many reduction reactions a mechanism of direct electron transfer from the electrode to the substrate could be demonstrated. It is only in individual cases involving electrodes with superior hydrogen adsorption that the mechanism above with an intermediate formation of adsorbed atomic hydrogen is possible. 

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