Oxidation-reduction acid-base reactions

Typically, small molecule drugs are produced using reactions such as oxidation-reduction, acid-base, halogenation, alkylation, and substitution. 

Coulometric titration procedures have been developed for a great number of oxidation-reduction, acid-base, precipitation, and complexation reactions. The sample systems as well as the electrochemical intemediates used for them are summarized in Table 4.1, and indicate the diversity and range of application for the method. An additional specialized form of coulometric titration involves the use of a spent Karl Fischer solution as the electrochemical intermediate for the determination of water at extremely low levels. For such a system the anode reaction regenerates iodine, which is the crucial component of the Karl Fischer titrant. This then reacts with the water in the sample system according to the... 

Chemical and electrochemical processes that cause materials corrosion usually involve both reduction-oxidations and acid-base reactions. The reduction-oxidation reaction is dependent on the electron energy level of the particles involved in the reaction, and hence managing the electrode potential of corroding materials may control the corrosion reaction. The acid-base reaction, on the other side, is determined by the HSAB characteristics (hard and soft acids and bases) of the particles involved in the reaction. It is mainly through the acid-base property that the environmental substances such as aggressive salts affect the corrosion of solid materials. 

The fate of organic contaminants in soils and sediments is of primary concern in environmental science. The capacity to which soil constituents can potentially react with organic contaminants may profoundly impact assessments of risks associated with specific contaminants and their degradation products. In particular, clay mineral surfaces are known to facilitate oxidation/reduction, acid/base, polymerization, and hydrolysis reactions at the mineral-aqueous interface (1, 2). Since these reactions are occurring on or at a hydrated mineral surface, non-invasive spectroscopic analytical methods are the preferred choice to accurately ascertain the reactant products and to monitor reactions in real time, in order to determine the role of the mineral surface in the reaction. Additionally, the in situ methods employed allow us to monitor the ultimate changes in the physico-chemical properties of the minerals. 

Show that the corrosion reaction in which Cu is converted to its basic carbonate (reaction 23.27) can be thought of in terms of a combination of oxidation-reduction, acid-base, and precipitation reactions. 

Although essentially inert m acid-base reactions alkanes do participate m oxidation-reduction reactions as the compound that undergoes oxidation Burning m air (combus tion) IS the best known and most important example Combustion of hydrocarbons is exothermic and gives carbon dioxide and water as the products... 

Several types of reactions are commonly used in analytical procedures, either in preparing samples for analysis or during the analysis itself. The most important of these are precipitation reactions, acid-base reactions, complexation reactions, and oxidation-reduction reactions. In this section we review these reactions and their equilibrium constant expressions. 

In addition to simple dissolution, ionic dissociation and solvolysis, two further classes of reaction are of pre-eminent importance in aqueous solution chemistry, namely acid-base reactions (p. 48) and oxidation-reduction reactions. In water, the oxygen atom is in its lowest oxidation state (—2). Standard reduction potentials (p. 435) of oxygen in acid and alkaline solution are listed in Table 14.10- and shown diagramatically in the scheme opposite. It is important to remember that if or OH appear in the electrode half-reaction, then the electrode potential will change markedly with the pH. Thus for the first reaction in Table 14.10 O2 -I-4H+ -I- 4e 2H2O, although E° = 1.229 V,... 

In titrimetric analysis (often termed volumetric analysis in certain books), the substance to be determined is allowed to react with an appropriate reagent added as a standard solution, and the volume of solution needed for complete reaction is determined. The common types of reaction which are used in titrimetry are (a) neutralisation (acid-base) reactions (b) complex-forming reactions (c) precipitation reactions (d) oxidation-reduction reactions. 

Two very important classes of chemical reactions are oxidation-reduction (redox) reactions and acid-base reactions, which are defined by molecules or ions accepting and donating electrons or protons, respectively. 

Because the breadth of chemical behavior can be bewildering in its complexity, chemists search for general ways to organize chemical reactivity patterns. Two familiar patterns are Br< )nsted acid-base (proton transfer) and oxidation-reduction (electron transfer) reactions. A related pattern of reactivity can be viewed as the donation of a pair of electrons to form a new bond. One example is the reaction between gaseous ammonia and trimethyl boron, in which the ammonia molecule uses its nonbonding pair of electrons to form a bond between nitrogen and boron ... 

The major processes affecting the geochemical fate of hazardous inorganics are acid-base adsorption-desorption, precipitation-dissolution, complexation, hydrolysis, oxidation-reduction, and catalytic reactions. The significance of these processes to inorganic wastes is discussed only briefly here additional information on individual elements is given in Table 20.16. 

The equivalent is defined in terms of a chemical reaction. It is defined in one of two different ways, depending on whether an oxidation-reduction reaction or an acid-base reaction is under discussion. For an oxidation-reduction reaction, an equivalent is the quantity of a substance that will react with or yield 1 mol of electrons. For an acid-base reaction, an equivalent is the quantity of a substance that will react with or yield 1 mol of hydrogen ions or hydroxide ions. Note that the equivalent is defined in terms of a reaction, not merely in terms of a formula. Thus, the same mass of the same compound undergoing different reactions can correspond to different numbers of equivalents. The ability to determine the number of equivalents per mole is the key to calculations in this chapter. 

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,... 

The acid-base reactions are (a) and (k) only, in which an acid reacts with a base to give a salt and water. In all acid-base reactions, no oxidation or reduction is involved. 

Selectivity in catalytic oxidation/reduction and acid-base reactions has been a long-term challenge in the catalysis field. While it has been recognized that the control of molecular activation and reaction intermediates is critical in achieving high selectivity, this issue has not been adequately addressed and is a serious challenge to the field. 

A first turning point in the dichotomy between radical and ionic chemistry is located at the level of the primary radical, usually an ion radical, formed upon single electron transfer to the substrate. If, for a reduction, the reaction medium is not too acidic (or electrophilic), and for an oxidation, not too basic (or nucleophilic), radical reactions involving the primary radical, such as self-coupling, have a first opportunity to compete successfully with acid-base reactions. In this competition, the acidity (for a reduction) or basicity (for an oxidation) of the substrate should also be taken into account insofar as they may lead to father-son acid-base reactions. It should also be taken into consideration that the primary radical may undergo spontaneous acid-base reactions such as expelling a base (or a nucleophile) after a reduction, and an acid (or an electrophile) after an oxidation. 

If the provoked or spontaneous acid-base reactions overcome the radical reactions of the primary radical, the secondary radical is easier to reduce, or to oxidize, than the substrate in most cases. Exceptions to this rule are scarce, but exist. They involve substrates that are particularly easy to reduce thanks to the presence of a strongly electron-withdrawing substituent (for reductions, electron-donating for oxidation), which is expelled upon electron transfer, thus producing a radical that lacks the same activation. Alkyl iodides and aryl diazonium cations are typical examples of such systems. 

Numerous types of chemical reactions pose potential hazards. Literature and incident data highlight the hazards of common industrial reactions, such as polymerization, decomposition, acid-base, oxidation-reduction (redox), and reactions with water. Polymerization and decomposition can be classified as self-reactions because they often involve just one chemical substance. However, other... 

In the same way that acid-base reactions involve the transfer of protons between proton donors and proton acceptors, redox reactions involve the transfer of electrons between electron donors, called reducing agents or reductants, and electron acceptors, called oxidizing agents or oxidants. Thus when a redox reaction takes place, a reductant loses electrons and is oxidized to its conjugate oxidaut ... 

The fact that complex 38 does not react further - that is, it does not oxidatively add the N—H bond - is due to the comparatively low electron density present on the Ir center. However, in the presence of more electron-rich phosphines an adduct similar to 38 may be observed in situ by NMR (see Section 6.5.3 see also below), but then readily activates N—H or C—H bonds. Amine coordination to an electron-rich Ir(I) center further augments its electron density and thus its propensity to oxidative addition reactions. Not only accessible N—H bonds are therefore readily activated but also C—H bonds [32] (cf. cyclo-metallations in Equation 6.14 and Scheme 6.10 below). This latter activation is a possible side reaction and mode of catalyst deactivation in OHA reactions that follow the CMM mechanism. Phosphine-free cationic Ir(I)-amine complexes were also shown to be quite reactive towards C—H bonds [30aj. The stable Ir-ammonia complex 39, which was isolated and structurally characterized by Hartwig and coworkers (Figure 6.7) [33], is accessible either by thermally induced reductive elimination of the corresponding Ir(III)-amido-hydrido precursor or by an acid-base reaction between the 14-electron Ir(I) intermediate 53 and ammonia (see Scheme 6.9). 

Lovgren, L. Sjoberg, S. Schindler, P.W. (1990) Acid/base reactions and aluminium(III). Complexation at the surface of goethite. Geochim. Cosmochim. Acta 54 1301-1306 Lovley, D.R. (1992) Microbial oxidation of organic matter coupled to the reduction of Fe(III) and Mn(IV) oxides. In Skinner,... 

As we have covered, titration is used to determine the concentration of an unknown substance in acid-base reactions through the use of a known concentration in a solution. It can also be used in oxidation-reduction reactions for the same analytical... 

With the exception of B = OH-, which relates in fact to an acid-base reaction, the other nucleophiles are potential reductants. After forming the reversible adducts [Eq. (5)], redox reactions are usually operative, leading to the reduction of nitrosyl and oxidation of the nucleophile in Eq. (6). Nevertheless, we will consider first the reaction with B = OH- for the sake of simplicity, and also because it allows for some generalizations to be made on the factors that influence the electrophilic reactivities of different nitrosyl complexes (51). We continue with new results for some N-binding nucleophiles (62,67), which throw light on the mecanisms of N20/N2 production and release from the iron centers. A description of the state of the art studies on the reactions with thiolate reactants as nucleophiles will be presented later. 

The goal of this chapter is to give you a stronger handle on the basics of chemical reactions, which were introduced in Chapter 2. Then in the following chapters we ll look at specific classes of chemical reactions, such as acid-base reactions, oxidation-reduction reactions, and reactions involving organic chemicals. 

As we learned in Chapter 9, chemicals that react with one another are called reactants. In the process of reacting, the reactants form new chemicals known as products. In most acid-base reactions, a proton is transferred from one reactant to the lone pair of another reactant. In this chapter we look at a class of reactions in which an electron or a series of electrons are transferred from one reactant to another.These types of reactions are called oxidation-reduction reactions. 

In me previous chapter we discussed acid-base reactions, which are chemical reactions involving the transfer of pro Lons from one reactant to another. In this chapter, we explored oxidation-reduction reactions, which involve the transfer of one or more electrons from one reactant to another. Oxidation-reduction reactions have many applications, such as in photography, batteries, fuel cells, the manufacture and corrosion of metals, and the combustion of non-metallic materials such as wood. 

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