Reduction reactions defined

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. 

Very limited investigations have been conducted with this alloy system. The results obtained to date suggest that A1 co-deposits with Fe from solutions of Fe(II) in both AlCl3-EtMeImCl at 25 °C [46] and AlCl3-NaCl at 160 °C [100]. In both studies, the A1 co-deposition process was found to commence at nearly the same potential as the Fe(II) reduction reaction therefore, it was difficult to observe a well-defined voltammetric limiting current for the latter process, regardless of the technique that was employed. This behavior is nearly identical to that seen in the Ni-Al system [47], However, a comparison of the voltammetric results recorded for some of the other... 

In general, TPR measurements are interpreted on a qualitative basis as in the example discussed above. Attempts to calculate activation energies of reduction by means of Expression (2-7) can only be undertaken if the TPR pattern represents a single, well-defined process. This requires, for example, that all catalyst particles are equivalent. In a supported catalyst, all particles should have the same morphology and all atoms of the supported phase should be affected by the support in the same way, otherwise the TPR pattern would represent a combination of different reduction reactions. Such strict conditions are seldom obeyed in supported catalysts but are more easily met in unsupported particles. As an example we discuss the TPR work by Wimmers et al. [8] on the reduction of unsupported Fe203 particles (diameter approximately 300 nm). Such research is of interest with regard to the synthesis of ammonia and the Fischer-Tropsch process, both of which are carried out over unsupported iron catalysts. 

A battery is an electrochemical cell, and is defined as a device comprising two or more redox couples (where each couple comprises two redox states of the same material). An oxidation reaction occurs at the negative pole of the battery in tandem with a reduction reaction at the positive pole. Both reactions proceed with the passage of current. The two redox couples are separated physically by an electrolyte. 

In the discussion of the Daniell cell, we indicated that this cell produces a voltage of 1.10 V. This voltage is really the difference in potential between the two half-cells. The cell potential (really the half-cell potentials) is dependent upon concentration and temperature, but initially we ll simply look at the half-cell potentials at the standard state of 298 K (25°C) and all components in their standard states (1M concentration of all solutions, 1 atm pressure for any gases and pure solid electrodes). Half-cell potentials appear in tables as the reduction potentials, that is, the potentials associated with the reduction reaction. We define the hydrogen half-reaction (2H+(aq) + 2e - H2(g)) as the standard and has been given a value of exactly 0.00 V. We measure all the other half-reactions relative to it some are positive and some are negative. Find the table of standard reduction potentials in your textbook. 

In organic chemistry, reduction is defined as a reaction in which a carbon atom forms fewer bonds to oxygen, O, or more bonds to hydrogen, H. Often, a C=0 bond or C=C bond is reduced to a single bond by reduction. A reduction that transforms double C=C or C=0 bonds to single bonds may also be classified as an addition reaction. Aldehydes, ketones, and carboxylic acids can be reduced to become alcohols. Alkenes and alkynes can be reduced by the addition of H2 to become alkanes. 

Rate of Electrochemical Reaction in Terms of Current. In this part of the derivation we start with a definition of the rate of reaction and the definition of the electric current. The rate of the reduction reaction v, reaction (6.6) from left to right, is defined as the number of moles m of Ox reacting per second and per unit area of the electrode surface ... 

The reduction-oxidation potential (typically expressed in volts) of a compound or molecular entity measured with an inert metallic electrode under standard conditions against a standard reference half-cell. Any oxidation-reduction reaction, or redox reaction, can be divided into two half-reactions, one in which a chemical species undergoes oxidation and one in which another chemical species undergoes reduction. In biological systems the standard redox potential is defined at pH 7.0 versus the hydrogen electrode and partial pressure of dihydrogen of 1 bar. 

The reaction of magnesium and oxygen is an example of an oxidation reaction. The combination of an element with oxygen was the traditional way to define an oxidation reaction. This definition of oxidation has been broadened by chemists to include reactions that do not involve oxygen. Our modern definition for oxidation is that oxidation takes place when a substance loses electrons. Anytime oxidation takes place and a substance loses one or more electrons, another substance must gain the electron(s). When a substance gains one or more electrons, the process is known as reduction. Reactions that involve the transfer of one or more electrons always involve both oxidation and reduction. These reactions are known as oxidation-reduction or redox reactions. 

Many half-reactions of interest to biochemists involve protons. As in the definition of AG °, biochemists define the standard state for oxidation-reduction reactions as pH 7 and express reduction potential as E °, the standard reduction potential at pH 7. The standard reduction potentials given in Table 13-7 and used throughout this book are values for E ° and are therefore valid only for systems at neutral pH Each value represents the potential difference when the conjugate redox pair, at 1 m concentrations and pH 7, is connected with the standard (pH 0) hydrogen electrode. Notice in Table 13-7 that when the conjugate pair 2ET/H2 at pH 7 is connected with the standard hydrogen electrode (pH 0), electrons tend to flow from the pH 7 cell to the standard (pH 0) cell the measured E ° for the 2ET/H2 pair is -0.414 V... 

We live under a blanket of the powerful oxidant 02. By cell respiration oxygen is reduced to H20, which is a very poor reductant. Toward the other end of the scale of oxidizing strength lies the very weak oxidant H+, which some bacteria are able to convert to the strong reductant H2. The 02 -H20 and H+ - H2 couples define two biologically important oxidation-reduction (redox) systems. Lying between these two systems are a host of other pairs of metabolically important substances engaged in oxidation-reduction reactions within cells. 

The loss of an electron by M, M + + e, is the process of oxidation in electrochemistry. The electron is then accepted by an electrode of well defined potential, so that the oxidation potential Eox is the free energy of the reaction, as was seen in Figure 4.1. Similarly the reduction potential Ered is the energy of the reduction reaction, e.g. N + e - N. By definition the molecule, which is oxidized, is the donor (M in this case), and the molecule, which is reduced, is the acceptor. The electron transfer from M to N is therefore equivalent to the combined oxidation of the donor and reduction of the acceptor, so that the energy balance is... 

Reasons for interest in the catalyzed reactions of NO, CO, and COz are many and varied. Nitric oxide, for example, is an odd electron, hetero-nuclear diatomic which is the parent member of the environmentally hazardous oxides of nitrogen. Its decomposition and reduction reactions, which occur only in the presence of catalysts, provide a stimulus to research in nitrosyl chemistry. From a different perspective, the catalyzed reactions of CO and COz have attracted attention because of the need to develop hydrocarbon sources that are alternatives to petroleum. Carbon dioxide is one of the most abundant sources of carbon available, but its utilization will require a cheap and plentiful source of hydrogen for reduction, and the development of catalysts that will permit reduction to take place under mild conditions. The use of carbon monoxide in the development of alternative hydrocarbon sources is better defined at this time, being directly linked to coal utilization. The conversion of coal to substitute natural gas (SNG), hydrocarbons, and organic chemicals is based on the hydrogen reduction of CO via methanation and the Fischer-Tropsch synthesis. Notable successes using heterogeneous catalysts have been achieved in this area, but most mechanistic proposals remain unproven, and overall efficiencies can still be improved. 

Today, the words oxidation and reduction have taken on a much broader meaning. An oxidation is now defined as the loss of one or more electrons by a substance—element, compound, or ion—and a reduction is the gain of one or more electrons by a substance. Thus, an oxidation-reduction reaction, or redox reaction, is a process in which electrons are transferred from one substance to another. 

Before we review the methods used to determine surface acidity, we wish to define the type of acidity that should be measured. An acid is an electron-pair acceptor. In our opinion, the term acid should be limited to this definition rather than broadening the term to include oxidizing agents as well. We agree with Flockhart and Pink (10) who suggest a clear distinction be made between Lewis acid-Lewis base reactions (which involve coordinate bond formation) and oxidation-reduction reactions (which involve complete transfer of one or more electrons). 

From the analytical equation (6.105) obtained for CV, the study of the current-potential response in these techniques can be performed along with the analysis of the influence of the key variables. First, the effect of the parameter co (Eq. (6.98)) is shown in Fig. 6.15 where the curves are plotted for a spherical electrode of 50 pm radius. Note that large upvalues relate to the situation where the complexes of the reactant species A are more stable than those of species B, whereas the opposite situation is found for small negative potentials when co increases on account of the hindering of the electro-reduction reaction due to the stabilitization of the oxidized species with respect to the reduced ones. According to Eq. (3.289), an apparent formal potential can be defined as follows ... 

An advantage of the mediator model (Equation 9) is that it can be used to simplify the problem of describing contaminant reduction reactions if the mediator is characterized more easily than the bulk donor. In this case, the bulk donor is best neglected and the problem reduced to the mediator and contaminant half-reactions. The advantage is greatest when a complex microbiological transformation process can be reduced to a reaction with a well defined biogenic mediators, such as quinones (98, 99), porphyrins, or corronoids (100-102). 

This chapter mainly focuses on the reactivity of 02 and its partially reduced forms. Over the past 5 years, oxygen isotope fractionation has been applied to a number of mechanistic problems. The experimental and computational methods developed to examine the relevant oxidation/reduction reactions are initially discussed. The use of oxygen equilibrium isotope effects as structural probes of transition metal 02 adducts will then be presented followed by a discussion of density function theory (DFT) calculations, which have been vital to their interpretation. Following this, studies of kinetic isotope effects upon defined outer-sphere and inner-sphere reactions will be described in the context of an electron transfer theory framework. The final sections will concentrate on implications for the reaction mechanisms of metalloenzymes that react with 02, 02 -, and H202 in order to illustrate the generality of the competitive isotope fractionation method. 

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