Redox 3 Standard Reduction Potentials

FIGURE 21.2 Experimental apparatus used to measure the standard reduction potential of the indicated redox couples (a) the acetaldehyde/ethanol couple, (b) the fumarate/succi-nate couple, (c) the Fe /Fe" couple. 

Some typical half-cell reactions and their respective standard reduction potentials are listed in Table 21.1. Whenever reactions of this type are tabulated, they are uniformly written as reduction reactions, regardless of what occurs in the given half-cell. The sign of the standard reduction potential indicates which reaction really occurs when the given half-cell is combined with the reference hydrogen half-cell. Redox couples that have large positive reduction potentials... 

We have already noted that the standard free energy change for a reaction, AG°, does not reflect the actual conditions in a ceil, where reactants and products are not at standard-state concentrations (1 M). Equation 3.12 was introduced to permit calculations of actual free energy changes under non-standard-state conditions. Similarly, standard reduction potentials for redox couples must be modified to account for the actual concentrations of the oxidized and reduced species. For any redox couple. 

Tlic power of these various concepts in codifying and rationalizing the redox chemistry of the clcineiUs is ilhislraled for Ihe case of nitrogen in tbe present section Standard reduction potentials and plots of volt equivalents against oxidation state fur odicr elements are presented in later chapters... 

It is clear from what has already been stated that standard reduction potentials may be employed to determine whether redox reactions are sufficiently complete... 

The calculation o E° for this cell illustrates an important feature of cell potentials. A standard cell potential is the difference between two standard reduction potentials. This difference does not change when one half-reaction is multiplied by 2 to cancel electrons in the overall redox reaction. 

Use tabulated standard reduction potentials to determine for the following redox reaction ... 

This is a quantitative calculation, so it is appropriate to use the seven-step problem-solving strategy. We are asked to determine an equilibrium constant from standard reduction potentials. Visualizing the problem involves breaking the redox reaction into its two half-reactions ... 

The order of catalytic activity was Fe > Ga > Sn > Ti, which is the same order as the standard reduction potential E°Mn+/M for these metals. This illustrates that redox properties rather than acid properties are responsible for the activity. Comparison of the activation energies between the different Fe-Si-TUD-1 samples was carried out by conducting the reaction at temperatures between 40° and 80°C. For Fei, Fe2, Fes and Feio the activation energy was 47, 85, 182 and 216 kJ/mol, respectively. The large difference in activation energies between these samples may... 

They are the basis of many products and processes, from batteries to photosynthesis and respiration. You know redox reactions involve an oxidation half-reaction in which electrons are lost and a reduction half-reaction in which electrons are gained. In order to use the chemistry of redox reactions, we need to know about the tendency of the ions involved in the half-reactions to gain electrons. This tendency is called the reduction potential. Tables of standard reduction potentials exist that provide quantitative information on electron movement in redox half-reactions. In this lab, you will use reduction potentials combined with gravimetric analysis to determine oxidation numbers of the involved substances. 

The titration is represented in Fig. 2.22 by plotting the Pt electrode potential versus the titration parameter k. BB is the voltage curve for titration of Fe2+ with Ce4+ and B B that for titration of Ce4+ with Fe2+ they correspond exactly to the pH curves BB and B B in Fig. 2.18, with the exception that the initial point in Fig. 2.22 would theoretically have an infinitely negative and an infinitely positive potential, respectively. In practice this is impossible, because even in the absence of any other type of redox potential there will be always a trace of Fe3+ in addition to Fe2+ and of Ce3+ in addition to Ce4+ present. Further, half way through the oxidation or reduction the voltage corresponds to the standard reduction potentials of the respective redox couples it also follows that the equivalence point is represented by the mean value of both standard potentials ... 

Many handbooks like the CRC Handbook of Chemistry and Physics provide, on behalf of electrochemistry investigation, values of standard reduction potentials, listed either in alphabetical order and/or in potential order. These must be considered as potentials of completely reversible redox systems. In current analytical practice one is interested in half-wave potentials of voltammetric, mostly polarographic analysis in various specific media, also in the case of irreversible systems. Apart from data such as those recently provided by Rach and Seiler (Spurenanalyse mit Polarographischen und Voltammetrischen Methoden, Hiithig, Heidelberg, 1984), these half-wave potentials are given in the following table (Application Note N-l, EG G Princeton Applied Research, Princeton, NJ, 1980). 

FIGURE3.7 The potential window for the redox chemistry of life. Redox chemistry in living cells is approximately limited by the standard potentials for reduction and oxidation of the solvent water at neutral pH. Approximate standard reduction potentials are also indicated for the commonly used oxidant ferricyanide and reductants NADH and dithionite. 

Figure 2.87 Schematic of the cyclic voltammogram expected from a reversible electrochemical redox system 0 + e + R having a standard reduction potential °. E is the potential of the working electrode, and I the current.

The overall cell potential is +0.96 V, showing that the redox reaction is indeed spontaneous. The standard reduction potential for the half cell Ag2S(s) + 2e - 2Ag(s) + S2 (aq) was obtained from the American Society for Metals (ASM) Handbook, available on the internet. 

FIGURE 14.3 Mnemonic devices, the arrows on the left, for predicting which chemicals will participate in a redox reaction and which will not. A segment of the table of standard reduction potentials (Table 14.1) is presented on the right as a help to understand the use of the arrows. See text for an example. 

The more the two half-reactions are separated in the table, the greater is the tendency for the net reaction to occur. This tendency for an overall redox reaction to occur, whether by direct contact or in an electrochemical cell, is determined from the standard reduction potentials, E° values, of the half-reactions involved, and the value of this potential are indications of the tendency of the overall redox reaction to occur. We will now present a scheme for determining this potential, which is symbolized E"d. ... 

In the following scheme, it is assumed that there is a proposed redox system given so that the halfreactions and standard reduction potentials can be found in Table 14.1, or other table of standard reduction potentials. An example follows ... 

Write the two half-reactions for the following redox reaction. Add the standard reduction potential and the standard oxidation potential to find the standard cell potential for the reaction. 

Use the given standard reduction potentials to calculate the standard cell potentials for the following redox reactions. 

Reduction potential is a measure of how thermodynamically favourable it is for a compound to gain electrons. A high positive value for a reduction potential indicates that a compound is readily reduced and consequently is a strong oxidising agent, i.e. it removes electrons from substances with lower reduction potentials. The oxidised and reduced form of a substance are known as a redox pair. Table 3.2 lists the standard reduction potentials for some typical redox pairs. 

Table 3.2 Standard reduction potential ( ) for some redox pairs relative to the standard hydrogen electrode potential 0...

I mm your understanding of the inert-pair clfeci anil the redox properties ol TI and I >. consider the apparent oxidation stale of 11 ui the compound I II and indicate what the realistic value is. flic standard reduction potential for the Tlm Tl1 couple is >. 25 V. 

We start with a simple reversible redox reaction for which we can directly measure the free energy of reaction, Ar<7, with a galvanic cell. This example helps us introduce the concept of using (standard) reduction potentials for evaluating the energetics (i.e., the free energies) of redox processes. Let us consider the reversible interconversion of 1,4-benzoquinone (BQ) and hydroquinone (HQ) (reaction 14-5 in Table 14.1). We perform this reaction at the surface of an inert electrode (e.g.,... 

Table 14.2 Standard Reduction Potentials and Average Standard Free Energies of Reaction (per Electron Transferred) at 25 °C of Some Redox Couples that Are Important in Natural Redox Processes (The reactions are ordered in decreasing 1 h(W) values.)a...

When two conjugate redox pairs are together in solution, electron transfer from the electron donor of one pair to the electron acceptor of the other may proceed spontaneously. The tendency for such a reaction depends on the relative affinity of the electron acceptor of each redox pair for electrons. The standard reduction potential, E°, a measure (in volts) of this affinity, can be determined in an experiment such as that described in Figure 13-14. Electrochemists have chosen as a standard of reference the half-reaction... 

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... 

Standard Reduction Potentials The standard reduction potential, E °, of any redox pair is defined for the half-cell reaction ... 

Redox pairs Oxidation (loss of electrons) of one compound is always accompanied by reduction (gain of electrons) of a second substance. For example, Figure 6.11 shows the oxidation of NADH to NAD+ accompanied by the reduction of FAD to FADH2. Such oxidation-reduction reactions can be written as the sum of two halfreactions an isolated oxidation reaction and a separate reduction reaction (see Figure 6.11). NAD+ and NADH form a redox pair, as do FAD and FADH2. Redox pairs differ in their tendency to lose electrons. This tendency is a characteristic of a particular redox pair, and can be quantitatively specified by a constant, E (the standard reduction potential), with units in volts. 

The rate constant for the redox step, kr, is unlikely to reflect a simple electron transfer from the monodentate diimine ligand to the metal center because replacement of coordinated water with coordinated hydroxide would be expected to decrease the oxidizing power of the metal-(III) center. This is well documented by the standard reduction potentials of the aqua and hydroxo complexes in Table IV, and it would seem... 

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