Thermodynamics standard electrode potentials

Thermodynamic data (4) for selected manganese compounds is given ia Table 3 standard electrode potentials are given ia Table 4. A pH—potential diagram for aqueous manganese compounds at 25°C is shown ia Figure 1 (9). 

The thermodynamics of electrochemical reactions can be understood by considering the standard electrode potential, the potential of a reaction under standard conditions of temperature and pressure where all reactants and products are at unit activity. Table 1 Hsts a variety of standard electrode potentials. The standard potential is expressed relative to the standard hydrogen reference electrode potential in units of volts. A given reaction tends to proceed in the anodic direction, ie, toward the oxidation reaction, if the potential of the reaction is positive with respect to the standard potential. Conversely, a movement of the potential in the negative direction away from the standard potential encourages a cathodic or reduction reaction. 

It should be noted that the simple Nernst equation cannot be used since the standard electrode potential is markedly temperature dependent. By means of irreversible thermodynamics equations have been computed to calculate these potentials and are in good agreement with experimentally determined results. 

The values in Table 2.16 show how the potentials obtained under service conditions differ from the standard electrode potentials which are frequently calculated from thermodynamic data. Thus aluminium, which is normally coated with an oxide film, has a more noble value than the equilibrium potential 3 + / = — 1-66V vs. S.H.E. and similar considerations apply to passive stainless steel (see Chapter 21). 

Equations 20.176 and 20.179 emphasise the essentially thermodynamic nature of the standard equilibrium e.m.f. of a cell or the standard equilibrium potential of a half-reaction E, which may be evaluated directly from e.m.f. meeisurements of a reversible cell or indirectly from AG , which in turn must be evaluated from the enthalpy of the reaction and the entropies of the species involved (see equation 20.147). Thus for the equilibrium Cu -)-2e Cu, the standard electrode potential u2+/cu> hence can be determined by an e.m.f. method by harnessing the reaction... 

In the introductory chapter we stated that the formation of chemical compounds with the metal ion in a variety of formal oxidation states is a characteristic of transition metals. We also saw in Chapter 8 how we may quantify the thermodynamic stability of a coordination compound in terms of the stability constant K. It is convenient to be able to assess the relative ease by which a metal is transformed from one oxidation state to another, and you will recall that the standard electrode potential, E , is a convenient measure of this. Remember that the standard free energy change for a reaction, AG , is related both to the equilibrium constant (Eq. 9.1)... 

The standard electrode potential of reaction (15.20) calculated thermodynamically is 1.229 V (SHE) at 25°C. For reachons (15.21) and (15.22), these values are 0.682 and 1.776 V, respechvely. The equihbrium potenhals of all these reactions have the same pH dependence as the potential of the reversible hydrogen electrode therefore, on the scale of potentials (against the RHE), these equilibrium potenhals are... 

The relationships of the type (3.1.54) and (3.1.57) imply that the standard electrode potentials can be derived directly from the thermodynamic data (and vice versa). The values of the standard chemical potentials are identified with the values of the standard Gibbs energies of formation, tabulated, for example, by the US National Bureau of Standards. On the other hand, the experimental approach to the determination of standard electrode potentials is based on the cells of the type (3.1.41) whose EMFs are extrapolated to zero ionic strength. 

To recall the basic concepts of the thermodynamics of cell operation, such as the electrode potential E, the standard electrode potential and the electromotive force (emf). 

Having revised a few basic electrochemical ideas, such as the nature of reference electrodes, the standard hydrogen electrode and the scale based on it, we next looked briefly at thermodynamic parameters such as the electrode potential E, the standard electrode potential f and emf, and then discussed how AG, AH and AS (where the prime indicates a frustrated cell equilibrium ) may be determined. 

Next, we need to decide on what we think is occurring in terms of the system actually before us. Let s suppose that we have a CV which looks as though it describes a simple single reversible electron-transfer reaction. From the experimental trace of current against potential, it should be easy to obtain the standard electrode potential E . In addition, before we start, we measure the area of the electrode. A, and the thermodynamic temperature, T. Next, knowing A, T and E , we estimate a value for the exchange current lo, run a simulation, and note how similar (or not) are... 

It has been mentioned that = E when the reference system is the oxidation of molecular hydrogen to solvated (hydrated) protons. The standard electrode potential of the hydrogen electrode is chosen as 0 V. Thermodynamically it means that not only the standard free energy of formation of hydrogen (/r ) is zero - which is a rule in thermodynamics (see Table 2) - but also that of the solvated hydrogen ion /U.S+ = O . (The old standard values of were calculated using = atm = 101325 Pa. The new ones are related to 10 Pa (1 bar). It causes a difference in the potential of the SHE of -i- 0.169 mV, that... 

Passage of 1.0 mol of electrons (one faraday, 96,485 A s) will produce 1.0 mol of oxidation or reduction—in this case, 1.0 mol of Cl- converted to 0.5 mol of Cl2, and 1.0 mol of water reduced to 1.0 mol of OH- plus 0.5 mol of H2. Thermodynamically, the electrical potential required to do this is given by the difference in standard electrode potentials (Chapter 15 and Appendix D) for the anode and cathode processes, but there is also an additional voltage or overpotential that originates in kinetic barriers within these multistep gas-evolving electrode processes. The overpotential can be minimized by catalyzing the electrode reactions in the case of chlorine evolution, this can be done by coating the anode with ruthenium dioxide. 

If we choose a set of standard conditions (cf. Section 2.3) and one convenient half-cell to serve as a reference for all others, then a set of standard half-cell EMFs or standard electrode potentials E° (Appendix D)1-9 can be measured while drawing a negligible electrical current, that is, with the cell working reversibly so that the equations of reversible thermodynamics... 

It is a relatively simple process to set up a scale of redox potentials in a non-aqueous medium using the standard hydrogen electrode in that medium as the fundamental reference electrode. Thus in liquid ammonia, which is a well studied non-aqueous solvent and for which there exists a considerable amount of thermodynamic information,31 the scale of standard electrode potentials is referred to the standard hydrogen electrode in liquid ammonia (equation 25), which is assigned the value of zero volts, and in which the H+ exists as a solvated species, i.e. NH4+. 

The electrochemical redox potential of several possible decomposition reactions at pH = 0 (relative to the potential of the saturated calomel electrode), which have been estimated from thermodynamic parameters (6,17-21), are shown schematically in Figure A. The band levels are shown for open-circuit conditions. The standard electrode potentials were calculated from the free energies of formation, which are summarized below in Table III. 

Thermodynamic and Kinetic Parameter Values. Values of Standard Electrode Potential (at 25 °C) and Exchange Current Density (at 80 °C) are Referenced to 101.3 kPa Gaseous Reactant Partial Pressure. 

The free energies in (18) are illustrated in Fig. 10. It can be seen that GA is that part of AG ° available for driving the actual reaction. The importance of this relation is that it allows AGXX Y to be calculated from the properties of the X and Y systems. In thermodynamics, from a list of n standard electrode potentials for half cells, one can calculate j (m — 1) different equilibrium constants. Equation (18) allows one to do the same for the %n(n— 1) rate constants for the cross reactions, providing that the thermodynamics and the free energies of activation for the symmetrical reactions are known. Using the... 

Here, AH(A-B) is the partial molar net adsorption enthalpy associated with the transformation of 1 mol of the pure metal A in its standard state into the state of zero coverage on the surface of the electrode material B, ASVjbr is the difference in the vibrational entropies in the above states, n is the number of electrons involved in the electrode process, F the Faraday constant, and Am the surface of 1 mol of A as a mono layer on the electrode metal B [70]. For the calculation of the thermodynamic functions in (12), a number of models were used in [70] and calculations were performed for Ni-, Cu-, Pd-, Ag-, Pt-, and Au-electrodes and the micro components Hg, Tl, Pb, Bi, and Po, confirming the decisive influence of the choice of the electrode material on the deposition potential. For Pd and Pt, particularly large, positive values of E5o% were calculated, larger than the standard electrode potentials tabulated for these elements. This makes these electrode materials the prime choice for practical applications. An application of the same model to the superheavy elements still needs to be done, but one can anticipate that the preference for Pd and Pt will persist. The latter are metals in which, due to the formation of the metallic bond, almost or completely filled d orbitals are broken up, such that these metals tend in an extreme way towards the formation of intermetallic compounds with sp-metals. The perspective is to make use of the Pd or Pt in form of a tape on which the tracer activities are electrodeposited and the deposition zone is subsequently stepped between pairs of Si detectors for a-spectroscopy and SF measurements. 

The thermodynamic information is normally summarized in a Pourbaix diagram7. These diagrams are constructed from the relevant standard electrode potential values and equilibrium constants and show, for a given metal and as a function of pH, which is the most stable species at a particular potential and pH value. The ionic activity in solution affects the position of the boundaries between immunity, corrosion, and passivation zones. Normally ionic activity values of 10 6 are employed for boundary definition above this value corrosion is assumed to occur. Pourbaix diagrams for many metals are to be found in Ref. 7. 

If both electrode processes operate under standard conditions, this voltage is E°, the equilibrium standard electrode potential difference. Values of E and E° may be conveniently measured with electrometers of so large an internal resistance that the current flow is nearly zero. Figure 3.1.6 illustrates the measurement and the equilibrium state. The value of E° is a most significant quantity characterizing the thermodynamics of an electrochemical cell. Various important features of E and E° will be addressed in the following chapters. 

The common oxidation states of iron are + 2 and + 3. The relative stability of the two oxidation states in acid aqueous solution is defined by the standard electrode potential of + 0.77 V for the Fe3+/Fe2+ couple.1 This potential is such that the hydrated Fe11 cation is thermodynamically unstable with respect to atmospheric oxidation (equation 1). The oxidation is even more favourable in basic solution (equation 2). It is apparent, therefore, that the chemistry of iron, including its... 

In order to satisfy the necessary criteria, a reversible redox couple is utilized in the reference electrode half-cell reaction. The potential of a reversible reference electrode is thermodynamically defined by its standard electrode potential, EP (see for example Compton and Sanders, 1996, for further discussion). Currently, the most commonly used reference electrode in voltammetric studies is the silver/silver chloride electrode (3), which has overtaken the calomel electrode (see for example Bott, 1995) for which the reaction is (4). 

Standard electrode potentials of the Ag-AgI electrode were determined in the temperature range 5 °-35°C in 20-80 wt % ethylene glycol + diethylene glycol mixtures by emf measurements on the cell Pt-H2(g, 1 atm)/HOAC (mt), NaOAC (m2) KX (m3)/AgX-Ag in the solvent. The standard molal potentials Em°, in the various solvent mixtures have been expressed as a function of temperature. The various thermodynamic parameters for the transfer of hydrogen iodide from ethylene glycol to these media at 25° C are reported, and their variation with solvent composition is discussed. The transfer free energies of the proton and the iodide at 25°C, on the basis of the ferrocene reference method with ethylene glycol as the reference solvent, are also reported in the mixtures. 

The single thermodynamically reversible electrode potential as measured against the standard hydrogen electrode is equal to the emf of the cell,... 

Backward electron (hole) transfer can be avoided thermodynamically only when the CB bottom and VB top are more positive and negative than standard electrode potentials of a reductant and an oxidant, respectively. 

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