Reversible electrochemical cells

As seen in previous sections, the standard entropy AS of a chemical reaction can be detemiined from the equilibrium constant K and its temperature derivative, or equivalently from the temperature derivative of the standard emf of a reversible electrochemical cell. As in the previous case, calorimetric measurements on the separate reactants and products, plus the usual extrapolation, will... 

For these reasons a somewhat different approach will be adopted here, and an attempt will be made to show how a corrosion reaction may be represented by a well-defined reversible electrochemical cell, although again there are a number of difficulties. Consider the corrosion of metallic zinc in a reducing acid... 

The potential difference of an ideal reversible electrochemical cell in open circuit is 0.965 V at 25 °C and 1 atm. The open-circuit potential was measured... 

We first take up the case where we have arrested the reaction at a particular stage for which the participating species involve a concomitant set of mole numbers n, such that the Gibbs free energy in the arrested stage at a specified T and P is given by G = Yli One method of achieving this state is to carry out the reaction in a reversible electrochemical cell, in the manner described in Chapter 4. A special case of particular interest, which requires no outside intervention, is the equilibrium state, with G — where the mole numbers n, and... 

If this is a reversible electrochemical cell reaction, we have as previously mentioned ... 

For a reversible electrochemical cell, the overpotential for concentration polarization is defined by Nemst equation. Using eq. (2.32) with the constant K = CxICo and the cathodic overpotenfial as 1) = E -Eo yields the cathodic overpotential in terms of concentration ratio... 

Determination of Thermodynamic Quantities using Reversible Electrochemical Cells... 

In sum, the relationship between the free energy and the cell potential for reversible electrochemical cells is one of the most important concepts in this chapter and is given by... 

Much of conventional thermodynamics developed from electrochemical work. The detailed investigation of the behaviour of reversible electrochemical cells and the reactions occurring within them contributed to the appreciation of the concept of standard free energy and led to the accurate determination of thermodynamic constants for cell reactions. Early work on the temperature dependence of reversible cell e.m.f. s contributed considerably to the formulation of the Third Law of Thermodynamics. 

It is, in fact, with the use and understanding of reversible electrochemical cells that many people see for the first time the significance and applicability of thermodynamic principles. Here thermodynamics may be seen to apply to tangible practical situations. 

The concept of the reversed fuel cell, as shown schematically, consists of two parts. One is the already discussed direct oxidation fuel cell. The other consists of an electrochemical cell consisting of a membrane electrode assembly where the anode comprises Pt/C (or related) catalysts and the cathode, various metal catalysts on carbon. The membrane used is the new proton-conducting PEM-type membrane we developed, which minimizes crossover. 

A regenerative fuel cell system can also be a single electrochemical cell in which both the oxidation of fuels (i.e., production of electric power) and reduction of CO2 (to obtain fuels) can be carried out by simply reversing the mode of operation. 

Reference Electrode an equilibrium (reversible) electrochemical half-cell of reproducible potential against which an unknown electrode potential can be measured. Examples of those commonly used in corrosion are the Pt, H /H (the hydrogen electrode), Hg/Hg Clj/Cl" (the calomel electrode), Cu/CuS04/Cu, Ag/AgCl/Cl", all with fixed activities of the dissolved ions. 

The value of this list is obvious. Any half-reaction can be combined with the reverse of another half-reaction (in the proportion for which electrons gained is equal to electrons lost) to give a possible chemical reaction. Our list permits us to predict whether equilibrium favors reactants or products. We would like to expand our list and to make it more quantitative. Electrochemical cells help us do this. 

For the electrochemical cell reaction, the reaction free energy AG is the utilizable electrical energy. The reaction enthalpy AH is the theoretical available energy, which is increased or reduced by an amount TAS. The product of the temperature and the entropy describes the amount of heat consumed or released reversibly during the reaction. With tabulated values for the enthalpy and the entropy it is possible to obtain AG. ... 

The reversible reaction heat of the cell is defined as the reaction entropy multiplied by the temperature [Eq. (15)]. For an electrochemical cell it is also called the Peltier effect and can be described as the difference between the reaction enthalpy AH and the reaction free energy AG. If the difference between the reaction free energy AG and the reaction enthalpy AH is below zero, the cell becomes warmer. On the other hand, for a difference larger than zero, it cools down. The reversible heat W of the electrochemical cell is therefore ... 

Other measurements of AfG involve measuring AG for equilibrium processes, such as the measurement of equilibrium constants, reversible voltages of electrochemical cells, and phase equilibrium measurements. These methods especially come into play in the measurement of Afand AfG for ions in solution, which are processes that we will now consider. 

It is often difficult to discharge an electrochemical cell in a reversible manner. We will return to this problem later. 

This is a quantitative problem, so we follow the standard strategy. The problem asks about an actual potential under nonstandard conditions. Before we determine the potential, we must visualize the electrochemical cell and determine the balanced chemical reaction. The half-reactions are given in the problem. To obtain the balanced equation, reverse the direction of the reduction half-reaction with the... 

An alternative ambient temperature design based on sodium ion reaction refers to the domain of the so-calledbatteries. The polysulfide bromide cell (PSB) provides a reversible electrochemical reaction between two salt solution electrolytes (sodium bromide and sodium polysulfide), according to the scheme... 

Analytical methods based upon oxidation/reduction reactions include oxidation/reduction titrimetry, potentiometry, coulometry, electrogravimetry and voltammetry. Faradaic oxidation/reduction equilibria are conveniently studied by measuring the potentials of electrochemical cells in which the two half-reactions making up the equilibrium are participants. Electrochemical cells, which are galvanic or electrolytic, reversible or irreversible, consist of two conductors called electrodes, each of which is immersed in an electrolyte solution. In most of the cells, the two electrodes are different and must be separated (by a salt bridge) to avoid direct reaction between the reactants. 

For a redox reaction in an electrochemical cell the decrease in free enthalpy (- AG) is in accordance with the energy delivered by the transfer of electrons through an external circuit if this takes place in a reversible way, i.e., at a rate slow enough to allow complete attainment of equilibrium, the conversion of 1 gram mole will deliver an electrical energy of - AG = z FE. In total cell reaction mred, + n ox2 m ox, + nred2, where m81 = nS2 electrons are transfered (<5, and S2 represent the respective valence differences of the two redox systems), we have... 

The electrochemical cell can again be of the regenerative or electrosynthetic type, as with the photogalvanic cells described above. In the regenerative photovoltaic cell, the electron donor (D) and acceptor (A) (see Fig. 5.62) are two redox forms of one reversible redox couple, e.g. Fe(CN)6-/4 , I2/I , Br2/Br , S2 /S2, etc. the cell reaction is cyclic (AG = 0, cf. Eq. (5.10.24) since =A and D = A ). On the other hand, in the electrosynthetic cell, the half-cell reactions are irreversible and the products (D+ and A ) accumulate in the electrolyte. The most carefully studied reaction of this type is photoelectrolysis of water (D+ = 02 and A = H2)- Other photoelectrosynthetic studies include the preparation of S2O8-, the reduction of C02 to formic acid, N2 to NH3, etc. 

Both carbon materials were tested for their initial electrochemical performance in the 2-electrode electrochemical cells with Li metal as a counter electrode. Our findings have shown that with both types of carbon materials, achieving near theoretical reversible capacity upon Li+ deintercalation was possible. Thus, in a typical half cell environment (a CR2016 type coin cell with graphite and Li metal electrodes, a 1M LiPF6,... 

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