Galvanic cells, activity

Sud] Galvanic cell Activity of Al in an Fe-1 mass% Al-1 mass% Si alloy... 

Galvanic cells in which stored chemicals can be reacted on demand to produce an electric current are termed primaiy cells. The discharging reac tion is irreversible and the contents, once exhausted, must be replaced or the cell discarded. Examples are the dry cells that activate small appliances. In some galvanic cells (called secondaiy cells), however, the reaction is reversible that is, application of an elec trical potential across the electrodes in the opposite direc tion will restore the reactants to their high-enthalpy state. Examples are rechargeable batteries for household appliances, automobiles, and many industrial applications. Electrolytic cells are the reactors upon which the electrochemical process, elec troplating, and electrowinning industries are based. 

The galvanic cell studied (shown in Fig. 5.24) utilizes a highly porous solid electrolyte that is a eutectic composition of LiCl and KCl. This eutectic has a melt temperature of 352 °C and has been carefully studied in prior electrochemical studies. Such solid electrolytes are typical of thermal battery technology in which galvanic cells are inert until the electrolyte is melted. In the present case, shock compression activates the electrolyte by enhanced solid state reactivity and melting. The temperature resulting from the shock compression is controlled by experiments at various electrolyte densities, which were varied from 65% to 12.5% of solid density. The lower densities were achieved by use of microballoons which add little mass to the system but greatly decrease the density. 

At this stage it should be pointed out that the original definition of pH = —log cH (due to Sorensen, 1909 and which may be written as pcH) is not exact, and cannot be determined exactly by electrometric methods. It is realised that the activity rather than the concentration of an ion determines the e.m.f. of a galvanic cell of the type commonly used to measure pH, and hence pH may be defined as... 

Trustworthy thermodynamic data for metal solutions have been very scarce until recently,25 and even now they are accumulating only slowly because of the severe experimental difficulties associated with their measurement. Thermodynamic activities of the component of a metallic solution may be measured by high-temperature galvanic cells,44 by the measurement of the vapor pressure of the individual components, or by equilibration of the metal system with a mixture of gases able to interact with one of the components in the metal.26 Usually, the activity of only one of the components in a binary metallic solution can be directly measured the activity of the other is calculated via the Gibbs-Duhem equation if the activity of the first has been measured over a sufficiently extensive range of composition. 

Wagner first proposed the use of such galvanic cells in heterogeneous catalysis, to measure in situ the thermodynamic activity of oxygen O(a) adsorbed on metal electrodes during catalytic reactions.21 This led to the technique of solid electrolyte potentiometry (SEP).22 26... 

C (298.15 K) and 1 bar. standard cell potential See standard emf. standard emf ( °) The emf when the concentration of each solute taking part in the cell reaction is 1 mol-L 1 (strictly, unit activity) and all the gases are at 1 bar. The standard emf of a galvanic cell is the difference between its two standard potentials E° = E°(cathode) — °(anode). 

Direct measurements of solute activity are based on studies of the equilibria in which a given substance is involved. The parameters of these equilibria (the distribution coefficients, equilibrium constants, and EMF of galvanic cells) are determined at different concentrations. Then these data are extrapolated to very low concentrations, where the activity coincides with concentration and the activity coefficient becomes unity. 

Electrochemical Cell Without Transference Assume that we want to determine the activities of HCl solutions of various concentrations. We assemble a galvanic cell with hydrogen and calomel electrode ... 

Two types of methods are used to measure activity coefficients. Potentiometric methods that measure the mean activity coefficient of the dissolved electrolyte directly will be described in Section 3.3.3. However, in galvanic cells with liquid junctions the electrodes respond to individual ion activities (Section 3.2). This is particularly true for pH measurement (Sections 3.3.2 and 6.3). In these cases, extrathermodynamical procedures defining individual ion activities must be employed. 

However, in contrast to the EMF of a galvanic cell, the resultant expressions contain the activities of the individual ions, which must be calculated by using the extrathermodynamic approach described in Section 1.3. 

Concentration cells are a useful example demonstrating the difference between galvanic cells with and without transfer. These cells consist of chemically identical electrodes, each in a solution with a different activity of potential-determining ions, and are discussed on page 171. 

Potentiometry is used in the determination of various physicochemical quantities and for quantitative analysis based on measurements of the EMF of galvanic cells. By means of the potentiometric method it is possible to determine activity coefficients, pH values, dissociation constants and solubility products, the standard affinities of chemical reactions, in simple cases transport numbers, etc. In analytical chemistry, potentiometry is used for titrations or for direct determination of ion activities. 

It has been emphasized repeatedly that the individual activity coefficients cannot be measured experimentally. However, these values are required for a number of purposes, e.g. for calibration of ion-selective electrodes. Thus, a conventional scale of ionic activities must be defined on the basis of suitably selected standards. In addition, this definition must be consistent with the definition of the conventional activity scale for the oxonium ion, i.e. the definition of the practical pH scale. Similarly, the individual scales for the various ions must be mutually consistent, i.e. they must satisfy the relationship between the experimentally measurable mean activity of the electrolyte and the defined activities of the cation and anion in view of Eq. (1.1.11). Thus, by using galvanic cells without transport, e.g. a sodium-ion-selective glass electrode and a Cl -selective electrode in a NaCl solution, a series of (NaCl) is obtained from which the individual ion activity aNa+ is determined on the basis of the Bates-Guggenheim convention for acr (page 37). Table 6.1 lists three such standard solutions, where pNa = -logflNa+, etc. 

Measurement of the potential of a galvanic cell, usually at zero current cell potential governed by the potential of an indicator electrode which responds to changes in the activity of the species of interest. 

In writing the Etudes de dynamique chimique (1884), van t Hoff drew on Helmholtz s 1882 paper but especially on the work of August Horstmann, a student of Bunsen, Clausius, and H. Landolt.59 As has often been discussed, van t Hoffs was an ambitious and original synthesis of disconnected ideas and theories about opposing forces, equilibrium, active masses, work and affinity, electromotive force, and osmotic pressure. He demonstrated that the heat of reaction is not a direct measure of affinity but that the so-called work of affinity may be calculated from vapor pressures (the affinity of a salt for its water of crystallization), osmotic pressure (affinity of a solute for a solution), or electrical work in a reversible galvanic cell (which he showed to be proportional to the electromotive force). 

Values for the parameters are determined by a least squares fit of experimental data using eq (5) for experiments such as galvanic cells measurements that measure solute activity and thus y/Yref values, and eq (6) for experiments such as vapor pressure measurements that measure solvent activity and thus (f) values. All the original data are used in a single fitting program to determine the best values for the parameters. A detailed description of the evaluation procedure has been illustrated for the system calcium chloride-water (Staples and Nuttall, 1977), and calculations deriving activity data from a variety of experimental technique measurements have also been described. 

Fig. 8.1 Variation of the activity (logarithmic scale) or galvanic cell voltage as a function of the composition (schematic). The plateaux indicate multi-phase regions in which the activity is fixed according to Gibbs phase rule.

Another kinetic aspect is observed if a component other than the electroactive species is predominantly mobile. The electroactive species are in this case made available to the electrolyte by the motion of the other components in the opposite direction. In a binary compound this does not make a difference to the electrode performance. But in the case of a compound with more than two components the composition is changed to values which are not expected from a thermodynamic point of view for the variation of the concentration of the electroactive species. Other phases are formed which may provide a lower or higher activity of the electroactive species than that expected thermodynamically. This has an influence both on the current and the cell voltage. Upon discharging and charging a galvanic cell, the composition of the electrode at the interface with the electrolyte may follow very different compositional pathways (Weppner, 1985). 

Electrochemical Reactions. Consider a simple galvanic cell, composed of two metal electrodes, zinc and copper, immersed in two different aqueous solutions of unit activity—in this case, 1.0 M ZnS04 and 1.0 M CUSO4, respectively, connected by an electrical circuit, and separated by a semipermeable membrane (see Figure 3.8). The membrane allows passage of ions, but not bulk flow of the aqueous solutions from one side of the cell to the other. Electrons are liberated at the anode by the oxidation (increase in the oxidation number) of the zinc electrode ... 

The voltage we measure is characteristic of the metals we use. As an additional example, unit activity solutions of CuCE and AgCl with copper and silver electrodes, respectively, give a potential difference of about 0.45 V. We could continue with this type of measurement for aU the different anode-cathode combinations, but the number of galvanic cells needed would be very large. Fortunately, the half-reactions for most metals have been calculated relative to a standard reference electrode, which is arbitrarily selected as the reduction of hydrogen ... 

The electrode in the half-cell in which oxidation is occurring is said to be the anode (here, the zinc metal), whereas the other is the cathode (here, the platinum). In principle, we could connect any pair of feasible half-cells to form a galvanic cell the identity of the half-cells will determine which electrode will act as the anode, and which the cathode. The electromotive force (EMF, in volts) of the cell will depend on the identity of the half cells, the temperature and pressure, the activities of the reacting species, and the current drawn. An EMF will also be generated by a cell in which the two half cells are the chemically identical except for a difference in reactant activities (concentrations) this is called a concentration cell. 

COj/Oj in the Off-Gas CO2 evolution from a bioreactor is closely related to the physiological state and the activity of microorganisms in a bioreactor because CO, evolves as a result of catabolism and respiration by microorganisms or cells. Therefore, it is helpful to measure the content of CO2/O2 in the exhaust gas in order to understand the physiological climate of a bioreactor. The CO2 and O2 content in the exhaust gas are taken from the streamline and analyzed by infrared spectrophotometer (CO2) and galvanic cell probe (O,). The wet off-gas must be desiccated before being introduced into the gas analyzer. 

The standard potential for a redox reaction is defined for a galvanic cell in which all activities are unity. The formal potential is the reduction potential that applies under a specified set of conditions (including pH, ionic strength, and concentration of complexing agents). Biochemists call the formal potential at pH 7 E° (read "E zero prime"). Table 14-2 lists E° values for various biological redox couples. 

If we now make a whole series of galvanic cells with solutions at unit activity and use the standard hydrogen electrode as one-half of every cell, then the measured cell voltage (Fceii) for each cell will be given, according to Equation 17-1, by either... 

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