Cell potential measuring

In the case of small ions, Hittorf transference cell measurements may be combined with conductivity data to give the mobility of the ion, that is, the velocity per unit potential gradient in solution, or its equivalent conductance. Alternatively, these may be measured more directly by the moving boundary method. 

As a result of a variable liquid-junction potential, the measured pH may be expected to differ seriously from the determined from cells without a liquid junction in solutions of high acidity or high alkalinity. Merely to affirm the proper functioning of the glass electrode at the extreme ends of the pH scale, two secondary standards are included in Table 8.14. In addition, values for a 0.1 m solution of HCl are given to extend the pH scale up to 275°C [see R. S. Greeley, Anal. Chem. 32 1717 (I960)] ... 

Calculate the molar concentration for the underlined component in the following cell if the cell potential is measured at +0.294 V... 

This method involves very simple and inexpensive equipment that could be set up m any laboratory [9, 10] The equipment consists of a 250-mL beaker (used as an external half-cell), two platinum foil electrodes, a glass tube with asbestos fiber sealed m the bottom (used as an internal half-cell), a microburet, a stirrer, and a portable potentiometer The asbestos fiber may be substituted with a membrane This method has been used to determine the fluoride ion concentration in many binary and complex fluondes and has been applied to unbuffered solutions from Willard-Winter distillation, to lon-exchange eluant, and to pyrohydrolysis distil lates obtained from oxygen-flask or tube combustions The solution concentrations range from 0 1 to 5 X 10 M This method is based on complexing by fluonde ions of one of the oxidation states of the redox couple, and the potential difference measured is that between the two half-cells Initially, each cell contains the same ratio of cerium(IV) and cerium(tll) ions... 

If electron flow between the electrodes is toward the sample half-cell, reduction occurs spontaneously in the sample half-cell, and the reduction potential is said to be positive. If electron flow between the electrodes is away from the sample half-cell and toward the reference cell, the reduction potential is said to be negative because electron loss (oxidation) is occurring in the sample halfcell. Strictly speaking, the standard reduction potential, is the electromotive force generated at 25°C and pH 7.0 by a sample half-cell (containing 1 M concentrations of the oxidized and reduced species) with respect to a reference half-cell. (Note that the reduction potential of the hydrogen half-cell is pH-dependent. The standard reduction potential, 0.0 V, assumes 1 MH. The hydrogen half-cell measured at pH 7.0 has an of —0.421 V.)... 

Accurate control of potential, stability, frequency response and uniform current distribution required the following low resistance of the cell and reference electrode small stray capacitances small working electrode area small solution resistance between specimen and point at which potential is measured and a symmetrical electrode arrangement. Their design appears to have eliminated the need for the usual Luggin capillary probe. 

Now if we combine a Zn-Zn+2 half-cell in its standard state with a H2-2H+ half-cell in its standard state, the voltage (potential) we measure (0.76 volt) is the value assigned to the halfreaction ... 

As the cell is discharged, Zn2+ ions are produced at the anode while Cu2+ ions are used up at the cathode. To maintain electrical neutrality, SO4- ions must migrate through the porous membrane,dd which serves to keep the two solutions from mixing. The result of this migration is a potential difference across the membrane. This junction potential works in opposition to the cell voltage E and affects the value obtained. Junction potentials are usually small, and in some cases, corrections can be made to E if the transference numbers of the ions are known as a function of concentration.ee It is difficult to accurately make these corrections, and, if possible, cells with transference should be avoided when using cell measurements to obtain thermodynamic data. 

FIGURE 12.5 The cell potential is measured with an electronic voltmeter, a device designed to draw negligible current so that the composition of the cell does not change during the measurement. The display shows a positive value when the + terminal of the meter is connected to the cathode of the galvanic cell. The salt bridge completes the electric circuit within the cell. 

A problem with compiling a list of standard potentials is that we know only the overall emf of the cell, not the contribution of a single electrode. A voltmeter placed between the two electrodes of a galvanic cell measures the difference of their potentials, not the individual values. To provide numerical values for individual standard potentials, we arbitrarily set the standard potential of one particular electrode, the hydrogen electrode, equal to zero at all temperatures ... 

Volta potentials are measured by means of voltaic cells, i.e., systems composed of conducting, condensed phases in series, with a gas, liquid dielectric (e.g., decane) or a vacuum (in the case of solid conductors such as metals) gap situated between two condensed phases. The gap, g, may contain a gas such as pure air or nitrogen, saturated with vapors of the liquids present. Owing to the presence of a dielectric, special methods are necessary for the investigation of voltaic cells (see Section IV). 

Knowledge of the Volta potential of a metal/solution interface is relevant to the interpretation of the absolute electrode potential. According to the modem view, the relative electrode potential (i.e., the emf of a galvanic cell) measures the value of the energy of the electrons at the Fermi level of the given metal electrode relative to the metal of the reference electrode. On the other hand, considered separately, the absolute value of the electrode potential measures the work done in transferring an electron from a metal surrounded by a macroscopic layer of solution to a point in a vacuum outside the solotion. ... 

Potentiometric methods are based on the measurement of the potential of an electrochemical cell consisting of two electrodes immersed in a solution. Since the cell potential is measured under the condition of zero cmrent, usually with a pH/mV meter, potentiometry is an equilibrium method. One electrode, the indicator electrode, is chosen to respond to a particular species in solution whose activity or concentration is to be measured. The other electrode is a reference electrode whose half-cell potential is invariant. 

It is relevant to follow up the description given above on reversible electrodes with attention focused on the potential difference of a cell. The potential difference measured under reversible conditions, is called the electromotive force, or emf, of the cell, E. It is clear that if a cell is reversible then it is implied that the half-cells of which it is composed are also reversible. 

The membrane potentials are measured by constructing a cell with a semipermeable membrane separating solutions 1 and 2 ... 

The electrochemical detection of pH can be carried out by voltammetry (amper-ometry) or potentiometry. Voltammetry is the measurement of the current potential relationship in an electrochemical cell. In voltammetry, the potential is applied to the electrochemical cell to force electrochemical reactions at the electrode-electrolyte interface. In potentiometry, the potential is measured between a pH electrode and a reference electrode of an electrochemical cell in response to the activity of an electrolyte in a solution under the condition of zero current. Since no current passes through the cell while the potential is measured, potentiometry is an equilibrium method. 

Electrochemical equipment and cells used for these investigations have also been described previously. (8.9 ) Polycrystalline Ag (Johnson Matthey, 99.9%) was mechanically polished with alumina (Buehler) to a mirror finish and sonicated in triply distilled H20 before each run. All potentials were measured and are reported versus a saturated calomel reference electrode (SCE). 

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