Electromotive force determination

Additional information concerning the mechanisms of solid—solid interactions has been obtained by many diverse experimental approaches, as the following examples testify adsorptive and catalytic properties of the reactant mixture [1,111], reflectance spectroscopy [420], NMR [421], EPR [347], electromotive force determinations [421], tracer experiments [422], and doping effects [423], This list cannot be comprehensive. Electron probe microanalysis has also been used as an analytical (rather than a kinetic) tool [422,424] for the determination of distributions of elements within the reactant mixture. Infrared analyses have been used [425] for the investigation of the solid state reactions between NH3 and S02 at low temperatures in the presence and in the absence of water. 

Over the last 20-30 years not too much effort has been made concerning the determination of standard potentials. It is mostly due to the funding policy all over the world, which directs the sources to new and fashionable research and practically neglects support for the quest for accurate fundamental data. A notable recent exception is the work described in Ref. 1, in which the standard potential of the cell Zn(Hg)jc (two phase) I ZnS O4 (aq) PbS O4 (s) Pb(Hg)jc (two phase) has been determined. Besides the measurements of electromotive force, determinations of the solubility, solubiKty products, osmotic coefficients, water activities, and mean activity coefficients have been carried out and compared with the previous data. The detailed analysis reveals that the uncertainties in some fundamental data such as the mean activity coefficient of ZnS04, the solubility product of Hg2S04, or even the dissociation constant of HS04 can cause uncertainties in the f " " values as high as 3-4 mV. The author recommends this comprehensive treatise to anybody who wants to go deeply into the correct determination of f " " values. 

Fig. 8. Diagram of paH response of an ethylene glycol glass electrode at +21 and - 19°C. Abscissa electromotive force determined between electrodes when immersed in ethylene glycol-water (50 50) buffer systems. Ordinate paH of the same media determined by indicator spectrophotometry. The points are the experimental results the straight lines represent the ideal behavior, (a) Chloroacetate, (b) acetate, (c) cacody-late, (d) Tris. From Larroque et al. (1976). Reprinted with permission of Analytical Biochemistry. Copyright by Academic Press.

The method has been applied by Cohen (1894) to the determination of transition temperatures. Thus the electromotive force of the cell ... 

Shedlovsky et al. studied mixtures of sodium decyl, dodecyl, and tetradecyl sulfates by electromotive force measurements and determined the extent of the dissociation of the sodium counterions by the micelles. From the data obtained strong interaction below the CMC was found for all of the mixtures except those containing more than 25 mol % of sodium decyl sulfate [122]. Commercial alcohol sulfates are mixtures of homologs with different hydrocarbon chains. It has been demonstrated [123] that the CMC of such products is lower than that expected by calculation from the linear relationship between log CMC and the number of carbon atoms of the alcohol as stated in Eq. (11). These results are shown in Fig. 9. 

In this cell, the following independent phases must be considered platinum, silver, gaseous hydrogen, solid silver chloride electrolyte, and an aqueous solution of hydrogen chloride. In order to be able to determine the EMF of the cell, the leads must be made of the same material and thus, to simplify matters, a platinum lead must be connected to the silver electrode. It will be seen in the conclusion to this section that the electromotive force of a cell does not depend on the material from which the leads are made, so that the whole derivation could be carried out with different, e.g. copper, leads. In addition to Cl- and H30+ ions (further written as H+), the solution also contains Ag+ ions in a small concentration corresponding to a saturated solution of silver chloride in hydrochloric acid. Thus, the following scheme of the phases can be written (the parentheses enclose the species present in the given phase) ... 

Wagner pioneered the use of solid electrolytes for thermochemical studies of solids [62], Electrochemical methods for the determination of the Gibbs energy of solids utilize the measurement of the electromotive force set up across an electrolyte in a chemical potential gradient. The electrochemical potential of an electrochemical cell is given by ... 

Potentiometry deals with the electromotive force (EMF) generated in a galvanic cell where a spontaneous chemical reaction is taking place. In practice, potentiometry employs the EMF response of a galvanostatic cell that is based on the measurement of an electrochemical cell potential under zero-current conditions to determine the concentration of analytes in measuring samples. Because an electrode potential generated on the metal electrode surface,... 

While this potential cannot he determined for a single electrode, a potential can be derived if the potential of the other electrode in a cell is defined, i.e. the potential of the standard hydrogen electrode (SHE) is arbitrarily taken as 0.(XXX)V. In this way. a potential scale can then be devised for single electrode potentials - see Section 3.2. t The abbreviation emf , in upright script, is often used in other lextNmks as a direct , i.e. non-variable, acronym for the electromotive force. Note, however, that in this present text it is used to represent a variable (cell potential) and is therefore. shown in italic script. 

The portion AQ = AH - AG = TAS of AH is transformed into heat. Ideal theoretical efficiencies % determined by the types and amounts of reactants and by the operating temperature. Fuel cells have an efficiency advantage over combustion engines because the latter are subdued to the Carnot limitation. High thermodynamic efficiencies are possible for typical fuel cell reactions (e.g., e,h = 0.83 (at 25°C) for H2 + I/2O2 -> H20(i)). The electrical potential difference between anode and cathode, = -AG/W(f, which is also called the electromotive force or open-circuit voltage, drives electrons through the external... 

Nernst equation phys chem The relationship showing that the electromotive force developed by a dry cell is determined by the activities of the reacting species, the temperature of the reaction, and the standard free-energy change of the overall reaction. nernst i,kwa-zh3n )... 

From this example it may be concluded that by measurement of the electromotive force in a cell, the activities for reactions can be determined. 

A unitless correction factor that relates the relative activity of a substance to the quantity of the substance in a mixture. Activity coefficients are frequently determined by emf (electromotive force) or freezing-point depression measurements. At infinite dilution, the activity coefficient equals 1.00. Activity coefficients for electrolytes can vary significantly depending upon the concentration of the electrolyte. Activity coefficients can exceed values of 1.00. For example, a 4.0 molal HCl solution has a coefficient of 1.76 and a 4.0 molal Li Cl has a value of... 

We may likewise obtain an estimate of the thickness of the adsorbed film by determining the maximum current density at which ions may be deposited at an electrode which is kept in rapid rotation. The ions being deposited must be regarded as migrating across a film of thickness S from a concentration equal to that in the bulk of the electrolyte to a region of zero concentration under the applied electromotive force. Thus Ackerberg Anorg. 

Determination of pH values may be done either by electromotive force measurements, by colormetric methods (indicator papers, or indicator solutions), or by the glass electrode method... 

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. 

Activity coefficients of ions are determined using electromotive force, freezing point, and solubility measurements or are calculated using the theoretical equation of Debye and Htickel. 

Electrolytes, depending upon their strength, dissociate to a greater or less extenl in polar solvents. The extent to which a weak electrolyte dissociates may be determined by electrical conductance, electromotive force, and freezing point depression methods. The electrical conductance method is the most used because of its accuracy and simplicity. Arrhenius proposed that the degree of dissociation, a. of a weak electrolyte at any concentration in solution could be found from the rutio of the equivalent conductance. A. of the electrolyte at the concentration in question to (he equivalent conductance at infinite dilution A0 of the electrolyte. Thus... 

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