Emf

After performing all the calculations taking into account the notations given in figure 2b, the induced emf becomes... 

Were the FlCl in its standard state, AC would equal where is the standard emf for the reaction. In general, for any reversible chemical cell without transference, i.e. one with a single electrolyte solution, not one with any kind of junction between two solutions. 

Thus, if the activities of the various species can be detennined or if one can extrapolate to infinite dilution, the measurement of the emf yields the standard free energy of the reaction. 

Thiis, when tables report the starrdard emf or starrdard free errergy of the chloride ion. 

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... 

Cells need not necessarily contain a reference electrode to obtain meaningfiil results as an example, if the two electrodes in figure A2.4.12 are made from the same metal, M, but these are now in contact with two solutions of the same metal ions, M but with differing ionic activities, which are separated from each other by a glass frit that pennits contact, but impedes diffusion, then the EMF of such a cell, temied a concentration cell, is given by... 

Equation A2.4.126 shows that the EMF increases by 0.059/z V for each decade change in the activity ratio in the two solutions. 

In fact, some care is needed with regard to this type of concentration cell, since the assumption implicit in the derivation of A2.4.126 that the potential in the solution is constant between the two electrodes, caimot be entirely correct. At the phase boundary between the two solutions, which is here a semi-pemieable membrane pemiitting the passage of water molecules but not ions between the two solutions, there will be a potential jump. This so-called liquid-junction potential will increase or decrease the measured EMF of the cell depending on its sign. Potential jumps at liquid-liquid junctions are in general rather small compared to nomial cell voltages, and can be minimized fiirther by suitable experimental modifications to the cell. 

If two redox electrodes both use an inert electrode material such as platinum, tlie cell EMF can be written down iimnediately. Thus, for the hydrogen/chlorine fiiel cell, which we represent by the cell Fl2(g) Pt FICl(m) Pt Cl2(g) and for which it is clear that the cathodic reaction is the reduction of CI2 as considered in section... 

Wlien an electrical coimection is made between two metal surfaces, a contact potential difference arises from the transfer of electrons from the metal of lower work function to the second metal until their Femii levels line up. The difference in contact potential between the two metals is just equal to the difference in their respective work fiinctions. In the absence of an applied emf, there is electric field between two parallel metal plates arranged as a capacitor. If a potential is applied, the field can be eliminated and at this point tire potential equals the contact potential difference of tlie two metal plates. If one plate of known work fiinction is used as a reference electrode, the work function of the second plate can be detennined by measuring tliis applied potential between the plates [ ]. One can detemiine the zero-electric-field condition between the two parallel plates by measuring directly the tendency for charge to flow through the external circuit. This is called the static capacitor method [59]. 

Emf values are given vs the reference-grade platinum of NIST (NBS Pt27) with the cold junction at the ice point. 

Two methods are used to measure pH electrometric and chemical indicator (1 7). The most common is electrometric and uses the commercial pH meter with a glass electrode. This procedure is based on the measurement of the difference between the pH of an unknown or test solution and that of a standard solution. The instmment measures the emf developed between the glass electrode and a reference electrode of constant potential. The difference in emf when the electrodes are removed from the standard solution and placed in the test solution is converted to a difference in pH. Electrodes based on metal—metal oxides, eg, antimony—antimony oxide (see Antimony AND ANTIMONY ALLOYS Antimony COMPOUNDS), have also found use as pH sensors (8), especially for industrial appHcations where superior mechanical stabiUty is needed (see Sensors). However, because of the presence of the metallic element, these electrodes suffer from interferences by oxidation—reduction systems in the test solution. 

Because of the very large resistance of the glass membrane in a conventional pH electrode, an input amplifier of high impedance (usually 10 —10 Q) is required to avoid errors in the pH (or mV) readings. Most pH meters have field-effect transistor amplifiers that typically exhibit bias currents of only a pico-ampere (10 ampere), which, for an electrode resistance of 100 MQ, results in an emf error of only 0.1 mV (0.002 pH unit). 

The reaction is especially useful because of the high emf (ca 2.2 V) of the Pb/Pb02 couple in dilute sulfuric acid (see Batteries, secondary). 

Ideally a standard cell is constmcted simply and is characterized by a high constancy of emf, a low temperature coefficient of emf, and an emf close to one volt. The Weston cell, which uses a standard cadmium sulfate electrolyte and electrodes of cadmium amalgam and a paste of mercury and mercurous sulfate, essentially meets these conditions. The voltage of the cell is 1.0183 V at 20°C. The a-c Josephson effect, which relates the frequency of a superconducting oscillator to the potential difference between two superconducting components, is used by NIST to maintain the unit of emf. The definition of the volt, however, remains as the Q/A derivation described. 

A particular concentration measure of acidity of aqueous solutions is pH which usually is regarded as the common logarithm of the reciprocal of the hydrogen-ion concentration (see Hydrogen-ION activity). More precisely, the potential difference of the hydrogen electrode in normal acid and in normal alkah solution (—0.828 V at 25°C) is divided into 14 equal parts or pH units each pH unit is 0.0591 V. Operationally, pH is defined by pH = pH(soln) + E/K, where E is the emf of the cell ... 

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