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2.4.5 Conductometry Determination of the conductivity of electrolyte solutions. The resistance of second class conductors is measured by the bridge method, similar to measurement of the resistance of first class conductors. Usually, alternating current is used, to avoid polarization of the electrodes (see 5). This involves certain technical difficulties, connected with the necessity of compensating the capacity and inductive components of the resistors and also with the fact that current can pass through the capacity coupling between the circuit and ground; similarly, strong magnetic fields produce induction effects. Direct current can only be used if a suitable unpolarizable electrode can be found for the given system (see page 209). Therefore, most often an a.c. supply of audio-frequency and an amplitude of a few millivolts is used. The bridge method is based on various modifications of the well-known Wheatstone bridge. Instruments for exact measurements usually have a sinusoidal current source and an electronic balance detector. The circuit is made as symmetrical as possible to avoid stray coupling. During measurement, the conductivity cell is filled with an electrolyte solution; this cell is usually made of glass with sealed platinum electrodes. Various shapes are used, depending on the purpose that it is to serve. Figure 2.9 depicts examples of suitable cell arrangements. The electrodes are covered with platinum black, to avoid electrode polarization. The electrodes are placed close to one another in poorly conductive solutions and further apart in more conductive solutions. For an evaluation of measurements the conductivity cell is calibrated with a solution of a known conductivity. Both the electrolyte and the solvent must be carefully purified.

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3 Intensity (arb.)

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Transport (transference) numbers are defined by Eqs (2.4.11) and (2.4.12). The experimental arrangement shown in Fig. 2.10 can be used to demonstrate this concept. In the cathode and anode compartments the electrolyte concentration is maintained homogeneous by stirring. The connecting tube is narrow, so that it contains a negligible amount of electrolyte compared with that in the electrode compartments. The electric field is homogeneously distributed and mass transfer occurs only through migration at sufficiently high field strengths. If the charge Q passes through this electrolysis cell, then Q/z+F moles of cations are discharged on the cathode and Q/\z-\F moles of anions on the anode. An amount of QtJ\z-\ F moles of anions migrates from the cathode space to the anode space and Qt+/z+F moles of cations in the opposite direction. Thus the cathode compartment will be depleted by a total of An+>c = Qt_/z+F moles of cations and A n _ c = Qf_/|z_| F moles of anions, and the anode compartment by An+ A = Qt+/z+F moles of cations and An_ A = Qt+/\z_\ F moles

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Wavelength (nm)

Fig. 2.10 Schematic design of a cell for the determination of transport numbers from measurements of the concentration decrease in electrode compartments (Hittorf s method)

102 of anions. As it obviously holds that n+ = \z_\n and n_ = z+n for the amounts of cations n+, anions n_ and salt n, respectively, then the decrease in the amount of the salt is Anc = Qt_/z+ |z_| F and AnA = Qt+/z+ |z_| F. Thus the decrease in the amount of salt in the cathode compartment is proportional to the transport number of the anion and the decrease in the amount of salt in the anode compartment is proportional to the transport number of the cation, t+ = A Anc + AnA and f = _ Anc + AnA (2.4.31)

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Figure 10.28. Re ection spectrum (1), uorescent emission spectrum (2) by excitation at 532 nm, and laser emission spectrum (3) by excitation with a second harmonic light of Nd-YAG laser of a Ch mixture of E44, S811, m-azo-8, and DCM (73.1/22.2/4.3/0.4 in wt%). Source: Kurihara et al., 2006.

Thus, the transport number can be found from measurement of the decrease in the amount of the salt in the electrode compartments. In view of Eq. (2.4.9), for a strong electrolyte,

5000 80

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1* 1*

4000 60 (arb.) (nm) 20 1000 0 5 10 15 20

(2A32)

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3000 Emission intensity, 40 2000

and, for a weak electrolyte,

0 25

(2-4-33)

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