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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 331 The principle of measurement of the EMF The EMF of a galvanic cell is a thermodynamic equilibrium quatity Thus, the potential of a cell must be measured under equilibrium conditions, ie without current flow The measured EMF must be compensated by a known external potential difference The measurement of the EMF of a cell is thus based on determination of a potential difference that exactly compensates the measured potential difference so that no current passes.

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400 450 Wavelength (nm) (c)

This is easily achieved by the Poggendorf compensation method (see Fig 313) At present, potentiometry is performed primarily using electronic instruments with solid-state elements The EMF can be measured by compensation measurement using a transistor voltmeter, ie according to the scheme in Fig 313, where the galvanometer is replaced by an amplifier and meter A second possibility is to measure the tiny current passed on connecting the cell with a large external resistance Typical instruments of this kind consist of three parts The first part is the input circuit, acting as an impedance transducer Mostly MOSFET elements or capacity diodes are used here The second part contains a power amplifier, permitting the use of a meter with large energy consumption Depending on whether the EMF measured by using an ac amplifier is modulated in the input circuit (by a dc.

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Figure 13.12. UV/visible spectra of Brij 56 templated TSUA-modi ed nanoporous lms. (a) After surfactant removal, re ection mode. (i) As-prepared, (ii) after UV irradiation of sample (i) for 30 min, and (iii) after heating sample (ii) at 1001C for 5 min. (b) Before surfactant removal, re ection mode. (i) As-prepared, (ii) after UV exposure of sample (i) for 20 min, and (iii) after room light exposure of sample (ii) for 60 min. (c) After surfactant removal, transmission mode. (i) Before UV exposure, (ii) UV exposure for 5 min.

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amplifier), an electronic demodulation circuit must be connected in the second part to rectify the amplified alternating voltage The third part is the indicator with a digital display If a cell is to be used as a potential standard, then it must be prepared as simply as possible from chemicals readily available in the required purity and, in the absence of current passage, it must have a known, defined, constant EMF that is practically independent of temperature In this case the efficiency, power, etc, required for cells used as electrochemical power sources is of no importance The electrodes of the standard cell must not be polarizable by the currents passing through them when the measuring circuit is not exactly compensated The mostly used Weston cell consists of mercurous sulphate and cadmium amalgam electrodes: Hg | Hg2SO4(s) | 3CdSO48H2O(sat) | Cd,Hg(125 weight % Cd) (331).

absorption coef cient of 259 104 M 1 cm 1 for the trans isomer, the trans isomer concentration in the lms was estimated to be 155, 152, and 112 M, respectively, for samples iii, i, and ii in Fig 1312a The molar concentrations of azobenzene ligands in the self-assembled lms greatly exceed those attainable by dye adsorption in mesoporous lms (Ogawa et al, 2000) As a control experiment, thin lms were prepared with the same sol, but without the Brij 56 surfactant In this case, the azobenzene ligands were randomly incorporated in a microporous silica matrix and exhibited no detectable photoisomerization Similarly, no signi cant photoisomerization was observed for the ordered self-assembled lms before solvent extraction of the surfactant templates (Fig 1312b) The pore volume required for photoisomerization was created only upon surfactant removal (estimated as 127 A3 (Victor and Torkelson, 1987)).

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Fig. 3.13 Poggendorfs compensation circuit. A uniform resistance wire is connected at its ends (points a and b) to a stable voltage source (e.g. a storage battery). A part of this voltage between one end of the potentiometric wire and the sliding contact c is fed into the other circuit containing the measured source of voltage Ex, the null instrument G and the key. If no current flows through G the electrical potential difference compensates the EMF, Ex. The voltage fed to the potentiometric wire is calibrated by means of a standard cell, usually Weston cell, Es by means of the same compensation procedure

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