Handbook of Reference Electrodes by György Inzelt Andrzej Lewenstam & Fritz Scholz

Author:György Inzelt, Andrzej Lewenstam & Fritz Scholz
Language: eng
Format: epub
Publisher: Springer Berlin Heidelberg, Berlin, Heidelberg

(6.1)

(6.2)

In Eq. (6.1), t is the ionic transport number, a is the electrolyte activity, and the subscripts 1 and 2 refer to the left and right sides of the junction. E j(a) = 0 for . In Eq. (6.2), is the standard Gibbs energy of transfer of i from solvent S1 to S2, and is equal to the difference in the standard chemical potential of i, , in S1 and S2.

Linear relations of unit slopes are generally observed between the actual (experimental) variations in component (a) and the values obtained by Eq. (6.1) (Fig. 6.4). Thus, Eq. (6.1) is applicable to estimate the values of component (a). The magnitudes are of the order of ±40 mV for the variation in electrolyte concentrations (c 1/c 2, mM) from 100/1 to 1/100.

Fig. 6.4Actual variation in component (a) versus component (a) calculated by Eq. (6.1). Junctions c 1 MX(S1)¦c 2 MX(S2). S1/S2, and M/X are shown on the lines and W, M, DS, and Et show H2O, MeOH, DMSO and Et4N, respectively; (c 1, c 2)/mM are, from left to right, (100, 1), (10, 1), (1, 1), (1,10), (1, 100); filled diamond (25, 25). Lines have unit slopes. The relation for “W/DS, Et/ClO4” deviates from linearity, but this is due to the influence of the electrolyte concentration on component (c)

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