Download e-book for iPad: Analytical Electochemistry. Second Edition by Wang Joseph

By Wang Joseph

ISBN-10: 0471228230

ISBN-13: 9780471228233

ISBN-10: 0471282723

ISBN-13: 9780471282723

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The diffuse double layer becomes small). Under these conditions, 1=CH ) 1=CG , 1=C 9 1=CH or C 9 CH . In contrast, for dilute solutions, CG is very small (compared to CH ) and C 9 CG . Figure 1-13 displays the experimental dependence of the double-layer capacitance upon the applied potential and electrolyte concentration. As expected for the parallel-plate model, the capacitance is nearly independent of the potential or concentration over several hundreds of millivolts. , the Epzc ) with dilute solutions, re¯ecting the contribution of the diffuse layer.

24 FUNDAMENTAL CONCEPTS FIGURE 1-15 Electrocapillary curves for different electrolytes showing the relative strength of speci®c adsorption. ) potential passes through the Epzc . Experimental electrocapillary curves have a nearly parabolic shape around Epzc . Such a parabolic shape corresponds to a linear change of the charge with the potential. The deviation from a parabolic shape depends on the solution composition, particularly on the nature of the anions present in the electrolyte. , halides) with the FIGURE 1-16 Electrocapillary curves of background (j), ethynylestradiol (), b-estradiol (m) and morgestrel (r).

The term a is thus a measure of the symmetry of the activation energy barrier. , FIGURE 1-10 Effect of a change in the applied potential on the free energies of activation for reduction and oxidation. 18 FUNDAMENTAL CONCEPTS an idealized curve). 5 are common for metallic electrodes with a simple electron transfer process. The barrier for reduction at E is thus given by z ‡ anFE DGcz ˆ DGc;0 …1-36† Similarly, examination of the ®gure reveals also that the new barrier for oxidation, z DGaz is lower than DGa;0 : z À …1 À a†nFE DGaz ˆ DGa;0 …1-37† By substituting the expressions for DGz (equations 1-36 and 1-37) in equation (1-34), we obtain for reduction z =RT Š exp‰ÀanFE=RT Š kf ˆ A exp‰ÀDGc;0 …1-38† z =RT Š exp‰…1 À a†nFE=RT Š kb ˆ A exp‰ÀDGa;0 …1-39† and for oxidation The ®rst two factors in equations (1-38) and (1-39) are independent of the potential, and thus these equations can be rewritten as kf ˆ kf exp‰ÀanFE=RT Š …1-40† kb ˆ kb exp‰…1 À a†nFE=RT Š …1-41† When the electrode is at equilibrium with the solution, and when the surface concentrations of O and R are the same, E ˆ E  , and kf and kb are equal: kf exp‰ÀanFE=RT Š ˆ kb exp‰…1 À a†nFE=RT Š ˆ k  …1-42† and correspond to the standard rate constant k  .

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Analytical Electochemistry. Second Edition by Wang Joseph


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