Electrochemical Science and Technology: Fundamentals and Applications, Keith B. Oldham, Jan C. Myland and Alan M. Bond. © 2011 John Wiley & Sons, Ltd.

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Presentation transcript:

Electrochemical Science and Technology: Fundamentals and Applications, Keith B. Oldham, Jan C. Myland and Alan M. Bond. © 2011 John Wiley & Sons, Ltd. Published 2011 by John Wiley & Sons, Ltd. Figure 8.1 When transport occurs along parallel fluxlines, the conservation equation takes the simple form given in equation 8:7.

Electrochemical Science and Technology: Fundamentals and Applications, Keith B. Oldham, Jan C. Myland and Alan M. Bond. © 2011 John Wiley & Sons, Ltd. Published 2011 by John Wiley & Sons, Ltd. Figure 8.2 When fluxlines are not parallel, the conservation law takes the form given in equation 8:8.

Electrochemical Science and Technology: Fundamentals and Applications, Keith B. Oldham, Jan C. Myland and Alan M. Bond. © 2011 John Wiley & Sons, Ltd. Published 2011 by John Wiley & Sons, Ltd. Figure 8.3 When fluxlines radiate from a point, equiconcentration surfaces are spheres, or portions thereof, and the conservation equation is as reported in 8:9.

Electrochemical Science and Technology: Fundamentals and Applications, Keith B. Oldham, Jan C. Myland and Alan M. Bond. © 2011 John Wiley & Sons, Ltd. Published 2011 by John Wiley & Sons, Ltd. Figure 8.4 The Grotthuss mechanism. The exchange of a proton H + between an ion and a water molecule mimics true migration and inflates the mobility.

Electrochemical Science and Technology: Fundamentals and Applications, Keith B. Oldham, Jan C. Myland and Alan M. Bond. © 2011 John Wiley & Sons, Ltd. Published 2011 by John Wiley & Sons, Ltd. Figure 8.5 The motion of the junction between two solutions of known conductivity is measured in the moving boundary method.

Electrochemical Science and Technology: Fundamentals and Applications, Keith B. Oldham, Jan C. Myland and Alan M. Bond. © 2011 John Wiley & Sons, Ltd. Published 2011 by John Wiley & Sons, Ltd. Figure 8.6 Typical apparatus for electrophoresis.

Electrochemical Science and Technology: Fundamentals and Applications, Keith B. Oldham, Jan C. Myland and Alan M. Bond. © 2011 John Wiley & Sons, Ltd. Published 2011 by John Wiley & Sons, Ltd. Figure 8.7 In the potential-leap experiment, the WE is suddenly brought to a potential large enough to denude the electrode surface of the electroreactant.

Electrochemical Science and Technology: Fundamentals and Applications, Keith B. Oldham, Jan C. Myland and Alan M. Bond. © 2011 John Wiley & Sons, Ltd. Published 2011 by John Wiley & Sons, Ltd. Figure 8.8 Concentration profiles resulting from the potential-leap experiment for a diffusivity D R = 1.00  10 –9 m 2 s –1. Note that, even after times as long 830 as 100 s, the concentration diminution is confined to a layer of only about one millimeter thickness, easily validating condition 8:27.

Electrochemical Science and Technology: Fundamentals and Applications, Keith B. Oldham, Jan C. Myland and Alan M. Bond. © 2011 John Wiley & Sons, Ltd. Published 2011 by John Wiley & Sons, Ltd. Figure 8.9 A narrow tube interconnects two electrode chambers that are gently stirred to ensure uniform composition in each chamber.

Electrochemical Science and Technology: Fundamentals and Applications, Keith B. Oldham, Jan C. Myland and Alan M. Bond. © 2011 John Wiley & Sons, Ltd. Published 2011 by John Wiley & Sons, Ltd. Figure 8.10 Poiseuille flow through a tube. The velocity profile, given by v (r) = 2V [R 2– r 2 ]/πR 4, where V is the flowrate (m 3 s 1 ), is shown in cross section.

Electrochemical Science and Technology: Fundamentals and Applications, Keith B. Oldham, Jan C. Myland and Alan M. Bond. © 2011 John Wiley & Sons, Ltd. Published 2011 by John Wiley & Sons, Ltd. Figure 8.11 Geometry of the rotating disk electrode, showing also the flowlines followed by the convecting solution.

Electrochemical Science and Technology: Fundamentals and Applications, Keith B. Oldham, Jan C. Myland and Alan M. Bond. © 2011 John Wiley & Sons, Ltd. Published 2011 by John Wiley & Sons, Ltd. Figure 8.12 Coordinates useful in describing the behavior of the solution adjacent to a rotating disk electrode.

Electrochemical Science and Technology: Fundamentals and Applications, Keith B. Oldham, Jan C. Myland and Alan M. Bond. © 2011 John Wiley & Sons, Ltd. Published 2011 by John Wiley & Sons, Ltd. Figure 8.13 The concentration profile at a rotating disk electrode according to equation 8:48. The graph is correctly scaled for the typical value b = (18 μm) 3.

Electrochemical Science and Technology: Fundamentals and Applications, Keith B. Oldham, Jan C. Myland and Alan M. Bond. © 2011 John Wiley & Sons, Ltd. Published 2011 by John Wiley & Sons, Ltd. Figure 8.14 Concentration profiles during the experiment analyzed in Web#852. The neutral species R and the cation O are involved in the electrode reaction R(soln) ⇄ e – + O(soln), while C and A are the cation and anion of the supporting electrolyte.

Electrochemical Science and Technology: Fundamentals and Applications, Keith B. Oldham, Jan C. Myland and Alan M. Bond. © 2011 John Wiley & Sons, Ltd. Published 2011 by John Wiley & Sons, Ltd. Figure 8.15 Flux density profiles corresponding to the concentrations shown in Figure Notice the transition from the transport being largely that of the electroactive species close to the electrode to being predominantly that of the supporting ions in the bulk. See Web#852 for details.