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Additional resources for Electroanalytical Chemistry: A Series Of Advances. Volume 21
20 Martin and Mitchell been reported. Assuming, for the sake of illustration, a value of 1 cm sϪ1, Nicholson’s theory shows that quasireversible Ru(NH 3 ) 63ϩ/2ϩ voltammograms will be obtained, at a macroelectrode, at scan rates above ϳ5 V sϪ1 . Figure 8A shows voltammograms at various scan rates for Ru(NH 3 ) 63ϩ/2ϩ at a 30NEE. 01 V sϪ1. Therefore, as expected, the transition to quasireversible behavior is observed at dramatically lower scan rates at the 30NEE than would be observed at a macroelectrode.
5 mM sodium nitrate. 079 cm 2 ). 18 Martin and Mitchell of scan rate. This latter point is proven by the agreement between the experimental and simulated voltammograms. The simulated data were obtained by assuming reversible electrochemistry at a macroelectrode with active area equivalent to the geometric area of the NEE. Other than assuming an arbitrarily high value for the standard heterogeneous rate constant, there are no adjustable parameters in these simulations. The quantitative agreement between the experimental and simulated voltammograms indicates that the reversible, total-overlap–limiting case is, indeed, operative at this NEE.
Continued permeate solution. Again, these data show that to our (now much more sensitive) ability to make the measurement, this membrane has cleanly separated these two molecules. This analysis also shows that if any quinine is present in the permeate solution, its concentration is less than 5 ϫ 10Ϫ9 M. These analytical data can be used to calculate a minimal selectivity coefficient, α min . Because the concentration of the smaller molecule in the permeate solution was 7 ϫ 10Ϫ5 M and the concentration of the larger molecule (if present at all) must be less than 5 ϫ 10Ϫ9 M, the minimal selectivity coefficient for the pyridine/quinine pair is α min ϭ 15,000.