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Applications of standard electrode potentials

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Fundamentals of Analytical Chemistry: 9th ed. Chapter 19 Chapter 19 19-1. The electrode potential of a system that contains two or more redox couples is the electrode potential of all half-cell processes at equilibrium in the system. 19-2. (a) Equilibrium is the state that a system assumes after each addition of reagent. Equivalence refers to a particular equilibrium state when a stoichiometric amount of titrant has been added. 19-4. For points before the equivalence point, potential data are computed from the analyte standard potential and the analytical concentrations of the analyte and its reaction product. Post-equivalence point data are based upon the standard potential for the titrant and its analytical concentrations. The equivalence point potential is computed from the two standard potentials and the stoichiometric relation between the analyte and titrant. 19-6. An asymmetric titration curve will be encountered whenever the titrant and the analyte react in a ratio that is not 1:1. 19-8. (a) Eright = −0.277 − Eleft = −0.763 − 0.0592 1 ⎛ ⎞ = −0.373 V log ⎜ −4 ⎟ 2 ⎝ 5.87 × 10 ⎠ 0.0592 ⎛ 1 ⎞ log ⎜ ⎟ = −0.793 V 2 ⎝ 0.100 ⎠ Ecell = Eright − Eleft = −0.373 − (−0.793) = 0.420 V Because Ecell is positive, the reaction would proceed spontaneously in the direction considered (oxidation on the left, reduction on the right). (b) Eright = 0.854 − Eleft = 0.771 − 0.0592 ⎛ 1 ⎞ log ⎜ ⎟ = 0.811 V 2 ⎝ 0.0350 ⎠ 0.05 ...
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