The free energy change, AG, in the homogenous cross-exchange ET reaction of [Ru(bpy)2]* and ferricytochrome c is -104.6 kJ mol¯1. The second-order activation-limited rate constant, kobs, is 2.5 × 108 M-1 s-1. Taking KDA = 1.0 M¹, N = 1 × 1011 s-1, and x = 1, estimate the values of AG* and 2. In what kinetic region is this reaction? Hint: By substituting the Marcus equation into the expression for the rate constant of an adiabatic homogenous ET reaction, the rate constant of a cross-exchange ET reaction may be written as (AG+2)² Ket = KVN exp - 4λRT and, by rearrangement, In Ket KV 1 (AG+ 2)² 1 AG2 1 AG == + constant 42 RT 42 RT 2 RT

The free energy change, AG, in the homogenous cross-exchange ET reaction of [Ru(bpy)2]* and ferricytochrome c is -104.6 kJ mol¯1. The second-order activation-limited rate constant, kobs, is 2.5 × 108 M-1 s-1. Taking KDA = 1.0 M¹, N = 1 × 1011 s-1, and x = 1, estimate the values of AG* and 2. In what kinetic region is this reaction? Hint: By substituting the Marcus equation into the expression for the rate constant of an adiabatic homogenous ET reaction, the rate constant of a cross-exchange ET reaction may be written as (AG+2)² Ket = KVN exp - 4λRT and, by rearrangement, In Ket KV 1 (AG+ 2)² 1 AG2 1 AG == + constant 42 RT 42 RT 2 RT

Chemistry & Chemical Reactivity

10th Edition

ISBN:9781337399074

Author:John C. Kotz, Paul M. Treichel, John Townsend, David Treichel

Publisher:John C. Kotz, Paul M. Treichel, John Townsend, David Treichel

Chapter14: Chemical Kinetics: The Rates Of Chemical Reactions

Section: Chapter Questions

Problem 89IL: The oxidation of iodide ion by the hypochlorite ion in the presence of hydroxide ions I(aq) +...

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