Numerical solution redox kinetics

Combining (2.137) and (2.138) with kinetic equation (2.135), and (2.138) and (2.139) with (2.136), integral equations are readily obtained as general solutions for each redox step. The numerical solution is represented by the following set of recursive formulas ... 

There are numerous reports of the existence of electrocatalysis via an attached redox center on a SAM (see Sect. 4.3), but few reports in which the rates of electron transfer between the electrode and the attached redox molecule and between the attached redox molecule and the solution redox molecule are measured. It would be interesting to study the electron-transfer kinetics in SAMs with multiple redox molecules linked along a single tether (such as porphyrins [157] or metal-terpyridine complexes) [122]. From such a system, one could derive the rate of electron transfer between two redox molecules connected by a molecular bridge and check the considerable data available on intramolecular transfer obtained by other methods [254]. For a variety of applications, measurements of the rates of electron transfer between an electrode and metal nanoparticles tethered to the SAM are also of interest [255]. 

The kinetics of electrochemical reactions are often modified by the nature of the electrode material, and by the presence of atomic and molecular species either adsorbed on the surface or in the bulk solution [14]. Electrocatalysis is primarily concerned with the study of this phenomenon and, particularly, with the factors that govern enhancements in the rates of redox processes. Implicit in this general statement is the ability of the species responsible for these effects, or electrocatalyst, or the electrode itself, to carry out the reaction numerous times before undergoing possible deactivation. Electrocatalytic processes in which the electrode simply serves as a source or sink of electrons to generate solution phase species that... 

The primary radicals generated in the radiolysis of aqueous solutions are well characterized with regard to spectra, redox potentials and chemical nature. Similarly, because reaction of a radical with a solute molecule or ion yields another unpaired>elec-tron species, many secondary radicals also are characterized. The secondary radicals can react with other solutes, etc., until kinetic and thermodynamic restrictions bring the chain to an end with the formation of stable products. Thus, numerous reactive radicals are available for pulse-radiolysis studies. Because the various radicals and their reaction products are formed via elementary reactions, the pathways are determined strictly from kinetic competition the reaction rates are dictated by the rate constants and the concentrations of the reactants. 

The kinetic characteristics of ligand exchange of thallium complexes in solution have been little explored, in contrast to the numerous equilibrium studies (4-6,41,57,61,66,67,90,92,93,96,97,112,214-246) and a large number of studies of redox reactions involving thallium (81, 100, 103, no, 246-288). 

A collection of numerical data covering a relatively large number of quantities used in physical chemistry and thermodynamics, mainly for inorganic species for example acidity constants including those found in non-aqueous solvents, solubility constants and complexation constants. Regarding electrochemistry, you can find the redox potentials for numerous couples, the molar conductivities for the main ions in aqueous solution, the activity coefficients for electrolytes, as well as a small number of kinetic features (exchange current density, and transfer coefficient, etc.). 

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