Estimation of the outer-sphere contribution to the activation parameters for homogeneous electron-transfer reactions using the mean spherical approximation

Fawcett, W. Ronald; Blum, L.

doi:10.1016/0009-2614(91)90503-2

Cited by 57 publications

(22 citation statements)

References 23 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…As Hupp and co-workers (22) have shown, it is the local solvent environment of the reactants that determines Av,,:, the most important contributor to AVcALc< Unfortunately, development of this concept requires a full molecular dynamics computational treatment, and this is probably not feasible at present.5 Besides, the traditional approach, in which phenomena are related to particular bulk properties of the various media, affords some conceptual satisfaction. As a compromise, the molecular nature of the solvent can be introduced into the dielectric-continuum MarcusHush theory through the Mean Spherical Approximation (MSA) approach (24)(25)(26). We find (27) 'By radioisotope sampling at high pressure.…”

Section: Self-exchange Reactions In Nonaqueous Solutionsmentioning

confidence: 99%

Reflections on the outer-sphere mechanism of electron transfer

Swaddle¹

1996

Can. J. Chem.

View full text Add to dashboard Cite

Abstract:The quantitative efficacy of the Stranks-Marcus-Hush theory of volumes of activation A v~ for outer-sphere electron transfer between metal complexes in solution is assessed. The theory predicts A v S accurately for several couples in aqueous solution, but is satisfactory for polar nonaqueous solvents only at pressures of ca. 100 MPa and above, and accuracy is not improved when the molecular nature of the solvent is allowed for through the Mean Spherical Approximation approach. At low pressures, the calculations become numerically unstable when the isothermal compressibility of the solvent is high and its relative permittivity is low, particularly for the more highly charged couples. For aqueous systems, departures from the predicted A v t afford insights into the role of the counterions, the incursion of inner-sphere pathways, the enhanced reactivity of CO""" cage complexes relative to conventional chelates, and the question of "spin forbiddenness" of electron transfer processes that involve a large change in spin multiplicity.Key words: redox kinetics, inorganic reaction mechanisms, pressure effects, Marcus-Hush theory, activation volumes. prkdites fournissent des renseignements sur le r6le des contre-ions, sur les incursions de voies impliquant les sphkres internes, I'augmentation de la rCactivitC des complexes de cage du CO""" par rapport aux chClates conventionnels et la question de l'<

show abstract

Section: Self-exchange Reactions In Nonaqueous Solutionsmentioning

confidence: 99%

Reflections on the outer-sphere mechanism of electron transfer

Swaddle¹

1996

Can. J. Chem.

View full text Add to dashboard Cite

show abstract

“…In the first approximation, the k o values are proportional to the solvent Pekar factor, c solv = (1/e op À 1/e s ), where e op and e s are the optical and static electric permittivity of the solvent, respectively. A better model, based on the mean spherical approximation, was developed by Fawcett and Blum [7]. However, for non-spherical reactants, in particular those having functional groups associated with ET process, Fawcett [3] showed later that experimental rate constants depend also on parameters describing the solvation of the reactant, such as the polarity function (e s À 1)/(e s + 2) or the acceptor number in the case of anions.…”

Section: Introductionmentioning

confidence: 99%

Anisole as a solvent for organic electrochemistry

Jaworski

Cembor

Orlik

2005

Journal of Electroanalytical Chemistry

View full text Add to dashboard Cite

“…Analysis of the experimental data revealed that the Marcus estimates of ΔG » os and ΔH » os are slightly bigger than the experimental values. However, smaller values for these quantities which are closer to the experimental values are obtained when they are estimated using the mean spherical approximation (MSA) [56]. The expression for ΔG » os in the MSA is…”

Section: The 1990smentioning

confidence: 99%

Fifty years of studies of double layer effects in electrode kinetics—a personal view

Fawcett

2011

J Solid State Electrochem

View full text Add to dashboard Cite

Developments in the treatment of double layer effects in electrode kinetics are outlined. These include discreteness-of-charge effects in the presence of specific adsorption, solvent effects in electron transfer reactions, and effects related to the distribution of charge in polyatomic reactants. The importance of studies at single crystal electrodes is emphasized, and the development of a single crystal ultramicroelectrode described. Finally, a method of improving the estimate of the diffuse layer potential drop on the basis of Monte Carlo simulations is presented.

show abstract

Estimation of the outer-sphere contribution to the activation parameters for homogeneous electron-transfer reactions using the mean spherical approximation

Cited by 57 publications

References 23 publications

Reflections on the outer-sphere mechanism of electron transfer

Reflections on the outer-sphere mechanism of electron transfer

Anisole as a solvent for organic electrochemistry

Fifty years of studies of double layer effects in electrode kinetics—a personal view

Contact Info

Product

Resources

About