Abstract
The physical basis of the solvent contribution to the intrinsic activation entropy, ΔS*int, for outer-sphere electron-transfer reactions in homogeneous solution is examined in terms of the entropic parameters for the constituent electrochemical half-reactions. A relationship for calculating ΔS*int is derived which takes into account specific reactant-solvent interactions for the isolated redox centers by employing electrochemical reaction entropy data. This relation yields rather larger and more structure-sensitive values of ΔS*int, than those deduced on the basis of the usual dielectric continuum treatment. These considerations indicate that the more negative values of ΔS*int typically extracted from experimental kinetic data arise largely from the modification to the specific reactant-solvent interactions within the precursor complex caused by the proximity of the other redox center.
| Original language | English |
|---|---|
| Pages (from-to) | 1860-1864 |
| Number of pages | 5 |
| Journal | Journal of Physical Chemistry |
| Volume | 88 |
| Issue number | 9 |
| Publication status | Published - 1984 |
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- Physical and Theoretical Chemistry
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Influence of specific reactant-solvent interactions on intrinsic activation entropies for outer-sphere electron-transfer reactions. / Hupp, Joseph T; Weaver, Michael J.
In: Journal of Physical Chemistry, Vol. 88, No. 9, 1984, p. 1860-1864.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Influence of specific reactant-solvent interactions on intrinsic activation entropies for outer-sphere electron-transfer reactions
AU - Hupp, Joseph T
AU - Weaver, Michael J.
PY - 1984
Y1 - 1984
N2 - The physical basis of the solvent contribution to the intrinsic activation entropy, ΔS*int, for outer-sphere electron-transfer reactions in homogeneous solution is examined in terms of the entropic parameters for the constituent electrochemical half-reactions. A relationship for calculating ΔS*int is derived which takes into account specific reactant-solvent interactions for the isolated redox centers by employing electrochemical reaction entropy data. This relation yields rather larger and more structure-sensitive values of ΔS*int, than those deduced on the basis of the usual dielectric continuum treatment. These considerations indicate that the more negative values of ΔS*int typically extracted from experimental kinetic data arise largely from the modification to the specific reactant-solvent interactions within the precursor complex caused by the proximity of the other redox center.
AB - The physical basis of the solvent contribution to the intrinsic activation entropy, ΔS*int, for outer-sphere electron-transfer reactions in homogeneous solution is examined in terms of the entropic parameters for the constituent electrochemical half-reactions. A relationship for calculating ΔS*int is derived which takes into account specific reactant-solvent interactions for the isolated redox centers by employing electrochemical reaction entropy data. This relation yields rather larger and more structure-sensitive values of ΔS*int, than those deduced on the basis of the usual dielectric continuum treatment. These considerations indicate that the more negative values of ΔS*int typically extracted from experimental kinetic data arise largely from the modification to the specific reactant-solvent interactions within the precursor complex caused by the proximity of the other redox center.
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UR - http://www.scopus.com/inward/citedby.url?scp=0011541570&partnerID=8YFLogxK
M3 - Article
AN - SCOPUS:0011541570
VL - 88
SP - 1860
EP - 1864
JO - Journal of Physical Chemistry
JF - Journal of Physical Chemistry
SN - 0022-3654
IS - 9
ER -