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It is well-known
that for an electron transfer reaction,
the electron-donating
ability of electron donors and the electron-accepting ability of electron
acceptors can be quantitatively described by the oxidation potential
of electron donors and the reduction potential of electron acceptors.
However, for an electron transfer reaction, the electron-donating
activity of electron donors and the electron-accepting activity of
electron acceptors cannot be quantitatively described by a characteristic
parameter of electron donors and a characteristic parameter of electron
acceptors till now. In this paper, a characteristic activity parameter
of electron donors and electron acceptors named as their thermo-kinetic
parameter is proposed to quantify the electron-donating activity of
electron donors and the electron-accepting activity of electron acceptors
in electron transfer reactions. At the same time, the thermo-kinetic
parameter values of 70 well-known electron donors and the corresponding
70 conjugated electron acceptors in acetonitrile at 298 K are determined.
The activation free energies of 4900 typical electron transfer reactions
in acetonitrile at 298 K are estimated according to the thermo-kinetic
parameter values of 70 electron donors and 70 conjugated electron
acceptors, and the estimated results have received good verification
of the corresponding independent experimental measurements. The physical
meaning of the thermo-kinetic parameter is examined. The relationship
of the thermo-kinetic parameter with the corresponding redox potential
as well as the relationship of the activation free energy with the
corresponding thermodynamic driving force of electron transfer reactions
is examined. The results show that the observed relationships between
the thermo-kinetic parameters and the redox potentials as well as
the observed relationships between the activation free energy and
the thermodynamic driving force depend on the choice of electron donors
and electron acceptors as well as the electron transfer reactions.
The greatest contribution of this paper is to realize the symmetry
and unification of kinetic equations and the corresponding thermodynamic
equations of electron transfer reactions.
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