Ov. Borzenko et al., ENERGETICS AND KINETICS OF HOMOGENEOUS ELECTROCHEMILUMINESCENT ELECTRON-TRANSFER REACTIONS IN NAPHTHALIMIDE SOLUTIONS, Russian journal of electrochemistry, 32(11), 1996, pp. 1273-1278
Free activation energies and rate constants for bimolecular reactions
of electron transfer (RET) between electrogenerated radical ions A(-.)
and A(+.) of electrochemiluminophores A (substituted naphthalimides)
are calculated. A correlation analysis is conducted for the first time
, yielding mechanisms and kinetics of RET that occur in an anomalous (
in terms of formation of nonexcited products) region of electron trans
itions. The correlation dependences of the electrochemiluminescence (E
CL) intensity on the free activation energy of RET are plotted. The co
rrelation coefficients pertaining to each series of naphthalimide comp
ounds under study are found for different electrolysis conditions. Com
paring the above dependences and coefficients shows adequacy of the ex
pressions proposed for the calculation of rate constants inherent in h
omogeneous RET. The calculations are made in the framework of the know
n theories, describing intermolecular exothermic electron transitions,
which most closely coincide with the experimental dependences of the
ECL intensity on the free activation energy.