We present here a survey of theoretical and experimental
studies performed in our: laboratories, which deal with influences
of homogeneous redox reactions in d. c. and a. c. polarography, with
primary emphasis on the latter. These jnvestigations date back to
the early 1960\u27s when effects of the catalytic mechanism on a. c.
polarography were examined. However, the main thrust in this
direction occurred in the past four years when theoretical strategies
for handling second order homogeneous reactions coupled to heterogeneous
electron transfer were perfected. This development permHted
a focused theo,retical effort on this topic which encompassed
a variety of mechani:srtic schemes, such as those involving disproportLonatiOl!
l, and »nuances« of the consecutive and parallel ECE
mechanisms. Experimental results obtained to date satisfactorily
support predictiOIIls of the theoretical rate Jaws. One concludes from
our studies and parallel efforts in other laboratories that kinetic
characteristics of homogeneous redox reactions can substantially
influence rthe polarographic observables under many circumstances.
The COl!lclusicm follows that kinetic characteristics of homogeneous
redox reactions are more broadly access1ble via polarographic, and
other electrochemical relaxation techniques than previously thought.
Also, proper care must be taken to account for, or show negligibility
of, homogeneous redox reaction effects in studies whose attention
is centered on the heterogeneous processes or on multi-component
analysis
