Rate Equations for Reversible Disproportionation Reactions and Fitting to Time-Course Data

Integrated
rate equations are straightforward to fit to experimental
data to verify a proposed mechanism and to extract kinetic parameters.
Such equations are derived for reversible disproportionation/comproportionation
reactions with any set of initial concentrations. Extraction of forward
and reverse rate constants from experimental data by fitting the rate
law to the data is demonstrated for the disproportionation of 2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl
(TEMPO) under acidic conditions where the approach to equilibrium
is observed.