A complete thermodynamic characterization of the chair-to-chair interconversion in beta-diphosphorylated piperidine-N-oxyl radicals was achieved by means of the analysis of temperature-dependent ESR spectra. A new two-dimensional simulation method was developed with the coordinates temperature and magnetic field, in which the entire set of spectra was simulated simultaneously by adjusting the coefficients in the power expansion, giving the temperature-dependent ESR parameters and the thermodynamic and kinetic parameters determining the site populations and exchange rates, respectively. The new method promotes elimination of the ambiguities inherent in the spectroscopic determination of thermodynamic parameters. Labile solvent-solute interactions can strongly influence the chemical exchange, producing a complex network of symmetric and asymmetric interconversions. The solvent dependence of magnetic relaxation was also analyzed.