MnCl+ and MnSO4 association constants to 170°C

Changes in electron spin resonance (ESR) spectra of the manganese (II) ion are used to determine thermodynamic association constants for MnCl⁺ and MnSO₄⁰ complexes from 25 to 170°C. The technique employed requires minimal sample handling and preparation. Pressure increase had a negligible effect on the association constants which increase from 4 m^–1 at 50°C to 200 m^–1 at 170°C for MnCl⁺ and from 200 m^–1 at 25°C to 5700 m^–1 at 170°C for MnSO₄⁰. The ratio of inner to outer sphere complexes decreases with increasing temperature to 120°C and then increases from 120 to 170°C for both chloride and sulfate complexes. Enthalpies, entropies, heat capacities, and Gibb's free energies determined for each of the reactions compare well with values determined by other methods. These results confirm the validity of the high temperature and pressure ESR approach, which can be used to study other high temperature association reactions of Mn⁺² and, by competitive effects, association reactions of metals that do not have an ESR signal.