Reaction energies thermodynamics high-accuracy

Thermodynamic data of high accuracy and reliability for the Ni - NiO system at high temperatures were obtained from electrochemical cells with yttria- or calcia-stabilised zirconia electrolytes. The experimental results are in excellent agreement with available calorimetric data as well as emf measurements of previous publications. The recommended Gibbs energy equation for the reaction ... 

Rate coefficients for recombination reactions are related to those for dissociation via the equilibrium constant, which can generally be calculated from thermodynamical information with a high degree of precision, although the accuracy depends on the quality of the thermodynamic data. The rate coefficients are pressure dependent and the theoretical framework of unimolecular reactions can therefore be used to describe them. Because there is little or no activation energy for the recombination process, rates of radical association reactions can be measured over a wide range of temperatures and can be used, in combination with thermodynamic information, to calculate rate coefficients for unimolecular dissociations. The availability of data for a number of radical recombination reactions over a wide range of pressures and temperatures makes these reactions excellent test beds for theoretical models of pressure dependent reactions. 

---