ABSTRACT
This chapter describes relationships between thermodynamics and kinetics, in the context of explaining the physical factors affecting aqueous reaction rates. The theoretical base is used to explain the effects of pressure and ionic strength on reaction rates. The driving force for change is the difference in energy between reactants and products. The attractive and repulsive forces between ions and/or neutral molecules are important in solution-phase kinetics because the reactants must approach each other closely if chemical reaction is to occur. Development of an accurate theoretical model for molecular interaction potentials that includes both short- and long-range interactions has proven elusive, but several empirical expressions are available. Development of an accurate theoretical model for molecular interaction potentials that includes both short- and long-range interactions has proven elusive, but several empirical expressions are available. The solvent-cage phenomenon has important implications for free radical formation by photo activation in solution.
