Steric factor
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Steric factor, P[1] is a term used in collision theory.
It is defined as the ratio between the experimental value of the rate constant and the one predicted by collision theory. It can also be defined as the ratio between the preexponential factor and the collision frequency, and it is most often less than unity.
Usually, the more complex the reactant molecules, the lower the steric factor. Nevertheless, some reactions exhibit steric factors greater than unity: the harpoon reactions, which involve atoms that exchange electrons, producing ions. The deviation from unity can have different causes: the molecules are not spherical, so different geometries are possible; not all the kinetic energy is delivered into the right spot; the presence of a solvent (when applied to solutions)...
When collision theory applied to reactions in solution the solvent cage has an effect on the reactant molecules, as several collisions can take place in a single encounter, which leads to predicted preexponential factors being too large. ρ values greater than unity can be attributed to favorable entropic contributions.
Unfortunately, steric factors cannot be calculated theoretically, so the applicability of collision theory is greatly diminished.
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