Thermodynamic efficiency hypothesis

The formulation of two types of ion-pair is an attractive hypothesis which has been used for other systems [130] to explain differences in reactivity. The polymerization of styrene-type monomers in ether solvents, all of which solvate small cations efficiently, seems to be a particularly favourable case for the formation of thermodynamically distinct species. Situations can be visualized, however, in which two distinct species do not exist but only a more gradual change in properties of the ion-pair occurs as the solvent properties are changed. These possibilities, together with the factors influencing solvent-separated ion-pair formation, are discussed elsewhere [131, 132]. In the present case some of the temperature variation of rate coefficient could be explained in terms of better solvation of the transition state by the more basic ethers, a factor which will increase at lower temperatures [111]. This could produce a decrease in activation energy, particularly at low temperatures. It would, however, be difficult to explain the whole of the fep versus 1/T curve in tetrahydrofuran with its double inflection by this hypothesis and the independent spectroscopic and conductimetric evidence lends confidence to the whole scheme. 

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