An investigation of the mechanism of the formation of phenylpyridinium ion from Konig's salt has been carried out. The rate of ring closure in methanol solution was increased by added base. An increase of base concentration increased the rate only up to the point at which the base concentration was equivalent to the salt concentration. The effect was independent of the nature of the base. A mechanism was postulated involving a rate determining valence isomerization of the free base derived from Konig's salt to a dihydropyridine. Similar results were shown to pertain with substituted Konig's salts. Rates were measured for methyl, methoxyl, chloride and fluorine containing salts. As a part of the mechanism a folding and unfolding process for the triene chain of the salt was proposed.