Other Important (and Some Lesser Known) Strategies of Rate Enhancement

The literature contains examples of several strategies of rate enhancement not covered in the previous chapters. Many of these are essentially strategies for individual reactions with little general appeal. On the other hand, a few are very important, and several others combine two or more strategies. Of these, photochemical and micellar enhancements are as important as the strategies considered earlier in this part. However, in photochemical enhancement, recent studies have shown that the basis of scale-up used so far is questionable (Cassano et al., 1995), and designs based on newer concepts are still in their infancy. In micellar catalysis, despite the advances made, there are few industrial applications. As a result, these are included in this chapter on other strategies. Hydrotropes and supercritical fluids, although “old” with respect to other uses, are emerging as strong contenders for rate enhancement and ease of processing. Hence these two strategies are considered at some length in this chapter. Also included are the use of microwaves and several combinatorial strategies such as PTC with electrochemical, enzymatic, or sonochemical techniques; the use of supercritical fluids in similar combinations; enzymatic reactions in micelles; and PTC reactions in supercritical fluids or membrane reactors. Interaction of light with a chemical species can initiate or enhance a chemical reaction. Reactions of this type are known as photochemical reactions. Of the many distinctive features of photochemistry, the following is particularly noteworthy: in thermal excitation processes, all three forms of energy, electronic, transational, and rotational, are raised to higher levels. In contrast, photoexcitation raises only the electronic energy level which leads to higher selectivity, as exemplified by the photochlorination of the methyl group of toluene without any ring chlorination. Further, photochemical reactions are ecologically clean and require much less aggressive methods than conventional syntheses. Examples of reactions initiated or enhanced by light are many, and a small number are in industrial use, particularly in the production of halogenated hydrocarbons, alkane sulfates, and fine organic chemicals, including vitamins and fragrances. But the potential is enormous.