Pure and Applied Chemistry

Abstract: At elevated temperature, several properties of water are strongly altered compared to what our daily experience tells us: the dielectric constant of water, for example, is reduced, so that water can more easily solubilize organic molecules. In addition, the self-dissociation constant of water is increased (by three orders of magnitude at 250 °C), thus favoring H⁺- and OH^–-catalyzed reactions. Surprisingly, while room-temperature water and supercritical water (SCW) are well known for promoting organic reactions, the middle temperature range still remains largely unexplored. Therefore, this contribution aims at giving an overview of organic reactions that may be promoted by superheated water.