Hydrothermal reactions of simple molecules by real-time infrared spectroscopy

Abstract

The relative roles of the materials of construction of the reactor (stainless steel or titanium) and the effects of Group 1 cations are discussed in terms of their effect on the rate of decarboxylation of acetic acid derivatives, RCO₂H. Past work indicates that the reaction container composition has a very large effect when R is CH3—. A smaller but significant effect is seen when R is electron neutral (i.e., R=H). When R is electron Withdrawing the rate depends less on the reactor type than the nature of R. The effect of the counter ion M on the rate of decarboxylation of monovalent malonate salts, HC&CHzC02M, is discussed for M=Li⁺, Na⁺, K⁺, Rb⁺, and Cs⁺. The rate generally increases with the ionic radius except that the Rb⁺ salt exhibits the fastest rate. Preliminary explanations are given.

Key Words:

• Catalysis
• Salt effects
• Kinetics
• Hydrothermal
• Reactions