Pure and Applied Chemistry

Abstract: Acid-catalyzed hydrocarbon reactions involve by far the largest amount of catalyst and the largest volume of transformation in oil refinery and chemical industry. However, despite the general agreement on the carbocationic nature of the reaction intermediates, the initial steps and the true nature of the cations on the surface are still open to debate. On these points our basic knowledge has gained enormously from landmark experiments in physical organic chemistry with spectroscopic observations using liquid superacids as solvents. As the range of superacidity covers over 11 logarithmic units of the Hammett acidity scale, the mechanistic behavior of small alkanes vary accordingly. This allows for comparison with strong solid acids such as zeolite or others used in industry. Isotopic labeling of the alkane and the acids is a powerful tool used to understand the nature of the intermediates, as well as the reaction mechanism in which carbenium and carbonium ions intervene.