Kinetics, basic of mutarotation

The work of Brpnsted and Pedersen (23) on the catalytic decomposition of nitramide and the kinetic studies of Lowry and Faulkner (24) on the mutarotation of tetramethylglucose led to the formulation of a more general viewpoint on acids and bases which logically showed that the hydrogen ion and hydroxyl ion were not the unique carriers of acid and basic properties. An acid was defined as any substance capable of donating a proton, and a base any substance capable of accepting a proton. In accordance with this definition (Lowry, 25 Brpnsted, 26), the following substances are typical acids and bases ... 

Perlin, A. S., Action of Lead Tetraacetate on the Sugars, 14, 9-61 PERLIN, A. S., [Obituary of] Clifford Burrough Purves, 23, 1-10 Phillips, G. O., Photochemistry of Carbohydrates, 18, 9-59 PHILLIPS, G. O., Radiation Chemistry of Carbohydrates, 16, 13-58 Pigman, Ward, and Isbell, Horace S., Mutarotation of Sugars in Solution Part I. History, Basic Kinetics, and... 

Pigman, Ward, and Isbell, Horace S., Mutarotation of Sugars in Solution Part I. History, Basic Kinetics, and Composition of Sugar Solutions, 23, 11-57... 

Intramolecular proton migration results in isomerization with mutarotation, whereas formation and protonation of a symmetrically solvated carbanion results in simultaneous racemization and isomerization. In all cases studied, the kinetic data support the assumption that proton abstraction by the basic catalyst is rate-limiting. 

Although basically a ternary reaction, mutarotation may follow first- or second-order kinetics. As indicated earlier (p. 50), under the usual experimental conditions which involve water as the solvent in large excess and a fixed hydrogen-ion concentration, first-order kinetics are followed. Actually, the reaction usually appears to be second-order in aqueous system when the concentration of the catalyst is taken into consideration. This special situa-... 

Mutarotation of sugars in solution. Part I. History, basic kinetics, and composition of sugar solutions, W. W. Pigman and H. S. Isbell, Adv. Carbohydr. Chem., 23 (1968). 

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