Enhanced Kinetics of Pseudo First-Order Hydrolysis in Liquid Phase Coexistent with Ice

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 117; no. 41; pp. 10619 - 10625
• Main Authors: Anzo, Kenji, Harada, Makoto, Okada, Tetsuo
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 17.10.2013
• Subjects: Basicity; Chemistry; Concentration (composition); Exact sciences and technology; Freezing; General and physical chemistry; Hydrolysis; Liquid phases; Reaction kinetics; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; Walls; Water; Hydrolysis; Fluorescein; pH; Ice; Acetate; Kinetics; Liquid phase; Triatomic molecule; Chemical reactivity; Inorganic compound
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp409126p

The reaction rate of the hydrolysis of fluorescein diacetate (FDA) is several times larger in the frozen state than that in the unfrozen solution of the same composition at the same temperature. The freeze concentration of reactants in the liquid phase expelled form ice crystals cannot explain the kinetic enhancement of pseudo first order reactions such as the FDA hydrolysis. However, the reaction rate increases as the freeze concentration ratio becomes larger at a constant temperature. Direct pH measurements have revealed that the basicity of the liquid phase is unchanged at any concentration ratio, suggesting that the reactivity enhancement is not caused by increased basicity. The reaction rate enhancement is clearly related to the size of the space in which the liquid phase is confined upon freezing. The ice wall itself or the water structure formed near the wall should thus be responsible for this kinetic enhancement.