Hot Water Induces an Acid-Catalyzed Reaction in Its Undissociated Form

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Abstract
Hot water in its undissociated form has been kinetically proven to induce a chemical reaction that does not undergo under ambient conditions in the absence of a strong acid. The water-induced and acid-catalyzed rate constants were separately determined for the dehydration of 1,4-butanediol by varying the oxonium ion (H+) concentration. It was found on the kinetic level over a wide range of temperature from moderate to supercritical that the undissociated form of water promotes the reaction at an effective acid concentration of 10−4–10−6 M. A strong density dependence of the reaction rate constant was further observed under supercritical condition, and is related to the anomalous temperature dependence of the rate constant near the critical point.

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