Anna Esperanza Quizon Legaspi, Yoshito Oshima, Makoto Akizuki
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Abstract
Water's effect on o-phthalic acid decarboxylation was studied by varying the pressure from (20 to 40) MPa at (380, 400, and 420) °C. The rate constants decreased with increasing pressure at (400 and 420) °C, but remained nearly constant at 380 °C. The trends at (400 and 420) °C were explained using Kirkwood theory, which proposed preferential solvation of the reactant over the transition state. The 380 °C trend was thought to be explained by solvent inhomogeneities and water's peculiar behavior near the critical point. Solvent inhomogeneities were most likely responsible when rates remained low despite low dielectric constant values. These inhomogeneities could have caused a higher local dielectric constant around the solute, suppressing the rate in a manner similar to the higher-pressure region. Water, according to these findings, has the greatest influence on the reaction via solvation.
期刊介绍：
The Journal of Supercritical Fluids is an international journal devoted to the fundamental and applied aspects of supercritical fluids and processes. Its aim is to provide a focused platform for academic and industrial researchers to report their findings and to have ready access to the advances in this rapidly growing field. Its coverage is multidisciplinary and includes both basic and applied topics.
Thermodynamics and phase equilibria, reaction kinetics and rate processes, thermal and transport properties, and all topics related to processing such as separations (extraction, fractionation, purification, chromatography) nucleation and impregnation are within the scope. Accounts of specific engineering applications such as those encountered in food, fuel, natural products, minerals, pharmaceuticals and polymer industries are included. Topics related to high pressure equipment design, analytical techniques, sensors, and process control methodologies are also within the scope of the journal.
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