title: Reaction kinetics and critical phenomena: iodination of acetone in isobutyric acid + water near the consolute point.
abstract: The rate of iodination of acetone has been measured as a function of temperature in the binary solvent isobutyric acid (IBA) + water near the upper consolute point. The reaction mixture was prepared by the addition of acetone, iodine, and potassium iodide to IBA + water at its critical composition of 38.8 mass % IBA. The value of the critical temperature determined immediately after mixing was 25.43 degrees C. Aliquots were extracted from the mixture at regular intervals in order to follow the time course of the reaction. After dilution of the aliquot with water to quench the reaction, the concentration of triiodide ion was determined by the measurement of the optical density at a wavelength of 565 nm. These measurements showed that the kinetics were zeroth order. When at the end of 24 h the reaction had come to equilibrium, the critical temperature was determined again and found to be 24.83 degrees C. An Arrhenius plot of the temperature dependence of the observed rate constant, k(obs), was linear over the temperature range 27.00-38.00 degrees C, but between 25.43 and 27.00 degrees C, the values of k(obs) fell below the extrapolation of the Arrhenius line. This behavior is evidence in support of critical slowing down. Our experimental method and results are significant in three ways: (1) In contrast to in situ measurements of optical density, the determination of the optical density of diluted aliquots avoided any interference from critical opalescence. (2) The measured reaction rate exhibited critical slowing down. (3) The rate law was pseudo zeroth order both inside and outside the critical region, indicating that the reaction mechanism was unaffected by the presence of the critical point.
authors.affiliation: Department of Chemistry and Materials Science Graduate Program, University of Alabama in Huntsville, Huntsville, Alabama 35899, USA.
authors.forename: Baichuan
authors.initials: B
authors.lastname: Hu
authors.forename: James K
authors.initials: JK
authors.lastname: Baird
mesh_terms: D000096:Acetone / Q000737:chemistry*; D002087:Butyrates / Q000737:chemistry*; D058610:Isobutyrates; D007700:Kinetics; D013696:Temperature; D013816:Thermodynamics; D014867:Water / Q000737:chemistry*
chemical_list: D002087:Butyrates; D058610:Isobutyrates; D014867:Water; D000096:Acetone; C020380:isobutyric acid