Assistant Professor of Chemistry
Location: Eshleman Science Center 306
What I Find Rewarding About D&E:
Small class sizes, campus amenities, ability to conduct independent research, friendly atmosphere, picturesque landscape.
- Ph.D. Physical Chemistry, Louisiana State University, Baton Rouge, La.
- B.S. Chemistry, University of Tennessee, Martin, Tenn.
- Department of Chemistry and Physics, Coastal Carolina University, 2010-2012
- Department of Chemistry and Physics, University of Tennessee at Martin, 2009-2010
- Department of Chemistry and Life Science, United States Military Academy at West Point, 1999-2003
- Department of Chemistry, United States Air Force Academy, 1988-1992
- General Chemistry
- Physical Chemistry
- Chemical Lab Principles
- Analytical Chemistry
- Analytical Techniques
- Quantitative Analysis
Research Interests/Professional Activities:
Temperature studies of the hydrolyses reactions of acid anhydrides. The aqueous hydrolysis of symmetric acid anhydrides leads to the formation of two molecules of acid. Much work has been done by other researchers in this general area, particularly with acetic and propionic anhydride. Studies have shown that the reactions occur both by simple hydrolysis and carboxylate-catalyzed hydrolysis (Butler, A. R., Gold, V.; J. Chem. Soc.; 1961; 2305). Temperature studies have been done on the simple hydrolysis of acetic anhydride (Rossall, B., Robertson, R. E.; Can. J. Chem.; 53; 1975; 869), but until now not on the acetate-catalyzed hydrolysis. Current studies have shown that the enthalpy and entropy of activation for the acetate-catalyzed hydrolysis are somewhat different than the corresponding values for simple hydrolysis (Wiseman, F. L. “New Insight on an Old Reaction – the Aqueous Hydrolysis of Acetic Anhydride”; Journal of Physical Organic Chemistry; Vol. 25; 2012; pp. 1105-1111.), suggesting a different transition structure. The studies further indicate the activation heat capacity is probably not a significant term, as was once thought. Instead the deviation from Eyring behavior at low temperatures as demonstrated by this study seems to indicate that the reverse step for the steady-state intermediate becomes unimportant at higher temperatures. In fact, the activation heat capacity has been implicated for the hydrolyses of several acid anhydrides. These reactions all need to be reinvestigated in light of the current findings.
Aqueous alcohol oxidation by the hypochlorite ion. It has recently been shown that organic alcohols can be oxidized to ketones in aqueous solution using the hypochlorite ion. In particular, some work has been done on the oxidation of cyclopentanol using the pH technique (Wiseman, F. L., unpublished results). In general, however, very little kinetic studies have been done on this type reaction. Preliminary results seem to indicate the mechanism may be pH dependent.
Development of a more accurate diffusion equation. Preliminary trajectory simulation studies on ideal vapor systems indicate that Fick’s second law of diffusion underestimates the rate of diffusion (Wiseman, F. L., unpublished results). Though yet to be proven, Fick’s second law likely represents the lowest diffusion rate possible (if this is the case, Fick’s law would be a limiting law). The upper limit for diffusion is effectively vacuum expansion, which can be easily derived from kinetic molecular theory. The rate term of the resulting equation is different from that in Fick’s second law. Although yet to be proven, the rate is likely dependent upon the relative masses of the bath and diffusing molecules. Simulation studies in which one-dimensional diffusion is monitored under a variety of conditions should guide the theoretical (or empirical) development of a more accurate diffusion equation.
- Wiseman, F. L.; “New Insight on an Old Reaction – the Aqueous Hydrolysis of Acetic Anhydride”; Journal of Physical Organic Chemistry; Vol. 25; 2012; pp. 1105-1111.
- Burns, D., Moore, B., Chynwat, V., Plitz, A., Rottmann, S., Wiseman, F.; “A Simplified Chemistry Module for Atmospheric Transport and Dispersion Models: Proof-of-Concept using SCIPUFF”; Atm. Env.; 2012; 56; 212.
- Wiseman, F. L.; “An Expression for the Drag Force of Small Spherical Particles in an Ideal-Gas Media Analyzed using Configuration-Specific Kinetic Molecular Theory”; Chem. Phys. Lett.; 2008; 465; 175.
- Wiseman, F. L.; “Configuration-Specific Kinetic Molecular Theory Applied to an Ideal Binary Gas Mixture”; J. Phys. Chem. A; 2006; 110; 11377.
- Wiseman, F. L.; “Configuration-Specific Kinetic Molecular Theory Applied to the Elastic Collisions of Hard Spherical Molecules”; J. Phys. Chem. A; 2006; 110; 6379.
- Wiseman, F. L.; “Monitoring the Rate of Solvolytic Decomposition of Benzenediazonium Tetrafluoroborate in Aqueous Media Using a pH Electrode”; J. Chem. Ed.; 2005; 82; 1841.
- Wells, J. R.; Wiseman, F. L.; Williams, D. C.; Baxley, J. S.; Smith, D. F.; “The Products of the Reaction of the Hydroxyl Radical with 2-Ethoxyethyl Acetate”; Int. J. Chem. Kin.; 1996; 28; 475.
- Wiseman, F. L.; Rice, A. G.; “Modifications to the Angle-Dependent Line of Normals Model for Gas-Phase Reaction Rate Constants”; J. Chem. Ed.; 1993; 70; 914.
- Wiseman, F. L.; Ozturk, F.; Zerner, M. C.; Eyler, J. R.; “Kinetic modeling of the reactions of C3H3+ with acetylene, deuteroacetylene, and diacetylene”; Int. J. Chem. Kin.; 1990; 22; Issue 11; 1189.
- Stone, D. A.; Wiseman, F. L.; Kilduff, J. E.; Koontz, S. L.; Davis, D. D.; “The Disappearance of Fuel Vapors in Fluorocarbon-Film Environmental Chambers. Experimental Observations and Kinetic Modeling”; Env. Sci. & Tech.; 1989; 23; 328.
- Wiseman, F. L.; Kestner, N. R.; “Theoretical studies of Broensted relations”; J. Phys. Chem.; 1984; 88; 4354.