 Professor, Born 1957
B.S. 1979, Yale University
Ph.D. 1985, Harvard University
Room: 7321a
Phone: 608-262-8098
Email: nathanso@chem.wisc.edu
Position: Professor
Reactive Collisions of Sulfur Dioxide with Molten Carbonates, Thomas Krebs and Gilbert M. Nathanson, Invited article for special issue on Atmospheric Chemistry, Proceedings of the National Academy of Sciences, February 1 issue, (2010). HCI Uptake through Films of Pentanoic Acid and Pentanoic Acid/Hexanol Mixtures at the Surface of Sulfuric Acid, Daniel K. Burden, Alexis M. Johnson, and Gilbert M. Nathanson, Journal of Physical Chemistry A, 113, 14131 (2009). Collisions of DCl with a Solution Covered with Hydrophobic and Hydrophilic Ions: Tetrahexylammonium Bromide in Glycerol, Susan M. Brastad, Daniel R. Albert, Mingwei Huang, and Gilbert M. Nathanson, Journal of Physical Chemistry A, 113, 7422 (2009). Surfactant Control of Gas Transport and Reactions at the Surface of Sulfuric Acid, Seong-Chan Park, Daniel K. Burden, and Gilbert M. Nathanson, Accounts of Chemical Research, 42, 379 (2009). Scavenging by F- in Collisions of DCI with KF-Glycerol Solutions: Evidence for Formation of Interfacial [CIDF]-, Jennifer L. DeZwaan, Susan M. Brastad, and Gilbert M. Nathanson, Journal of Physical Chemistry C, 112, 15449 (2008). The Roles of Salt Concentration and Cation Charge in Collisions of Ar and DCl with Salty Glycerol Solutions of NaI and CaI2, Jennifer L. DeZwaan, Susan M. Brastad, and Gilbert M. Nathanson, Journal of Physical Chemistry C, 112, 3008 (2008). The Inhibition of N₂O₅ Hydrolysis in Sulfuric Acid by 1-Butanol and 1-Hexanol Surfactant Coatings, Seong-Chan Park, Daniel K. Burden, and Gilbert M. Nathanson, Journal of Physical Chemistry A, 111, 2921 (2007). Interfacial Interactions of DCl with Salty Glycerol Solutions of KI, NaI, LiI, and NaBr, Annabel H. Muenter, Jennifer L. DeZwaan, and Gilbert M. Nathanson, Journal of Physical Chemistry C, 111, 15043 (2007). Collisions of DCl with Pure and Salty Glycerol: Enhancement of Interfacial D→H Exchange by Dissolved NaI", Annabel H. Muenter, Jennifer L. DeZwaan, and Gilbert M. Nathanson, Journal of Physical Chemistry B, 110, 4881 (2006). Evaporation of Water and Uptake of HCl and HBr through Hexanol Films at the Surface of Supercooled Sulfuric Acid", Samuel V. Glass, Seong-Chan Park, and Gilbert M. Nathanson, Journal of Physical Chemistry A, 110, 7593 (2006). Collisions and Reactions of n-Propanol with Molten NaOH/KOH”, David J. Castro, Sonia M. Dragulin, Michelle Manning, and Gilbert M. Nathanson, Journal of Chemical Physics, 125, #144715 (2006). The Evaporation of Water through Butanol Films at the Surface of Supercooled Sulfuric Acid", Jennifer R. Lawrence, Samuel V. Glass, and Gilbert M. Nathanson, Journal of Physical Chemistry A, 109, 7449 (2005). Surfactant Control of Gas Uptake: The Effects of Butanol on HCl Entry into Supercooled Sulfuric Acid", Jennifer R. Lawrence, Samuel V. Glass, and Gilbert M. Nathanson, Journal of Physical Chemistry A, 109, 7458 (2005).
| Research Description
Molecular beam scattering experiments have blossomed into a universal technique for understanding and controlling reactions in the gas phase and on solid surfaces. Our research confronts a third frontier: reactions at the surfaces of pure liquids, solutions, and monolayer films. We use gas-liquid scattering experiments to explore collisions and reactions of gas molecules with liquids ranging from crude oils and liquid metals to pure and salty glycerol, sulfuric acid, and molten sodium hydroxide and sodium carbonate. These liquids are important industrially and in the atmosphere, where sulfuric acid aerosols play a role in ozone destruction. We are now embarking on experiments employing liquid microjets, which open up the possibility of investigating reactions with high vapor pressure liquids including hydrocarbon fuels and water itself.
The questions we ask are simple: what does the surface of a liquid "look like" atom by atom and "feel like" during the short time scale of a gas-liquid collision? How does an acidic molecule such as HCl dissolve and dissociate in liquid glycerol or in supercooled sulfuric acid? What are the interfacial analogs of bulk solvation, hydrogen bonding, the "like dissolves like" rule, proton exchange, and acid-base reactions?
Molecular beam scattering experiments can answer these questions. We direct a highly collimated and nearly monoenergetic beam of molecules at the surface of a continuously renewed, low vapor pressure liquid inside a vacuum chamber. These gases range from inert atoms and organic molecules to HCl, HBr, and SO2. After striking the liquid, the  molecules either scatter from the liquid or stick and dissolve, perhaps reacting with solvent molecules in the interfacial region of the liquid. A fraction of the reaction products may then desorb into the vacuum. The identity of the recoiling and desorbing molecules and their direction and velocity are monitored by a mass spectrometer. In many cases,we also measure interfacial and bulk reaction probabilities and the residence times of the gas molecules in the liquid. The data allow us to develop a true "blow-by-blow" description of the ways in which these gas molecules bounce off, dissolve in, and react with each liquid.
One example is shown in the animation on the right, which depicts collisions of HCl molecules with a droplet of sulfuric acid coated with hexanol, a soluble surfactant. HCl may dissolve in the acid by first protonating the alcohol and entering as Cl- and H+ (orange trajectory), providing an unexpected mechanism for the uptake of acidic gases into atmospheric aerosols. Other HCl molecules may bounce off the surface without reacting (green trajectory). These reactions are among many that control ozone concentrations in the atmosphere.
Our studies bring together the most recent advances in chemical kinetics and theories of liquid structure and dynamics. By carrying out controlled collisions between a gaseous solute molecule and a liquid solvent, we are helping to construct an intimate picture of the chemistry of gas-liquid interfaces.
Last Updated: February 8. 2010
University of Wisconsin Chancellor’s Distinguished Teaching Award, 2006 Fellow, American Association for the Advancement of Science, 2005 Chair, Gordon Research Conference on Dynamics at Surfaces, 2005 Closs Lecturer, Department of Chemistry, University of Chicago, 2003 Fellow of the American Physical Society, 2002 NSF Grant Continuation Award for Special Creativity, 2000 University of Wisconsin Romnes Faculty Fellowship, 1998 Welch Foundation Lecturer, Conference on Chemical Dynamics, 1994 Presidential Young Investigator Award, 1990-94 Upjohn Teaching Award, Department of Chemistry, University of Wisconsin, 1993 Camille and Henry Dreyfus Teacher-Scholar Award, 1992 Camille and Henry Dreyfus Young Faculty Award, 1988
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