1Institute for Marine and Atmospheric research Utrecht, Utrecht University, Utrecht, The Netherlands
2Institut für Chemie und Dynamik der Geosphäre ICG-2, Forschungszentrum Jülich GmbH, Jülich, Germany
3Faculty of Mathematics and Natural Sciences, University of Wuppertal, Wuppertal, Germany
*now at: Institut für Meteorologie und Klimaforschung, Karlsruhe Institute of Technology, Karlsruhe, Germany
Received: 04 Nov 2009 – Published in Atmos. Chem. Phys. Discuss.: 25 Nov 2009
Abstract. Formaldehyde of known, near-natural isotopic composition was photolyzed in the SAPHIR atmosphere simulation chamber under ambient conditions. The isotopic composition of the product H2 was used to determine the isotope effects in formaldehyde photolysis. The experiments are sensitive to the molecular photolysis channel, and the radical channel has only an indirect effect and cannot be effectively constrained. The molecular channel kinetic isotope effect KIEmol, the ratio of photolysis frequencies j(HCHO→CO+H2)/j(HCDO→CO+HD) at surface pressure, is determined to be KIEmol=1.63−0.046+0.038. This is similar to the kinetic isotope effect for the total removal of HCHO from a recent relative rate experiment (KIEtot=1.58±0.03), which indicates that the KIEs in the molecular and radical photolysis channels at surface pressure (≈100 kPa) may not be as different as described previously in the literature.
Revised: 26 Apr 2010 – Accepted: 11 May 2010 – Published: 16 Jun 2010
Röckmann, T., Walter, S., Bohn, B., Wegener, R., Spahn, H., Brauers, T., Tillmann, R., Schlosser, E., Koppmann, R., and Rohrer, F.: Isotope effect in the formation of H2 from H2CO studied at the atmospheric simulation chamber SAPHIR, Atmos. Chem. Phys., 10, 5343-5357, doi:10.5194/acp-10-5343-2010, 2010.