Pressure dependent isotopic fractionation in the photolysis of formaldehyde-d2

Abstract

The isotope effects in formaldehyde photolysis are the key link between the δD of methane emissions and the δD of atmospheric in situ hydrogen production. A few recent studies have suggested that a pressure dependence in the isotopic fractionation can partly explain enrichment of deuterium with altitude in the atmosphere. The mechanism and the extent of this pressure dependency is, however, not adequately described. In the present work D2CO and H2CO were photolyzed in a static reaction chamber at bath gas pressures of 50, 200, 400, 600 and 1000 mbar; these experiments compliment and extend our earlier work with HDCO vs. H2CO. The UV lamps used for photolysis emit light at wavelengths that primarily dissociate formaldehyde into molecular products, CO and H2 or D2. The isotope effect k (H2CO)/ k (D2CO) Combining double low line 3.16 ± 0.03 at 1000 mbar is in good agreement with results from previous studies. Similarly to what was previously shown for k (H2CO)/ k (HDCO), the isotope effect decreased as pressure decreased. In addition, a model was constructed using RRKM theory to calculate the lifetime of excited formaldehyde on the S 0 surface, to investigate its role in the observed pressure dependent photolytic fractionation of deuterium. The model shows that part of the fractionation is a result of competition between the isotopologue dependent rates of unimolecular dissociation and collisional relaxation. We suggest that the remaining fractionation is due to isotope effects in the rate of the non-radiative transition from S 1 to S 0, which are not considered in the present model. © 2014 Author(s).