Nitrile Chemistry in Titan's Atmosphere: Low Temperature Rate Constants for H + Cyanoacetylene Reaction

Details Nitrile Chemistry in Titan's Atmosphere: Low Temperature Rate Constants for H + Cyanoacetylene Reaction Nitrile Chemistry in Titan's Atmosphere: Low Temperature Rate Constants for H + Cyanoacetylene Reaction

May 2003

adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=2003dps....35.1202c&link_type=abstract

American Astronomical Society, DPS meeting #35, #12.02; Bulletin of the American Astronomical Society, Vol. 35, p.931

Astronomy and Astrophysics

Astronomy

1

Scientific paper

Cyanoacetylene (HC3N) is one of the few nitrile compounds observed in the atmosphere of Titan by Voyager and from the ground. The three body reaction H + HC3N + M -> products (1) constitutes one of the important loss processes for cyanoacetylene in the photochemical models of the Titan atmosphere; e.g. the 1984 model of Yung, Allen and Pinto and the 1995 model of Toublanc et al. The models calculate a mixing ratio for HC3N that differs considerably from that derived from the observations. The rate constant for Reaction 1 has never been measured. The models use a value equal to that for the reaction H + C2H2 + M. We have measured the rate constant for Reaction 1 at T = 298 K, 250 K, and 200 K with helium as the bath gas at a pressure of 1 Torr; additionally, measurements of k1 were made at T = 298 K with P = 0.5 and 2.0 Torr. The experimental technique is discharge fast flow with mass spectrometric detection and monitoring of the first order decay of HC3N. The H atom, which is the excess reactant by a factor of 100-660, is generated via the fast reaction F + H2 -> H + HF. For each temperature and pressure, first order rate constants (kobs) were measured for a range of [H] 1 - 13 x 1013 molecule cm-3. The bimolecular rate constants (k1) were derived from the slopes of the plots of kobs versus [H]. Within our experimental uncertainty, we did not see a pressure dependence of the bimolecular rate constant for the limited pressure range of 0.5 - 2 Torr at T = 298K. This indicates that the rate constant has reached its high-pressure limit by 1 Torr for T <= 298 K. The results are k1(298K) = 2.1x10--13, k1(250K) = 1.5x10--13 and k1(200K) = 0.93x10--13, all in units of cm3 molecule-1 s-1. These rate constants can be fit by the Arrhenius expression k1 = 1.1x10-12exp(-500/T) cm3 molecule-1 s-1. These measured rate constants are about a factor of 50 faster than those estimated by analogy with the H + C2H2 reaction and have a much weaker temperature dependence. Theoretical calculations of the rate constant were performed to understand the temperature dependence of Reaction 1. These results could render Reaction 1 a more important loss process in Titan's atmosphere than previously estimated.
The Planetary Atmospheres Program of NASA Headquarters supported this research.

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