Journal of Physical Chemistry A, Vol.107, No.39, 7809-7817, 2003
The atmospheric fate of C-3-C-6 hydroxyalkyl nitrates
Rate coefficients for the reaction of OH radical with eleven C-3-C-6 hydroxyalkyl nitrates and with two C-4 hydroxy nitrates containing a double bond were determined at atmospheric pressure and 296 +/- 2 K. The rate coefficients were measured in a photochemical reactor by the relative rate technique, employing solid-phase microextraction (SPME) coupled to gas chromatography (GC) for detection of the organic reactants. Hydroxyalkyl nitrates react faster than alkyl nitrates with the OH radical. The rate coefficients increase with increasing chain length and separation between the hydroxy and the nitrooxy groups. By including different loss processes such as photolysis, gas-phase reactions, and solubility, the tropospheric lifetime of C-3-C-6 hydroxyalkyl nitrates is estimated to range between 0.5 and 4.5 days. Due to their higher reactivity and solubility, hydroxyalkyl nitrates have a shorter atmospheric lifetime than alkyl nitrates.