Journal of Physical Chemistry A, Vol.121, No.44, 8474-8483, 2017
Quantum Yields of Nitrite (NO2-) from the Photolysis of Nitrate (NO3-) in Ice at 313 nm
Photochemical reactions of nitrate in snow release reactive nitrogen species via two channels, which produce (l) nitrogen dioxide (NO2) and hydroxyl radical ((OH)-O-center dot) and (2) nitrite (NO2-) and oxygen atom (O(P-3)). Quantum yields (phi) for these channels are generally well characterized, except for channel 2 in ice. In this study, we quantify phi(NO2-) in water ices and examine the impacts of pH and organic scavengers of (OH)-O-center dot. Compared to solution results, we find that nitrite quantum yields in ice are more sensitive to pH and that (OH)-O-center dot scavengers are less effective, although 2-propanol appears to work well. The temperature dependence (-30 to 25 degrees C) of phi(NO2-) in samples containing 2-propanol is well described by a single regression line, ln(phi(NO2-)) =-(1330 +/- 100)(1/T(K)) + (0.09 +/- 0.39). At -10 degrees C, the resulting quantum yield is 4.6 times larger than the previously reported (and recommended) value without an (OH)-O-center dot scavenger. Although some reports suggest nitrite is a minor product from nitrate photolysis, based on our current and past results, rates of photoproduction of NO2- and NO2 are similar at room temperature, while NO2- production dominates at lower temperatures in solution and ice.