Reaction of Chlorine Nitrate with Hydrogen Chloride and Water at Antarctic Stratospheric Temperatures

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Science  27 Nov 1987:
Vol. 238, Issue 4831, pp. 1258-1260
DOI: 10.1126/science.238.4831.1258


Laboratory studies of heterogeneous reactions important for ozone depletion over Antarctica are reported. The reaction of chlorine nitrate (ClONO2) with H20 and hydrogen chloride (HCl) on surfaces that simulate polar stratospheric clouds [ice and nitric acid (HNO3)—ice and sulfuric acid] are studied at temperatures relevant to the Antarctic stratosphere. The reaction of ClONO2 on ice and certain mixtures of HNO3 and ice proceeded readily. The sticking coefficient of ClONO2 on ice of 0.009 ± 0.002 was observed. A reaction produced gas-phase hypochlorous acid (HOCl) and condensed-phase HNO3; HOC1 underwent a secondary reaction on ice producing dichlorine monoxide (Cl2O). In addition to the reaction with H20, ClONO2 reacted with HCl on ice to form gas-phase chlorine (Cl2) and condensed-phase HNO3. Essentially all of the HCl in the bulk of the ice can react with ClONO2 on the ice surface. The gaseous products of the above reactions, HOCl, Cl20, and Cl2, could readily photolyze in the Antarctic spring to produce active chlorine for ozone depletion. Furthermore, the formation of condensed-phase HNO3 could serve as a sink for odd nitrogen species that would otherwise scavenge the active chlorine.