HETEROGENEOUS INTERACTIONS OF CLONO2 AND HCL WITH SULFURIC-ACID TETRAHYDRATE - IMPLICATIONS FOR THE STRATOSPHERE

The reaction probabilities for ClONO2 + H2O --> HOCl + HNO3 (1) and Cl ONO2 + HCl --> Cl-2 + HNO3 (2) have been investigated on sulfuric acid tetrahydrate (SAT, H2SO4.4H(2)O) surfaces at temperatures between 190 and 230 K and at reactant concentrations that are typical in the lowe r stratosphere, using a fast-flow reactor coupled to a quadrupole mass spectrometer. The results indicate that the reaction probabilities as well as HCl uptake depend strongly on the thermodynamic state of SAT surface: they decrease significantly with decreasing H2O partial press ure at a given temperature, and decrease with increasing temperature a t a given H2O partial pressure, as the SAT changes from the H2O-rich f orm to the H2SO4-rich form. For H2O-rich SAT at 195 K gamma(1) approxi mate to 0.01 and gamma(2) greater than or equal to 0.1, whereas the va lues for H2SO4-rich SAT decrease by more than 2 orders of magnitude. A t low concentrations of HCl, close to those found in the stratosphere, the amount of HCl taken up by H2O-rich SAT films corresponds to a cov erage of the order of a tenth of a monolayer (approximate to 10(14) mo lecules cm(-2)); H2SO4-rich SAT films take up 2 orders of magnitude le ss HCl (<10(12) molecules cm(-2)). Substantial HCl uptake at high HCl concentrations is also observed, as a result of surface melting. The d ata reveal that frozen stratospheric sulfate aerosols may play an impo rtant role in chlorine activation in the winter polar stratosphere via processes similar to those occurring on the surfaces of polar stratos pheric cloud particles.