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Hydrolysis of N 2 O 5 and ClONO 2 on the H 2 SO 4 /HNO 3 /H 2 O ternary solutions under stratospheric conditions
Author(s) -
Zhang Renyi,
Leu MingTaun,
Keyser Leon F.
Publication year - 1995
Publication title -
geophysical research letters
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.007
H-Index - 273
eISSN - 1944-8007
pISSN - 0094-8276
DOI - 10.1029/95gl01177
Subject(s) - sulfuric acid , hydrolysis , analytical chemistry (journal) , chemistry , chemical ionization , mass spectrometry , chemical reaction , reaction rate constant , chemical kinetics , ionization , inorganic chemistry , kinetics , organic chemistry , chromatography , physics , ion , quantum mechanics
The reaction probabilities of N 2 O 5 and ClONO 2 with H 2 O on liquid sulfuric acid surfaces have been reexamined to determine the effect of HNO 3 on these two hydrolysis rates, using a fast flow reactor coupled to a chemical ionization mass spectrometer. The measurements were carried out by maintaining constant H 2 O and HNO 3 partial pressures and by varying temperatures between 227 and 195 K in order to mimic compositions representative of stratospheric aerosols. For experiments excluding HNO 3 , the reaction probability of N 2 O 5 hydrolysis was found to be near 0.1, independent of temperature and H 2 SO 4 content. This is in agreement with results previously measured under similar conditions. In the presence of gaseous HNO 3 at stratospheric concentrations, the reaction probability was observed to decrease from about 0.09 at 218 K to about 0.02–0.03 at 195 K for P H2O = 3.8 × 10 −4 −1.0 × 10 −3 Torr, showing that incorporation of HNO 3 into liquid sulfuric acid greatly retarded the N 2 O 5 hydrolysis. The ClONO 2 reaction with H 2 O on liquid sulfuric acid, on the other hand, did not appear to be affected by the presence of HNO 3 .