Infrared studies of sulfuric acid and its impact on polar and global ozone

• Main Author: Iraci, Laura Tracy
• Format: Dissertation
• Language: English
• Published: ProQuest Dissertations & Theses 01-01-1997
• Subjects: Analytical chemistry; Atmosphere; Atmospheric sciences
• ISBN: 9780591637083; 0591637081

Sulfuric acid aerosols are present throughout the lower stratosphere and play an important role in both polar and global ozone depletion. In the polar regions, stratospheric sulfate aerosols (SSAs) act as nuclei for the growth of polar stratospheric clouds (PSCs). Heterogeneous reactions can occur on these PSCs, leading to chlorine activation and catalytic ozone destruction. This thesis addresses the issue of polar ozone depletion through laboratory studies which examine the nucleation of PSCs on sulfuric acid. In addition, chemistry which occurs directly on sulfate aerosols may impact ozone at midlatitudes, and studies describing one such reaction are presented as well. To study the growth of type I PSCs on sulfuric acid, thin $\rm H\sb2SO\sb4$ films were exposed to water and nitric acid vapors at stratospheric temperatures. Fourier transform infrared spectroscopy was used to probe the phase of the sulfuric acid and to identify the HNO$\sb3$/H$\sb2$O films which condensed. Supercooled liquid sulfuric acid films showed uptake of HNO$\sb3$ to form ternary solutions, followed by crystallization of nitric acid trihydrate (NAT). When crystalline sulfuric acid tetrahydrate (SAT) films were exposed to nitric acid and water, condensation of a supercooled HNO$\sb3$/H$\sb2$O layer was often observed. As predicted by theory, some of the SAT crystal then dissolved, creating a ternary $\rm H\sb2SO\sb4/HNO\sb3/H\sb2O$ solution. From this solution, NAT nearly always crystallized, halting the phase change of sulfuric acid. If a supercooled nitric acid layer did not condense on frozen sulfuric acid, crystalline NAT was not deposited from the gas phase when S$\rm\sb{NAT}\leq41.$ At significantly higher supersaturations, NAT could be forced to condense on sulfuric acid, regardless of its phase. Calculations of the contact parameter from experimental data indicate that $m<0.79$ for NAT on SAT, predicting a significant barrier to nucleation of NAT from the gas phase. While PSCs can form only in the cold polar regions of the stratosphere, sulfuric acid aerosols can themselves provide surfaces for heterogeneous reactions on a global scale. Studies described here show that formaldehyde is taken up readily and indefinitely by sulfuric acid, and infrared spectra of the condensed phase suggest that polymerization of formaldehyde occurs in acidic solution, even at temperatures as low as 197 K. Reaction of formaldehyde with nitric acid in sulfuric acid has also been observed, converting HNO$\sb3$ to oxidized species and formaldehyde to formic acid. This reaction may have considerable impact on the atmospheric HNO$\sb3$/NO$\rm\sb{x}$ ratio, as its rate is likely comparable to the HNO$\sb3$ photolysis rate.