Engineering topics

Iraci, Laura T.

Publications and source records attributed to Iraci, Laura T..

40 records · Page 3

NASA NTRS2001

Heterogeneous Uptake and Conversion of HOBr on H2SO4 at Upper Tropospheric and Stratospheric Temperatures (255 - 210 K)

Halogen species are known to catalytically destroy ozone in several different regions of the atmosphere. In addition to directly destroying ozone, bromine compounds can indirectly enhance ozone loss through coupling to other radical families. Hypobromous acid (HOBr), a key species in the linkage of BrOx to ClOx and HOx, is produced by the hydrolysis of BrONO2 on sulfate aerosols, and thus the heterogeneous behavior of HOBr must be understood. We have measured the solubility of HOBr in 45 to 70 percent by weight sulfuric acid solutions. Over the temperature range 208 to 255 K, HOBr is very soluble in sulfuric acid, H(*) = 10(exp 4) to 10(exp 8) M/atm. The solubility is temperature dependent, and our results agree well with those of Waschewsky and Abbott for 60 percent by weight H2SO4. HOBr is nearly as soluble as HBr, indicating that equilibrium concentrations of HOBr could approach those of HBr in sulfuric acid aerosols. Despite the high solubility of HOBr, stratospheric aerosol volumes are not large enough to sequester a significant fraction of inorganic bromine from the gas phase. Uptake of HOBr was nearly always accompanied by reaction, producing Br2O and possibly Br2. The effect of this bromine conversion pathway on the HOx and ClOx families, particularly at temperatures as warm as 255 K, will be considered.

Iraci, Laura T.↗

NASA NTRS2001

Methanol Uptake By Low Temperature Aqueous Sulfuric Acid Solutions

To evaluate the role of upper tropospheric and lower stratospheric aerosols in the global budget of methanol, the solubility and reactivity of CH3OH in aqueous sulfuric acid solutions are under investigation. Using standard uptake techniques in a Knudsen cell reactor, we have measured the effective Henry's law coefficient, H(*), for methanol dissolution into 45 to 70 percent by weight H2SO4. We find that methanol solubility ranges from 10(exp 5) to 10(exp 8) M/atm and increases with decreasing temperature and with increasing sulfuric acid content. These solubility measurements include uptake due to physical solvation and all rapid equilibria which are established in solution. Our data indicate that simple uptake by aqueous sulfuric acid particles will not be a significant sink for methanol in the UT/LS. These results differ from those recently reported in the literature, and an explanation of this disparity will be presented. In addition to solvation, reaction between primary alcohols and sulfuric acid does occur, leading to the production of alkyl sulfates. Literature values for the rate of this reaction suggest that formation of CH3OSO3H may proceed in the atmosphere but is not significant under our experimental conditions. Results obtained using a complementary equilibrium measurement technique confirm this directly. In addition, the extent of methanol sequestration via formation of mono- and dimethylsulfate will be evaluated under several atmospheric conditions.

Iraci, Laura T.↗

NASA NTRS1994

Growth of nitric acid hydrates on thin sulfuric acid films

Type I polar stratospheric clouds (PSCs) are thought to nucleate and grow on stratospheric sulfate aerosols (SSAs). To model this system, thin sulfuric acid films were exposed to water and nitric acid vapors (1-3 x 10(exp -4) Torr H2O and 1-2.5 x 10(exp -6) Torr HNO3) and subjected to cooling and heating cycles. Fourier Transform Infrared (FTIR) spectroscopy was used to probe the phase of the sulfuric acid and to identify the HNO3/H2O films that condensed. Nitric acid trihydrate (NAT) was observed to grow on crystalline sulfuric acid tetrahydrate (SAT) films. NAT also condensed in/on supercooled H2SO4 films without causing crystallization of the sulfuric acid. This growth is consistent with NAT nucleation from ternary solutions as the first step in PSC formation.

Iraci, Laura T.↗

NASA NTRS1993

Fourier transform-infrared studies of thin H2SO4/H2O films: Formation, water uptake, and solid-liquid phase changes

Fourier transform-infrared (FTIR) spectroscopy was used to examine films representative of stratospheric sulfuric acid aerosols. Thin films of sulfuric acid were formed in situ by the condensed phase reaction of SO3 with H2O. FTIR spectra show that the sulfuric acid films absorb water while cooling in the presence of water vapor. Using stratospheric water pressures, the most dilute solutions observed were greater than 40 wt % before simultaneous ice formation and sulfuric acid freezing occurred. FTIR spectra also revealed that the sulfuric acid films crystallized mainly as sulfuric acid tetrahydrate (SAT). Crystallization occurred either when the composition was about 60 wt% H2SO4 or after ice formed on the films at temperatures 1-4 K below the ice frost point. Finally, we determined that the melting point for SAT depended on the background water pressure and was 216-219 K in the presence of 4 x 10(exp -4) Torr H2O. Our results suggest that once frozen, sulfuric acid aerosols in the stratosphere are likely to melt at these temperatures, 30 K colder than previously thought.

Middlebrook, Ann M.↗