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At least 19 records

H2O-H2SO4 system in Venus' clouds and OCS, CO, and H2SO4 profiles in Venus' troposphere

A coupled problem of diffusion and condensation is solved for the H2SO4-H2O system in Venus' cloud layer. The position of the lower cloud boundary and profiles of the H2O and H2SO4 vapor mixing ratios and of the H2O/H2SO4 ratio of sulfuric acid aerosol and its flux are calculated as functions of the column photochemical production rate of sulfuric acid, Phi(sub H2SO4). Variations of the lower cloud boundary are considered. Our basic model, which is constrained to yield f(sub H2O) (30 km) = 30 ppm (Pollack et al. 1993), predicts the position of the lower cloud boundary at 48.4 km coinciding with the mean Pioneer Venus value, the peak H2SO4 mixing ratio of 5.4 ppm, and the H2SO4 production rate Phi(sub H2SO4) = 2.2 x 10(exp 12)/sq cm/s. The sulfur to sulfuric acid mass flux ratio in the clouds is 1:27 in this model, and the mass loading ratio may be larger than this value if sulfur particles are smaller than those of sulfuric acid. The model suggests that the extinction coefficient of sulfuric acid particles with radius 3.7 micrometers (mode 3) is equal to 0.3/km in the middle cloud layer. The downward flux of CO is equal to 1.7 x 10(exp 12)/sq cm/s in this model. Our second model, which is constrained to yield f(sub H2O) = 10 ppm at the lower cloud boundary, close to the value measured by the Magellan radiooccultations, predicts the position of this boundary to be at 46.5 km, which agrees with the Magellan data; f(sub H2O) (30 km) = 90 ppm, close to the data of Moroz et al. (1983) at this altitude; Phi(sub H2SO4) = 6.4 x 10(exp 12)/sq cm/s; and Phi(sub co) = 4.2 x 10(exp 12)/sq cm/s. The S/H2SO4 flux mass ratio is 1:18, and the extinction coefficient of the mode 3 sulfuric acid particles is equal to 0.9 km in the middle cloud layer. A strong gradient of the H2SO4 vapor mixing ratio near the bottom of the cloud layer drives a large upward flux of H2SO4, which condenses and forms the excessive downward flux of liquid sulfuric acid, which is larger by a factor of 4-7 than the flux in the middle cloud layer. This is the mechanism of formation of the lower cloud layer. Variations of the lower cloud layer are discussed. Our modeling of the OCS and CO profiles in the lower atmosphere measured by Pollack et al. (1993) provides a reasonable explanation of these data and shows that the rate coefficient of the reaction SO3 + CO yields CO2 + SO2 is equal to 10(exp -11) exp(-(13,100 +/- 1000)/T) cc/s. The main channel of the reaction between SO3 and OCS is CO2 + (SO)2, and its rate coefficient is equal to 10(exp -11) exp(-(8900 +/- 500)/T) cc/s. In the conditions of Venus' lower atmosphere, (SO)2 is removed by the reaction (SO)2 + OCS yields CO + S2 + SO2. The model predicts an OCS mixing ratio of 28 ppm near the surface.

Krasnopolsky, V. A.↗

H2O-H2SO4 system in Venus' clouds and OCS, CO, and H2SO4 profiles in Venus' troposphere

A coupled problem of diffusion and condensation is solved for the H2SO4-H2O system in Venus' cloud layer. The position of the lower cloud boundary, profiles of the H2O and H2SO vapor mixing ratios, and of the H2O/H2SO4 ratio of sulfuric acid aerosol and its flux are calculated as functions of the column photochemical production rate of sulfuric acid. Variations of the lower cloud boundary are considered. Our basic model, which is constrained to yield f(sub H2O)(30km) = 30 ppm, predicts the position of the lower cloud boundary at 48.4 km coinciding with the mean Pioneer Venus value, the peak H2SO4 mixing ratio of 5.4 ppm, and the H2SO4 production rate phi(sub H2SO4) = 2.2 x 10(exp 12) cm(exp -2)s(exp -1).

Krasnopolsky, V. A.↗

H2SO4-HNO3-H2O ternary system in the stratosphere

Estimation of the equilibrium vapor pressure over the ternary system H2SO4-HNO3-H2O to study the possibility of stratospheric aerosol formation involving HNO3. It is shown that the vapor pressures for the ternary system H2SO4-HNO3-H2O with weight composition around 70-80% H2SO4, 10-20% HNO3, 10-20% H2O at -50 C are below the order of 10 to the minus 8th mm Hg. It is concluded that there exists more than sufficient nitric acid and water vapor in the stratosphere to participate in ternary system aerosol formation at -50 C. Therefore, HNO3 should be present in stratospheric aerosols, provided that H2SO4 is also present.

Kiang, C. S.↗

Results from 13-cm absorptivity and H2SO4 abundance profiles from the Season 10 (1986) Pioneer Venus Orbiter radio occultation experiment

Results are reported from 13-cm radio-occultation absorptivity measurements of H2SO4 in the northern-hemisphere atmosphere of Venus, obtained by the Pioneer Venus Orbiter on 23 orbits during late 1986 and early 1987. The theoretical basis of the occultation measurements is explained; the error-analysis procedures are outlined; and the data are presented in tables and graphs. The abundance and distribution of gaseous H2SO4 in the equatorial zone (11-25 deg N) are found to be significantly different from those at latitudes above 36 deg N, and evidence for a reduction in H2SO4 abundance since the 1979 measurements is detected.

Jenkins, Jon M.↗

Laboratory measurement of the millimeter wave properties of liquid sulfuric acid (H2SO4)

The methodology and the results of laboratory measurements of the millimeter wave properties of liquid sulfuric acid are presented. Measurements conducted at 30-40 and 90-100 GHz are reported, using different concentrations of liquid H2SO4. The measured data are used to compute the expected opacity of H2SO4 condensates and their effects on the millimeter wave emission from Venus. The cloud condensate is found to have an effect on the emission from Venus. The calculated decrease in brightness temperature is well below the observed decrease in brightness temperature found by de Pater et al. (1991). It is suggested that other constituents such as gaseous H2SO4 also affect the observed variation in the brightness temperature.

Fahd, Antoine K.↗

An Experimental Study of Atmospheric Homogeneous Nucleation: Cluster Growth and Gas-Particle Reactions of H2SO4

The work proposed on this project included both field and laboratory studies. The laboratory studies were to consist of measurements of H2SO4 uptake and evaporation from aerosols of varying chemical composition, while the field component would include measurements of H2SO4 and other compounds which would be conducted as part of a large field campaign. By chance, the opportunity to conduct such an H2SO4/aerosol/ultrafine particle study in conjunction with an OH intercomparison/photochemistry study became available very early in this project (September 1993). This study was conducted at Caribou, Colorado in conjunction with several other groups from NCAR, NOAA and a number of universities. Our group measured OH, H2SO4, SO2, and H20, while Dr. McMurfy's group measured ultrafine particles, and total particle number and size distribution. In addition measurements of HO2/RO2, O3, NO, NO2, NO(y) CO, hydrocarbons, CH2O, and other chemical compounds and meteorological parameters were performed by the other participants and a new laser oblation/mass spectrometry technique was also employed by the NOAA Aeronomy Laboratory to study aerosol composition. The study of aerosol production and growth in conjunction with photochemical measurements is highly advantageous because particle growth precursors such as H2SO4.or MSA are formed by OH initiated sulfur oxidation. The large number of hydrocarbon measurements included in this study were also important in understanding particle growth.

Eisele, F. L.↗

High-resolution spectroscopy of H2SO4, HDSO4, and D2SO4 vapor in the region 1200-10,000 cm(-1)

The high-resolution (0.05 cm(-1)) spectra of gas-phase H2SO4, HDSO4, and D2SO4 were measured over the frequency region 1200-10,000 cm(-1) using Fourier-transform infrared spectroscopy. The increased resolution of this work compared with previous studies has lead to an improved vibrational analysis of H2SO4. This study has answered unresolved questions about combination bands and overlapping features from previous gas-phase spectroscopic studies of H2SO4 and marks the first experimental measurement of the nu8 and nu15 torsional vibrations in this molecule. This work leads to a brief discussion on vibrational mode mixing in sulfuric acid.

Deuterium/chemistry↗

Materials Data on H2SO4 by Materials Project

H2SO4 crystallizes in the monoclinic P2_1/c space group. The structure is one-dimensional and consists of two H2SO4 ribbons oriented in the (0, 1, 0) direction. there are two inequivalent H1+ sites. In the first H1+ site, H1+ is bonded in a distorted linear geometry to two O2- atoms. There is one shorter (1.02 Å) and one longer (1.63 Å) H–O bond length. In the second H1+ site, H1+ is bonded in a distorted linear geometry to two O2- atoms. There is one shorter (1.01 Å) and one longer (1.63 Å) H–O bond length. S6+ is bonded in a tetrahedral geometry to four O2- atoms. There are a spread of S–O bond distances ranging from 1.44–1.56 Å. There are four inequivalent O2- sites. In the first O2- site, O2- is bonded in a bent 120 degrees geometry to one H1+ and one S6+ atom. In the second O2- site, O2- is bonded in a distorted water-like geometry to one H1+ and one S6+ atom. In the third O2- site, O2- is bonded in a bent 120 degrees geometry to one H1+ and one S6+ atom. In the fourth O2- site, O2- is bonded in a bent 150 degrees geometry to one H1+ and one S6+ atom.

36 MATERIALS SCIENCE↗

Materials Data on H2SO4 by Materials Project

H2SO4 crystallizes in the monoclinic C2 space group. The structure is two-dimensional and consists of two H2SO4 sheets oriented in the (0, 0, 1) direction. H1+ is bonded in a distorted single-bond geometry to two O2- atoms. There is one shorter (1.01 Å) and one longer (1.66 Å) H–O bond length. S6+ is bonded in a tetrahedral geometry to four O2- atoms. There is two shorter (1.44 Å) and two longer (1.56 Å) S–O bond length. There are two inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one H1+ and one S6+ atom. In the second O2- site, O2- is bonded in a bent 120 degrees geometry to one H1+ and one S6+ atom.

36 MATERIALS SCIENCE↗

Materials Data on H2SO4 by Materials Project

H2SO4 crystallizes in the monoclinic C2/c space group. The structure is two-dimensional and consists of two H2SO4 sheets oriented in the (0, 0, 1) direction. H1+ is bonded in a distorted single-bond geometry to two O2- atoms. There is one shorter (1.01 Å) and one longer (1.66 Å) H–O bond length. S6+ is bonded in a tetrahedral geometry to four O2- atoms. There is two shorter (1.44 Å) and two longer (1.56 Å) S–O bond length. There are two inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one H1+ and one S6+ atom. In the second O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one H1+ and one S6+ atom.

36 MATERIALS SCIENCE↗

Infrared Absorption Spectra of H2SO4, SO3, SO2, and H2O at 300C and 350C

Mid infrared absorption spectra of sulfuric acid (H2SO4), sulfur trioxide (SO3), sulfur dioxide (SO2), and water (H2O) were collected in a high temperature gas cell operating at either 300C or 350C. The spectra were collected using tunable external cavity quantum cascade lasers (ECQCLs) tuning, which were capable of operating over the wavelength range from approximately 7 microns to 9 microns, where H2SO4 and SO3 have their strongest absorption features. The spectra can be used as a library for developing gas sensors.

infrared absorption↗

Knowledge of the systems H2O-SO3-N2O3. Report 1: The system H2SO4-H2O-N2O3

The amount of N2O3 being absorbed in 50-100% H2SO4 at 19, 60, and 95 C is directly proportional to the acid concentration and inversely proportional to the temperature. NO+ formation according to the above-formulated equation occurs only at H2SO4 concentrations greater than 52%. Absorption in highly concentrated sulfuric acid results in the formation of crystalline NOHSO4.

Stopperka, K.↗

Experimental study of cluster formation in binary mixture of H2O and H2SO4 vapors in the presence of an ionizing radiation source

Molecular clusters formed in pure nitrogen containing H2O and H2SO4 vapors and exposed to a 3 mCi Ni63 beta source were studied in the mass range 50 to 780 amu using a quadrupole mass spectrometer. Measurements were made under several combinations of relative humidity and relative acidity ranging from 0.7 to 7.5 percent and 0.00047 to 0.06333 percent, respectively. The number of H2SO4 molecules in the clusters observed ranged from 1 to 7 whereas the number of H2O molecules ranged from 1 to 16. The experimental cluster spectra differ considerably from those calculated using the classical nucleation theory. First order calculations using modified surface tension values and including the effects of multipole moments of the nucleating molecules indicate that these effects may be enough to explain the difference between the measured and the calculated spectra.

Singh, J. J.↗

Calculation of composition distribution of ultrafine ion-H2O-H2SO4 clusters using a modified binary ion nucleation theory

Thomson's ion nucleation theory was modified to include the effects of curvature dependence of the microscopic surface tension of field dependent, nonlinear, dielectric properties of the liquid; and of sulfuric acid hydrate formation in binary mixtures of water and sulfuric acid vapors. The modified theory leads to a broadening of the ion cluster spectrum, and shifts it towards larger numbers of H2O and H2SO4 molecules. Whether there is more shifting towards larger numbers of H2O or H2SO4 molecules depends on the relative humidity and relative acidity of the mixture. Usually, a broadening of the spectrum is accompanied by a lowering of the mean cluster intensity. For fixed values of relative humidity and relative acidity, a similar broadening pattern is observed when the temperature is lowered. These features of the modified theory illustrate that a trace of sulfuric acid can facilitate the formation of ultrafine, stable, prenucleation ion clusters as well as the growth of the prenucleation ion clusters towards the critical saddle point conditions, even with low values of relative humidity and relative acidity.

Singh, J. J.↗

Satellite remote sensing of H2SO4 aerosol using the 8- to 12-microns window region: Application to Mount Pinatubo

Monitoring stratospheric aerosols containing H2SO4 using the brightness temperature (BT) difference between 11 and 8.3 microns (BT(sub 8)-BT(sub 11)) spectral channels is demonstrated using theoretical calculations and satellite observations. Assuming an aqueous solution of 50% and 75% sulfuric acid, radiative transfer calculations indicate that over oceans an increase in the optical depth of the stratospheric aerosol results in an increase in BT(sub 8)-BT(sub 11). Theoretical simulations suggest that the technique is sensitive to visible optical depths greater than approximately 0.15. The simulations also demonstrate a lack of sensitivity to the particle size distribution. Changes in pre- and post-Pinatubo observations by the High-resolution Infrared Radiation Sounder 2 (HIRS2) on board the NOAA 10 are consistent with observed optical depth measurements and confirm the sensitivity of these channels to the presence of the aerosol. The technique is also applied to cold tropical convective clouds and desert regions where the signal, though evident, is less conclusive. Time series analysis is applied to the NOAA 10 and NOAA 12 combined BT(sub 8-BT(sub 11) observations to detect the periodicity of the spread of the volcanic aerosol. Over a region of the southern Pacific a 18- to 26-day period is present. Model simulations were conducted to demonstrate a trispectral with observations near 8, 11, and 12 microns. The trispectral approach has high potential in that the spectral signature of cirrus, water vapor, and H2SO4 aerosols are different. Observations from NOAA 10 and NOAA 11 are combined to demonstrate the capabilities of these infrared wavelengths of detecting the aerosol. The signal is clearly evident when a region of the South Atlantic is compared for pre- and post-Pinatubo conditions.

Ackerman, Steven A.↗

Measurement of OH, H2SO4, MSA, and HNO3 Aboard the P-3B Aircraft

This paper addresses the measurement of OH, H2SO4, MSA, and HNO3 aboard the P-3B aircraft under the following headings: 1) Performance Report; 2) Highlights of OH, H2SO4, and MSA Measurements Made Aboard the NASA P-3B During TRACE-P; 3) Development and characteristics of an airborne-based instrument used to measure nitric acid during the NASA TRACE-P field experiment.

Eisele, F. L.↗

Materials Data on H2SO4 by Materials Project

H2SO4 is Protactinium-like structured and crystallizes in the monoclinic Cc space group. The structure is zero-dimensional and consists of four sulfuric acid molecules. there are two inequivalent H1+ sites. In the first H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.99 Å. In the second H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.99 Å. S6+ is bonded in a tetrahedral geometry to four O2- atoms. There are a spread of S–O bond distances ranging from 1.44–1.58 Å. There are four inequivalent O2- sites. In the first O2- site, O2- is bonded in a single-bond geometry to one S6+ atom. In the second O2- site, O2- is bonded in a distorted water-like geometry to one H1+ and one S6+ atom. In the third O2- site, O2- is bonded in a bent 120 degrees geometry to one H1+ and one S6+ atom. In the fourth O2- site, O2- is bonded in a single-bond geometry to one S6+ atom.

36 MATERIALS SCIENCE↗

Materials Data on H2SO4 by Materials Project

H2SO4 crystallizes in the monoclinic Cc space group. The structure is zero-dimensional and consists of four sulfuric acid molecules. there are two inequivalent H1+ sites. In the first H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.99 Å. In the second H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.98 Å. S6+ is bonded in a tetrahedral geometry to four O2- atoms. There are a spread of S–O bond distances ranging from 1.43–1.59 Å. There are four inequivalent O2- sites. In the first O2- site, O2- is bonded in a single-bond geometry to one S6+ atom. In the second O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one H1+ and one S6+ atom. In the third O2- site, O2- is bonded in a water-like geometry to one H1+ and one S6+ atom. In the fourth O2- site, O2- is bonded in a single-bond geometry to one S6+ atom.

36 MATERIALS SCIENCE↗