Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “H2SO4”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 109 records · Page 6

Crystallization of supercooled solutions

Crystallization of uniformly supercooled solutions (Na2SO4, NaCl, H2SO4, HNO3, HCl) was studied. It is shown how crystal growth velocity and habit depend on solution and concentration. The segregation coefficient for the solute in ice is measured by analysis of ice and solution, separated immediately after initial freezing, at different supercoolings. Subsequent solidification gives ion rejection at a varying rate depending on the geometry of the freezing, and may result in separation of hydrates, particularly when the initial concentration is high, as in haze (inactivated) droplets and low temperatures found in the Antarctic stratosphere. Electrical effects associated with rapid freezing are also investigated. Results suggest that more extensive measurements need to be made in solutions at different supercoolings, and that substantial electrical effects may be present for higher concentrations under these conditions. Damage to vegetation could occur under specific conditions as concentrated solutions (possibly H2SO4) are rejected in the freezing of rime or dew.

Harrison, K.↗

Observations of the microwave emission of Venus from 1.3 to 3.6 cm

An account is given of the methodology as well as the results of coordinated Venus emission observations conducted at four wavelengths between 1.35 and 3.6 cm; the results are compared with other observations and with calculated mission spectra, with a view to suggestions that the microwave spectrum of Venus could be sensitive to the subcloud abundance of such constituents as SO2 and gaseous H2SO4. The observed emission spectrum is consistent with an average subcloud abundance of gaseous H2SO4 in equatorial and midlatitude regions of about 5 ppm. An upper limit is established for the subcloud SO2 abundance.

Steffes, Paul G.↗

Nitric acid uptake by sulfuric acid solutions under stratospheric conditions - Determination of Henry's Law solubility

The uptake of nitric acid by sulfuric acid solutions representative of stratospheric particulate at low temperatures was measured to determine the solubility of nitric acid in sulfuric acid solutions as a function of H2SO4 concentration and solution temperature. Solubilities are reported for sulfuric acid solutions ranging from 58 to 87 wt pct H2SO4 over a temperature range from 188 to 240 K, showing that, in general, the solubility of nitric acid increases with decreasing sulfuric acid concentration and with decreasing temperature. The measured solubilities indicate that nitric acid in the global stratosphere will be found predominantly in the gas phase.

Reihs, Christa M.↗

Pioneer-Venus radio occultation (ORO) data reduction: Profiles of 13 cm absorptivity

In order to characterize possible variations in the abundance and distribution of subcloud sulfuric acid vapor, 13 cm radio occultation signals from 23 orbits that occurred in late 1986 and 1987 (Season 10) and 7 orbits that occurred in 1979 (Season 1) were processed. The data were inverted via inverse Abel transform to produce 13 cm absorptivity profiles. Pressure and temperature profiles obtained with the Pioneer-Venus night probe and the northern probe were used along with the absorptivity profiles to infer upper limits for vertical profiles of the abundance of gaseous H2SO4. In addition to inverting the data, error bars were placed on the absorptivity profiles and H2SO4 abundance profiles using the standard propagation of errors. These error bars were developed by considering the effects of statistical errors only. The profiles show a distinct pattern with regard to latitude which is consistent with latitude variations observed in data obtained during the occultation seasons nos. 1 and 2. However, when compared with the earlier data, the recent occultation studies suggest that the amount of sulfuric acid vapor occurring at and below the main cloud layer may have decreased between early 1979 and late 1986.

Steffes, Paul G.↗

Laboratory evaluation and application of microwave absorption properties under simulated conditions for planetary atmospheres

Laboratory measurements of microwave and millimeter wave properties of the simulated atmosphere of the outer planets and their satellites has continued. One of the focuses is on the development of a radiative transfer model of the Jovian atmosphere at wavelengths from 1 mm to 10 cm. This modeling effort led to laboratory measurements of the millimeter wave opacity of hydrogen sulfide (H2S) under simulated Jovian conditions. Descriptions of the modeling effort, the Laboratory experiment, and the observations are presented. Correlative studies of measurements with Pioneer-Venus radio occultation measurements with longer wavelength emission measurements have provided new ways for characterizing temporal and spatial variations in the abundance of both gases H2SO4 and SO2, and for modeling their roles in the subcloud atmosphere. Laboratory measurements were conducted on 1.35 cm (and 13 cm) opacity of gaseous SO2 and absorptivity of gaseous SO2 at the 3.2 mm wavelength under simulated Venus conditions. Laboratory measurements were completed on millimeter wave dielectric properties of liquid H2SO4, in order to model the effects of the opacity of the clouds of Venus onto millimeter wave emission spectrum.

Steffes, Paul G.↗

A global three-dimensional model of the stratospheric sulfuric acid layer

A 3D model which encompasses SO2 production from OCS, followed by its oxidation to gaseous H2SO4, the condensation-evaporation equilibrium of gaseous and particulate H2SO4, and finally particle condensation and rainout, is presently used to study processes maintaining the nonvolcanically-perturbed stratosphere's sulfuric acid layer. A comparison of the results thus obtained with remotely sensed stratospheric aerosol extinction data shows the model to simulate the general behavior of stratospheric aerosol extinction.

Golombek, Amram↗

Physical chemistry of the H2SO4/HNO3/H2O system - Implications for polar stratospheric clouds

Polar stratospheric clouds (PSCs) play a key role in stratospheric ozone depletion. Surface-catalyzed reactions on PSC particles generate chlorine compounds that photolyze readily to yield chlorine radicals, which in turn destroy ozone very efficiently. The most prevalent PSCs form at temperatures several degrees above the ice frost point and are believed to consist of HNO3 hydrates; however, their formation mechanism is unclear. Results of laboratory experiments are presented which indicate that the background stratospheric H2SO4/H2O aerosols provide an essential link in this mechanism: These liquid aerosols absorb significant amounts of HNO3 vapor, leading most likely to the crystallization of nitric acid trihydrate (NAT). The frozen particles then grow to form PSCs by condensation of additional amounts of HNO3 and H2O vapor. Furthermore, reaction probability measurements reveal that the chlorine radical precursors are formed readily at polar stratospheric temperatures not just on NAT and ice crystals, but also on liquid H2SO4 solutions and on solid H2SO4 hydrates. These results imply that the chlorine activation efficiency of the aerosol particles increases rapidly as the temperature approaches the ice frost point regardless of the phase or composition of the particles.

Molina, M. J.↗

Photochemical modelling of Venus clouds using Pioneer Venus data

In order to understand the evolution of water on Venus, we must know the hydrogen escape flux as a function of the tropospheric water abundance. We have studied the connection between total stratospheric hydrogen and exobase hydrogen available to non-thermal escape processes and examined the details of the photochemical trap for water at the Venus cloud tops. Our immediate goal is to calculate the stratospheric water abundance as a function of the tropospheric water abundance. Photochemical production of H2SO4 acts as a sink for both water and sulfur and is capable of keeping stratospheric abundances low if a proper balance exists between the tropospheric abundances. If production of H2SO4 were the only sink for H2O and SO2, the excess in tropospheric abundance of one over the other would reach the stratosphere, and the functional dependence of stratospheric H2O on tropospheric H2O would be linear near the present state. On Venus, however, sulfuric acid condenses at cloud top temperatures and the resulting aerosols can absorb additional water of hydration. This complicates the water budget, increasing the efficiency of sulfur as a sink for water. We have investigated the balance between tropospheric H2O and SO2 and how delicate the balance is. Our major conclusions from this work are the following: (1) H2O and SO2 are mutually limiting if proper tropospheric balance is maintained; (2) changes in tropospheric abundances on the order of 5 ppm are significant; and (3) changes in mixing rates near the cloud tops can cause dramatic changes in SO2 without causing dramatic changes in H2O.

Mcelroy, Michael B.↗

Global blackout following the K/T Chicxulub impact: Results of impact and atmospheric modeling

Several recent studies have suggested that shock decomposition of anhydrite (CaSO4) target rocks during the K/T Chicxulub impact would have ejected tremendous amounts of sulfur gas into the stratosphere. One of the many potential biospheric effects of this sulfur gas is the generation of a sulfuric acid (H2SO4) aerosol layer capable of causing darkness and severe disruption of photosynthesis for periods of years. In this paper we report the preliminary results of our modeling of shock pressures within the anhydrites and of light attenuation by the H2SO4 aerosol cloud. These models indicate that earlier studies over-estimated the amount of sulfur gas produced, but that more than enough was produced to extend global blackout conditions 4-6 times longer than the approximately 3 month predictions for silicate dust alone.

Pope, K. O.↗

Ion-assisted tropospheric OH measurement technique

The present technique measures atmospheric OH concentrations by first titrating OH into isotopically labeled H2(exp 34)SO4 by a series of gas phase reactions in an effectively wall-less flow tube reactor on a time-scale which is short in comparison to the OH lifetime. The gas phase H2SO4 concentration is then determined by reacting it with NO3(-)(center dot)HNO3 ions in a flow tube, and subsequently measuring the resulting (HSO4(-))/(NO3(-)) ion ratio. Since the determination of H2SO4 concentration does not depend on the measurement of an absolute photon flux or chemical concentration but rather only on the relative concentration measurement of two fairly similar mass ions in conjunction with a fixed reaction time and reaction rate coefficient, no in-field calibration technique should be required. The ion-assisted OH measurement technique provides a concentration measurement about once each 10 to 20 seconds and had a detection sensitivity less than or equal to 1 x 10(exp 5) molecules/cu cm (2 standard deviations) with an integration time of 5 minutes during the past field study. Typically, the total background signal level is in the low 10(exp 6) molecule/cu cm range with the scatter in this background (or background noise in 5 minutes) in the mid 10(exp 4) molecules/cu cm range.

Eisele, Fred L.↗

Reduction and analysis of seasons 15 and 16 (1991 - 1992) Pioneer Venus radio occulation data and correlative studies with observations of the near infrared emission of Venus

In this study, we sought to characterize variations in the abundance and distribution of subcloud H2SO4(g) in the Venus atmosphere by using a number of 13cm radio occultation measurements conducted with the Pioneer Venus Orbiter near the inferior conjunction of 1991. A total of ten data sets were examined and analyzed, producing vertical profiles of temperature and pressure in the neutral atmosphere, and sulfuric acid vapor abundance below the main cloud layer. Two of the vertical profiles of the abundance of H2SO4(g) were correlated with NIR images of the night side of Venus made during the same period of time by Boris Ragent (under a separate PVO Guest Investigator Grant). Initially, we had hoped that the combination of these two different types of data would make it possible to constrain or identify the composition of the large particles causing the features observed in the NIR images. However, the sparseness of the radio occultation data set, combined with the sparseness of the NIR data set (one image per day over an 8 day period) made it impossible to draw strong conclusions. Considered on their own, however, the parameters retrieved from the radio occultation experiments are valuable science products.

Jenkins, Jon M.↗

A model for studying the composition and chemical effects of stratospheric aerosols

We developed polynomial expressions for the temperature dependence of the mean binary and water activity coefficients for H2SO4 and HNO3 solutions. These activities were used in an equilibrium model to predict the composition of stratospheric aerosols under a wide range of environmental conditions. For typical concentrations of H2O, H2SO4, HNO3, HCl, HBr, HF, and HOCl in the lower stratosphere, the aerosol composition is estimated as a function of the local temperature and the ambient relative humidity. For temperatures below 200 K, our results indicate that (1) HNO3 contributes a significant mass fraction to stratospheric aerosols, and (2) HCl solubility is considerably affected by HNO3 dissolution into sulfate aerosols. We also show that, in volcanically disturbed periods, changes in stratospheric aerosol composition can significantly alter the microphysics that leads to the formation of polar stratospheric clouds. The effects caused by HNO3 dissolution on the physical and chemical properties of stratospheric aerosols are discussed.

Tabazadeh, Azadeh↗

Observation of hydration of single, modified carbon aerosols

We have compared the hydration behavior of single carbon particles that have been treated by exposure to gaseous H2SO4 with that of untreated particles. Untreated carbon particles did not hydrate as the relative humidity varied from 0 to 80% at 23 C. In contrast, treated particles hydrated under subsaturation conditions; mass increases of up to 30% were observed. The mass increase is consistent with sulfuric acid equilibration with the ambient relative humidity in the presence of inert carbon. For the samples studied, the average amount of absorbed acid was 14% +/- 6% by weight, which corresponds to a surface coverage of approximately 0.1 monolayer. The mass fraction of surface-absorbed acid is comparable to the soluble mass fraction observed by Whitefield et al. (1993) in jet aircraft engine aerosols. Estimates indicate this mass fraction corresponds to 0.1% of the available SO2 exiting an aircraft engine ending up as H2SO4 on the carbon aerosol. If this heterogeneous process occurs early enough in the exhaust plume, it may compete with homogeneous nucleation as a mechanism for producing sulfuric acid rich aerosols.

Wyslouzil, B. E.↗

Heterogeneous Reactions of ClONO2, HCl, and HOCl on Liquid Sulfuric Acid Surfaces

The heterogeneous reactions of ClONO2 + H2O yields HNO3 + HOCl (1), ClONO2 + HCl yields C12 + HNO3 (2), and HOCl + HCl yields Cl2 + H2O (3) on liquid sulfuric acid surfaces have been studied using a fast flow reactor coupled to a quadrupole mass spectrometer. The main objectives of the study are to investigate: (a) the temperature dependence of these reactions at a fixed H2O partial pressure typical of the lower stratosphere (that is, by changing temperature at a constant water partial pressure, the H2SO4 content of the surfaces is also changed), (b) the relative importance or competition between reactions 1 and 2, and (c) the effect of HNO3 on the reaction probabilities due to the formation of a H2SO4/HNO3/H2O ternary system. The measurements show that all the reactions depend markedly on temperature at a fixed H2O partial pressure: they proceed efficiently at temperatures near 200 K and much slower at temperatures near 220 K. The reaction probability (gamma(sub 1)) for ClONO2 hydrolysis approaches 0.01 at temperatures below 200 K, whereas the values for gamma(sub 2) and gamma(sub 3) are on the order of a few tenths at 200 K. Although detailed mechanisms for these reactions are still unknown, the present data indicate that the competition between ClONO2 hydrolysis and ClONO2 reaction with HCl may depend on temperature (or H2SO4 Wt %): in the presence of gaseous HCl at stratospheric concentrations, reaction 2 is dominant at lower temperatures (less than 200 K), but reaction 1 becomes important at temperatures above 210 K. Furthermore, reaction probability measurements performed on the H2SO4/HNO3/ H2O ternary solutions do not exhibit noticeable deviation from those performed on the H2SO4/H2O binary system, suggesting little effect of HNO3 in sulfate aerosols on the ClONO2 and HOCl reactions with HCl. The results reveal that significant reductions in the chlorine-containing reservoir species (such as ClONO2 and HCl) can take place on stratospheric sulfate aerosols at high latitudes in winter and early spring, even at temperatures too warm for Polar Stratospheric Clouds (PSCs) to form or in regions where nucleation of PSCs is sparse. This is particularly true under elevated sulfuric acid loading, such as that after the eruption of Mt. Pinatubo. Comparisons between our results and those presently available have also been made.

Zhang, Renyi↗

Modeling Macro- and Micro-Scale Turbulent Mixing and Chemistry in Engine Exhaust Plumes

Simulation of turbulent mixing and chemical processes in the near-field plume and plume-vortex regimes has been successfully carried out recently using a reduced gas phase kinetics mechanism which substantially decreased the computational cost. A detailed mechanism including gas phase HOx, NOx, and SOx chemistry between the aircraft exhaust and the ambient air in near-field aircraft plumes is compiled. A reduced mechanism capturing the major chemical pathways is developed. Predictions by the reduced mechanism are found to be in good agreement with those by the detailed mechanism. With the reduced chemistry, the computer CPU time is saved by a factor of more than 3.5 for the near-field plume modeling. Distributions of major chemical species are obtained and analyzed. The computed sensitivities of major species with respect to reaction step are deduced for identification of the dominant gas phase kinetic reaction pathways in the jet plume. Both the near field plume and the plume-vortex regimes were investigated using advanced mixing models. In the near field, a stand-alone mixing model was used to investigate the impact of turbulent mixing on the micro- and macro-scale mixing processes using a reduced reaction kinetics model. The plume-vortex regime was simulated using a large-eddy simulation model. Vortex plume behind Boeing 737 and 747 aircraft was simulated along with relevant kinetics. Many features of the computed flow field show reasonable agreement with data. The entrainment of the engine plumes into the wing tip vortices and also the partial detrainment of the plume were numerically captured. The impact of fluid mechanics on the chemical processes was also studied. Results show that there are significant differences between spatial and temporal simulations especially in the predicted SO3 concentrations. This has important implications for the prediction of sulfuric acid aerosols in the wake and may partly explain the discrepancy between past numerical studies (that employed parabolic or temporal approximations) and the measured data. Finally to address the major uncertainty in the near-field plume modeling related to the plume processing of sulfur compounds and advanced model was developed to evaluate its impact on the chemical processes in the near wake. A comprehensive aerosol model is developed and it is coupled with chemical kinetics and the axisymmetric turbulent jet flow models. The integrated model is used to simulate microphysical processes in the near-field jet plume, including sulfuric acid and water binary homogeneous nucleation, coagulation, non-equilibrium heteromolecular condensation, and sulfur-induced soot activation. The formation and evolution of aerosols are computed and analyzed. The computed results show that a large number of ultra-fine (0.3--0.6 nm in radius) volatile HSO4 - HO embryos are generated in the near-field plume. These embryos further grow in size by self coagulation and condensation. Soot particles can be activated by both heterogeneous nucleation and scavenging of H2SO4-H2O aerosols. These activated soot particles can serve as water condensation nuclei for contrail formation. Conditions under which ice contrails can form behind aircrafts are studied. The sensitivities of the threshold temperature for contrail formation with respect to aircraft propulsion efficiency, relative humidity, and ambient pressure are evaluated. The computed aerosol properties for different extent of fuel sulfur conversion to S(VI) (SO3 and H2SO4) in engine are examined and the results are found to be sensitive to this conversion fraction.

Menon, Suresh↗

Trace Chemistry

The goals of the trace chemistry group were to identify the processes relevant to aerosol and aerosol precursor formation occurring within aircraft gas turbine engines; that is, within the combustor, turbine, and nozzle. The topics of discussion focused on whether the chemistry of aerosol formation is homogeneous or heterogeneous; what species are important for aerosol and aerosol precursor formation; what modeling/theoretical activities to pursue; what experiments to carry out that both support modeling activities and elucidate fundamental processes; and the role of particulates in aerosol and aerosol precursor formation. The consensus of the group was that attention should be focused on SO2, SO3, and aerosols. Of immediate concern is the measurement of the concentration of the species SO3, SO2, H2SO4 OH, HO2, H2O2, O, NO, NO2, HONO, HNO3, CO, and CO2 and particulates in various engines, both those currently in use and those in development. The recommendation was that concentration measurements should be made at both the combustor exit and the engine exit. At each location the above species were classified into one of four categories of decreasing importance, Priority I through IV, as follows: Combustor exit: Priority I species - SO3:SO2 ratio, SO3, SO2, and particulates; Priority II species: OH and O; Priority III species - NO and NO2; and Priority IV species - CO and CO2. For the Engine exit: Priority I species - SO3:SO2 ratio, SO3, SO2,H2SO4, and particulates; Priority II species: OH,HO2, H2O2, and O; Priority III species - NO, NO2, HONO, and HNO3; and Priority IV species - CO and CO2. Table I summarizes the anticipated concentration range of each of these species. For particulate matter, the quantities of interest are the number density, size distribution, and composition. In order to provide data for validating multidimensional reacting flow models, it would be desirable to make 2-D, time-resolved measurements of the concentrations of the above species and, in addition, of the pressure, temperature, and velocity. A near term goal of the experimental program should be to confirm the nonlinear effects of sulfur speciation, and if present, to provide an explanation for them. It is also desirable to examine if the particulate matter retains any sulfur. The recommendation is to examine the effects on SOx production of variations in fuel-bound sulfur and aromatic content (which may affect the amount of particulates formed). These experiments should help us to understand if there is a coupling between particulate formation and SO, concentration. Similarly, any coupling with NOx can be examined either by introducing NOx into the combustion air or by using fuel-bound nitrogen. Also of immediate urgency is the need to establish and validate a detailed mechanism for sulfur oxidation/aerosol formation, whose chemistry is concluded to be homogeneous, because there is not enough surface area for heterogeneous effects. It is envisaged that this work will involve both experimental and theoretical programs. The experimental work will require, in addition to the measurements described above, fundamental studies in devices such as flow reactors and shock tubes. Complementing this effort should be modeling and theoretical activities. One impediment to the successful modeling of sulfur oxidation is the lack of reliable data for thermodynamic and transport properties for several species, such as aqueous nitric acid, sulfur oxides, and sulfuric acid. Quantum mechanical calculations are recommended as a convenient means of deriving values for these properties. Such calculations would also help establish rate constants for several important reactions for which experimental measurements are inherently fraught with uncertainty. Efforts to implement sufficiently detailed chemistry into computational fluid dynamic codes should be continued. Zero- and one-dimensional flow models are also useful vehicles for elucidating the minimal set of species and reactions that must be included in two- and three-dimensional modeling studies.

Radhakrishnan, Krishnan↗

Freezing Behavior of Stratospheric Sulfate Aerosols Inferred from Trajectory Studies

Temperature histories based on 10-day back growth trajectories for six ER-2 flights during AASE I (1989) and AAOE (1987) are presented. These trajectories along with the properties of the observed PSC (polar stratospheric cloud) particles are used here to infer the physical state of the pre-existing sulfuric acid aerosols. Of all the ER-2 flights described here, only the PSCs observed on the flights of January 24 and 25, 1989 are consistent with the thermodynamics of liquid ternary solutions of H2SO4/HNO3/H2O Ib PSCs). For these two days, back trajectories indicate that the air mass was exposed to SAT (sulfuric acid tetrahydrate) melting temperatures about 24 hours prior to being sampled by the ER-2. For the remaining ER-2 flights (January, 16, 19, and 20 for the AASE I campaign and August 17 for the AAOE campaign), the observed PSCs were probably composed of amorphous solid solutions of HNO3 and H2O (Type Ic PSCs). Formation of such Type Ic PSCs requires the presence of solid H2SO4 aerosols since liquid aerosols yield ternary solutions. The 10-day back trajectories of these flights indicate that the air mass was not exposed to SAT melting temperatures during the past week and had experienced cooling/warming cycles prior to being sampled by the ER-2. These temperature histories, recent laboratory measurements and the properties of glassy solids suggest that stratospheric H2SO4 aerosols may undergo a phase transition to SAT upon warming at approximately 198 K after going through a cooling cycle to about 194 K or lower.

Tabazadeh, A.↗

Methanol Uptake by Low Temperature Aqueous Sulfuric Acid Solutions

The global methanol budget is currently unbalanced, with source terms significantly larger than the sinks terms. To evaluate possible losses of gaseous methanol to sulfate aerosols, the solubility and reactivity of methanol in aqueous sulfuric acid solutions representative of upper tropospheric and lower stratospheric aerosols is under investigation. Methanol will partition into sulfate aerosols according to its Henry's law solubility. Using standard uptake techniques in a Knudsen cell reactor, we have measured the effective Henry's law coefficient, H*, for cold (196 - 220 K) solutions ranging between 45 and 70 wt % H2SO4. We have found that methanol solubility ranges from approx. 10(exp 5) - 10(exp 7) M/atm for UT/LS conditions. Solubility increases with decreasing temperature and with increasing sulfuric acid content. Although methanol is slightly more soluble than are acetone and formaldehyde, current data indicate that uptake by clean aqueous sulfuric acid particles will not be a significant sink for methanol in the UT/LS. These solubility measurements include uptake due to physical solvation and any rapid equilibria which are established in solution. 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 is not significant over our experimental time scale for solutions below 80 wt % H2SO4. To confirm this directly, results obtained using a complementary equilibrium measurement technique will also be presented.

Iraci, L. T.↗