The applications of chemical thermodynamics and chemical kinetics to planetary atmospheres research

A review of the applications of chemical thermodynamics and chemical kinetics to planetary atmospheres research during the past four decades is presented with an emphasis on chemical equilibrium models and thermochemical kinetics. Several current problems in planetary atmospheres research such as the origin of the atmospheres of the terrestrial planets, atmosphere-surface interactions on Venus and Mars, deep mixing in the atmospheres of the gas giant planets, and the origin of the atmospheres of outer planet satellites all require laboratory data on the kinetics of thermochemical reactions for their solution

Kinetics of thermochemical gas-solid reactions important in the Venus sulfur cycle

The thermochemical net reaction CaCO3 + SO2 yields CaSO4 + CO is predicted to be an important sink for incorporation of SO2 into the Venus crust. The reaction rate law was established to understand the dependence of rate on experimental variables such as temperature and partial pressure of SO2, CO2, and O2. The experimental approach was a variant of the thermogravimetric method often employed to study the kinetics of thermochemical gas-solid reactions. Clear calcite crystals were heated at constant temperature in SO2-bearing gas streams for varying time periods. Reaction rate was determined by three independent methods. A weighted linear least squares fit to all rate data yielded a rate equation. Based on the Venera 13, 14 and Vega 2 observations of CaO content of the Venus atmosphere, SO2 at the calculated rate would be removed from the Venus atmosphere in about 1,900,00 years. The most plausible endogenic source of the sulfur needed to replenish atmospheric SO2 is volcanism. The annual amount of erupted material needed for the replenishment depends on sulfur content; three ratios are used to calculate rates ranging from 0.4 to 11 cu km/year. This geochemically derived volcanism rate can be used to test if geophysically derived rates are correct. The work also suggests that Venus is less volcanically active than the Earth

Non-equilibrium chemistry in the solar nebula and early solar system: Implications for the chemistry of comets

Theoretical models of solar nebula and early solar system chemistry which take into account the interplay between chemical, physical, and dynamical processes have great utility for deciphering the origin and evolution of the abundant chemically reactive volatiles (H, O, C, N, S) observed in comets. In particular, such models are essential for attempting to distinguish between presolar and solar nebula products and for quantifying the nature and duration of nebular and early solar system processing to which the volatile constituents of comets have been subjected. The diverse processes and energy sources responsible for chemical processing in the solar nebula and early solar system are discussed. The processes considered include homogeneous and heterogeneous thermochemical and photochemical reactions, and disequilibration resulting from fluid transport, condensation, and cooling whenever they occur on timescales shorter than those for chemical reactions

Silicon Tetrafluoride on Io

Silicon tetrafluoride (SiF4) is observed in terrestrial volcanic gases and is predicted to be the major F - bearing species in low temperature volcanic gases on Io (Schaefer and Fegley, 2005b). SiF4 gas is also a potential indicator of silica-rich crust on Io. We used F/S ratios in terrestrial and extraterrestrial basalts, and gas/lava enrichment factors for F and S measured at terrestrial volcanoes to calculate equilibrium SiF4/SO2 ratios in volcanic gases on Io. We conclude that SiF4 can be produced at levels comparable to the observed NaCl/SO2 gas ratio. We also considered potential loss processes for SiF4 in volcanic plumes and in Io's atmosphere including ion-molecule reactions, electron chemistry, photochemistry, reactions with the major atmospheric constituents, and condensation. Photochemical destruction (tchem ~ 266 days) and/or condensation as Na2SiF6 (s) appear to be the major sinks for SiF4. We recommend searching for SiF4 with infrared spectroscopy using its 9.7 micron band as done on Earth.Comment: 16 pages, 2 figures, 1 table; Icarus, in pres

Workshop on Innovative Instrumentation for the In Situ Study of Atmosphere-Surface Interactions on Mars

The speakers in the first session of the workshop addressed some of the continuing enigmas regarding the atmospheric composition, surface composition, and atmosphere-surface interactions on Mars; provided a description of a database of proposed payloads and instruments for SEI missions that is scheduled to be accessible in 1993; discussed potential uses of atmospheric imaging from landed stations on Mars; and advocated the collection and employment of high-spectral-resolution reflectance and emission data

The rate of volcanism on Venus

The maintenance of the global H2SO4 clouds on Venus requires volcanism to replenish the atmospheric SO2 which is continually being removed from the atmosphere by reaction with calcium minerals on the surface of Venus. The first laboratory measurements of the rate of one such reaction, between SO2 and calcite (CaCO3) to form anhydrite (CaSO4), are reported. If the rate of this reaction is representative of the SO2 reaction rate at the Venus surface, then we estimate that all SO2 in the Venus atmosphere (and thus the H2SO4 clouds) will be removed in 1.9 million years unless the lost SO2 is replenished by volcanism. The required rate of volcanism ranges from about 0.4 to about 11 cu km of magma erupted per year, depending on the assumed sulfur content of the erupted material. If this material has the same composition as the Venus surface at the Venera 13, 14 and Vega 2 landing sites, then the required rate of volcanism is about 1 cu km per year. This independent geochemically estimated rate can be used to determine if either (or neither) of the two discordant (2 cu km/year vs. 200 to 300 cu km/year) geophysically estimated rates is correct. The geochemically estimated rate also suggests that Venus is less volcanically active than the Earth

Biospheric traumas caused by large impacts and predicted relics in the sedimentary record

When a large asteroid or comet impacts the Earth the supersonic plume ejected on impact causes severe shock heating and chemical reprocessing of the proximal atmosphere. The resultant NO is converted rapidly to NO2, foliage damage due to exposure to NO2 and HNO3, toxicosis resulting from massive mobilization of soil trace metals, and faunal asphyxiation due to exposure to NO2. One class of relic evidence for the above effects arises because extinction of species caused by these chemically induced traumas would be selective. A second class of relic evidence arises because the acid rain will cause massive weathering of continental rocks and soils characterized by large ratios of the relatively insoluble metals, to the more soluble metals. This weathering would be best recorded in fossils in unperturbed deltaic, neritic, or limnetic sediments and for metals with very long oceanic residence times in deep ocean sediments as well. This evidence is discussed

Lyman Alpha Photochemistry in the Solar Nebula

The purpose of the project "Lyman Alpha Photochemistry in the Solar Nebula" was to model photochemistry in the primitive solar nebula and the early solar systems. As part of the modeling, it was necessary to model the composition of the gas and dust accreted by the solar nebula. This final report contains a list of publications where the results of this project have been published