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The thermochemistry of the Si-O-H system has been extensively studied both experimentally and theoretically due to its importance in chemical processes, degradation of silica-protected materials in combustion, and geological processes. In this paper, we review past studies and use quantum mechanical methods to generate a new data set. Molecular geometries were generated with DFT using the B3LYP functional. Energetics were calculated with RCCSD(T) methods extrapolated to the complete basis set (CBS/45) limit. Particular attention was given to the treatment of the vibrational modes. A rigid rotor model was used, corrections for anharmonicity were applied, and the Pitzer-Gwinn treatment of the hindered rotation of the M-OH groups was applied. The generated enthalpies of formation at 298 K are compared to those of experiments and other calculations. Generally, the agreement is good. A set of thermodynamic data (enthalpy of formation at 298 K, entropy at 298 K, and heat capacity polynomial to 3000 K) is presented for SiOH, SiO(OH), Si(OH) 2 , SiO(OH) 2 , Si(OH) 3 , Si(OH) 4 , Si 2 O(OH) 6 , and Si 3 O 2 (OH) 8 . These can be added to any of the common computational thermodynamics packages. The application of these data to high-temperature corrosion and geological problems is discussed.

The chemical and isotopic signatures of moderately volatile elements are useful for understanding processes of volatile depletion in planetary formation and differentiation. However, the fractionation factors between gas and melt phases during evaporation that are required to model these planetary volatile depletion processes are still sparse. In this study, twenty heating experiments were conducted in 1 atm gas-mixing furnaces to constrain the behavior of K, Cu, and Zn evaporation and isotopic fractionation from basaltic melts at high temperatures. The temperatures range from 1300 °C to 1400 °C, and durations are from 2 to 8 days. Oxygen fugacities ( f O 2 ) range from one log unit below to ten log units above that of the iron-wüstite buffer (IW-1 to IW+10, corresponding to log f O 2 of -10.7 to -0.68 at 1400 °C). The conditions were selected to achieve an evaporation-dominated regime (where timescales of diffusion << evaporation for trace elements) in order to avoid diffusion-limited evaporation. Our results show during evaporation Zn behaved as the most volatile, followed by Cu and then K, regardless of temperature and oxygen fugacity. Partitioning of Zn into spinel layers within experimental capsules, however, has been observed, which has substantial effects on the Zn isotope fractionation factor. Therefore, Zn results are presented but further discussion is excluded. Element loss depends on both temperature and oxygen fugacity, where higher temperatures and lower oxygen fugacities promote evaporation. However, with varying temperature and oxygen fugacity, the kinetic isotopic fractionation factors, α (where, R R 0 = f α - 1 ), for K and Cu remain constant, thus these factors can be applied to a wider range of conditions than those in this study. The experimentally determined fractionation factors for K, and Cu during evaporation from basaltic melts are 0.9944, and 0.9961, respectively. The fractionation factors for these elements with varying volatilities are all significantly larger than the "apparent observed fractionation factors," which approach one and are inferred from lunar basalts relative to the Bulk Silicate Earth. This observation suggests near-equilibrium conditions during volatile-element loss from the Moon as the "apparent observed fractionation factors" of lunar basalts are similar for all three elements.

The Moon may have formed from an Earth-orbiting disk of vapor and melt produced by a giant impact. 1 The Moon and Earth's mantles have similar compositions. However, it is unclear why lunar samples are more depleted in volatile elements than terrestrial mantle rocks 2-3 , given that an evaporative escape mechanism 4 appears inconsistent with expected disk conditions. 5 Dynamical models 6-7 suggest that the Moon initially accreted from the outermost disk, but later acquired up to 60% of its mass from melt originating from the inner disk. Here we combine dynamical, thermal and chemical models to show that volatile depletion in the Moon can be explained by preferential accretion of volatile-rich melt in the inner disk to the Earth, rather than to the growing Moon. Melt in the inner disk is initially hot and volatile-poor, but volatiles condense as the disk cools. In our simulations, the delivery of inner disk melt to the Moon effectively ceases when gravitational interactions cause the Moon's orbit to expand away from the disk, and this termination of lunar accretion occurs prior to condensation of potassium and more volatile elements. Thus, the portion of the Moon derived from the inner disk is expected to be volatile depleted. We suggest that this mechanism may explain part or all of the Moon's volatile depletion, depending on the degree of mixing within the lunar interior.

Sulfurization of meteoritic metal in H2S-H2 gas produced three different sulfides: monosulfide solid solution [(Fe,Ni)1-xS], pentlandite [(Fe,Ni)9-xS8], and a phosphorus-rich sulfide. The composition of the remnant metal was unchanged. These results are contrary to theoretical predictions that sulfide formation in the solar nebula produced troilite (FeS) and enriched the remaining metal in nickel. The experimental sulfides are chemically and morphologically similar to sulfide grains in the matrix of the Alais (class CI) carbonaceous chondrite, suggesting that these meteoritic sulfides may be condensates from the solar nebula.

Intense bombardment of the moon and terrestrial planets approximately 3.9-4.0 x 10(9) years ago could have caused the chemical reprocessing of the Earth's primitive atmosphere. In particular, the shock heating and rapid quenching caused by the impact of large bodies into the atmosphere could produce molecules such as HCN and H2CO4 which are important precursors for the abiotic synthesis of complex organic molecules. Here we model the production of HCN and H2CO by thermochemical equilibrium and chemical kinetic calculations of the composition of shocked air parcels for a wide range of temperatures, pressures and initial compositions. For atmospheres with C/O > or = 1, our results suggest that bolide impacts cause HCN volume mixing ratios of approximately 10(-3) to 10(-5) in the impact region and global average ratios of 10(-5) to 10(-12). The corresponding H2CO mixing ratios in the impact region are 10(-7) to 10(-9); no-global mixing can occur, however, as H2CO is rapidly destroyed or rained out of the atmosphere within days to hours. Rainout to the oceans of 3-15% of the HCN produced can provide approximately (3-14) x 10(11) mol HCN per year. This is somewhat larger than other predicted sources of HCN and H2CO on the primitive Earth.

Several recently suggested Venus cloud condensates, including aluminum chloride and halides, oxides, and sulfides of arsenic and antimony, are assessed for their thermodynamic and geochemical plausibility. Aluminum chloride can confidently be ruled out, and condensation of arsenic sulfides on the surface will cause arsenic compounds to be too rare to produce the observed clouds. Antimony may be sufficiently volatile, but the expected molecular form is gaseous antimony sulfide, not the chloride. Arsenic and antimony compounds in the atmosphere will be regulated at very low levels by sulfide precipitation, irrespective of the planetary inventory of arsenic and antimony. Thus arguments for a volatile-deficient origin for Venus based on depletion of water and mercury (relative to the earth) cannot be tested by a search for atmospheric arsenic or antimony.