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M D Schulte

Publications and source records attributed to M D Schulte.

7 recordsLinked to original sources
PubMed1999

Volumes of aqueous alcohols, ethers, and ketones to T = 523 K and p = 28 MPa.

Densities of dilute aqueous solutions of isopropanol, 1,5-pentanediol, cyclohexanol, benzyl alcohol, diethyl ether, 1,2-dimethoxyethane, acetone, and 2,5-hexanedione were measured by means of a vibrating-tube flow densimeter at temperatures near T = (302, 373, 423, 473, and 521) K at a pressure of p = 28 MPa. At the lowest and highest temperatures, measurements were also made close to the saturation vapour pressure of water to investigate the effect of pressure on the volumes of solutes. Apparent molar volumes were calculated for each solute and extrapolated to give partial molar volumes at infinite dilution. The variation of the volume with temperature, pressure, and structure of solute is discussed qualitatively, and group contributions are determined at the temperatures of measurements and p = 28 MPa. Several equations proposed in the literature for correlating the partial molar volumes at infinite dilution as a function of state parameters are tested. Parameters of one selected equation are tabulated allowing calculation of the partial molar volumes at infinite dilution at temperatures and pressures up to T = 573 K and p = 40 MPa. respectively.

2-Propanol↗
PubMed1995

Geochemical constraints on chemolithoautotrophic reactions in hydrothermal systems.

Thermodynamic calculations provide the means to quantify the chemical disequilibrium inherent in the mixing of reduced hydrothermal fluids with seawater. The chemical energy available for metabolic processes in these environments can be evaluated by taking into account the pressure and temperature dependence of the apparent standard Gibbs free energies of reactions in the S-H2-H2O system together with geochemical constraints on pH, activities of aqueous sulfur species and fugacities of H2 and/or O2. Using present-day mixing of hydrothermal fluids and seawater as a starting point, it is shown that each mole of H2S entering seawater from hydrothermal fluids represents about 200,000 calories of chemical energy for metabolic systems able to catalyze H2S oxidation. Extrapolating to the early Earth, which was likely to have had an atmosphere more reduced than at present, shows that this chemical energy may have been a factor of two or so less. Nevertheless, mixing of hydrothermal fluids with seawater would have been an abundant source of chemical energy, and an inevitable consequence of the presence of an ocean on an initially hot Earth. The amount of energy available was more than enough for organic synthesis from CO2 or CO, and/or polymer formation, indicating that the vicinity of hydrothermal systems at the sea floor was an ideal location for the emergence of the first chemolithoautotrophic metabolic systems.

Archaea↗
PubMed1993

Aldehydes in hydrothermal solution: standard partial molal thermodynamic properties and relative stabilities at high temperatures and pressures.

Aldehydes are common in a variety of geologic environments and are derived from a number of sources, both natural and anthropogenic. Experimental data for aqueous aldehydes were taken from the literature and used, along with parameters for the revised Helgeson-Kirkham-Flowers (HKF) equations of state, to estimate standard partial molal thermodynamic data for aqueous straight-chain alkyl aldehydes at high temperatures and pressures. Examples of calculations involving aldehydes in geological environments are given, and the stability of aldehydes relative to carboxylic acids is evaluated. These calculations indicate that aldehydes may be intermediates in the formation of carboxylic acids from hydrocarbons in sedimentary basin brines and hydrothermal systems like they are in the atmosphere. The data and parameters summarized here allow evaluation of the role of aldehydes in the formation of prebiotic precursors, such as amino acids and hydroxy acids on the early Earth and in carbonaceous chondrite parent bodies.

Aldehydes↗
PubMed1990

Amino-acid synthesis in carbonaceous meteorites by aqueous alteration of polycyclic aromatic hydrocarbons

It has been suggested that amino acids and other organic compounds found in carbonaceous meteorites formed by aqueous alteration in the meteorite parent bodies. Observations of carbonaceous material in interstellar grains and interplanetary dust particles indicate that condensed organic compounds may have been present in meteorite parent bodies at the time of aqueous alteration. One group of compounds thought to be representative of this carbonaceous material is the polycyclic aromatic hydrocarbons (PAHs). Recently it was proposed that PAHs condense on SiC grains in the molecular envelopes of carbon-rich red-giant stars, which would allow for their subsequent incorporation into meteorite parent bodies during accretion. This incorporation mechanism is supported by the identification of SiC grains in carbonaceous chondrites. The possibility therefore exists that PAHs, and/or other condensed organic compounds, represent the starting material for aqueous alteration which leads to the formation of amino acids and other water-soluble organic compounds. Here we present calculations of the distribution of aqueous organic compounds in metastable equilibrium with representative PAHs as functions of the fugacities of O2, CO2 and NH3. The results reported here for pyrene and fluoranthene, two PAHs with different structures but the same stoichiometry, differ greatly but indicate that the formation of amino and carboxylic acids is energetically favourable at probable parent-body alteration conditions. The actual reaction mechanisms involved could be revealed by consideration of isotope data for PAHs, amino acids, other organic compounds and carbonates in carbonaceous chondrites.

Amino Acids↗
PubMed1990

Summary and implications of reported amino acid concentrations in the Murchison meteorite

A study of literature reports of the concentrations of amino acids in extracts from the Murchison meteorite shows that many of the concentration ratios are constant. There are two possible interpretations of these ratios. One is that they are controlled by the pathways through which the amino acids formed, from which it follows that the amino acids are distributed in the same proportions throughout the meteorite. The other interpretation is that the ratios result from the analytical procedures used to extract the amino acids from the meteorite. These methods rely heavily on high-temperature (100 degrees C) aqueous extraction and subsequent high-temperature acid hydrolysis. A correlation was observed in the present study between the relative concentrations of several amino acids in the meteorite extracts and their relative aqueous solubilities at 100 degrees C (alanine, valine, leucine, isoleucine, norleucine, aspartic acid, glutamic acid and glycine). The extract solutions are dilute, and far from the saturation limits, but these correlations suggest that the sampling procedure affects directly the reported concentrations for these amino acids. Ratios of the concentration of serine to those of glycine are also constant but cannot be accounted for solely by relative solubilities, and, as suggested elsewhere, serine as well as phenylalanine and methionine may be terrestrial contaminants. Data for beta-alanine, alpha-aminobutyric acid, proline, sarcosine, alloisoleucine, beta-aminoisobutyric acid, beta-aminobutyric acid, and threonine also show constant abundances relative to glycine, but lack of solubility data at extraction conditions prohibits evaluating the extent of possible sampling bias for these amino acids. If the extraction process does not bias the results, and all extractable amino acids are removed from meteorite samples, then the properties of amino acids which control both their solubilities and their concentrations in the meteorite need to be established. The possibility of sampling bias needs to be tested experimentally before concluding that extraction is complete, and that the constant relative abundances indicate that the relative concentrations of amino acids are homogeneous in the meteorite.

Amino Acids↗