Composition of aqueous solutions in equilibrium with sulfides and oxides of iron at 3500°C

Solutions of potassium chloride (pH-buffered and 1-molat) equilibrated at 350°C with pyrrhotite, pyrite, and magnetite contained approximately 1 millimole of reduced sulfur and less than 0.1 millimole of oxidized sulfur per kilogram. Similar solutions equilibrated with pyrite, magnetite, and hematite contained approximately 1 millimole of reduced sulfur, but 3 to 6 millimoles of oxidized sulfur per kilogram. Both types of solutions contained less than 0.1 millimole of iron per kilogram at pH ≥ 6 and approximately 100 millimoles per kilogram at pH 2.

Vapor-liquid equilibrium data for the system n-heptane-n-butyl alcohol at medium pressures

Vapor-liquid equilibrium data for the system n-heptane-n-butyl alcohol at pressures of 1445, 2205, 2965, and 3725 mm. of Hg have been reported. The data are correlated with Chao's modified Redlich-Kister equation.

Vapor-liquid equilibrium data for the systems diisopropyl ether-n-heptane and diisopropyl ether-carbon tetrachloride at medium pressures

Vapor-liquid equilibrium data for the systems diisopropyl ether-n-heptane and diisopropyl ether-carbon tetrachloride have been reported at pressures of 760, 1520, and 2280 mm. of Hg. The systems form ideal mixtures under the pressure range studied.

Isobaric vapor-liquid equilibrium of n-heptane-n-butanol system

Vapor-liquid equilibrium data for the system n-heptane-n-butanol have been reported. The thermodynamic consistency of the data was tested with Chao's modified Redlich-Kister equation and Tao's method.

Hydrochlorination of methanol to methyl chloride in fixed catalyst beds

The vapor phase hydrochlorination of methanol to methyl chloride in fixed beds with silica gel-alumina (88 to 12) and γ-alumina catalysts was studied in a glass tubular reactor in the temperature range of 300° to 390°C. Of the two catalysts studied, γ-alumina gave nearly equilibrium conversions under the experimental conditions. The data are expressed in the form of second-order irreversible rate equations for both the catalysts studied.

Pd and Pt ions as highly active sites for the water-gas shift reaction over combustion synthesized zirconia and zirconia-modified ceria

Noble metal substituted ionic catalysts were synthesized by solution combustion technique. The compounds were characterized by X-ray diffraction, FT-Raman spectroscopy, and X-ray photoelectron spectroscopy. Zirconia supported compounds crystallized in tetragonal phase. The solid solutions of ceria with zirconia crystallized in fluorite structure. The noble metals were substituted in ionic form.The water-gas shift reaction was carried out over the catalysts.Negligible conversions were observed with unsubstituted compounds. The substitution of a noble metal ion was found to enhance the reaction rate. Equilibrium conversion was obtained below 250 degrees C in the presence of Pt ion substituted compounds. The formation of Bronsted acid-Bronsted base pairs was proposed to explain the activity of zirconia catalysts. The effect of oxide ion vacancies on the reactions over substituted ceria-zirconia solid solutions was established. (c)2010 Elsevier B.V. All rights reserved.

Extraordinary high strain rate superplasticity in electrodeposited nano-nickel and alloys

Superplastic materials exhibit very large elongations to failure,typically >500%, and this enables commercial forming of complex shaped components at slow strain rates of similar to 10(-4) s(-1). We report extraordinary record superplastic elongations to failure of up to 5300% at both high strain rates and low temperature in electrodeposited nanocrystalline Ni and some Ni alloys. Superplasticity is not related to the presence of sulfur or a low melting phase at grain boundaries. (C) 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Truthful and Quality Conscious Query Incentive Networks

Query incentive networks capture the role of incentives in extracting information from decentralized information networks such as a social network. Several game theoretic tilt:Kids of query incentive networks have been proposed in the literature to study and characterize the dependence, of the monetary reward required to extract the answer for a query, on various factors such as the structure of the network, the level of difficulty of the query, and the required success probability.None of the existing models, however, captures the practical andimportant factor of quality of answers. In this paper, we develop a complete mechanism design based framework to incorporate the quality of answers, in the monetization of query incentive networks. First, we extend the model of Kleinberg and Raghavan [2] to allow the nodes to modulate the incentive on the basis of the quality of the answer they receive. For this qualify conscious model. we show are existence of a unique Nash equilibrium and study the impact of quality of answers on the growth rate of the initial reward, with respect to the branching factor of the network. Next, we present two mechanisms; the direct comparison mechanism and the peer prediction mechanism, for truthful elicitation of quality from the agents. These mechanisms are based on scoring rules and cover different; scenarios which may arise in query incentive networks. We show that the proposed quality elicitation mechanisms are incentive compatible and ex-ante budget balanced. We also derive conditions under which ex-post budget balance can beachieved by these mechanisms.

An evaluation of rate-controlling obstacles for low-temperature deformation of zirconium

The low-temperature plastic flow of alpha-zirconium was studied by employing constantrate tensile tests and differential-stress creep experiments. The activation parameters, enthalpy and area, have been obtained as a function of stress for pure, as well as commercial zirconium. The activation area is independent of grain size and purity and falls to about 9b2 at high stresses. The deformation mechanism below about 700° K is found to be controlled by a single thermally activated process, and not a two-stage activation mechanism. Several dislocation mechanisms are examined and it is concluded that overcoming the Peierls energy humps by the formation of kink pairs in a length of dislocation is the rate-controlling mechanism. The total energy needed to nucleate a double kink is about 0.8 eV in pure zirconium and 1 eV in commercial zirconium

Monte Carlo simulations of molecular clusters in nucleation

A better understanding of the limiting step in a first order phase transition, the nucleation process, is of major importance to a variety of scientific fields ranging from atmospheric sciences to nanotechnology and even to cosmology. This is due to the fact that in most phase transitions the new phase is separated from the mother phase by a free energy barrier. This barrier is crossed in a process called nucleation. Nowadays it is considered that a significant fraction of all atmospheric particles is produced by vapor-to liquid nucleation. In atmospheric sciences, as well as in other scientific fields, the theoretical treatment of nucleation is mostly based on a theory known as the Classical Nucleation Theory. However, the Classical Nucleation Theory is known to have only a limited success in predicting the rate at which vapor-to-liquid nucleation takes place at given conditions. This thesis studies the unary homogeneous vapor-to-liquid nucleation from a statistical mechanics viewpoint. We apply Monte Carlo simulations of molecular clusters to calculate the free energy barrier separating the vapor and liquid phases and compare our results against the laboratory measurements and Classical Nucleation Theory predictions. According to our results, the work of adding a monomer to a cluster in equilibrium vapour is accurately described by the liquid drop model applied by the Classical Nucleation Theory, once the clusters are larger than some threshold size. The threshold cluster sizes contain only a few or some tens of molecules depending on the interaction potential and temperature. However, the error made in modeling the smallest of clusters as liquid drops results in an erroneous absolute value for the cluster work of formation throughout the size range, as predicted by the McGraw-Laaksonen scaling law. By calculating correction factors to Classical Nucleation Theory predictions for the nucleation barriers of argon and water, we show that the corrected predictions produce nucleation rates that are in good comparison with experiments. For the smallest clusters, the deviation between the simulation results and the liquid drop values are accurately modelled by the low order virial coefficients at modest temperatures and vapour densities, or in other words, in the validity range of the non-interacting cluster theory by Frenkel, Band and Bilj. Our results do not indicate a need for a size dependent replacement free energy correction. The results also indicate that Classical Nucleation Theory predicts the size of the critical cluster correctly. We also presents a new method for the calculation of the equilibrium vapour density, surface tension size dependence and planar surface tension directly from cluster simulations. We also show how the size dependence of the cluster surface tension in equimolar surface is a function of virial coefficients, a result confirmed by our cluster simulations.

Molecular Dynamics Simulations of Homogeneous Nucleation

Nucleation is the first step in a phase transition where small nuclei of the new phase start appearing in the metastable old phase, such as the appearance of small liquid clusters in a supersaturated vapor. Nucleation is important in various industrial and natural processes, including atmospheric new particle formation: between 20 % to 80 % of atmospheric particle concentration is due to nucleation. These atmospheric aerosol particles have a significant effect both on climate and human health. Different simulation methods are often applied when studying things that are difficult or even impossible to measure, or when trying to distinguish between the merits of various theoretical approaches. Such simulation methods include, among others, molecular dynamics and Monte Carlo simulations. In this work molecular dynamics simulations of the homogeneous nucleation of Lennard-Jones argon have been performed. Homogeneous means that the nucleation does not occur on a pre-existing surface. The simulations include runs where the starting configuration is a supersaturated vapor and the nucleation event is observed during the simulation (direct simulations), as well as simulations of a cluster in equilibrium with a surrounding vapor (indirect simulations). The latter type are a necessity when the conditions prevent the occurrence of a nucleation event in a reasonable timeframe in the direct simulations. The effect of various temperature control schemes on the nucleation rate (the rate of appearance of clusters that are equally able to grow to macroscopic sizes and to evaporate) was studied and found to be relatively small. The method to extract the nucleation rate was also found to be of minor importance. The cluster sizes from direct and indirect simulations were used in conjunction with the nucleation theorem to calculate formation free energies for the clusters in the indirect simulations. The results agreed with density functional theory, but were higher than values from Monte Carlo simulations. The formation energies were also used to calculate surface tension for the clusters. The sizes of the clusters in the direct and indirect simulations were compared, showing that the direct simulation clusters have more atoms between the liquid-like core of the cluster and the surrounding vapor. Finally, the performance of various nucleation theories in predicting simulated nucleation rates was investigated, and the results among other things highlighted once again the inadequacy of the classical nucleation theory that is commonly employed in nucleation studies.